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1.
The volatization of Rhenium (Re) from melts of natural basalt, dacite and a synthetic composition in the CaO-MgO-Al2O3-SiO2 system has been investigated at 0.1 MPa and 1250-1350 °C over a range of fO2 conditions from log fO2 = −10 to −0.68. Experiments were conducted using open top Pt crucibles doped with Re and Yb. Analysis of quenched glasses by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) normal to the melt/gas interface showed concentration profiles for Re, to which a semi-infinite one-dimensional diffusion model could be applied to extract diffusion coefficients (D). The results show Re diffusivity in basalt at 1300 °C in air is log DRe = −7.2 ± 0.3 cm2/s and increases to log DRe = −6.6 ± 0.3 cm2/s when trace amounts of Cl were added to the starting material. At fO2 conditions below the nickel-nickel oxide (NNO) buffer Re diffusivity decreases to and to in dacitic melt. In the CMAS composition, . The diffusivity of Re is comparable to Ar and CO2 in basalt at 500 MPa favoring its release as a volatile. Our results support the contention that subaerial degassing is the cause of lower Re concentrations in arc-type and ocean island basalts compared to mid-ocean ridge basalts.  相似文献   

2.
Measurable uranium (U) is found in metal sulfide liquids in equilibrium with molten silicate at conditions appropriate for a planetary magma ocean: 1-10 GPa, 1750-2100 °C, 0-28 wt% S, and fO2 2 log units below IW. However, the transfer of U from metal sulfide to silicate under our experimental conditions is so complete that insufficient U would remain so as to be of any importance to the core’s heat budget. U content in the sulfide phase increases strongly with S content but shows no significant variability with either pressure or temperature. Maximum is 0.001 while most values are considerably lower.  相似文献   

3.
Os equilibrium solubilities were determined at 1350 °C over a wide range of oxygen fugacities (−12 < log fO2 < −7) applying the mechanically assisted equilibration technique (MAE) at 105 Pa (= 1 bar). Os concentrations in the glass samples were analysed using ID-NTIMS. Additional LA-ICP-MS and SEM analyses were performed to detect, visualize and analyse the nature and chemistry of “nanonuggets.” Os solubilities determined range at a constant temperature of 1350 °C from 0.63 ± 0.04 to 37.4 ± 1.16 ppb depending on oxygen fugacity. At the highest oxygen fugacities, Os3+ can be confirmed as the main oxidation state of Os. At low oxygen fugacities (below log fO2 = −8), samples are contaminated by nanonuggets which, despite the MAE technique, were still not removed entirely from the melt. However, the present results indicate that applying MAE technology does reduce the amount of nanonuggets present significantly, resulting in the lowest Os solubility results reported to date under these experimental conditions, and extending the experimentally accessible range of fO2 for these studies to lower values. Calculated metal/silicate melt partition coefficients are therefore higher compared to previous studies, making Os more siderophile. Neglecting the as yet unknown temperature dependence of the Os metal/silicate melt partition coefficient, extrapolation of the obtained Os solubilities to conditions for core-mantle equilibrium, results in a , while metallic alloy/silicate melt partition coefficients range from 1.4 × 106 to 8.6 × 107, in agreement with earlier findings. Therefore remains too high by 2-4 orders of magnitude to explain the Os abundance in the Earth’s mantle as result of core-mantle equilibrium during core formation.  相似文献   

