Gold and copper partitioning in magmatic-hydrothermal systems at 800 °C and 100 MPa

Porphyry-type ore deposits sometimes contain fluid inclusion compositions consistent with the partitioning of copper and gold into vapor relative to coexisting brine at the depositional stage. However, this has not been reproduced experimentally at magmatic conditions. In an attempt to determine the conditions under which copper and gold may partition preferentially into vapor relative to brine at temperatures above the solidus of granitic magmas, we performed experiments at 800 °C, 100 MPa, oxygen fugacity () buffered by Ni-NiO, and fixed at either 3.5 × 10⁻² by using intermediate solid solution-pyrrhotite, or 1.2 × 10⁻⁴ by using intermediate solid solution-pyrrhotite-bornite. The coexisting vapor (∼3 wt.% NaCl eq.) and brine (∼68 wt.% NaCl eq.) were composed initially of NaCl + KCl + HCl + H₂O, with starting HCl set to <1000 μg/g in the aqueous mixture. Synthetic vapor and brine fluid inclusions were trapped at run conditions and subsequently analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Our experiments demonstrate that copper and gold partitioned strongly into the magmatic volatile phase(s) (MVP) (i.e., vapor or brine) relative to a silicate melt over the entire imposed range of . Nernst style partition coefficients between coexisting brine (b) and melt (m), D^b/m (±1σ), range from 3.6(±2.2) × 10¹ to 4(±2) × 10² for copper and from 1.2(±0.6) × 10² to 2.4(±2.4) × 10³ for gold. Partition coefficients between coexisting vapor (v) and melt, D^v/m range from 2.1 ± 0.7 to 18 ± 5 and 7(±3) × 10¹ to 1.6(±1.6) × 10² for copper and gold, respectively. Partition coefficients for all experiments between coexisting brine and vapor, D^b/v (±1σ), range from 7(±2) to 1.0(±0.4) × 10² and 1.7(±0.2) to 15(±2) for copper and gold, respectively. Observed average D^b/v at an of 1.2 × 10⁻⁴ were elevated, 95(±5) and 15 ± 1 for copper and gold, respectively, relative to those at the higher of 3.5 × 10⁻² where D^b/v were 10(±5) for copper and 7(±6) for gold. Thus, there is an inverse relationship between the and the D^b/v for both copper and gold with increasing resulting in a decrease in the D^b/v signifying increased importance of the vapor phase for copper and gold transport. This suggests that copper and gold may complex with volatile S-species as well as Cl-species at magmatic conditions, however, none of the experiments of our study at 800 °C and 100 MPa had a D^b/v ? 1. We did not directly determine speciation, but infer the existence of some metal-sulfur complexes based on the reported data. We suggest that copper and gold partition preferentially into the brine in most instances at or above the wet solidus. However, in most systems, the mass of vapor is greater than the mass of brine, and vapor transport of copper and gold may become more important in the magmatic environment at higher , lower , or near the critical point in a salt-water system. A D^b/v ? 1 at subsolidus hydrothermal conditions may also occur in response to changes in temperature, , , and/or acidity.Additionally, both copper and gold were observed to partition into intermediate solid solution and bornite much more strongly than into vapor, brine or silicate melt. This suggests that, although vapor and brine are both efficient at removing copper and gold from a silicate melt, the presence of Cu-Fe sulfides can sequester a substantial portion of the copper and gold contained within a silicate melt if the Cu-Fe sulfides are abundant.     

An XAS study of the structure and thermodynamics of Cu(I) chloride complexes in brines up to high temperature (400 °C, 600 bar)

