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1.
The abundances of the highly siderophile elements (HSE) Re, Os, Ir, Ru, Pt, Rh, Pd and Au, and 187Os/188Os isotope ratios have been determined for a set of carbonaceous, ordinary, enstatite and Rumuruti chondrites, using an analytical technique that permits the precise and accurate measurement of all HSE from the same digestion aliquot. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS analysis. The monoisotopic elements Rh and Au were quantified relative to the abundance of Ir.Differences in HSE abundances and ratios such as Re/Os, 187Os/188Os, Pd/Ir and Au/Ir between different chondrite classes are further substantiated with new data, and additional Rh and Au data, including new data for CI chondrites. Systematically different relative abundances of Rh between different chondrite classes are reminiscent of the behaviour of Re. Carbonaceous chondrites are characterized by low average Rh/Ir of 0.27 ± 0.03 (1s) which is about 20% lower than the ratio for ordinary (0.34 ± 0.02) and enstatite chondrites (EH: 0.33 ± 0.01; EL: 0.32 ± 0.01). R chondrites show higher and somewhat variable Rh/Ir of 0.37 ± 0.07.Well-defined linear correlations of HSE, in particular for bulk samples of ordinary and EL chondrites, are explained by binary mixing and/or dilution by silicates. The HSE carriers responsible for these correlations have a uniform chemical composition, indicating efficient homogenization of local nebular heterogeneities during or prior to the formation of the host minerals in chondrite components. Excepting Rumuruti chondrites and Au in carbonaceous chondrites, these correlations also suggest that metamorphism, alteration and igneous processes had negligible influence on the HSE distribution on the bulk sample scale.Depletion patterns for Rh, Pd and Au in carbonaceous chondrites other than CI are smoothly related to condensation temperatures and therefore consistent with the general depletion of moderately volatile elements in carbonaceous chondrites. Fractionated HSE abundance patterns of ordinary, enstatite and Rumuruti chondrites, however, are more difficult to explain. Fractional condensation combined with the removal of metal phases at various times, and later mixing of early and late formed metal phases may provide a viable explanation. Planetary fractionation processes that may have affected precursor material of chondrite components cannot explain the HSE abundance patterns of chondrite groups. HSE abundances of some, but not all Rumuruti chondrites may be consistent with solid sulphide-liquid sulphide fractionation processes during impact induced melting.  相似文献   

2.
A 187Re-187Os isochron including data for all twelve IVB irons gives an age of 4579 ± 34 Ma with an initial 187Os/188Os of 0.09531 ± 0.00022, consistent with early solar system crystallization. This result, along with the chemical systematics of the highly siderophile elements (HSE) are indicative of closed-system behavior for all of the HSE in the IVB system since crystallization.Abundances of HSE measured in different chunks of individual bulk samples, and in spot analyses of different portions of individual chunks, are homogeneous at the ±10% level or better. Modeling of HSE in the IVB system, therefore, is not impacted by sample heterogeneities. Concentrations of some other elements determined by spot analysis, such as P, Cr and Mn, however, vary by as much as two orders of magnitude and reflect the presence of trace phases.Assuming initial S in the range of 0 to 2 wt.%, the abundances of the HSE Re, Os, Ir, Ru, Pt, Rh, Pd and Au in bulk IVB irons are successfully accounted for via a fractional crystallization model. For these elements, all IVB irons can be interpreted as being representative of equilibrium solids, liquids, or mixtures of equilibrium solids and liquids.Our model includes changes in bulk D values (ratio of concentration in the solid to liquid) for each element in response to expected increases in S and P in the evolving liquid. For this system, the relative D values are as follow: Os > Re > Ir > Ru > Pt > Rh > Pd > Au. Osmium, Re, Ir and Ru were compatible elements (favor the solid) throughout the IVB crystallization sequence; Rh, Pd and Au were incompatible (favor the liquid). Extremely limited variation in Pt concentrations throughout the IVB crystallization sequence requires that D(Pt) remained at unity.In general, D values derived from the slopes of logarithmic plots, compared with those calculated from recent parameterizations of D values for metal systems are similar, but not identical. Application of D values obtained by the parameterization method is problematic for comparisons of the compatible elements with similar partitioning characteristics. The slope-based approach works well for these elements. In contrast, the slope-based approach does not provide viable D values for the incompatible elements Pd and Au, whereas the parameterization method appears to work well. Modeling results suggest that initial S for this system may have been closer to 2% than 0, but the elements modeled do not tightly constrain initial S.Consistent with previous studies, our calculated initial concentrations of HSE in the IVB parent body indicate assembly from materials that were fractionated via high temperature condensation processes. As with some previous studies, depletions in redox sensitive elements and corresponding high concentrations of Re, Os and Ir present in all IVB irons are interpreted as meaning that the IVB core formed in an oxidized parent body. The projected initial composition of the IVB system was characterized by sub-chondritic Re/Os and Pt/Os ratios. The cause of this fractionation remains a mystery. Because of the refractory nature of these elements, it is difficult to envision fractionation of these elements (especially Re-Os) resulting from the volatility effects that evidently affected other elements.  相似文献   