4.
The partitioning of silver in a sulfur-free rhyolite melt-vapor-brine assemblage has been quantified at 800 °C, pressures of 100 and 140 MPa and fO2≈NNO (nickel-nickel oxide). Silver solubility (±2σ) in rhyolite increases 5-fold from 105 ± 21 to 675 ± 98 μg/g as pressure increases from 100 to 140 MPa. Nernst-type partition coefficients describing the mass transfer of silver at 100 MPa between vapor and melt, brine and melt and vapor and brine are 32 ± 30, 1151 ± 238 and 0.026 ± 0.004, respectively. At 140 MPa, values for for vapor and melt, brine and melt, and vapor and brine are 32 ± 10, 413 ± 172 and 0.06 ± 0.03, respectively. Apparent equilibrium constant values (±2σ) describing the exchange of silver and sodium between vapor and melt, , at 100 and 140 MPa are 105 ± 68 and 14 ± 6. The average values (±2σ) for silver and sodium exchange between brine and melt, , at 100 and 140 MPa are 313 ± 288 and 65 ± 12. These data indicate that the mass transfer of silver from rhyolite melt to an exsolved volatile phase(s) is enhanced at 100 MPa relative to 140 MPa, suggesting that decompression increases the silver ore-generative potential of an evolving silicate magma. Model calculations using the new data suggest that the evolution of low-density, aqueous fluid (i.e., vapor) may be responsible for the the silver tonnage of many porphyry-type and perhaps epithermal-type ore deposits. For example, Halter et al. (Halter W. E., Pettke T. and Heinrich C. A. (2002) The origin of Cu/Au ratios in porphyry-type ore deposits. Science296, 1842-1844) used detailed silicate and sulfide melt inclusion and vapor and brine fluid inclusions analyses to estimate a melt volume on the order of 15 km3 to satisfy the copper budget at the Bajo de la Alumbrera copper-, gold-, silver-ore deposit. Using their melt volume estimate with the data presented here, model calculations for a 15-km3 felsic melt, saturated with pyrrhotite and magnetite, suggest that a low-salinity magmatic vapor may scavenge on the order of 7 × 1012 g of silver from the melt. This quantity of silver exceeds the discovered 2 × 109 g of Ag at Alumbrera. Calculated tonnages for numerous other deposits yield similar results. The excess silver in the vapor, remaining after porphyry formation, is then available to precipitate at lower PTconditions in the stratigraphically higher epithermal environment. These data suggest that silver, and perhaps other ore metals, in the porphyry-epithermal continuum may be derived solely from the time-integrated flux of dominantly low-salinity vapor exsolved from a series of sequential magma batches.  相似文献   

5.
Copper partitioning in a melt-vapor-brine-magnetite-pyrrhotite assemblage   总被引：4，自引：0，他引：4  
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   

6.
The partitioning of Pt in sulphide melt (matte) has been studied as a function of fS2 and fO2 at 1200 and 1300 °C. The results show that the solubility of Pt in mattes increases strongly with increasing fS2 and decreases weakly with increasing fO2. The increase in Pt solubility with increasing fS2 is attributed to Pt dissolving in the melt as a sulphide species and the weak inverse dependence of Pt solubility on fO2 to the diluting effect of increasing O in the melt at high fO2. These results, coupled with measurements of Pt solubility in silicate melts taken from the literature, allow the calculation of Pt matte/silicate-melt partition coefficients () for a range of conditions pertinent to the formation of Pt-rich horizons in layered intrusions. The calculated values range between 107 and 1011, depending on fO2 and fS2, several orders of magnitude higher than previously published values. Our preferred value for for conditions appropriate to the Merensky Reef is 107 and for the Stillwater Pt-rich horizon 108. The new results are consistent with the magmatic hypothesis for Pt-rich horizons in layered intrusions.  相似文献   

7.
Comparative concentrations of carbonate and hydroxide complexes in natural solutions can be expressed in terms of reactions with bicarbonate that have no explicit pH dependence (). Stability constants for this reaction with n = 1 were determined using conventional formation constant data expressed in terms of hydroxide and carbonate. Available data indicate that stability constants appropriate to seawater at 25 °C expressed in the form are on the order of 104.2 for a wide range of cations (Mz+) with z = +1, +2 and +3. Φ1 is sufficiently large that species appear to substantially dominate MOHz−1 species in seawater. Evaluations of comparative stepwise carbonate and hydroxide stability constant behavior leading to the formation of n = 2 and n = 3 complexes suggest that carbonate complexes generally dominate hydroxide complexes in seawater, even for cations whose inorganic speciation schemes in seawater are currently presumed to be strongly dominated by hydrolyzed forms (). Calculated stability constants, and , indicate that the importance of carbonate complexation is sufficiently large that carbonate and hydroxide complexes would be generally comparable even if calculated Φ2 and Φ3 values are overestimated by two or more orders of magnitude. Inclusion of mixed ligand species in carbonate-hydroxide speciation models allows cation complexation intensities (MT/[Mz+]) to be expressed in the following form:
  相似文献   

