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1.
The partitioning of As and Au between rhyolite melt and low-salinity vapor (2 wt% NaCl eq.) in a melt-vapor-Au metal ± magnetite ± pyrrhotite assemblage has been quantified at 800 °C, 120 MPa and fO2=NNO. The S-bearing runs have calculated values for the fugacities of H2S, SO2 and S2 of logfH2S=1.1, logfSO2=-1.5, and logfS2=-3.0. The ratio of H2S to SO2 is on the order of 400. The experiments constrain the effect of S on the partitioning behavior of As and Au at magmatic conditions. Calculated average Nernst-type partition coefficients (±1σ) for As between vapor and melt, , are 1.0 ± 0.1 and 2.5 ± 0.3 in the S-free and S-bearing assemblages, respectively. These results suggest that sulfur has a small, but statistically meaningful, effect on the mass transfer of As between silicate melt and low-salinity vapor at the experimental conditions. Efficiencies of removal, calculated following Candela and Holland (1986), suggest that the S-free and S-bearing low-salinity vapor can scavenge approximately 41% and 63% As from water-saturated rhyolite melt, respectively, during devolatilization assuming that As is partitioned into magnetite and pyrrhotite during second boiling. The S-free data are consistent with the presence of arsenous acid, As(OH)3 in the vapor phase. However, the S-bearing data suggest the presence of both arsenous acid and a As-S complex in S-bearing magmatic vapor. Apparent equilibrium constants, , describing the partitioning of As between melt and vapor are −1.3 (0.1) and −1.1 (0.1) for the S-free and S-bearing runs, respectively. The increase in the value of with the addition of S suggests a role for S in complexing and scavenging As from the melt during degassing.The calculated vapor/melt partition coefficients (±1σ) for Au between vapor and melt, , in S-free and S-bearing assemblages are 15 ± 2.5 and 12 ± 0.3, respectively. Efficiencies of removal (Candela and Holland, 1986) for the S-free melt, calculated assuming that magnetite is the dominant Au-sequestering solid phase during crystallization (Simon et al., 2003), suggest that magmatic vapor may scavenge on the order of 72% Au from a water-saturated melt. Efficiencies of removal calculated for the S-bearing assemblage, assuming pyrrhotite and magnetite are the dominant Au-sequestering solid phases, indicate that vapor may scavenge on the order of 60% Au from the melt. These model calculations suggest that the loss of pyrrhotite and magnetite from a melt, owing to punctuated differentiation during ascent and emplacement, does not prohibit the ability of a rhyolite melt to generate a large-tonnage Au deposit. Apparent equilibrium constants describing the partitioning of Au between melt and vapor were calculated using the mean values for the S-free and S-bearing assemblages; only S-bearing data from runs longer than 400 h were used as shorter runs may not have reached equilibrium with respect only to vapor/melt partitioning of Au. The values for are −4.4 (0.1) and −4.2 (0.2) for the S-free and S-bearing runs, respectively. These data suggest that the presence of S does not affect the mass transfer of Au from degassing silicate melt to an exsolved, low-salinity vapor in a low-fS2 assemblage (i.e., pyrrhotite-magnetite at NNO) at the experimental conditions reported here. Efficiencies of removal are calculated and used to model the mass transfer of Au from a crystallizing silicate melt to an exsolved, low-salinity vapor phase. The calculations suggest that the model, absolute tonnage of Au scavenged and transported by S-free and S-bearing vapors, from a crystallizing melt, would be comparable and that the time-integrated flux of low-salinity vapor could be responsible for a significant quantity of the Au in magmatic-hydrothermal ore deposits. 相似文献
2.
We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g−1 to 0.64 μg g−1 at FMQ + 4, and 0.54 μg g−1 to 0.1 μg g−1 at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g−1). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO2 values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed. 相似文献
3.
