The abundance of barium in stony meteorites

The concentration of Ba in 7 carbonaceous chondrites, 18 ordinary chondrites, 3 achondrites and 1 stony-iron meteorite has been determined by the stable isotope dilution technique using solid source mass spectrometry. Analysis of the C1 chondrite Orgueil indicates a small adjustment of the “cosmic” abundance of Ba to 4.2 on the Si=10⁶ abundance scale. The present work provides a more complete coverage of a number of meteorite classes than has so far been available for the abundance of Ba in stony meteorites.     

Lu-Hf and Sm-Nd isotopic systematics in chondrites and their constraints on the Lu-Hf properties of the Earth

Sm-Nd and Lu-Hf isotopic data are presented for 19 chondritic meteorites: six carbonaceous chondrites, five L-chondrites, seven H-chondrites, and a single enstatite chondrite. The primary goal of the study is to better define the Bulk Silicate Earth (BSE) reference values for Hf isotopes. Except for one sample with lower Sm/Nd, the Sm-Nd data define a cluster around the accepted reference values for chondrites and terrestrial planets, giving a mean ¹⁴⁷Sm/¹⁴⁴Nd of 0.1960±0.0005, and a mean ¹⁴³Nd/¹⁴⁴Nd of 0.512631±0.000010 (uncertainties are two standard errors). It seems appropriate to retain the presently accepted Sm-Nd reference parameters, ¹⁴⁷Sm/¹⁴⁴Nd=0.1966 and ¹⁴³Nd/¹⁴⁴Nd=0.512638 (when fractionation-corrected to ¹⁴⁶Nd/¹⁴⁴Nd=0.7219).Lu-Hf isotopic data are not clustered, but spread along an approximate 4.5-Ga isochron trend, with a range of ¹⁷⁶Lu/¹⁷⁷Hf from 0.0301 to 0.0354. The data are similar to many of the samples of chondrites presented by Bizzarro et al. [Nature 421 (2003) 931], but lack the range to lower Lu/Hf shown by those authors. Our chondrite data define a regression line of 4.44±0.34 Ga when 1.867×10⁻¹¹ year⁻¹ is used for the decay constant of ¹⁷⁶Lu [Science 293 (2001) 683; Earth Planet. Sci. Lett. 219 (2004) 311-324]. Combining our data with the main population of analyses from Bizzarro et al. [Nature 421 (2003) 931] yields 4.51±0.24 Ga. Unless samples of eucrite meteorites and deviating replicates of chondrites with ¹⁷⁶Lu/¹⁷⁷Hf less than 0.030 are employed, no combination of the main population of chondrite Lu-Hf data yields a regression with sufficiently low error to constrain the decay constant of ¹⁷⁶Lu. Sample heterogeneity seems to hinder the acquisition of reproducible Lu-Hf analyses from small, manually ground pieces of chondrites, and we suggest that analysis of powders prepared from large volumes of meteorite will be needed to adequately characterize the Lu-Hf isotope systematics of chondritic reservoirs and of BSE. Our results for carbonaceous chondrites show higher average ¹⁷⁶Lu/¹⁷⁷Hf and ¹⁷⁶Hf/¹⁷⁷Hf than ordinary chondrites, and the mean of carbonaceous chondrites also coincides with replicate analyses of a powder representing a large volume of meteorite, the Allende powder from the Smithsonian Institution. Use of the carbonaceous chondrite mean for BSE Lu-Hf characteristics results in a BSE Hf-Nd point that lies well within the array of terrestrial compositions, and leads to plausible initial ε_Hf values for Precambrian rocks. An improved objective resolution of meteorite data and of meteoritic models for the Earth needs to occur before BSE can be established for Lu-Hf.     

Isotopic lead ages of chondritic meteorites

The isotopic composition of lead was determined for two carbonaceous, two H, and two L chondrites. All are falls. The²⁰⁶Pb/²⁰⁴Pb ratios cover a range from 9.45 to 37.33; the²⁰⁷Pb/²⁰⁴Pb ratios range from 10.39 to 26.10. The isotopic data define a²⁰⁷Pb/²⁰⁶Pb age of 4.635 AE. Uranium and lead concentration data indicate that the isotopic lead ages for the Bruderheim chondrite are concordant within approximately 20%. This contrasts with lead data in the literature for chondrites, which consistently indicate discordant isotopic lead ages due to large excesses of radiogenic lead by factors of two or more. The isotopic lead ages for Pultusk may be concordant; those for a sample of Richardton are not. The lack of concordance for Richardton is not due to the analytical procedures, rather it is likely a result of the handling history of the chondrite prior to analysis.The L-3 chondrite, Mezo-Madaras contains such a high concentration of lead - 5.27 PPM - that accurate ratios for primordial lead can be obtained. These are ²⁰⁶Pb/²⁰⁴Pb= 9.310;²⁰⁷Pb/²⁰⁴Pb= 10.296, values which are in close agreement with a recently reported measurement on lead in troilite from the Canyon Diablo iron meteorite.     