8.
The concentration and distribution of Pt and Au in a fluid-melt system has been investigated by reacting the metals with S-free, single-phase aqueous brines (20, 50, 70 wt% eq. NaCl) ± peraluminous melt at a confining pressure of 1.5 kbar and temperatures of 600 to 800 °C, trapping the fluid in synthetic fluid inclusions (quartz-hosted) and vesicles (silicate melt-hosted), and quantifying the metal content of the trapped fluid and glass by laser ablation ICP-MS. HCl concentration was buffered using the assemblage albite-andalusite-quartz and fO2 was buffered using the assemblage Ni-NiO. Over the range of experimental conditions, measured concentrations of Pt and Au in the brines (, ) are on on the order of 1-103 ppm. Concentrations of Pt and Au in the melt (, ) are ∼35-100 ppb and ∼400-1200 ppb, respectively. Nernst partition coefficients (, ) are on the order of 102-103 and vary as a function of (non-Henry’s Law behavior). Trapped fluids show a significant range of metal concentrations within populations of inclusions from single experiments (∼ 1 log unit variability for Au; ∼2-3 log unit variability for Pt). Variability in metal concentration within single inclusion groups is attributed to premature brine entrapment (prior to metal-fluid-melt equilibrium being reached); this allows us to make only minimum estimates of metal solubility using metal concentrations from primary inclusions. The data show two trends: (i) maximum and average values of and in inclusions decrease ∼2 orders of magnitude as fluid salinity () increases from ∼4 to 40 molal (20 to 70 wt % eq. NaCl) at a constant temperature; (ii) maximum and average values of increase approximately 1 order of magnitude for every 100°C increase temperature at a fixed . The observed behavior may be described by the general expression:
  相似文献   

9.
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly.  相似文献   

10.
The electrical conductivities of aqueous solutions of Li2SO4 and K2SO4 have been measured at 523-673 K at 20-29 MPa in dilute solutions for molalities up to 2 × 10−2 mol kg−1. These conductivities have been fitted to the conductance equation of Turq, Blum, Bernard, and Kunz with a consensus mixing rule and mean spherical approximation activity coefficients. In the temperature interval 523-653 K, where the dielectric constant, ε, is greater than 14, the electrical conductance data can be fitted by a solution model which includes ion association to form , , and , where M is Li or K. The adjustable parameters of this model are the first and second dissociation constants of the M2SO4. For the 673 K and 300 kg m−3 state point where the Coulomb interactions are the strongest (dielectric constant, ε = 5), models with more extensive association give good fits to the data. In the case of the Li2SO4 model, including the multi-ion associate, , gave an extremely good fit to the conductance data.  相似文献   

11.
The temperature dependence of the solubilities of Pt and Rh in a haplobasaltic (anorthite-diopside 1-bar eutectic composition) melt has been investigated at 1 bar and 1300 to 1550°C using the mechanically assisted equilibration technique (Dingwell et al., 1994). The experiments were performed at almost constant oxygen fugacity (log fO2 = −2.5 ± 0.3) over the entire temperature range. Major element concentrations in the quenched glass samples were determined using an electron microprobe. Pt and Rh concentrations were obtained by laser ablation inductive coupled plasma mass spectrometry. From our data, we obtain the following expressions for the solubilities of pure Pt and pure Rh in anorthite-diopside eutectic melt at 1 bar and log fO2 = −2.5:
  相似文献   

12.
The influence on olivine/melt transition metal (Mn, Co, Ni) partitioning of substitution in the tetrahedral network of silicate melt structure has been examined at ambient pressure in the 1450-1550 °C temperature range. Experiments were conducted in the systems NaAlSiO4-Mg2SiO4- SiO2 and CaAl2Si2O8-Mg2SiO4-SiO2 with about 1 wt% each of MnO, CoO, and NiO added. These compositions were used to evaluate how, in silicate melts, substitution and ionization potential of charge-balancing cations affect activity-composition relations in silicate melts and mineral/melt partitioning.The exchange equilibrium coefficient, , is a positive and linear function of melt Al/(Al + Si) at constant degree of melt polymerization, NBO/T. The is negatively correlated with the ionic radius, r, of the M-cation and also with the ionization potential (Z/r2, Z = electrical charge) of the cation that serves to charge-balance Al3+ in tetrahedral coordination in the melts. The activity coefficient ratio, (γM/γMg)melt, is therefore similarly correlated.These melt composition relationships are governed by the distribution of Al3+ among coexisting Q-species in the peralkaline (depolymerized) melts coexisting with olivine. This distribution controls Q-speciation abundance, which, in turn, controls (γM/γMg)melt and . The relations between melt structure and olivine/melt partitioning behavior lead to the suggestion that in natural magmatic systems mineral/melt partition coefficients are more dependent on melt composition and, therefore, melt structure the more alkali-rich and the more felsic the melt. Moreover, mineral/melt partition coefficients are more sensitive to melt composition the more highly charged or the smaller the ionic radius of the cation of interest.  相似文献   