Hydrothermal experiments were conducted to determine the partitioning of Cl between rhyolitic to rhyodacitic melts, apatite, and aqueous fluid(s) and the partitioning of F between apatite and these melts at ca. 200 MPa and 900-924 °C. The number of fluid phases in our experiments is unknown; they may have involved a single fluid or vapor plus saline liquid. The partitioning behavior of Cl between apatite and melt is non-Nernstian and is a complex function of melt composition and the Cl concentration of the system. Values of DClapat/melt (wt. fraction of: Cl in apatite/Cl in melt) vary from 1 to 4.5 and are largest when the Cl concentrations of the melt are at or near the Cl-saturation value of the melt. The Cl-saturation concentrations of silicate melts are lowest in evolved, silica-rich melts, so with elevated Cl concentrations in a system and with all else equal, the maximum values of DClapat/melt occur with the most felsic melt. In contrast, values of DFapat/melt range from 11 to 40 for these felsic melts, and many of these are an order of magnitude greater than those applying to basaltic melts at 200 MPa and 1066-1150 °C. The Cl concentration of apatite is a simple and linear function of the concentration of Cl in fluid. Values of DClfluid/apat for these experiments range from 9 to 43, and some values are an order of magnitude greater than those determined in 200-MPa experiments involving basaltic melts at 1066-1150 °C.In order to determine the concentrations and interpret the behavior of volatile components in magmas, the experimental data have been applied to the halogen concentrations of apatite grains from chemically evolved rocks of Augustine volcano, Alaska; Krakatau volcano, Indonesia; Mt. Pinatubo, Philippines; Mt. St. Helens, Washington; Mt. Mazama, Oregon; Lascar volcano, Chile; Santorini volcano, Greece, and the Bishop Tuff, California. The F concentrations of these magmas estimated from apatite-melt equilibria range from 0.06 to 0.12 wt% and are generally equivalent to the concentrations of F determined in the melt inclusions. In contrast, the Cl concentrations of the magmas estimated from apatite-melt equilibria (e.g., ca. 0.3-0.9 wt%) greatly exceed those determined in the melt inclusions from all of these volcanic systems except for the Bishop Tuff where the agreement is good. This discrepancy in estimated Cl concentrations of melt could result from several processes, including the hypothesis that the composition of apatite represents a comparatively Cl-enriched stage of magma evolution that precedes melt inclusion entrapment prior to the sequestration of Cl by coexisting magmatic aqueous and/or saline fluid(s). 相似文献
4.
Temperature dependence of sulfide and sulfate solubility in olivine-saturated basaltic magmas 总被引：2，自引：0，他引：2
The sulfur concentration at pyrrhotite- and anhydrite-saturation in primitive hydrous basaltic melt of the 2001-2002 eruption of Mt. Etna was determined at 200 MPa, T = 1050-1250 °C and at log fO2 from FMQ to FMQ+2.2 (FMQ is Fayalite-Magnetite-Quartz oxygen buffer). At 1050 °C Au sample containers were used. A double-capsule technique, using a single crystal olivine sample container closed with an olivine piston, embedded in a sealed Au80Pd20 capsule, was developed to perform experiments in S-bearing hydrous basaltic systems at T > 1050 °C. Pyrrhotite is found to be a stable phase coexisting with melt at FMQ-FMQ+0.3, whereas anhydrite is stable at FMQ+1.4-FMQ+2.2. The S concentration in the melt increases almost linearly from 0.12 ± 0.01 to 0.39 ± 0.02 wt.% S at FeS-saturation and from 0.74 ± 0.01 to 1.08 ± 0.04 wt.% S at anhydrite-saturation with T ranging from 1050-1250 °C. The relationships between S concentration at pyrrhotite and/or anhydrite saturation, MgO content of the olivine-saturated melt, T, and log fO2 observed in this study and from previous data are used to develop an empirical model for estimating the magmatic T and fO2 from the S and MgO concentrations of H2O-bearing olivine-saturated basaltic melts. The model can also be used to determine maximum S concentrations, if fO2 and MgO content of the melt are known. The application of the model to compositions of melt inclusions in olivines from Mt. Etna indicates that the most primitive magmas trapped in inclusions might have been stored at log fO2 slightly higher than FMQ+1 and at T = 1100-1150 °C, whereas more evolved melts could have been trapped at T ? 1100 °C. These values are in a good agreement with the estimates obtained by other independent methods reported in the literature. 相似文献
5.