3.
Liquid MgSiO3 is a model for the Earth’s magma ocean and of remnant melt present near the core-mantle boundary. Here, models for molten MgSiO3 are computed employing empirical potential molecular dynamics (EPMD) and results are compared to published results including two EPMD studies and three first-principles molecular dynamics (FPMD) models and to laboratory data. The EPMD results derived from the Oganov (OG) potential come closest to the density of MgSiO3 liquid at the 1-bar melting point inferred from the melting curve. At higher P, EPMD densities calculated from the OG potential and FPMD broadly match shock wave studies, with the OG potential yielding the better comparison. Matsui (M) potential results deviate from other studies above ∼50 GPa. Overall, results based on the OG potential compare best to experimental densities over the P-T range of the mantle. Isothermally, upon increasing P the mean coordination numbers () of oxygen around Si and Mg monotonically increase with pressure. Tetrahedral Si and octahedral Si monotonically increase and decrease, respectively, whereas pentahedral Si maximizes at 10-20 GPa. Tetrahedral Mg decreases monotonically as P increases whereas pentahedral, octahedral and higher coordination polyhedra each show similar behavior first increasing and then decreasing after attaining a maximum; the P of the maximum for each polyhedra type migrates to higher P as the CN increases. Free oxygen and oxygen with one nearest neighbor of either Si or Mg decreases whereas Si or Mg with two or three nearest oxygens (i.e., tricluster oxygen) increases with increasing P isothermally. The increase of tricluster oxygen is consistent with spectroscopy on MgSiO3 glass quenched from 2000 K and 0-40 GPa and high-energy X-ray studies constraining the coordination of O around Mg and around Si at 2300 K and 1 bar. Coordination statistics from FPMD studies for O around Si and Si around O are in agreement with the EPMD results based on the M and OG potentials. Mg self-diffusivity is greater than O and Si self-diffusivities for both the M and OG potentials. All D values monotonically decrease with increasing pressure isothermally and all atoms are more diffusive in the M liquid compared to the OG liquid except at T > ∼5000 K and P > 100 GPa. Previously published EPMD diffusivities fall between values given by the M and OG potentials, at least up to 45 GPa. The M liquid is generally less viscous than the OG liquid except at P > ∼80 GPa. Activation energy and volume are around 96 kJ/mol and 1.5 cm3/mol, respectively. The FPMD viscosity results at 120 GPa and 4000 and 4500 K are essentially identical to the values from the M and OG potentials. FPMD viscosity results are similar to the OG results for P < 60 GPa; at higher P, the FPMD viscosities are higher. At 4000 K and 100 GPa the shear viscosity of liquid MgSiO3 is ∼0.1 Pa s. More extensive laboratory results are required to better define the thermodynamic, transport and structural properties of MgSiO3 liquids and for comparison with computational studies.  相似文献   