13.
We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300-1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO-FeO-MgO-Al2O3-TiO2-SiO2 system. Ilmenite-melt and armalcolite-melt partition coefficients (D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( 0.0020 ± 0.0010 to 0.069 ± 0.010 for ilmenite; 0.0048 ± 0.0023 to 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: 0.0013 ± 0.0008, 0.0035 ± 0.0015 and 0.039 ± 0.005, and for armalcolite 0.008 ± 0.003, 0.0048 ± 0.0022 and 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. 0.28 ± 0.05 and : 0.76 ± 0.07). Both minerals fractionate the high field strength elements with DTa/DNb and DHf/DZr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with DHf/DW = 12-13 compared to 6.7-7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite (D ∼ 7.5) and V in armalcolite (D ∼ 8.1). D values show no clear variation with pressure in the small range covered.Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals.Our results are used to model the Lu-Hf-Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO2 contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.  相似文献   

14.
The solubility of carbon in Fe and Fe-5.2 wt.% Ni melts, saturated with graphite, determined by electron microprobe analysis of quenched metal melts was 5.8 ± 0.1 wt.% at 2000 °C, 6.7 ± 0.2 wt.% at 2200 °C, and 7.4 ± 0.2 wt.% at 2410 °C at 2 GPa, conditions relevant for core/mantle differentiation in a shallow magma ocean. These solubilities are slightly lower than low-pressure literature values and significantly beneath calculated values for even higher pressures [e.g., Wood B. J. (1993) Carbon in the core. Earth Planet. Sci. Lett.117, 593-607]. The trend of C solubility versus temperature for Fe-5.2 wt.% Ni melt, within analytical uncertainties, is similar to or slightly lower (∼0.2-0.4 wt.%) than that of pure Fe. Carbon content of core melts and residual mantle silicates derived from equilibrium batch or fractional segregation of core liquids and their comparison with our solubility data and carbon content estimate of the present day mantle, respectively, constrain the partition coefficient of carbon between silicate and metallic melts, in a magma ocean. For the entire range of possible bulk Earth carbon content from chondritic to subchondritic values, of 10−4 to 1 is derived. But for ∼1000 ppm bulk Earth carbon, is between 10−2 and 1. Using the complete range of possible for a magma ocean at ∼2200 °C, we predict maximum carbon content of the Earth’s core to be ∼6-7 wt.% and a preferred value of 0.25 ± 0.15 wt.% for a bulk Earth carbon concentration of ∼1000 ppm.  相似文献   

15.
Olivine/melt partitioning of ΣFe, Fe2+, Mg2+, Ca2+, Mn2+, Co2+, and Ni2+ has been determined in the systems CaO-MgO-FeO-Fe2O3-SiO2 (FD) and CaO-MgO-FeO-Fe2O3-Al2O3-SiO2 (FDA3) as a function of oxygen fugacity (fO2) at 0.1 MPa pressure. Total iron oxide content of the starting materials was ∼20 wt%. The fO2 was to used to control the Fe3+/ΣFe (ΣFe: total iron) of the melts. The Fe3+/ΣFe and structural roles of Fe2+ and Fe3+ were determined with 57Fe resonant absorption Mössbauer spectroscopy. Changes in melt polymerization, NBO/T, as a function of fO2 was estimated from the Mössbauer data and existing melt structure information. It varies by ∼100% in melts coexisting with olivine in the FDA3 system and by about 300% in the FD system in the Fe3+/ΣFe range of the experiments (0.805-0.092). The partition coefficients ( in olivine/wt% in melt) are systematic functions of fO2 and, therefore, NBO/T of the melt. There is a -minimum in the FDA3 system at NBO/T-values corresponding to intermediate Fe3+/ΣFe (0.34-0.44). In the Al-free system, FD, where the NBO/T values of melts range between ∼1 and ∼2.9, the partition coefficients are positively correlated with NBO/T (decreasing Fe3+/ΣFe). These relationships are explained by consideration of solution behavior in the melts governed by Qn-unit distribution and structural changes of the divalent cations in the melts (coordination number, complexing with Fe3+, and distortion of the polyhedra).  相似文献   