In order to (1) explain the worldwide association between epithermal gold-copper-molybdenum deposits and arc magmas and (2) test the hypothesis that adakitic magmas would be Au-specialized, we have determined the solubility of Au at 4 kbar and 1000 °C for three intermediate magmas (two adakites and one calc-alkaline composition) from the Philippines. The experiments were performed over a fO2 range corresponding to reducing (∼NNO−1), moderately oxidizing (∼NNO+1.5) and strongly oxidizing (∼NNO+3) conditions as measured by solid Ni-Pd-O sensors. They were carried out in gold containers, the latter serving also as the source of gold, in presence of variable amounts of H2O and, in a few additional experiments, of S. Concentrations of Au in glasses were determined by LA-ICPMS. Gold solubility in melt is very low (30-240 ppb) but increases with fO2 in a way consistent with the dissolution of gold as both Au1+ and Au3+ species. In the S-bearing experiments performed at ∼NNO−1, gold solubility reaches much higher values, from ∼1200 to 4300 ppb, and seems to correlate with melt S content. No systematic difference in gold solubility is observed between the adakitic and the non-adakitic compositions investigated. Oxygen fugacity and the sulfur concentration in melt are the main parameters controlling the incorporation and concentration of gold in magmas. Certain adakitic and non-adakitic magmas have high fO2 and magmatic S concentrations favorable to the incorporation and transport of gold. Therefore, the cause of a particular association between some arc magmas and Au-Cu-Mo deposits needs to be searched in the origin of those specialized magmas by involvement of Au- and S-rich protoliths. The subducted slab, which contains metal-rich massive sulfides, may constitute a potentially favorable protolith for the genesis of magmas specialized with respect to gold. 相似文献
6.
Zoltán Zajacz Werner E. Halter Marcel Guillong 《Geochimica et cosmochimica acta》2008,72(8):2169-2197
Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO2 = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (DPb ∼ 6 ∗ mCl, DZn ∼ 8 ∗ mCl, DAg ∼ 4 ∗ mCl, DFe ∼ 1.4 ∗ mCl, where mCl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of DMo ∼ 20, DB ∼ 15, DAs ∼ 13, DSb ∼ 8, DBi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (DCu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (DSn = 0.3-42, DW = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity. 相似文献
7.
We have performed a series of molecular dynamics simulations aimed at the evaluation of the solubility of CO2 in silicate melts of natural composition (from felsic to ultramafic). In making in contact within the simulation cell a supercritical CO2 phase with a silicate melt of a given composition, we have been able to evaluate (i) the solubility of CO2 in the P-T range 1473-2273 K and 20-150 kbar, (ii) the density change experienced by the CO2-bearing melt, (iii) the respective concentrations of CO2 and species in the melt, (iv) the lifetime and the diffusivity of these species and (v) the structure of the melt around the carbonate groups. The main results are the following:(1) The solubility of CO2 increases markedly with the pressure in the three investigated melts (a rhyolite, a mid-ocean ridge basalt and a kimberlite) from about ∼2 wt% CO2 at 20 kbar to ∼25 wt% at 100 kbar and 2273 K. The solubility is found to be weakly dependent on the melt composition (as far as the present compositions are concerned) and it is only at very high pressure (above ∼100 kbar) that a clear hierarchy between solubilities occurs (rhyolite < MORB < kimberlite). Furthermore at a given pressure the calculated solubility is negatively correlated with the temperature.(2) In CO2-saturated melts, the proportion of carbonate ions is positively correlated with the pressure at isothermal condition and is negatively correlated with the temperature at isobaric condition (and vice versa for molecular CO2). Furthermore, at fixed (P, T) conditions the proportion of carbonate ions is higher in CO2-undersaturated melts than in the CO2-saturated melt. Although the proportion of molecular CO2 decreases when the degree of depolymerization of the melt increases, it is still significant in CO2-saturated basic and ultrabasic compositions at high temperatures. This finding is at variance with experimental data on CO2-bearing glasses which show no evidence of molecular CO2 as soon as the degree of depolymerization of the melt is high (e.g. basalt). These conflicting results can be reconciled with each other by noticing that a simple low temperature extrapolation of the simulation data predicts that the proportion of molecular CO2 in basaltic melts might be negligible in the glass at room temperature.