Compressibility of brownmillerite (Ca2Fe2O5): effect of vacancies on the elastic properties of perovskites

The evolution with pressure of the unit-cell parameters brownmillerite (Ca₂Fe₂O₅), a stoichiometric defect perovskite structure, has been determined to a maximum pressure of 9.46 GPa, by single-crystal X-ray diffraction measurements at room temperature. Brownmillerite does not exhibit any phase transitions in this pressure range. A fit of a third-order Birch–Murnaghan equation-of-state to the P–V data yields values of K_T0=127.0(5) GPa and K₀′=5.99(13). Analysis of the unit-cell parameter data shows that the structure compresses anisotropically. Compressional moduli for the axes are K_a0=141(1) GPa, K_b0=118(3) GPa and K_c0=122.2(2) GPa, with K_a0′=8.9(3), K_b0′=6.2(6) and K_c0′=4. The stiffest direction (i.e. along a) coincides with the direction of the FeO₄ tetrahedral chains. Comparison of these data with the elasticity systematics of Ca-perovskites shows that the presence of oxygen vacancies in the brownmillerite structure softens the structure by ∼25% and that the ordering of vacancies in the perovskite structure increases the anisotropy of compression.     

Volume-temperature relationship for iron at 330 GPa and the Earth's core density deficit

Estimates of core density deficit (cdd) of the Earth's outer core recently reported by Anderson and Isaak [Another look at the core density deficit of Earth's outer core, Phys. Earth Planet Int. 131 (2002) 19-27] are questionable in view of the serious errors in the pressure-volume and bulk modulus data due to an inadequacy in the calibration process used by Mao et al. [Static compression of iron to 300 GPa and Fe_0.8Ni_0.2 alloy to 200 GPa: implications for the core, J. Geophys. Res. 94 (1990) 21737-21742]. The data used by Anderson and Isaak deviate significantly from the corresponding values derived from seismology. In the present study we have used the input data on density, isothermal bulk modulus and its pressure derivative from Stacey and Davis [High pressure equations of state with application to lower mantle and core, Phys. Earth Planet Int. 142 (2004) 137-184] which are consistent with the seismological data. Volumes of hexagonal close-packed iron have been calculated at different temperatures under isobaric conditions at P = 330 GPa, the inner core boundary (ICB) pressure using the relationship between thermal pressure and volume expansion based on the lattice potential theory originally due to Born and Huang [Dynamical Theory of Crystal Lattices, Oxford University Press, Oxford, 1954, p. 50]. The formulation for thermal pressure used by Anderson and Isaak has been modified by taking into account the variations of thermal expansivity α and isothermal bulk modulus K_T with temperature. Values of cdd are then estimated corresponding to different temperatures ranging from 4000 to 8000 K. The results for cdd at different temperatures obtained in the present study are significantly higher than those estimated by Anderson and Isaak suggesting that the cdd for the Earth's outer core is nearly 10%. The effects of nickel when an Fe-Ni alloy replaces Fe are estimated and found to be insignificant.     

Investigations on cosmic-ray-produced nuclides in iron meteorites, 3. Exposure ages,meteoroid sizes and sample depths determined by mass spectrometric analyses of potassium and rare gases

Three physical quantities define the essentials of the cosmic ray exposure history of a sample of an iron meteorite: (1) the cosmic ray exposure age T, (2) the pre-atmospheric “size” S of the irradiated body, and (3) the location, i.e. the “depth” D, of the samples within the body. To establish these quantities for a given sample three independent quantities must be determined experimentally. In the present work T is ascertained by the ⁴¹K/⁴⁰K method and the ⁴He and ²¹Ne concentrations (C₄ and C₂₁) are measured by the isotope dilution method. Signer and Nier's evaluation of the rare gas distribution in the meteorite Grant and the measured exposure age for this meteorite provide the relationships allowing to ascertain for any meteorite the quantities S and D from the ²¹Ne production rate (P₂₁ = C₂₁/T) and the ⁴He/²¹Ne ratio.Earlier measurements have provided data on the isotopic composition of potassium in 74 different iron meteorites. New rare gas measurements are reported for some 40 samples. Results on the age, size and depth are obtained for almost 60 samples. These data suggest that Signer and Nier's model is well suited for describing not only the rare gas distribution in a single selected meteorite (Grant) but also the exposure histories of the great majority of all irons. For a few samples, however, secondary breakups of the meteoroid and a two- or multiple-stage irradiation must be invoked. Further measurements are proposed for testing and, possibly, refining the still somewhat uncertain relationships between the abundances of cosmogenic nuclides and the quantities T, S, and D in very large meteorites.Histograms are presented showing the age distributions for irons of different chemical groups and of different size ranges.The feasibility and the relative merits of other methods for the determination of T, S, and D are discussed.     