4.
Water speciation in rhyolitic melts with dissolved water ranging from 0.8 to 4 wt% under high pressure was investigated. Samples were heated in a piston-cylinder apparatus at 624-1027 K and 0.94-2.83 GPa for sufficient time to equilibrate hydrous species (molecular H2O and hydroxyl group, H2Om + O ? 2OH) in the melts and then quenched roughly isobarically. The concentrations of both hydrous species in the quenched glasses were measured with Fourier transform infrared (FTIR) spectroscopy. For the samples with total water content less than 2.7 wt%, the equilibrium constant (K) is independent of total H2O concentration. Incorporating samples with higher water contents, the equilibrium constant depends on total H2O content, and a regular solution model is used to describe the dependence. K changes with pressure nonmonotonically for samples with a given water content at a given temperature. The equilibrium constant does not change much from ambient pressure to 1 GPa, but it increases significantly from 1 to 3 GPa. In other words, more molecular H2O reacts to form hydroxyl groups as pressure increases from 1 GPa, which is consistent with breakage of tetrahedral aluminosilicate units due to compression of the melt induced by high pressure. The effect of 1.9 GPa (from 0.94 to 2.83 GPa) on the equilibrium constant at 873 K is equivalent to a temperature effect of 49 K (from 873 K to 922 K) at 0.94 GPa. The results can be used to evaluate the role of speciation in water diffusion, to estimate the apparent equilibrium temperature, and to infer viscosity of hydrous rhyolitic melts under high pressure.  相似文献   

5.
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6.
We investigate the degassing of volatile heavy metals from natural basalt and dacite and synthetic rhyolite melts doped with Bi, Pb, Tl, Au, Re, Sb, Sn, Cd, Mo, As, Cu in Pt capsules over a range of temperatures (1200-1430 °C) exposed to air at 0.1 MPa. We also investigated the effects of ligands on degassing by adding known concentrations of Cl and S. During the experiments concentration gradients normal to the melt/gas interface arose for the trace metals Au, Tl, As, Cd, Re, Bi and Pb, as shown by measurements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the quenched glasses. In contrast, erratic concentration gradients occurred for Cu, Mo, Sn, Sb due to the development of compositional cords in the glass for those elements. The diffusivities for Au, Tl, As, Cd, Re, Bi and Pb (in decreasing order of volatility) followed an Arrhenius relationship with log D at 1260 °C varying from −12 to −17. The addition of Cl and S were shown to increase by two-to five-fold the volatilities of all metals, with S having a more profound effect. Diffusivities from the experiments were applied in a bubble growth model to examine the behavior of Tl and Pb in volcanic gases. The Tl/Pb ratio in gases shows much greater variation than can be explained by partitioning and magma composition alone, with diffusion serving to drastically enrich or deplete the Tl/Pb of gases to values significantly different from that of the melt.  相似文献   

7.
Phase relations on the diopside (Di)-hedenbergite (Hd)-jadeite (Jd) system modeling mineral associations of natural eclogites were studied for the compositions (mol %) Di70Jd30, Di50Jd50, Di30Jd70, Di20Hd80, and Di40Hd10Jd50 using a toroidal anvil-with-hole (7 GPa) and a Kawai-type 6-8 multianvil apparatus (12-24 GPa). We established that Di, Hd, and Jd form complete series of solid solutions at 7 GPa, and melting temperatures of pure Di (1980 °C) and Jd (1870 °C) for that pressure were estimated experimentally. The melting temperature for the Di50Jd50 composition at 15.5 GPa is 2270 °C. The appearance of garnet is clearly dependent on initial clinopyroxene composition: at 1600 °C the first garnet crystals are observed at 13.5 GPa in the jadeite-rich part of the system (Di30Jd70), whereas diopside-rich starting material (Di70Jd30) produces garnet only above 17 GPa. The proportion of garnet increases rapidly above 18 GPa as pyroxene dissolves in the garnet structure and pyroxene-free garnetites are produced from diopside-rich starting materials. In all experiments, garnet coexists with stishovite (St). At a pressure above 18 GPa, pyroxene is completely replaced by an assemblage of majorite (Maj) + St + CaSiO3-perovskite (Ca-Pv) in Ca-rich systems, whereas Maj is associated with almost pure Jd up to a pressure of 21.5 GPa. Above ∼22 GPa, Maj, and St are associated with NaAlSiO4 with calcium ferrite structure (Cf). We established that an Hd component also spreads the range of pyroxene stability up to 20 GPa. In the Di70Jd30 system at 24 GPa an assemblage of Maj + Ca-Pv + MgSiO3 with ilmenite structure (Mg-Il) was obtained. The experimentally established correlation between Na, Si, and Al contents in Maj and pressure in Grt(Maj)-pyroxene assemblages, may be the basis for a “majorite” geobarometer. The results of our experiments are applicable to the upper mantle and the transition zone of the Earth (400-670 km), and demonstrate a wide range of transformations from eclogite to perovskite-bearing garnetite. In addition, the mineral associations obtained from the experiments allowed us to simulate parageneses of inclusions in diamonds formed under the conditions of the transition zone and the lower mantle.  相似文献   