(3) The carbonate ions are found to be transient species in the liquid phase, with a lifetime increasing exponentially with the inverse of the temperature. Contrarily to a usual assumption, the diffusivity of carbonate ions into the liquid silicate is not vanishingly small with respect to that of CO2 molecules: in MORB they differ from each other by a factor of ∼6 at 1473 K and only a factor of ∼2 at 2273 K. Although the bulk diffusivity of CO2 is governed primarily by the diffusivity of CO2 molecules, the carbonate ions contribute significantly to the diffusivity of CO2 in depolymerized melts.(4) Concerning the structure of the CO2-bearing silicate melt, the carbonate ions are found to be preferentially associated with NBO’s of the melt, with an affinity for NBOs which exceeds that for BOs by almost one order of magnitude. This result explains why the concentration in carbonate ions is positively correlated with the degree of depolymerization of the melt and diminishes drastically in fully polymerized melts where the number of NBO’s is close to zero. Furthermore, the network modifier cations are not randomly distributed in the close vicinity of carbonate groups but exhibit a preferential ordering which depends at once on the nature of the cation and on the melt composition. However at the high temperatures investigated here, there is no evidence of long lived complexes between carbonate groups and metal cations. 相似文献
8.
Angela Johnson 《Geochimica et cosmochimica acta》2011,75(7):1773-1784
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
9.
The sulfur concentration in silicate melts at sulfide saturation (SCSS) was experimentally investigated in a temperature range from 1150 to 1450 °C and a pressure range from 500 MPa to 1 GPa in a piston-cylinder apparatus. The investigated melt compositions varied from rhyolitic to basaltic and water concentrations varied from 0 to ∼9 wt%. All experiments were saturated with FeS melt or pyrrhotite crystals. Temperature was confirmed to have a positive effect on the SCSS. Experimental oxygen fugacities were either near the carbon-carbon monoxide buffer or one log unit above the nickel-nickel oxide buffer, and found to positively affect the SCSS. Combining our results with data from the literature we constructed a model to predict the SCSS in melts ranging in composition from komatiitic to rhyolitic, with water concentrations from 0 to 9 wt%, at pressures from 1 bar to 9 GPa and oxygen fugacities between ∼2 log units below the fayalite-magnetite-quartz buffer to ∼2 log units above it. The coefficients were obtained by multiple linear regression of experimental data and the best model found for the prediction of the SCSS is:
10.
G.K. Benedix R.A. Ketcham T.J. McCoy D.H. Garrison S. Xue R. Middleton 《Geochimica et cosmochimica acta》2008,72(9):2417-2428
The L chondrite Patuxent Range (PAT) 91501 is an 8.5-kg unshocked, homogeneous, igneous-textured impact melt that cooled slowly compared to other meteoritic impact melts in a crater floor melt sheet or sub-crater dike [Mittlefehldt D. W. and Lindstrom M. M. (2001) Petrology and geochemistry of Patuxent Range 91501 and Lewis Cliff 88663. Meteoritics Planet. Sci. 36, 439-457]. We conducted mineralogical and tomographic studies of previously unstudied mm- to cm-sized metal-sulfide-vesicle assemblages and chronologic studies of the silicate host. Metal-sulfide clasts constitute about 1 vol.%, comprise zoned taenite, troilite, and pentlandite, and exhibit a consistent orientation between metal and sulfide and of metal-sulfide contacts. Vesicles make up ∼2 vol.% and exhibit a similar orientation of long axes. 39Ar-40Ar measurements probably date the time of impact at 4.461 ± 0.008 Gyr B.P. Cosmogenic noble gases and 10Be and 26Al activities suggest a pre-atmospheric radius of 40-60 cm and a cosmic ray exposure age of 25-29 Myr, similar to ages of a cluster of L chondrites. PAT 91501 dates the oldest known impact on the L chondrite parent body. The dominant vesicle-forming gas was S2 (∼15-20 ppm), which formed in equilibrium with impact-melted sulfides. The meteorite formed in an impact melt dike beneath a crater, as did other impact melted L chondrites, such as Chico. Cooling and solidification occurred over ∼2 h. During this time, ∼90% of metal and sulfide segregated from the local melt. Remaining metal and sulfide grains oriented themselves in the local gravitational field, a feature nearly unique among meteorites. Many of these metal-sulfide grains adhered to vesicles to form aggregates that may have been close to neutrally buoyant. These aggregates would have been carried upward with the residual melt, inhibiting further buoyancy-driven segregation. Although similar processes operated individually in other chondritic impact melts, their interaction produced the unique assemblage observed in PAT 91501. 相似文献
11.
