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1.
Thirty-three whole-rock drill core samples and thirteen olivine, chromite, and sulfide separates from three differentiated komatiite lava flows at Alexo and Pyke Hill, Canada, were analyzed for PGEs using the Carius tube digestion ID-ICP-MS technique. The emplaced lavas are Al-undepleted komatiites with ∼27% MgO derived by ∼50% partial melting of LILE-depleted Archean mantle. Major and minor element variations during and after emplacement were controlled by 30 to 50% fractionation of olivine Fo93-94. The emplaced lavas are characterized by (Pd/Ir)N = 4.0 to 4.6, (Os/Ir)N = 1.07, and Os abundances of ∼2.3 ppb. Variations in PGE abundances within individual flows indicate that Os and Ir were compatible (bulk DOs,Ir = 2.4-7.1) and that Pt and Pd were incompatible (bulk DPt,Pd < 0.2) during lava differentiation, whereas bulk DRu was close to unity. Analyses of cumulus olivine separates indicate that PGEs were incompatible in olivine (DPGEsOl-Liq = 0.04-0.7). The bulk fractionation trends cannot be accounted for by fractionation of olivine alone, and require an unidentified Os-Ir-rich phase. The composition of the mantle source (Os = 3.9 ppb, Ir = 3.6 ppb, Ru = 5.4 ppb, Pt and Pd = 5.7 ppb) was constrained empirically for Ru, Pt, and Pd; the Os/Ir ratio was taken to be identical to that in the emplaced melt, and the Ru/Ir ratio was taken to be chondritic, so that the absolute IPGE abundances of the source were determined by Ru. This is the first estimate of the PGE composition of a mantle source derived from analyses of erupted lavas. The suprachondritic Pd/Ir and Os/Ir of the inferred Abitibi komatiite mantle source are similar to those in off-craton spinel lherzolites, orogenic massif lherzolites, and enstatite chondrites, and are considered to be an intrinsic mantle feature. Bulk partition coefficients for use in komatiite melting models derived from the source and emplaced melt compositions are: DOs,Ir = 2.3, DRu = 1.0, DPt,Pd = 0.07. Ruthenium abundances are good indicators of absolute IPGE abundances in the mantle sources of komatiite melts with 26 to 29% MgO, as Ru fractionates very little during both high degrees of partial melting and lava differentiation.  相似文献   

2.
Despite the growing interest for Li and B as geochemical tracers, especially for material transfer from subducting slabs to overlying peridotites, little is known about the behaviour of these two elements during partial melting of mantle sources. In particular, mineral/melt partition coefficients for B and to a lesser extent Li are still a matter of debate. In this work, we re-equilibrated a synthetic basalt doped with ~10 ppm B and ~6 ppm Li with an olivine powder from a spinel lherzolite xenolith at 1 GPa–1,330°C, and we analyzed Li and B in the run products by secondary ion mass spectrometry (SIMS). In our experiment, B behaved as a highly incompatible element with mineral/melt partition coefficients of the order of 10−2 (D ol/melt = 0.008 (0.004–0.013); D opx/melt = 0.024 (0.015–0.033); D cpx/melt = 0.041 (0.021–0.061)), and Li as a moderately incompatible element (D ol/melt = 0.427 (0.418–0.436); D opx/melt = 0.211 (0.167–0.256); D cpx/melt = 0.246 (0.229–0.264)). Our partition coefficients for Li are in good agreement with previous determinations. In the case of B, our partition coefficients are equal within error to those reported by Brenan et al. (1998) for all the mineral phases analyzed, but are lower than other coefficients from literature for some of the phases (up to 5 times for cpx). Our measurements complement the data set of Ds for modelling partial melting of the upper mantle and basalt generation, and confirm that, in this context, B is more incompatible than previously anticipated.  相似文献   