8.
We perform first principles molecular dynamics simulations of Mg2SiO4 liquid and crystalline forsterite. On compression by a factor of two, we find that the Grüneisen parameter of the liquid increases linearly from 0.6 to 1.2. Comparison of liquid and forsterite equations of state reveals a temperature-dependent density crossover at pressures of ∼12-17 GPa. Along the melting curve, which we calculate by integration of the Clapeyron equation, the density crossover occurs within the forsterite stability field at P = 13 GPa and T = 2550 K. The melting curve obtained from the root mean-square atomic displacement in forsterite using the Lindemann law fails to match experimental or calculated melting curves. We attribute this failure to the liquid structure that differs significantly from that of forsterite, and which changes markedly upon compression, with increases in the degree of polymerization and coordination. The mean Si coordination increases from 4 in the uncompressed system to 6 upon twofold compression. The self-diffusion coefficients increase with temperature and decrease monotonically with pressure, and are well described by the Arrhenian relation. We compare our equation of state to the available highpressure shock wave data for forsterite and wadsleyite. Our theoretical liquid Hugoniot is consistent with partial melting along the forsterite Hugoniot at pressures 150-170 GPa, and complete melting at 170 GPa. The wadsleyite Hugoniot is likely sub-liquidus at the highest experimental pressure to date (200 GPa).  相似文献   

9.
Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO2 conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO2 yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO2 conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.  相似文献   

10.
Synthesis, characterization and thermochemistry of a Pb-jarosite   总被引：1，自引：0，他引：1  
The enthalpy of formation from the elements of a well-characterized synthetic Pb-jarosite sample corresponding to the chemical formula (H3O)0.74Pb0.13Fe2.92(SO4)2(OH)5.76(H2O)0.24 was measured by high temperature oxide melt solution calorimetry. This value ( = −3695.9 ± 9.7 kJ/mol) is the first direct measurement of the heat of formation for a lead-containing jarosite. Comparison to the thermochemical properties of hydronium jarosite and plumbojarosite end-members strongly suggests the existence of a negative enthalpy of mixing possibly related to the nonrandom distribution of Pb2+ ions within the jarosite structure. Based on these considerations, the following thermodynamic data are proposed as the recommended values for the enthalpy of formation from the elements of the ideal stoichiometric plumbojarosite Pb0.5Fe3(SO4)2(OH)6:  = −3118.1 ± 4.6 kJ/mol,  = −3603.6 ± 4.6 kJ/mol and S° = 376.6 ± 4.5 J/(mol K). These data should prove helpful for the calculation of phase diagrams of the Pb-Fe-SO4-H2O system and for estimating the solubility product of pure plumbojarosite. For illustration, the evolution of the estimated solubility product of ideal plumbojarosite as a function of temperature in the range 5-45 °C was computed (Log(Ksp) ranging from −24.3 to −26.2). An Eh-pH diagram is also presented.  相似文献   