The thermodynamic, structural and transport properties of natural silicate melts under pressure are investigated by molecular dynamics simulation with the help of a force field recently introduced by us [Guillot B. and Sator N. (2007) A computer simulation study of natural silicate melts. Part I: low pressure properties. Geochim. Cosmochim. Acta71, 1249-1265]. It is shown that the simulation reproduces accurately the bulk moduli of a large variety of silicate liquids as evaluated from ultrasonic studies. The equations of state (EOS) of the simulated melts are in good agreement with the density data on mid-ocean ridge basalt, komatiite, peridotite and fayalite as obtained either by sink/float experiments or by shock-wave compression. From the structural point of view it is shown that the population of [5]Al and [6]Al species increases rapidly upon initial compression (0-50 kbar) whereas for Si these highly coordinated species are found in a significant abundance (>5%) only above ∼50 kbar for [5]Si and ∼100-150 kbar for [6]Si. This increase of the coordination of network formers is not the only response of the melt structure to the densification: there is also a large redistribution of the T-O-T (T = Si, Al) bond angles with the pressure and noticeably upon initial compression in rhyolitic and basaltic liquids. Furthermore, a detailed analysis of the population of bridging oxygens (BO) and nonbridging oxygens (NBO) points out that the polymerization of the melt generally increases when the pressure increases, the magnitude of this polymerization enhancement being all the more important that the melt is depolymerized at low pressure. The role of triclusters (threefold coordinated oxygens to network former cations) is particularly emphasized in acidic and basaltic liquids. The pressure-induced redistribution of the oxygen atoms through the melt structure is also stressed. Finally, the simulation predicts a nonmonotonic behavior of the diffusivity of network former ions when the pressure increases, a feature with depends on the melt composition. This could have a counterpart in the electrical conductivity at sufficiently high temperature when the viscosity of the liquid is low. 相似文献
12.
Jan A. Schuessler Ronny Schoenberg Harald Behrens Friedhelm von Blanckenburg 《Geochimica et cosmochimica acta》2007,71(2):417-433
A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using 57Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H2O) and natural pyrrhotites (Fe1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ 56Fe/54Fepyrrhotite-melt = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe2+/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe2+/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems. 相似文献
13.
In order to improve our understanding of HSE geochemistry, we evaluate the effect of Fe on the solubility of Pd in silicate melts. To date, experimentally determined Pd solubilities in silicate melt are only available for Fe-free anorthite-diopside eutectic compositions. Here we report experiments to study the solubility of Pd in a natural picritic melt as a function of pO2 at 1300 °C in a one atm furnace. Palladium concentrations in the run products were determined by laser-ablation-ICP-MS. Palladium increases from 1.07 ± 0.26 ppm at FMQ-2, to 306 ± 19 ppm at FMQ+6.6. At a relative pO2 of FMQ the slope in log Pd concentration vs. log pO2 space increases considerably, and Pd concentrations are elevated over those established for AnDi melt compositions. In the same pO2 range, ferric iron significantly increases relative to ferrous iron. Furthermore, at constant pO2 (FMQ+0.5) Pd concentrations significantly increase with increasing XFeO-total in the melt. Therefore, we consider ferric Fe to promote the formation of Pd2+ enhancing the solubility of Pd in the picrite melt significantly.The presence of FeO in the silicate melt has proven to be an important melt compositional parameter, and should be included and systematically investigated in future experimental studies, since most natural compositions have substantial FeO contents. 相似文献
14.