3.
Mineral-melt partition coefficients of all noble gases (min/meltDi) have been obtained for olivine (ol) and clinopyroxene (cpx) by UV laser ablation (213 nm) of individual crystals grown from melts at 0.1 GPa mixed noble gas pressure. Experimental techniques were developed to grow crystals virtually free of melt and fluid inclusions since both have been found to cause profound problems in previous work. This is a particularly important issue for the analysis of noble gases in crystals that have very low partition coefficients relative to coexisting melt and fluid phases. The preferred partitioning values obtained for the ol-melt system for He, Ne, Ar, Kr, and Xe are 0.00017(13), 0.00007(7), 0.0011(6), 0.00026(16), and , respectively. The respective cpx-melt partition coefficients are 0.0002(2), 0.00041(35), 0.0011(7), 0.0002(2), and . The data confirm the incompatible behaviour of noble gases for both olivine and clinopyroxene but unlike other trace elements these values show little variation for a wide range of atomic radius. The lack of dependence of partitioning on atomic radius is, however, consistent with the partitioning behaviour of other trace elements which have been found to exhibit progressively lower dependence of min/meltDi on radius as the charge decreases. As all noble gases appear to exhibit similar min/meltDi values we deduce that noble gases are not significantly fractionated from each other by olivine and clinopyroxene during melting and fractional crystallisation. Although incompatible, the partitioning values for noble gases also suggest that significant amounts of primordial noble gases may well have been retained in the mantle despite intensive melting processes. The implication of our data is that high primordial/radiogenic noble gas ratios (3He/4He, 22Ne/21Ne, and 36Ar/40Ar) characteristic of plume basalt sources can be achieved by recycling a previously melted (depleted) mantle source rather than reflecting an isolated, non-degassed primordial mantle region.  相似文献   

4.
The solubility behavior of K2O, Na2O, Al2O3, and SiO2 in silicate-saturated aqueous fluid and coexisting H2O-saturated silicate melts in the systems K2O-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O has been examined in the 1- to 2-GPa pressure range at 1100°C. Glasses of Na- and K-tetrasilicate compositions with 0, 3, and 6 mol% Al2O3 were used as starting materials. In both systems, the oxides dissolve incongruently in aqueous fluid and silicate melt. When recalculated to an anhydrous basis, the aqueous fluids are enriched in alkalis and depleted in silica and alumina relative to their proportions in the starting materials. The extent of incongruency is more pronounced in the Na2O-Al2O3-SiO2-H2O system than in the K2O-Al2O3-SiO2-H2O system.The partition coefficients of the oxides, Doxidefluid/melt, are linear and positive functions of the oxide concentration in the fluid for each composition. There is a slight dependence of the partition coefficients on bulk composition. No effect of pressure could be discerned. For alkali metals, the fluid/melt partition coefficients range from 0.06 to 0.8. For Al2O3 this range is 0.01 to 0.2, and for SiO2, it is 0.01 to 0.32. For all compositions, DK2Ofluid/melt∼DNa2Ofluid/melt>DSiO2fluid/melt>DAl2O3fluid/melt for the same oxide concentration in the fluid. DK2Ofluid/melt, DNa2Ofluid/melt, and DSiO2fluid/melt correlate negatively with the Al2O3 content of the systems. This correlation is consistent with a solubility model of alkalis that involve associated KOH°, NaOH°, silicate, and aluminate complexes.  相似文献   

5.
The distribution equilibrium of Au and Re between nickel-iron and basaltic melts was studied at 1400–1600°C, using radioactive tracers. Metal/silicate distribution coefficients were 1–3 orders of magnitude higher than earlier estimates, as follows. Mauna Loa basalt—Fe10Ni90: DAu = 3.3 × 104, DRe = (2.4?89) × 104. Gorda Ridge basalt—Fe10Ni90: DAu = (18?75) × 104. Synthetic lunar basalt—Fe70 Ni30: DAu≥ 2 × 104, DRe ≥ 2 × 103. The experimental ΔG1800° for the distribution of Au between nickel-iron and Mauna Loa basalt is ?40 kcal/mole, compared to a calculated value of about ?110 kcal/mole for a reaction involving simple Au3+ ions. Presumably the difference represents stabilization of Au(III) by complex formation with ligands such as Cl?, H2O, etc.Gold abundances in lunar basalts are roughly consistent with the measured DAu, but those in terrestrial basalts are two orders of magnitude too high. This discrepancy may reflect complexing by volatiles in the Earth's upper lithosphere, as well as oxidative destruction of metal in the final stages of accretion. In the absence of a metal phase, siderophile trace elements would remain trapped in the upper mantle and crust.  相似文献   

6.
The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of DClapatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing DClapatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which DClapatite/melt and DClfluid/melt begin to increase also depends on composition. The experiments reveal that DFapatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so DFapatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.  相似文献   