11.
We investigate two key transport properties, self-diffusion and viscosity, of Mg2SiO4 liquid as a function of temperature and pressure using density functional theory-based molecular dynamics method. Liquid dynamics in a 224-atom supercell was captured in equilibrium simulations of relatively long durations (50-300 ps) to obtain an acceptable convergence. Our results show that Mg and Si are, respectively, the most and least mobile species at most conditions studied and all diffusivities become similar at high pressure. With increasing temperature from 2200 to 6000 K at ambient pressure, the self-diffusivities increase by factors of 25 (Mg), 80 (Si) and 65 (O), and the viscosity decreases by a factor of 30. The predicted temperature variations of all transport coefficients closely follow the Arrhenian law. However, their pressure variations show a significant non-Arrhenian behavior and also are sensitive to temperature. At 3000 K, the diffusivity (viscosity) decreases (increases) by more than one order of magnitude between 0 and 50 GPa with their activation volumes increasing on compression. Over the entire mantle pressure range, the variations at 4000 K are of two orders of magnitude with nearly constant activation volumes whereas the variations at 6000 K are within one order of magnitude with decreasing activation volumes. The predicted complex dynamical behavior of Mg2SiO4 liquid can be associated with the structural changes occurring on compression. We also estimate the diffusivity and viscosity profiles along a magma ocean isentrope, which suggest that the melt transport properties vary modestly over the relevant magma ocean depth ranges.  相似文献   

12.
We present new high-pressure temperature experiments on melting phase relations of Fe-C-S systems with applications to metallic core formation in planetary interiors. Experiments were performed on Fe-5 wt% C-5 wt% S and Fe-5 wt% C-15 wt% S at 2-6 GPa and 1050-2000 °C in MgO capsules and on Fe-13 wt% S, Fe-5 wt% S, and Fe-1.4 wt% S at 2 GPa and 1600 °C in graphite capsules. Our experiments show that: (a) At a given P-T, the solubility of carbon in iron-rich metallic melt decreases modestly with increasing sulfur content and at sufficiently high concentration, the interaction between carbon and sulfur can cause formation of two immiscible melts, one rich in Fe-carbide and the other rich in Fe-sulfide. (b) The mutual solubility of carbon and sulfur increases with increasing pressure and no super-liquidus immiscibility in Fe-rich compositions is likely expected at pressures greater than 5-6 GPa even for bulk compositions that are volatile-rich. (c) The liquidus temperature in the Fe-C-S ternary is significantly different compared to the binary liquidus in the Fe-C and Fe-S systems. At 6 GPa, the liquidus of Fe-5 wt% C-5 wt% S is 150-200 °C lower than the Fe-5 wt% S. (d) For Fe-C-S bulk compositions with modest concentration of carbon, the sole liquidus phase is iron carbide, Fe3C at 2 GPa and Fe7C3 at 6 GPa and metallic iron crystallizes only with further cooling as sulfur is concentrated in the late crystallizing liquid. Our results suggest that for carbon and sulfur-rich core compositions, immiscibility induced core stratification can be expected for planets with core pressure less than ∼6 GPa. Thus planetary bodies in the outer solar system such as Ganymede, Europa, and Io with present day core-mantle boundary (CMB) pressures of ∼8, ∼5, and 7 GPa, respectively, if sufficiently volatile-rich, may either have a stratified core or may have experienced core stratification owing to liquid immiscibility at some stage of their accretion. A similar argument can be made for terrestrial planetary bodies such as Mercury and Earth’s Moon, but no such stratification is predicted for cores of terrestrial planets such as Earth, Venus, and Mars with the present day core pressure in the order ?136 GPa, ?100 GPa, and ?23 GPa. (e) Owing to different expected densities of Fe-rich (and carbon-bearing) and sulfur-rich metallic melts, their settling velocities are likely different; thus core formation in terrestrial planets may involve rain of more than one metallic melt through silicate magma ocean. (f) For small planetary bodies that have core pressures <6 GPa and have a molten core or outer core, settling of denser carbide-rich liquid or flotation of lighter, sulfide-rich melt may contribute to an early, short-lived geodynamo.  相似文献   