We develop a physical model of the thermal history of the ureilite parent body (UPB) that numerically tracks the history of its heating, hydration, dehydration, partial melting and smelting as a function of its formation time and the initial values of its composition, formation temperature and water ice content. Petrologic and chemical data from the main group (non-polymict) ureilite meteorites, which sample the interior of the UPB between depths corresponding to pressures in the range 3-10 MPa, are used to constrain the model. We find that to achieve the ∼30% melting inferred for ureilites from all sampled depths, the UPB must have had a radius between ∼80 and ∼130 km and must have accreted about 0.55 Ma after CAI formation. Melting began in the body at ∼1 Ma after CAI, and the time at which 30% melting was reached varied with depth in the asteroid but was always between ∼4.5 and ∼5.8 Ma after CAI. The total rate at which melt was produced in the UPB varied from more than 100 m3 s−1 in the very early stages of melting at ∼1 Ma after CAI to ∼5 m3 s−1 between 2 and 3 Ma after CAI, decreasing to extremely small values as the end of melting was approached beyond ∼5 Ma. Although the initial period of high melt production occupied only a short time around 1 Ma after CAI, it corresponded to ∼half (16%) of total silicate melting, and all strictly basaltic (i.e. plagioclase-saturated) melts must have been produced during this period.A very efficient melt transport network, consisting of a hierarchy of veins and larger pathways (dikes), developed quickly at the start of melting, ensuring rapid (timescales of months) transport of any single parcel of melt to shallow levels, thus ensuring that chemical interaction between melts and the rocks through which they subsequently passed was negligible. Volatile (mainly carbon monoxide) production due to smelting began at the start of silicate melting in the shallowest parts of the UPB and at later times at greater depths. Except at the very start and very end of melting, the volatile content of the melts produced was always high - generally between 15 and 35 mass % - and most of the melt produced was erupted at the surface of the UPB with speeds well in excess of the escape velocity and was lost into space. However, we show that 30% melting at the 3 MPa pressure level was only possible if ∼15% of the total melt produced in the asteroid was retained as a small number (∼5) of very extensive, sill-like intrusions centered at a depth of ∼7 km below the surface, near the base of the ∼8 km thick outer crust of the asteroid that was maintained at temperatures below the basalt solidus by conductive heat loss to the surface. The horizontal extents of these sills occupied about 75% of the surface area of the UPB, and the sills acted as buffers between the steady supply of melt from depth and the intermittent explosive eruption of the melt into space. We infer that samples from these intrusions are preserved as the rare feldspathic (loosely basaltic) clasts in polymict ureilites, and show that the cooling histories of the sills are consistent with these clasts reaching isotopic closure at ∼5 Ma after CAI, as given by 26Al-26Mg, 53Mn-53Cr and Pb-Pb age dates. 相似文献
15.
The abundances of the highly siderophile elements (HSE) Ru, Pd, Re, Os, Ir, and Pt were determined by isotope dilution mass spectrometry for 22 ureilite bulk rock samples, including monomict, augite-bearing, and polymict lithologies. This report adds significantly to the quantity of available Pt and Pd abundances in ureilites, as these elements were rarely determined in previous neutron activation studies. The CI-normalized HSE abundance patterns of all ureilites analyzed here except ALHA 81101 show marked depletions in the more volatile Pd, with CI chondrite-normalized Pd/Os ratios (excluding ALHA 81101) averaging 0.19 ± 0.23 (2σ). This value is too low to be directly derived from any known chondrite group. Instead, the HSE bulk rock abundances and HSE interelement ratios in ureilites can be understood as physical mixtures of two end member compositions. One component, best represented by sample ALHA 78019, is characterized by superchondritic abundances of refractory HSE (RHSE—Ru, Re, Os, Ir, and Pt), but subchondritic Pd/RHSE, and is consistent with residual metal after extraction of a S-bearing metallic partial melt from carbonaceous chondrite-like precursor materials. The other component, best represented by sample ALHA 81101, is RHSE-poor and has HSE abundances in chondritic proportions. The genesis of the second component is unclear. It could represent regions within the ureilite parent body (UPB), in which metallic phases were completely molten and partially drained, or it might represent chondritic contamination that was added during disruption and brecciation of the UPB. Removal of carbon-rich melts does not seem to play an important role in ureilite petrogenesis. Removal of such melts would quickly deplete the ureilite precursors in Re/Os and As/Au, which is inconsistent with measured osmium isotope abundances, and also with literature As/Au data for the ureilites. Removal of 26Al during silicate melting may have acted as a switch that turned off further metal extraction from ureilite source regions. 相似文献
16.