7.
Trace element partitioning in plagioclase feldspar   总被引：4，自引：0，他引：4  
Compilation and interpretation of experimental and natural Nernst partition coefficient (plagioclase/meltD) data show that, with a few exceptions, increases in plagioclase/meltD correlate with decreasing anorthite-content of plagioclase. In contrast, increases of plagioclase/meltD for Ga, Sc, Cu, Zn, Zr, Hf and Ti, are better correlated against decreasing melt MgO or increasing melt SiO2 contents. plagioclase/meltD for Ti and the rare earth elements (REE) show little dependence on temperature, but increase as the melt water content increases. plagioclase/meltD for K and Sr are sensitive to pressure. Variations of D0 (the strain compensated partition coefficient), r0 (the size of the site into which REE substitute), and E (Young’s Modulus of this site) were parameterized against variations of melt SiO2, the An-content of plagioclase, and other combinations of variables, allowing plagioclase/meltDREE-Y to be calculated from a variety of input parameters. The interrelations of temperature, melt MgO and SiO2 content, and plagioclase anorthite-content for wet and dry systems were also parameterized to facilitate interpolation where such data are lacking. When combined, these semi-empirical parameterizations yield plagioclase/meltD results comparable to available experimental and natural data.  相似文献   

8.
The concentrations of Ir, Ru, Pt and Pd have been determined in 29 Mid-Oceanic Ridge basaltic (MORB) glasses from the Pacific (N = 7), the Atlantic (N = 10) and the Indian (N = 11) oceanic ridges and the Red Sea (N = 1) spreading centers. The effect of sulfide segregation during magmatic differentiation has been discussed with sample suites deriving from parental melts produced by high (16%) and low (6%) degrees of partial melting, respectively. Both sample suites define positive and distinct covariation trends in platinum-group elements (PGE) vs. Ni binary plots. The high-degree melting suite displays, for a given Ni content, systematically higher PGE contents relative to the low-degree melting suite. The mass fraction of sulfide segregated during crystallization (Xsulf), the achievement of equilibrium between sulfide melt and silicate melts (Reff), and the respective proportions between fractional and batch crystallization processes (Sb) are key parameters for modeling the PGE partitioning behavior during S-saturated MORB differentiation. Regardless of the model chosen, similar sulfide melt/silicate melt partition coefficients for Ir, Ru, Pt and Pd are needed to model the sulfide segregation process, in agreement with experimental data. When corrected for the effect of magmatic differentiation, the PGE data display coherent variations with partial melting degrees. Iridium, Ru and Pt are found to be compatible in nonsulfide minerals whereas the Pd behaves as a purely chalcophile element. The calculated partition coefficients between mantle sulfides and silicate melts (assuming a PGE concentration in the oceanic mantle at ∼0.007 × CI-chondritic abundances) increase from Pd (∼103) to Ir (∼105). This contrasting behavior of PGE during S-saturated magmatic differentiation and mantle melting processes can be accounted for by assuming that Monosufide Solid Solution (Mss) controls the PGE budget in MORB melting residues whereas MORB differentiation processes involve Cu-Ni-rich sulfide melt segregation.  相似文献   

9.
The concentrations of Rh, Au and other highly siderophile elements (HSE: Re, Os, Ir, Ru, Pt, Rh, Pd and Au), and 187Os/188Os isotope ratios have been determined for samples from peridotite massifs and xenoliths in order to further constrain HSE abundances in the Earth's mantle and to place constraints on the distributions processes accounting for observed HSE variations between fertile and depleted mantle lithologies. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS. The monoisotopic elements Rh and Au were quantified by standardization relative to the concentrations of Ru and Ir, respectively, and were determined from the same digestion aliquot as other HSE. The measurement precision of the concentration data under intermediate precision conditions, as inferred from repeated analyses of 2 g test portions of powdered samples, is estimated to be better than 10% for Rh and better than 15% for Au (1 s).Fertile lherzolites display non-systematic variation of Rh concentrations and constant Rh/Ir of 0.34 ± 0.03 (1 s, n = 57), indicating a Rh abundance for the primitive mantle of 1.2 ± 0.2 ng/g. The data also suggest that Rh behaves as a compatible element during low to moderate degrees of partial melting in the mantle or melt–mantle interaction, but may be depleted at higher degrees of melting. In contrast, Au concentrations and Au/Ir correlate with peridotite fertility, indicating incompatible behaviour of Au during magmatic processes in the mantle. Fertile lherzolites display Au/Ir ranging from 0.20 to 0.65, whereas residual harzburgites have Au/Ir < 0.20. Concentrations of Au and Re are correlated with each other and suggest similar compatibility of both elements. The primitive mantle abundance of Au calculated from correlations displayed by Au/Ir with Al2O3 and Au with Re is 1.7 ± 0.5 ng/g (1 s).The depletion of Pt, Pd, Re and Au relative to Os, Ir, Ru and Rh displayed by residual harzburgites, suggests HSE fractionation during partial melting. However, the HSE abundance variations of fertile and depleted peridotites cannot be explained by a simple fractionation process. Correlations displayed by Pd/Ir, Re/Ir and Au/Ir with Al2O3 may reflect refertilization of previously melt depleted mantle rocks due to reactive infiltration of silicate melts.Relative concentrations of Rh and Au inferred for the primitive mantle model composition are similar to values of ordinary and enstatite chondrites, but distinct from carbonaceous chondrites. The HSE pattern of the primitive mantle is inconsistent with compositions of known chondrite groups. The primitive mantle composition may be explained by late accretion of a mixture of chondritic with slightly suprachondritic materials, or alternatively, by meteoritic materials mixed into mantle with a HSE signature inherited from core formation.  相似文献   