The transport and deposition of copper in saline hydrothermal fluids are controlled by the stability of copper(I) complexes with ligands such as chloride. Despite their role in the formation of most hydrothermal copper deposits, the nature and stability of Cu(I) chloride complexes in highly saline brines remains controversial. We present new X-ray absorption data (P = 600 bar, T = 25-400 °C, salinity up to 17.2 m Cl), which indicate that the linear (x = 1, 2) complexes are stable up to supercritical conditions. Distorted trigonal planar complexes predominate at room temperature and at high salinity (>3 m LiCl): subtle changes in the XANES spectrum with increasing salinity may reflect geometric distortions of this complex. Similar changes were observed in UV-Vis data [Liu, W., Brugger, J., McPhail, D.C., Spiccia, L., 2002. A spectrophotometric study of aqueous copper(I) chloride complexes in LiCl solutions between 100 °C and 250 °C. Geochim. Cosmochim. Acta66, 3615-3633], and were erroneously interpreted as a new species, . Our XAS data and ab-initio XANES calculations show that this tetrahedral species is not present to any significant degree in our solutions. The stability of the complexe decreases with increasing temperature; under supercritical conditions and in brines under magmatic-hydrothermal conditions (e.g., 15.58 m Cl, 400 °C, 600 bar), only the linear Cu(I) chloride complexes were observed. This result and the instability of the complex are also consistent with the recent ab-initio molecular dynamic calculations of Sherman [Sherman D. M.(2007) Complexation of Cu⁺ in hydrothermal NaCl brines: ab-initio molecular dynamics and energetics. Geochim. Cosmochim. Acta71, 714-722]. This study illustrates the power of the quantitative nature of XANES and EXAFS measurements for deciphering the speciation of weak transition metal complexes up to magmatic-hydrothermal conditions.The systematic XANES data are used to retrieve the formation constant for at 150 °C, which is in good agreement with the reinterpretation of the UV-Vis data of Liu et al. (Liu et al., 2002). At high temperatures (?400 °C), the solubility of chalcopyrite in equilibrium with hematite-magnetite-pyrite and K-feldspar-muscovite-quartz calculated with the new properties is lower than that calculated using the previous model, and the calculated solubilities are at the lower end of the range of values measured in brine inclusions from porphyry copper systems.     

An in situ XAS study of copper(I) transport as hydrosulfide complexes in hydrothermal solutions (25-592 °C, 180-600 bar): Speciation and solubility in vapor and liquid phases

Chloride and hydrosulfide are the principal ligands assumed to govern transport of copper in hydrothermal fluids. Existing solubility experiments suggest that Cu(I)-hydrosulfide complexes are dominant compared to chloride complexes at low salinities in alkaline solutions (H₂S_(aq)/HS⁻ pH buffer), and may be important in transporting Cu in low density magmatic vapors, potentially controlling the liquid-vapor partitioning of Cu. This study provides the first in situ evidence of the solubility of copper sulfides and the nature and structure of the predominant Cu species in sulfur-containing fluids at temperatures up to 592 °C and pressures of 180-600 bar. XANES and EXAFS data show that at elevated T (?200 °C), Cu solubility occurs via a linear Cu complex. At 428 °C in alkaline solutions, Cu is coordinated by two sulfur atoms in a distorted linear coordination (angle ∼150-160°). This geometry is consistent with the species predicted by earlier solubility studies. In addition, in situ measurements of the solubility of chalcocite in 2 m NaHS solutions performed in this study are in remarkably good agreement with the solubilities calculated using available thermodynamic data for Cu(I)-hydrosulfide complexes, also supporting the interpretation of speciation in these studies and validating the extrapolation of low-T thermodynamic properties for to high P-T. Data on phase separation for the 2 m NaHS solution show that while significant amounts of copper can be partitioned into the vapor phase, there is no indication for preferential partitioning of Cu into the vapor. This is consistent with recent partitioning experiments conducted in autoclaves by Pokrovski et al. (2008a) and Simon et al. (2006). XANES data suggest that the species present in the low density phase is very similar to that present in the high density liquid, i.e., , although Cu(HS)(H₂S)⁰ cannot be excluded on the basis of XAS data.     