Adam C. Simon Thomas Pettke Philip M. Piccoli 《Geochimica et cosmochimica acta》2006,70(22):5583-5600
The effect of sulfur on the partitioning of Cu in a melt-vapor-brine ± magnetite ± pyrrhotite assemblage has been quantified at 800 °C, 140 MPa, fO2 = nickel-nickel oxide (NNO), logfS2=-3.0 (i.e., on the magnetite-pyrrhotite curve at NNO), logfH2S=-1.3 and logfSO2=-1. All experiments were vapor + brine saturated. Vapor and brine fluid inclusions were trapped in silicate glass and self-healed quartz fractures. Vapor and brine are dominated by NaCl, KCl and HCl in the S-free runs and NaCl, KCl and FeCl2 in S-bearing runs. Pyrrhotite served as the source of sulfur in S-bearing experiments. The composition of fluid inclusions, glass and crystals were quantified by laser-ablation inductively coupled plasma mass spectrometry. Major element, chlorine and sulfur concentrations in glass were quantified by using electron probe microanalysis. Calculated Nernst-type partition coefficients (±2σ) for Cu between melt-vapor, melt-brine and vapor-brine are , , and , respectively, in the S-free system. The partition coefficients (±2σ) for Cu between melt-vapor, melt-brine and vapor-brine are , , and , respectively, in the S-bearing system. Apparent equilibrium constants (±1σ) describing Cu and Na exchange between vapor and melt and brine and melt were also calculated. The values of are 34 ± 21 and 128 ± 29 in the S-free and S-bearing runs, respectively. The values of are 33 ± 22 and60 ± 5 in the S-free and S-bearing runs, respectively. The data presented here indicate that the presence of sulfur increases the mass transfer of Cu into vapor from silicate melt. Further, the nearly threefold increase in suggests that Cu may be transported as both a chloride and sulfide complex in magmatic vapor, in agreement with hypotheses based on data from natural systems. Most significantly, the data demonstrate that the presence of sulfur enhances the partitioning of Cu from melt into magmatic volatile phases. 相似文献
17.
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
18.
The structure of silicate melts in the system Na2O·4SiO2 saturated with reduced C-O-H volatile components and of coexisting silicate-saturated C-O-H solutions has been determined in a hydrothermal diamond anvil cell (HDAC) by using confocal microRaman and FTIR spectroscopy as structural probes. The experiments were conducted in-situ with the melt and fluid at high temperature (up to 800 °C) and pressure (up to 1435 MPa). Redox conditions in the HDAC were controlled with the reaction, Mo + H2O = MoO2 + H2, which is slightly more reducing than the Fe + H2O = FeO + H2 buffer at 800 °C and less.The dominant species in the fluid are CH4 + H2O together with minor amounts of molecular H2 and an undersaturated hydrocarbon species. In coexisting melt, CH3 - groups linked to the silicate melt structure via Si-O-CH3 bonding may dominate and possibly coexists with molecular CH4. The abundance ratio of CH3 - groups in melts relative to CH4 in fluids increases from 0.01 to 0.07 between 500 and 800 °C. Carbon-bearing species in melts were not detected at temperatures and pressures below 400 °C and 730 MPa, respectively. A schematic solution mechanism is, Si-O-Si + CH4?Si-O-CH3+H-O-Si. This mechanism causes depolymerization of silicate melts. Solution of reduced (C-O-H) components will, therefore, affect melt properties in a manner resembling dissolved H2O. 相似文献
19.