10.
Summary We report here new data on the solubility of Au in silicate melts of anorthite-diopside eutectic composition at a wide range of oxygen fugacities, from pure oxygen to 10–8 atm, and at a temperature range of 1300 °C to 1480 °C. Because experiments were done with metal loops at temperatures above the Au-melting temperature, PdAu-metal-alloys had to be used. Pd-solubility data derived from the same set of experiments agree with earlier data obtained from experiments with pure Pd-metal (Borisov et al., 1994a). The results of the present experiments show that Pd-solubilities are by a factor of 2 to 6 higher than Au-solubilities. Both, Au and Pd solubilities decrease with decreasing oxygen fugacity. At oxygen fugacities below the iron-wiistite buffer (IW) Au solubility increases with decreasing fO2 probably reflecting formation of Au-silicides at such reducing conditions. Compared to Pd, Au has higher activity coefficients in Fe-metal and lower solubility in silicate melts. This leads to similar metal-silicate partition coefficients for both elements. At a temperature of 1350 °C and an oxygen fugacity corresponding to IW-2 DAu (met/sil) is about 2.5 · 107 and DPd (met/sil) about 1.6 · 107. Thus similar behavior is expected during metal separation in planetary bodies including core formation in the Earth. The metal/silicate partition coefficient of Ir is, however, by several orders of magnitudes higher (Borisov and Palme, 1995a). Equilibration with chondritic metal will therefore lead to grossly non-chondritic Pd/Ir or Au/Ir ratios in coexisting silicate phases. Chondritic ratios are thus indicative of the presence of unfractionated meteoritic components. Samples from the upper mantle of the Earth, for example, reflect the admixture of a late unfractionated (chondritic) veneer (e.g.,Kimura et al., 1974;Jagoutz et al., 1979).Solubilities of Pd and Au in silicate melts are much higher than the contents in terrestrial basalts implying that the abundances of these two elements are not buffered by residual PGE- and Au-containing alloys. The most likely process for fractionating PGEs in terrestrial magmas are mineral-melt (e.g., olivine/melt) equilibria.
Experimentelle Bestimmung der Löslichkeit von Au in Silikatschmelzen
Zusammenfassung In der vorliegenden Arbeit wird über die Ergebnisse der Bestimmung der Löslichkeit von Au in Silikatschmelzen mit der Zusammensetzung des Anorthit-Diopsid Eutektikums berichtet. Die Versuche wurden mittels Metallschlaufe über einen weiten Sauerstoffpartialdruckbereich, von reinem Sauerstoff bis zu 10–8 atm und in einem Temperaturbereich von 1300 °C bis 1480 °C, durchgeführt. Da diese Temperaturen jedoch den Au-Schmelzpunkt überschreiten, wurde mit AuPd-Legierungen gearbeitet. Die Ergebnisse der dadurch zusätzlich erhaltenen Pd-Versuche stimmen mit früher bestimmten, mit reinen Pd-Schlaufen durchgeführten Pd-Löslichkkeiten überein (Borisov et al., 1994a). Die auf reine Metalle zurückgerechneten Löslichkeiten von Pd sind um einen Faktor 2 bis 6 mal höher als die entsprechenden Au-Löslichkeiten. Die Löslichkeiten beider Metalle nehmen mit abnehmendem Sauerstoffpartialdruck ab. Unter noch stärker reduzierenden Bedingungen (Eisen-Wüstit Gleichgewicht) nimmt die Löslichkeit von Au jedoch zu. Dies könnte auf die Bildung von Au-Siliziden zurückzuführen sein.Im Vergleich zu Pd sind die Aktivitätskoeffizienten von Au in metallischem Eisen höher, die Löslichkeiten in Silikatschmelzen jedoch niedriger. Das führt zu ähnlichen Metall/Silikat Verteilungskoeffizienten von Au und Pd. Bei einer Temperatur von 1350 °C und einer Sauerstoffugazität von IW-2 ergeben sich für DAu (met/sil) 2.5 · 107 und für DPd (met/sil) 1.6* 107. Der Metall/Silikat-Verteilungskoeffizient von Ir ist jedoch unter den gleichen Bedingungen um mehrere Größenordnungen höher (Borisov andPalme, 1995a). Ein chondritisches Pd/Ir- oder Au/Ir-Verhältnis kann also auf die Anwesenheit einer unfraktionierten chondritischen Komponente zurückgeführt werden. Dies gilt beispielsweise für Proben aus dem oberen Erdmantel. Hier handelt es sich vermutlich um Zumischung einer späten chondritischen Akkretionskomponente, die sich nicht mehr mit einer metallischen Phase (Kern) ins Gleichgewicht gesetzt hat (z.B.Kimura et al., 1974,Jagoutz et al., 1979).Die Löslichkeiten von Pd und Au in Silikatschmelzen sind wesentlich höher als ihre Gehalte in basaltischen und komatiitischen Laven. Dies bedeutet, daß Au und Pd in Schmelzen aus dem Erdmantel nicht durch residuale Au- und/oder Pd-haltige Metall phasen bestimmt sind. Gleichgewichte zwischen Schmelze und Mineralen (z.B. Olivin) sind die wahrscheinlichsten Fraktionierungsmechanismen für Platingruppenelemente in terrestrischen Magmen.