Composition of the core,II. Effect of high pressure on solubility of FeO in molten iron

An experimental and theoretical investigation of the effect of pressure on the solubility of FeO in molten iron has been carried out. Analyses of shock-wave compression data on iron oxides combined with measurements of the FeO bond length in “metallic” oxides suggest that the partial molar volume of FeO(V^*) dissolved in molten iron is substantially smaller than that of molten wüstite. Hence the effect of high pressure should be to increase the solubility of FeO in molten iron at a given temperature. This inference is confirmed by an experimental investigation of the effect of pressure on the position of the FeFeO eutectic. Thermodynamic calculations based on these experiments yield an estimate forV^* which is in reasonable agreement with the theoretical estimates. The experimental value ofV^* is used to calculate the effect of high pressure upon the FeFeO phase diagram. Solubility of FeO in molten iron increases sharply with pressure, the liquid immiscibility region contracts and disappears around 20 GPa and it is predicted that the FeFeO phase diagram should resemble a simple eutectic system above about 20 GPa. Analogous calculations predict that the solubility of FeO in molten iron in equilibrium with magnesiowüstite (Mg_0.8Fe_0.2)O at 2500°C increase from 14 mol.%(P = 0) to above 25 mol.% at 20 GPa. If the core formed by segregation of metallic iron originally dispersed throughout the earth, it seems inevitable that it would dissolved large amounts of FeO, thereby accounting for the observation that the density of the outer core is substantially smaller than that of pure iron under correspondingP, T conditions.     

辉长岩在冲击加载下的相变及物态方程

岩石相变关系对限定地球内部物质成分和动力学关系有着重要意义.利用光探针在14~39 GPa压力区间对热压烧结的辉长岩样品进行了冲击波加载实验.从16 GPa开始,D-u线斜率发生明显变化,说明样品内发生了相变.利用原始的Hugoniot曲线结合地震波状态方程（Seismic Equation of State）得到了Birch-Murnaghan型的等熵压缩线和相变能.结合前人的实验结果,得到了辉长岩的Grü neisen参数γ₀,约为2.3.计算得到相变后的矿物集合体在零压下的密度为3.41 g·cm^-3.根据以上参数分析得出,在此压力段辉长岩相变主要由长石的分解反应和石英的高压相变控制.     

Determination of phase transition pressures of ZnTe under quasihydrostatic conditions

Pressure behavior of ZnTe at room temperature was studied using an X-ray energy dispersive method on a DIA type cubic anvil apparatus (SAM-85) at NSLS-X17B1. By using powdered polyethylene, the sample and NaCl for a pressure scale were held under quasihydrostatic conditions, which were confirmed by X-ray diffraction method. Two high-pressure phase transitions were confirmed using X-ray powder diffraction simultaneously with electrical resistance measurements. The phase transition pressures under quasihydrostatic conditions were determined to be 9.6 GPa, at which the resistance increased, and 12.0 GPa, which was the midpoint of a large resistance decrease. Errors in the pressure determinations were estimated to be less than 0.2 GPa. These pressure values may depend on grain size and anisotropic stress effects on the calibrant. From X-ray observation of ZnTe, the bulk modulus of the zinc blende structure was calculated to beK ₀=51(3) GPa andK ₀ =3.6(0.8), and the first transition at 9.6 GPa was found to have about 9% volume change. It was consistent with an anomaly in the pressure generating curves.     