Rubidium and strontium partitioning experiments between haplogranitic melts and aqueous fluids (water or 1.16-3.56 m (NaCl + KCl) ± HCl) were conducted at 750-950 °C and 0.2-1.4 GPa to investigate the effects of melt and fluid composition, pressure, and temperature. In addition, we studied if the applied technique (rapid and slow quench, and in-situ determination of trace element concentration in the fluid) has a bearing on the obtained data. There is good agreement of the data from different techniques for chloridic solutions, whereas back reactions between fluid and melt upon cooling have a significant effect on results from the experiments with water.The Rb fluid-melt partition coefficient shows no recognizable dependence on melt composition and temperature.For chloridic solutions, it is ∼0.4, independent of pressure. In experiments with water, it is one to two orders of magnitude lower and increases with pressure. The strontium fluid-melt partition coefficient does not depend on temperature. It increases slightly with pressure in Cl free experiments. In chloridic fluids, there is a sharp increase in the Sr partition coefficient with the alumina saturation index (ASI) from 0.003 at an ASI of 0.8 to a maximum of 0.3 at an ASI of 1.05. At higher ASI, it decreases slightly to 0.2 at an ASI of 1.6. It is one to two orders of magnitude higher in chloridic fluids compared to those found in H2O experiments. The Rb/Sr ratio in non-chloridic solutions in equilibrium with metaluminous melts increases with pressure, whereas the Rb/Sr ratio in chloridic fluids is independent of pressure and decreases with fluid salinity.The obtained fluid-melt partition coefficients are in good agreement with data from natural cogenetic fluid and melt inclusions. Numerical modeling shows that although the Rb/Sr ratio in the residual melt is particularly sensitive to the degree of fractional crystallization, exsolution of a fluid phase, and associated fluid-melt partitioning is not a significant factor controlling Rb and Sr concentrations in the residual melt during crystallization of most granitoids. 相似文献
20.
Anastassia Yu. Borisova Michel Pichavant Michael Wiedenbeck Frédéric Candaudap 《Geochimica et cosmochimica acta》2006,70(14):3702-3716
The dacite pumice erupted from Mt. Pinatubo on June 15, 1991 (whole-rock, rhyolitic groundmass glasses and homogenized melt inclusions) has been analyzed using inductively coupled plasma-mass spectrometry (ICP-MS), nanosecond and femtosecond laser ablation ICP-MS and secondary ion mass spectrometry (SIMS) to evaluate its ore-forming potential. Data suggest that adakite magmas are metal-rich and concentrate ore metals during magmatic differentiation. Sulfides segregate in limited amounts under the hydrous, oxidizing conditions typical of adakitic magmas resulting in incompatible behavior for Au (6-22 ppb), Cu (26-77 ppm), and Pb, Mo, As, and Sb in melts of dacitic to rhyolitic compositions. Metal transfer from this adakite magma to the coexisting aqueous phase was favored by the peraluminous composition of the rhyolitic melt and high aqueous chloride concentrations. Mass balance calculations suggest that the pre-eruptive aqueous phase could have extracted a minimum of 100 t Au and 5 × 105 t Cu from the Mt. Pinatubo magma. Our data suggest that intrusives having adakitic signatures are genetically associated with Au-Cu and Cu-Mo mineralization, auriferous porphyry copper deposits, and epithermal gold veins. High H2O, Cl, Sr/Y, Pb/Ce, Mo/Ce, As/Ce and Sb/Ce in Mt. Pinatubo melts reflect the contribution of deep fluids derived from subducted sediments and altered MORBs in the dacite genesis. The slab-derived fluids carrying mobile elements are likely responsible for the enrichment of adakite magmas in gold, associated metals and H2O, and may explain the exceptional ore-forming potential of adakite magmatism. 相似文献