16.
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   

17.
The origin of Zn isotope fractionation in sulfides   总被引：2，自引：0，他引：2  
Isotope fractionation of Zn between aqueous sulfide, chloride, and carbonate species (Zn2+, Zn(HS)2, , , ZnS(HS)−, ZnCl+, ZnCl2, , and ZnCO3) was investigated using ab initio methods. Only little fractionation is found between the sulfide species, whereas carbonates are up to 1‰ heavier than the parent solution. At pH > 3 and under atmospheric-like CO2 pressures, isotope fractionation of Zn sulfides precipitated from sulfidic solutions is affected by aqueous sulfide species and the δ66Zn of sulfides reflect these in the parent solutions. Under high PCO2 conditions, carbonate species become abundant. In high PCO2 conditions of hydrothermal solutions, Zn precipitated as sulfides is isotopically nearly unfractionated with respect to a low-pH parent fluid. In contrast, negative δ66Zn down to at least −0.6‰ can be expected in sulfides precipitated from solutions with pH > 9. Zinc isotopes in sulfides and rocks therefore represent a potential indicator of mid to high pH in ancient hydrothermal fluids.  相似文献   

18.
The effect of sulfur dissolved as sulfide (S2−) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al2O3-SiO2 (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S2− were varied from zero to sulfide saturation, reaching 4100 μg g−1 S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S2− in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M2+, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S2− nor of Mg#ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S2− depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10−3 (±1.3 × 10−3) K per μg g−1 of S2−, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO2 content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10−3. The ratio / is well constrained at 0.611 ± 0.016.  相似文献   

19.
Experiments were performed to determine the partitioning of molybdenum, tungsten and manganese among a rhyolitic melt (melt), pyrrhotite (po), and an immiscible Fe-S-O melt (Fe-S-O). Sulfide phases such as these may be isolated from a silicate melt along with other crystallizing phases during the evolution of arc magma, and partition coefficients are required to model the effect of this process on molybdenum and tungsten budgets.We developed an experimental design to take advantage of properties of the phases under study. Careful control of temperature allowed pyrrhotite and magnetite to be stable along with an Fe-S-O melt, and this phase assemblage allowed the composition of run-product pyrrhotite to be used to calculate both fS2 and fO2 for the experiments. At run temperature, (1042 ± 2 °C), a rhyolitic melt can be formed at low pressure, under nominally dry conditions, which removed the need for confining pressure as well as externally imposed fugacities. The silica-saturated melt allowed the charges to be contained in sealed evacuated silica tubes without danger of reaction, and with closed system behavior for molybdenum and tungsten.Experiments were run for durations up to 2000 min. Molybdenite (mb) and wolframite (wo) were added to the experiments as sources for molybdenum and tungsten, respectively. Manganese was added to the system as both a component of the starting rhyolitic pumice, and of Mn-bearing wolframite. Oxygen fugacity in these experiments was fixed at the Ni-NiO oxygen fugacity buffer. Sulfur fugacity was 10−1 bar. Run products were analyzed by EPMA and LA-ICP-MS. Analysis of the run products yielded ( standard deviation of the mean): , , , and . The partition coefficients for manganese in this system are and .Simple Rayleigh fractionation modeling suggests that oxidized felsic melts produced through fractional crystallization may have lost as much as 14% of their initial molybdenum, but only 2% of their initial tungsten, through the removal of an Fe-S-O melt along with crystalline phases. Modeling consistent with conditions of oxygen and sulfur fugacity influenced by assimilation of sulfide (with low concentrations of molybdenum and tungsten) from, for example, sedimentary rock, results in evolved magmas significantly depleted in molybdenum, but only moderately depleted in tungsten. The molybdenum:tungsten ratio can vary by two orders of magnitude. These systematics may help to explain some of the variability in metal ratios of intrusion-related hydrothermal ore deposits.  相似文献   

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