Cosmogenic neon produced from sodium in meteoritic minerals

Cosmogenic neon in sodium-rich oligoclase feldspar from the ordinary chondrites St. Severin and Guaren?a is characterized by an unusually high²²Ne/²¹Ne = 1.50 ± 0.02. This high ratio is due to the cosmogenic²²Ne/²¹Ne production ratio in sodium which is 2.9 ± 0.3, two to three times the production ratio in any other target element. The relative production rate of²¹Ne per gram sodium is one quarter the production rate per gram magnesium. The striking enrichment of²²Ne relative to²¹Ne in sodium arises from enhanced indirect production from²³Na via²²Na.The unusual composition of cosmogenic neon in sodium and sodium-rich minerals explains the high²²Ne/²¹Ne ratios observed in inclusions of the Allende carbonaceous chondrite, and observed during low-temperature extraction of neon from ordinary chondrites. The isotopic composition of cosmogenic neon released during the stepwise heating of a trapped gas-rich meteorite containing sodium-rich phases can be expected to vary, and use of a constant cosmogenic neon composition to derive the composition of the trapped gas may not be justified. Preferential loss of this²²Ne-enriched cosmogenic neon from meteoritic feldspar can result in a 2–3% drop in the measured cosmogenic²²Ne/²¹Ne ratio in a bulk meteorite sample. This apparent change in composition can lead to overestimation of the minimum pre-atmospheric mass of the meteorite by a factor of two.     

Melting of forsterite Mg2SiO4 up to 15 GPa

The melting curve of forsterite has been studied by static experiment up to a pressure of 15 GPa. Forsterite melts congruently at least up to 12.7 GPa. The congruent melting temperature is expressed by the Kraut-Kennedy equation in the following form: T_m(K)=2163 (1+3.0(V₀ ? V)/V₀), where the volume change with pressure was calculated by the Birch-Managhan equation of state with the isothermal bulk modulus K₀ = 125.4 GPa and its pressure derivative K′ = 5.33. The triple point of forsterite-β-Mg₂SiO₄-liquid will be located at about 2600°C and 20 GPa, assuming that congruent melting persists up to the limit of the stability field of forsterite. The extrapolation of the previous melting data on enstatite and periclase indicates that the eutectic composition of the forsterite-enstatite system should shift toward the forsterite component with increasing pressure, and there is a possibility of incongruent melting of forsterite into periclase and liquid at higher pressure, although no evidence on incongruent melting has been obtained in the present experiment.     

南丹铁陨石物态方程用于地核的研究

从南丹铁陨石的物态方程和地球的PREM模型出发,求得内外地核交界面处的物质密度为12.83-13.419/cm~3,温度为5440-5680K;地心处物质密度为13.12-13.73g/cm~3,温度为5660-5990K,推估内地核可能由铁镍合金组成.     

Disproportionation of kyanite to corundum plus stishovite at high pressure and temperature

Natural kyanite (Al₂SiO₅) has been found to disproportionate into a mixture of its component oxides, corundum and stishovite, at a loading pressure of about 160 kbar and temperature between 1000–1400°C in a diamond-anvil press. The exact transition pressure is not certain due to transient increases in pressure during the local and rapid heating by a continuous YAG laser. The phase boundary, however, has been estimated to be P(kbar) = (138 ～ 174) + 0.011 T (°C) on the basis of the available thermodynamic data. The shock-wave Hugoniot data above 650 kbar for andalusite (Al₂SiO₅) and sillimanite (Al₂SiO₅) as starting materials are consistent with the present results.     

Petrogenesis of complex veins in the Chantonnay (L6f) chondrite

Two cross-cutting veins in the Chantonnay (L6f) chondrite illustrate different patterns of fractionation of total chondritic shock melts. The earlier vein, which is dark-colored and bears abundant host rock xenoliths, is strongly reduced and sodium-poor relative to the bulk meteorite. It resembles and may be cogenetic with melt pockets in Chantonnay. The later vein, which is lighter-colored and somewhat vesicular, lacks evidence of either Na loss or reduction but shows modest internal differentiation. Its metal and total iron contents (26.5 wt.%) are higher than normal for L-group chondrites.The trend of chemical fractionation recorded in the earlier Chantonnay vein resembles that reported for chondrules in ordinary chondrites, suggesting that chemical variations among chondrules in part reflect variations among their parental shock melts.     

Shock temperature in calcite (CaCO3) at 95-160 GPa

The temperatures induced in crystalline calcite (CaCO₃) upon planar shock compression (95-160 GPa) are reported from two-stage light gas gun experiments. Temperatures of 3300-5400 K are obtained by fitting six-channel optical pyrometer radiances in the 450-900 nm range to the Planck gray-body radiation law. Thermodynamic calculations demonstrate that these temperatures are some 400-1350 K lower than expected for vibronic excitations of the lattice with a 3R/mole-atom specific heat (R is gas constant). The temperature deficit along the Hugoniot is larger than that expected from only melting. In addition to melting, it appears likely that shock-induced decomposition of calcite occurs behind the shock front. We modeled disproportionation of calcite into CaO (solid) plus CO₂ (gas). For temperature calculations, specific heat at constant volume for 1 mole of CO₂ is taken to be 6.7R as compared to 9R in the solid state; whereas a mole of calcite and a mole of CaO have their solid state values 15R and 6R, respectively. Calculations suggest that the calcite decomposes to CaO and CO₂ at ∼110±10 GPa along the Hugoniot. Recent reanalysis of earlier VISAR measurements of particle velocity profiles [1] indicates that calcite shocked to 18 GPa undergoes disproportionation at much lower pressures upon isentropic expansion.     