With 5 Figures  相似文献   

11.
Zircon was grown from trace-element doped hydrous peralkaline rhyolite melts with buffered oxygen fugacities in cold-seal experiments at 0.1 and 0.2 GPa and 800 °C and piston-cylinder experiments at 1.5 GPa and 900-1300 °C. Zircon and glass were present in all run products, and small monazite crystals were present in eight of the 12 experiments. Average diameters of zircon crystals ranged from 5 to 20 μm at 800 °C to 30-50 μm at 1300 °C. Zircon crystals have thin rims, and adjacent glass has a narrow (∼1 μm thick) compositional boundary layer. Concentrations obtained through in-situ analysis of cores of run product zircon crystals and melt pools were used to calculate trace-element partition coefficients Dzircon/melt for P, Sc, Ti, V, Y, La, Ce, Pr, Nd, Eu, Gd, Ho, Yb, Lu, Hf, Th, and U. In most cases Lu was the most (D 12-105) and La the least (0.06-0.95) compatible elements. D values from this study fall within the range of previously measured values for Rare Earth Elements (REE). However, D values measured experimentally show less fractionation than those recently measured using natural phenocryst/matrix pairs. For example, DLu/DLa measured experimentally in this study range between 27 and 206 compared to a value of 706,522 for a natural zircon/dacite pair [Sano, Y., Terada, K., and Fukuoka, T. 2002 High mass resolution ion microprobe analysis of rare earth elements in silicate glass, apatite and zircon: lack of matrix dependency. Chem. Geol.184, 217-230]. Although D values from this study show good agreement with the lattice strain model, D values from natural phenocryst/matrix pairs combined with measured zircon compositions better reproduce host-rock (magma) compositions of igneous rocks. They also yield more reasonable estimates of magma compositions when combined with compositions of ‘‘out-of-context” zircons. For example, compositions of the Hadean detrital zircons from Jack Hills, Australia yield LREE-enriched magmas when combined with D values from phenocryst/matrix pairs yields, but yield LREE-depleted magmas when experimentally determined D values are used. We infer that experimentally measured Dzircon/melt values represent disequilibrium partitioning resulting from rapid zircon growth during short laboratory timescales. Rapid growth causes development of observed diffusive boundary layers in the melt adjacent to zircon crystals. D values from phenocryst/matrix pairs are therefore recommended for petrogenetic modeling.  相似文献   