13.
Molecular dynamics simulations are carried out to systematically address the effects of composition and pressure on melts along the MgO-SiO2 join and elucidate the role of structural modifier content on silicate melt properties. The MgO-SiO2 system shows non-ideal mixing with a negative excess volume of mixing at low pressures, but the mixing becomes closer to ideal at higher pressures. At atmospheric pressure, the viscosities and diffusivities vary by more than 3 orders of magnitude as the composition is varied along this join, with the low SiO2 melts characterized by lower viscosities and higher diffusivities; these results are in quantitative agreement with experimental results for the dependence of viscosity and diffusivity on structural modifier content in a wide range of silicate systems. The transport properties of melts in this system converge at higher pressures; at pressures greater than ∼15 GPa the viscosity and diffusivities vary by less than an order of magnitude across the entire range of compositions. The relevance of equations that relate the viscosity and diffusivity is also addressed.  相似文献   

14.
Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe3C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe3C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe3C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe3C. Fe3C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe3C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe3C.  相似文献   

15.
As paleoceanographic archives, deep sea coral skeletons offer the potential for high temporal resolution and precise absolute dating, but have not been fully investigated for geochemical reconstructions of past ocean conditions. Here we assess the utility of skeletal P/Ca, Ba/Ca and U/Ca in the deep sea coral D. dianthus as proxies of dissolved phosphate (remineralized at shallow depths), dissolved barium (trace element with silicate-type distribution) and carbonate ion concentrations, respectively. Measurements of these proxies in globally distributed D. dianthus specimens show clear dependence on corresponding seawater properties. Linear regression fits of mean coral Element/Ca ratios against seawater properties yield the equations: P/Cacoral (μmol/mol) = (0.6 ± 0.1) P/Casw(μmol/mol) - (23 ± 18), R2 = 0.6, n = 16 and Ba/Cacoral(μmol/mol) = (1.4 ± 0.3) Ba/Casw(μmol/mol) + (0 ± 2), R2 = 0.6, n = 17; no significant relationship is observed between the residuals of each regression and seawater temperature, salinity, pressure, pH or carbonate ion concentrations, suggesting that these variables were not significant secondary dependencies of these proxies. Four D. dianthus specimens growing at locations with Ωarag ? 0.6 displayed markedly depleted P/Ca compared to the regression based on the remaining samples, a behavior attributed to an undersaturation effect. These corals were excluded from the calibration. Coral U/Ca correlates with seawater carbonate ion: U/Cacoral(μmol/mol) = (−0.016 ± 0.003) (μmol/kg) + (3.2 ± 0.3), R2 = 0.6, n = 17. The residuals of the U/Ca calibration are not significantly related to temperature, salinity, or pressure. Scatter about the linear calibration lines is attributed to imperfect spatial-temporal matches between the selected globally distributed specimens and available water column chemical data, and potentially to unresolved additional effects. The uncertainties of these initial proxy calibration regressions predict that dissolved phosphate could be reconstructed to ±0.4 μmol/kg (for 1.3-1.9 μmol/kg phosphate), and dissolved Ba to ±19 nmol/kg (for 41-82 nmol/kg Basw). Carbonate ion concentration derived from U/Ca has an uncertainty of ±31μmol/kg (for ). The effect of microskeletal variability on P/Ca, Ba/Ca, and U/Ca was also assessed, with emphasis on centers of calcification, Fe-Mn phases, and external contaminants. Overall, the results show strong potential for reconstructing aspects of water mass mixing and biogeochemical processes in intermediate and deep waters using fossil deep-sea corals.  相似文献   