Another look at the core density deficit of Earth’s outer core

A constraint adopted in several geochemical studies of core composition is that the core density deficit (cdd) is 10%, with the implication that this number is based on robust geophysical evidence. The cdd is the perceived difference between the density of pure iron at core conditions and the seismically-determined density of the outer core. The importance of the cdd is that it limits the concentration of allowable light elements, such as sulfur and silicon, which, when mixed with Fe, or an Fe-Ni alloy, comprise the geochemical model of the inner core.We present evidence that the value of 10% for the cdd of the outer core is too high. Using a thermal-pressure equation-of-state, we find that for assumed melting temperatures of pure iron at the inner-outer core (ICB) pressure of 330 GPa ranging from 7500 to 4800 K, the cdd ranges from 2.9 to 7%, respectively. Reports that the cdd value of the outer core is less than 10% are found in a number of shock-wave studies, but the values reported here are apparently the lowest. Our cdd value for an assumed melting temperature of 6000 K for iron at 330 GPa is 5.4% and is compatible with proposed concentrations of Si and S impurities found from solubility studies at high P and T.     

Characteristics in naturally and experimentally shocked chondrites: A clue to P-T conditions of impacted asteroids

The aim of this study is to compare the experimentally shock-induced features with those in naturally shocked chondrites and to test the feasibility of experimentally calibrating naturally induced features in shocked H- and L-chondrites. Samples of the Jilin chondrite (H5) were experimentally shock-loaded at the following peak pressures: 12, 27, 39, 53, 78, 83, 93 and 133 GPa respectively. Chondritic melts were first obtained at P>78 GPa and more than 60% melting was achieved at P~133 GPa. No high-pressure phases were observed in any of the shocked samples, neither in the deformed nor in the molten regions. Textural relations and mineral assemblages of the shocked samples are comparable to those encountered in the heavily shocked H-chondrite Yanzhuang but differ considerably from those found in heavily shocked L6 chondrites. Shock melt veins in L6 chondrites contain high-pressure polymorphs of olivine and pyroxene and high pressure liquidus phases. Scaling from shock experiments on millimeter-sized samples to natural shock features on kilometer-sized asteroids poses considerable problems in quantifying the P-T conditions during natural shock events on asteroids.     

High-pressure phase transformations and isothermal compression in CaTiO3 (perovskite)

A polycrystalline CaTiO₃ (perovskite) was investigated under static pressures up to 38 GPa and temperatures up to 1000°C by using a diamond anvil pressure cell, a YAG laser, and the ruby fluorescence pressure calibration system. In situ x-ray diffraction data reveal that at room temperature, the orthorhombic CaTiO₃(I) transforms into a hexagonal CaTiO₃(II) at ∼ 10 GPa with a volume of change of 1.6%. At 1000°C, the orthorhombic CaTiO₃(I) first transforms into a tetragonal CaTiO₃(III) at 8.5 GPa and then transforms further into a hexagonal CaTiO₃(II′) at ∼ 15 GPa with molar volume changes of 0% and 1.6%, respectively. All three high-pressure polymorphs found in this study are nonquenchable.Isothermal compressibility of the orthorhombic CaTiO₃ was derived from measurements under truly hydrostatic environments (i.e., ⩽ 10.4 GPa). By assuming K^′₀ = 5.6 obtained ultrasonically on SrTiO₃ perovskite, the value of the bulk modulus (K₀) was calculated with the Birch-Murnaghan equation to be 210 ± 7 GPa.     

Melting of Mg2GeO4 under pressure

Melting point of germanate forsterite, Mg₂GeO₄, was raised by compression at the rate of 30°C/GPa. The triple point, at which three phases of olivine- and spinel-type solids and liquid coexisted, was fixed at 1950°C and 3.5GPa. Wen these results are combined with the thermodynamical data of forsterite, Mg₂SiO₄, it is estimated that the triple point of forsterite lies in a region ranging from 2700° to 3000°C in temperature and from 20 to 30GPa in pressure.