12.
Solubility experiments for nitrogen and noble gases (Ar and Ne) in silicate melts were conducted using two experimental configurations: one was conducted at 1 atmospheric pressure, T =1300°C and oxygen fugacity (fO2) of IW + 0.9 (i.e., 0.9 log units higher than the iron-wüstite buffer) and the other at high pressures (Ptotal ∼ 2 × 108 Pa), 1500°C and fO2 ∼ IW + 6. For the former experiment, isotopically labeled-nitrogen (15N15N-enriched) was used to distinguish dissolved nitrogen from contaminating atmospheric or organic nitrogen and to examine dissolution mechanisms of nitrogen in silicate melts. The results obtained for the two series of experiments are consistent with each other, suggesting that Henry's law is satisfied for fN2 of up to ∼250 atm (2.5 × 107 Pa). The results are also consistent with our earlier results (Miyazaki et al., 1995) obtained at highly oxidizing conditions (fO2 ∼ IW + 10). All these results support physical dissolution of nitrogen as N2 molecules in silicate melts for fO2 from ∼IW + 10 down to ∼IW. The observed solubility (Henry's constant) of nitrogen (3-5 × 10−9 mol/g/atm) is comparable to that of Ar (2-4 × 10−9 mol/g/atm), and much lower than that of Ne (11-14 × 10−9 mol/g/atm) at 1300°C. A preliminary experiment was also performed for partitioning of nitrogen and noble gases between clinopyroxene (cpx) and basaltic melt using a piston cylinder-type apparatus at 1.5 GPa and at 1270 to 1350°C. The obtained cpx/melt partition coefficient of nitrogen is 0.06, slightly lower than those of noble gases (∼0.1 for Ne to Xe), suggesting that nitrogen is as incompatible as or even slightly more incompatible than noble gases. The present results imply that a large nitrogen/Ar fractionation would not be produced by magmatic processes. Therefore, the two orders of magnitude difference between the N2/36Ar ratios in the Earth's atmosphere (∼104) and that in the mantle (∼106) must be explained by some other processes, such as incomplete segregation of metal blobs into the core and their later oxidation.  相似文献   

13.
Burnham (1975a, b) has shown that in several alumino-silicate systems Henry's law constant is independent of silicate melt composition up to XmeltH2O = 0.5. He has used this fact to conclude that such silicate melts behave ideally over a wide range of compositions based on the application of the Gibbs-Duhem relation. Unless Henry's law is valid up to XmeltH2O = 1.0, the application of the Gibbs—Duhem relation to three component systems only shows that if one component obeys Henry's law, the other two components follow the two component Gibbs-Duhem equation. There is no thermodynamic requirement of ideality.  相似文献   

14.
The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D 0, r 0 and E) as functions of pressure, temperature, and compositions of cpx and melt. D 0 is found to positively correlate with Al in tetrahedral site (Al T ) and Mg in the M2 site (MgM2) of cpx and negatively correlate with temperature and water content in the melt. r 0 is negatively correlated with Al in M1 site (AlM1) and MgM2 in cpx. And E is positively correlated with r 0. During adiabatic melting of spinel lherzolite, temperature, Al T , and MgM2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.  相似文献   

15.
Experiments from 640 to 680?°C, 200 MPa H2O at?f O2?≈?NNO, employing a natural?F-rich?vitrophyric rhyolite from Spor Mountain, Utah, assessed the effect of variable Mg′ [100Mg/(Mg?+?Mn?+?Fe)] on the partitioning of fluorine and chlorine between biotite (Bt) and melt. Over this temperature interval, Bt (?±?fluorite, ?±?quartz) is the sole liquidus phase. Partition coefficients for fluorine between biotite and glass (DF Bt/melt) show a strong dependence on the Mg′ of Bt.?DF Bt/melt varies from???1.5 to 7.2 over the range of Mg′ from 21 to 76. A strong linear correlation between?DF Bt/melt?and Mg′ has a slope of 9.4 and extrapolates through the origin (i.e., DF Bt/melt?≈?0 at Mg′?=?0, an annite-siderophyllite solid solution in these experiments). DCl Bt/melt values (???1 to 6) in the same experiments vary inversely with Mg′. The Al-content of biotite does not vary with the aluminum saturation index (ASI?=?molar Al2O3/Σ alkali and alkaline earth oxides) of melt, but two exchange mechanisms involving Al appear to operate in these micas: (1) Alvi?+?Aliv?? Siiv?+?Mgiv, and Mgiv?+?2Aliv? 2Siiv?+?□iv. The effects of other components such as Li or other intensive parameters including f O2 have yet to be evaluated?systematically. At comparable Mg′ of Bt, however, the Spor Mountain rhyolite yields higher DF Bt/melt values than an Li-rich, strongly peraluminous melt previously investigated. The results indicate that the Mg′ of Bt exerts the principal control on halogen partitioning, with ASI and T as second-order variables. The experimental partition coefficients compare well with other experimental results but not with most volcanic rocks. Magmatic Bt from most rhyolites records higher DF Bt/melt due to reequilibration with degassed (H2O-depleted) magma and perhaps with F2O?1 exchange that may accompany oxidation ([Fe3+O] [Fe2+OH]?1). This behavior is evident in magmatic biotite from a zoned peraluminous rhyolite complex near Morococala, Bolivia: Bt is sharply zoned with F-rich rims, but Bt(core)-melt inclusion pairs fall on our experimental curve for DF Bt/melt. These experimental data can be used in part to assess the preservation of magmatic volatile contents in plutonic or volcanic silicic rocks. For plutonic rocks, the actual F-content of melt, not a relative activity ratio involving HF species, can be reasonably estimated if the mica has not undergone subsolidus reequilibration. This information is potentially useful for some shallow-level Ca-poor magmas that are thought to be rich in F (e.g., A- and S-type granites) but do not conserve F well as rocks.  相似文献   