16.
The 2.7 Ga Kambalda Sequence comprises a mafic to ultramafic dominated volcanic rock sequence of the Kalgoorlie Terrane, Yilgarn Craton, Western Australia. The Sequence is divided into Lower and Upper Units separated by the Kambalda Komatiite Formation. Five basalt suites of the Lower Unit are tholeiitic where MgO spans 5-10 wt.% MgO, with minor assimilation-fractional crystallization (AFC), whereas six volcanic suites identified in the Upper Unit are tholeiitic to komatiitic-basalts with MgO 24-5 wt.% having generally greater degrees of AFC. Upper suites plot at Al2O3/TiO2 (17-26) close to the primitive mantle ratio of 21, and Pt + Pd (19-31 ppb), whereas the PGE-depleted Lower basalts plot at generally lower Al2O3/TiO2 (<16) and Pt + Pd (<10 ppb). Most suites have an average Pt/Pd ratio of 1.11, despite large variations in MgO contents, broadly consistent with the Pt/Pd ratio in the primitive mantle. On primitive mantle-normalised PGE plots, Upper suites generally display less fractionated patterns of the IPGE (Os, Ir, Ru and Rh) from the PPGE (Pt and Pd) relative to the Lower basalts. Most suites exhibit patterns with positive slopes reflecting relative enrichment of Pd, Pt, Au and Cu relative to Ni and IPGE. In suites of both Units, the concentrations of Ir and Ru fall with decreasing MgO contents, indicating their broadly compatible behaviour during magmatic evolution that involved AFC. Platinum and Pd behave as incompatible elements in the high-MgO suites, whereas Pt and Pd behave compatibly during crystallisation of the Lower basalt magmas, an interpretation consistent with progressively higher Cu/Pt and Cu/Pd ratios at decreasing MgO contents, and with falling Pt/Ti, collectively due to sulphur saturation induced by AFC as recorded in an antivariance of Pd/Ir with Nb/Th, a monitor of AFC.Collectively, the data suggest that several of the Lower Basalt suites crystallised under sulphide-saturated conditions, whereas most of the Upper Basalt Sequences remained sulphur undersaturated during magmatic evolution. Alteration, and fractional crystallisation of silicate and oxide phases, can be ruled out as factors governing PGE distribution in these mafic-ultramafic suites. Instead, the data suggest that discrete PGE-bearing phase (s) fractionated from the magmas. Such phases could be platinum group minerals (PGM; e.g., laurite) and/or alloys, or discrete PGE-rich nuggets or sulphides.  相似文献   

17.
Infrared spectra of C-O-H micro-inclusions were collected from a micro-inclusion bearing diamond during step-heating and freezing experiments to examine fluid speciation as a function of pressure and temperature. The inclusions contain H2O, CO2, carbonate, apatite, quartz and mica, which together represent the oxidising remnant mantle fluid composition after diamond crystallisation. The internal pressure of the inclusions, measured from calibrated shifts of the quartz peaks, increases from 1.3 GPa at ambient temperature, to approximately 4-5 GPa at 737 °C, close to the conditions of crystallisation of the host diamond in the mantle.  相似文献   

18.
Halogen diffusion in a basaltic melt   总被引：2，自引：0，他引：2  
The diffusion of the halogens fluorine, chlorine and bromine was measured in a hawaiitic melt from Mt. Etna at 500 MPa and 1.0 GPa, 1250 to 1450 °C at anhydrous conditions; the diffusion of F and Cl in the melt was also studied with about 3 wt% of dissolved water. Experiments were performed using the diffusion-couple technique in a piston cylinder. Most experiments were performed with only one halogen diffusing between the halogen-enriched and halogen-poor halves of the diffusion couple, but a few experiments with a mixture of halogens (F, Cl and Br) were also performed in order to investigate the possibility of interactions between the halogens during diffusion. Fluorine and chlorine diffusivity show a very similar behavior, slightly diverging at low temperature. Bromine diffusion is a factor of about 2-5 lower than the other halogens in this study. Diffusion coefficients for fluorine range between 2.3 × 10−11 and 1.4 × 10−10 m2 s−1, for chlorine between 1.1 × 10−11 and 1.3 × 10−10 and for bromine between 9.4 × 10−12 and 6.8 × 10−11 m2 s−1. No pressure effect was detected at the conditions investigated. In experiments involving mixed halogens, the diffusivities appear to decrease slightly (by a factor of ∼3), and are more uniform among the three elements. However, activation energies for diffusion do not appear to differ between experiments with individual halogens or when they are all mixed together. The effect of water increases the diffusion coefficients of F and Cl by no more than a factor of 3 compared to the anhydrous melt (DF = 4.0 × 10−11 to 1.6 × 10−10 m2 s−1; DCl = 3.0 × 10−11 to 1.9 × 10−10 m2 s−1). Comparing our results to the diffusion coefficients of other volatiles in nominally dry basaltic melts, halogen diffusivities are about one order of magnitude lower than H2O, similar to CO2, and a factor of ∼5 higher than S. The contrasting volatile diffusivities may affect the variable extent of volatile degassing upon melt depressurization and vesiculation, and can help our understanding of the compositions of rapidly grown magmatic bubbles.  相似文献   