16.
Water partitioning between mantle minerals from peridotite xenoliths   总被引：1，自引：1，他引：1  
The speciation and amount of water dissolved in nominally anhydrous silicates comprising eight different mantle xenoliths has been quantified using synchrotron micro-FTIR spectroscopy. Samples studied are from six geographic localities and represent a cross-section of the major upper mantle lithologies from a variety of tectonic settings. Clinopyroxene contains between 342 and 413 ppm H2O. Orthopyroxene, olivine and garnet contain 169–201, 3–54 and 0 to <3 ppm H2O, respectively. Pyroxenes water contents and the distribution of water between ortho- and clinopyroxene is identical regardless of sample mineralogy (D watercpx/opx = 2.1 ± 0.1). The total water contents of each xenolith are remarkably similar (113 ± 14 ppm H2O). High-resolution spectroscopic traverses show that the concentration and speciation of hydrous defects dissolved in each phase are spatially homogeneous within individual crystals and identical in different crystals interspersed throughout the xenolith. These results suggest that the amount of water dissolved in the silicate phases is in partial equilibrium with the transporting melt. Other features indicate that xenoliths have also preserved OH signatures of equilibrium with the mantle source region: Hydroxyl stretching modes in clinopyroxene show that garnet lherzolites re-equilibrated under more reducing conditions than spinel lherzolites. The distribution of water between pyroxenes and olivine differs according to xenolith mineralogy. The distribution of water between clinopyroxene and olivine from garnet peridotites (D watercpx/oliv(gnt) = 22.2 ± 24.1) is a factor of four greater than mineral pairs from spinel-bearing xenoliths (D watercpx/oliv(sp) = 88.1 ± 47.8). Such an increase in olivine water contents at the spinel to garnet transition is likely a global phenomenon and this discontinuity could lead to a reduction of the upper mantle viscosity by 0.2–0.7 log units and a reduction of its electrical resistivity by a factor of 0.5–0.8 log units.  相似文献   

17.

This study presents a new set of quantitative experimental data on the partitioning of Ta, Nb, Mn, and F between aqueous F-bearing fluid and water-saturated, Li- and F-rich haplogranite melts with varying alumina/alkali content at T = 650–850 °C and P = 100 MPa. The starting homogeneous glasses were preliminary obtained by melting of three gel mixtures of K2O-Na2O-Al2O3-SiO2 composition with a variable Al2O3/(Na2O+K2O) ratio, ranging from 0.64 (alkaline) and 1.1 (near-normal) to 1.7 (alumina-rich). Ta, Nb, and Mn were originally present in glass only, whereas F was load in both the glass and the solution. The solutionto-glass weight ratio was 1.5–3.0. The compositions of quenched glass were measured by an electronic microprobe, and those of the aqueous solution, with the ICP-MS and ICP-AES methods. The F concentration in the quenched solution was calculated from the mass balance. Under experimental conditions the partition coefficients of Ta, Nb, and Mn between the fluid and the granitic melt (weight ratio fluid C Ta/melt C Ta = fluid/melt D Ta) are shown to be extremely low (0.001–0.008 for Ta, 0.001–0.022 for Nb, and 0.002–0.010 for Mn); thus, these metals partition preferentially into the melt. The coefficients fluid/melt D Ta and fluid/melt D Nb generally increase either with increasing alumina ratio A/NKM in the glass composition, or with rising temperature. The experiments also demonstrated that F preferentially concentrates in the melt; and the partition coefficients of F are below 1, being within the range of 0.1–0.7.

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18.
To estimate the behavior of Au, Pd, REE, and Y in magmatic and postmagmatic processes, a series of experimental studies on the solubility of noble metals and REE in magma, magmatic fluid, and hydrothermal solutions has been performed in wide temperature and pressure ranges (300–400°C, 860–1350°C; 1–14 kbar). The coefficients of Au and Pd partitioning (D F/L) between fluid and tholeiitic melt have been determined. Depending on P, T, and the composition of the system, they vary from 1 to 11 for Au and 0.02 to 1 for Pd. The phase solubility technique was used to determine Au and Pd solubility in hydrothermal fluid. The effects of temperature, composition, and fluid acidity on Au and Pd solubility have been estimated. The high solubility of these metals in aqueous chloride solutions has been established for both Au (28–803 mg/kg at T = 300°C, 305–1123 mg/kg at T = 350°C, and 330–1400 mg/kg at T = 400°C) and Pd (40–126 mg/kg at T = 300°C, 62–152 mg/kg at T = 350°C, and 20–210 mg/kg at T = 400°C). The coefficients of REE and Y partitioning (D F/L) between fluid and tholeiitic or alkaline melts have been determined. They vary from 0.00n to 2 depending on P, T, and fluid composition. The experimental data on Au and Pd solubility in solutions and magmatic fluids and the wide variation of REE D F/L between fluid and melt show that magmatic and hydrothermal fluids are efficient agents of Au, Pd, and REE transfer and fractionation. The obtained experimental data were used for elucidating sources of fluids and their role in the genesis of Au-Pd-REE occurrences in the Subpolar Urals.  相似文献   

19.
We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D Cl olivine/fluid varying between 10?5 and 10?3, whereas D Cl orthopyroxene/fluid and D Cl clinopyroxene/fluid are ~10?4 and D Cl amphibole/fluid is ~5 × 10?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D amph/fluid ≈ D cpx/fluid > D opx/fluid > D ol/fluid but that D mineral/fluid for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm?1. In F ± TiO2-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm?1. Absorption bands at ~3,530 and ~3,570 cm?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.  相似文献   

20.
《Geochimica et cosmochimica acta》1999,63(23-24):3967-3982
The partitioning of transition elements (Sc, Ti, V, Cr, Mn, Co, Ni) between orthopyroxene (opx) and clinopyroxene (cpx) in carefully selected garnet peridotite, spinel peridotite and garnet websterite xenoliths was determined by electron probe microanalyses (EPMA) and secondary ion mass spectrometry (SIMS). Xenoliths studied cover a wide compositional range and equilibrated under variable upper mantle conditions at temperatures between about 760 and 1370°C (two-pyroxene thermometer based on the enstatite-diopside solvus) and pressures between about 0.8 and 3.6 GPa (Al-in-opx and Ca-in-olivine barometers). We found that the partitioning of transition elements between opx and cpx (expressed as DM = concentration of element M in opx [cations per formula unit]/concentration of M in cpx [cations per formula unit]) is mainly controlled by temperature and to a much lesser degree by pressure. Variations in major element compositions of pyroxenes (e.g., variable XMg, AlIV or Na) have no influence on DM. For Sc, V, Cr, Mn, and Co, our data result in good correlations between ln DM and reciprocal absolute temperature, with correlation coefficients (r) between 0.950 and 0.981. It is therefore possible to use the partitioning of these elements between opx and cpx from peridotites and websterites as geothermometers. On the basis of our data, we suggest the following empirical thermometer equations: TSc = [(17.64 · P + 5663)/(3.25 − ln DSc)], TV = [(18.06 · P + 3975)/(2.27 − ln DV)], TCr = [(11.00 · P + 2829)/(1.56 − ln DCr)], TMn = [(−0.20 · P − 2229)/(−1.37 − ln DMn)], TCo = [(−4.31 · P − 2358)/(−0.98 − ln DCo)], where T is the absolute temperature in Kelvin and P the pressure in kilobars. For Ti and Ni observed correlations between ln DM and 1/T are less well defined.  相似文献   

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