19.
Carbon has been proposed as a potential light element in planetary cores, included in models of planetary core formation, and found in meteoritic samples and minerals. To better understand the effect of C on the partitioning behavior of elements, solid/liquid partition coefficients (D = (solid metal)/(liquid metal)) were determined for 17 elements (As, Au, Co, Cr, Cu, Ga, Ge, Ir, Ni, Os, Pd, Pt, Re, Ru, Sb, Sn, and W) over a range of C contents in the Fe-Ni-C system at 1 atm. The partition coefficients for the majority of the elements increased as the C content of the liquid increased, an effect analogous to that of S for many of the elements. In contrast, three of the elements, Cr, Re, and W, were found to have anthracophile (C-loving) preferences, partitioning more strongly into the metallic liquid as the C content increased, resulting in decreases to their partition coefficients. For half of the elements examined, the prediction that partitioning in the Fe-Ni-S and Fe-Ni-C systems could be parameterized using a single set of variables was not supported. The effects of S and C on elemental partitioning behavior can be quite different; consequently, the presence of different non-metals can result in different fractionation patterns, and that uniqueness offers the opportunity to gain insight into the evolution of planetary bodies.  相似文献   

20.
We performed density measurements on a synthetic equivalent of lunar Apollo 17 74,220 “orange glass”, containing 9.1 wt% TiO2, at superliquidus conditions in the pressure range 0.5-8.5 GPa and temperature range 1723-2223 K using the sink/float technique. In the lunar pressure range, two experiments containing pure forsterite (Fo100) spheres at 1.0 GPa and 1727 K, and at 1.3 GPa-1739 K, showed neutral buoyancies, indicating that the density of molten orange glass was equal to the density of Fo100 at these conditions (3.09 ± 0.02 g cm−3). A third tight sink/float bracket using Fo90 spheres corresponds to a melt density of 3.25 ± 0.02 g cm−3 at ∼2.8 GPa and ∼1838 K.Our data predict a density crossover for the molten orange glass composition with equilibrium orthopyroxene at ∼2.8 GPa, equivalent to a depth of ∼600 km in the lunar mantle, and a density of ∼3.25 g cm−3. This crossover depth is close to the orange glass multiple saturation point, representing its minimum formation depth, at the appropriate oxygen fugacity (2.8-2.9 GPa). A density crossover with equilibrium olivine is predicted to fall outside the lunar pressure range (>4.7 GPa), indicating that molten orange glass is always less dense than its equilibrium olivines in the Moon. Our data therefore suggest that that lunar liquids with orange glass composition are buoyant with respect to their source region at P < ∼2.8 GPa, enabling their initial rise to the surface without the need for additional external driving forces.Fitting the density data to a Birch-Murnaghan equation of state at 2173 K leads to an array of acceptable solutions ranging between 16.1 and 20.3 GPa for the isothermal bulk modulus K2173 and 3.6-8 for its pressure derivative K′, with best-fit values K2173 = 18.8 GPa and K′ = 4.4 when assuming a model 1 bar density value of 2.86 g cm−3. When assuming a slightly lower 1 bar density value of 2.84 g cm−3 we find a range for K2173 of 14.4-18.0 and K′ 3.7-8.7, with best-fit values of 17.2 GPa and 4.5, respectively.  相似文献   

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