A potentiometric study of the stability of aqueous yttrium-acetate complexes from 25 to 175 °C and 1-1000 bar

The stability of yttrium-acetate (Y-Ac) complexes in aqueous solution was determined potentiometrically at temperatures 25-175 °C (at P_s) and pressures 1-1000 bar (at 25 and 75 °C). Measurements were performed using glass H⁺-selective electrodes in potentiometric cells with a liquid junction. The species YAc²⁺ and were found to dominate yttrium aqueous speciation in experimental solutions at 25-100 °C (log [Ac⁻] < −1.5, pH < 5.2), whereas at 125, 150 and 175 °C introduction of into the Y-Ac speciation model was necessary. The overall stability constants β_n were determined for the reaction

     

Oxygen and hydrogen isotope fractionation in serpentine-water and talc-water systems from 250 to 450 °C, 50 MPa

Oxygen and hydrogen isotope fractionation factors in the talc-water and serpentine-water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D-H exchange was much more rapid than ¹⁸O-¹⁶O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of ¹⁸O-¹⁶O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc-water and serpentine-water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln  = 11.70 × 10⁶/T² − 25.49 × 10³/T + 12.48 and 1000 ln  = 3.49 × 10⁶/T² − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc-water D-H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 10⁶/T² − 41.52 × 10³/T + 5.61 where T is temperature in Kelvin. Our D-H serpentine-water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D-H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln  = 3.436 × 10⁶/T² − 34.736 × 10³/T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D-H and ¹⁸O-¹⁶O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings.     

Characterization of elemental release during microbe-basalt interactions at T = 28 °C

This study used batch reactors to characterize the rates and mechanisms of elemental release during the interaction of a single bacterial species (Burkholderia fungorum) with Columbia River Flood Basalt at T = 28 °C for 36 days. We primarily examined the release of Ca, Mg, P, Si, and Sr under a variety of biotic and abiotic conditions with the aim of evaluating how actively metabolizing bacteria might influence basalt weathering on the continents. Four days after inoculating P-limited reactors (those lacking P in the growth medium), the concentration of viable planktonic cells increased from ∼10⁴ to 10⁸ CFU (Colony Forming Units)/mL, pH decreased from ∼7 to 4, and glucose decreased from ∼1200 to 0 μmol/L. Mass-balance and acid-base equilibria calculations suggest that the lowered pH resulted from either respired CO₂, organic acids released during biomass synthesis, or H⁺ extrusion during uptake. Between days 4 and 36, cell numbers remained constant at ∼10⁸ CFU/mL and pH increased to ∼5. Purely abiotic control reactors as well as control reactors containing inert cells (∼10⁸ CFU/mL) showed constant glucose concentrations, thus confirming the absence of biological activity in these experiments. The pH of all control reactors remained near-neutral, except for one experiment where the pH was initially adjusted to 4 but rapidly rose to 7 within 2 days. Over the entire 36 day period, P-limited reactors containing viable bacteria yielded the highest Ca, Mg, Si, and Sr release rates. Release rates inversely correlate with pH, indicating that proton-promoted dissolution was the dominant reaction mechanism. Both biotic and abiotic P-limited reactors displayed low P concentrations. Chemical analyses of bacteria collected at the end of the experiments, combined with mass-balances between the biological and fluid phases, demonstrate that the absence of dissolved P in the biotic reactors resulted from microbial P uptake. The only P source in the basalt is a small amount of apatite (∼1.2%), which occurs as needles within feldspar grains and glass. We therefore conclude that B. fungorum utilized apatite as a P source for biomass synthesis, which stimulated elemental release from coexisting mineral phases via pH lowering. The results of this study suggest that actively metabolizing bacteria have the potential to influence elemental release from basalt in continental settings.     

Solubility of tin in (Cl, F)-bearing aqueous fluids at 700 °C, 140 MPa: A LA-ICP-MS study on synthetic fluid inclusions

Synthetic fluid inclusions in quartz were grown from cassiterite-saturated fluids in cold-seal pressure vessels at and subsequently analyzed by laser ablation-ICP-MS. Most inclusions were synthesized using a new technique that allows entrapment of fluid that had no immediate contact to the capsule walls, such that potential disequilibrium effects due to alloying could be avoided. Measured Sn solubilities increase with increasing ligand concentration in the fluid, ranging from 100 to 800 ppm in NaCl-bearing fluids (5-35 wt% NaCl), from 70 to 2000 ppm in HF-bearing fluids (0.5-3.2 m HF), and from 0.8 to 11 wt% in HCl-bearing fluids (0.5-4.4 m HCl). Two runs performed with the in-situ cracking method after 1 week of pre-equilibration demonstrate that the speed of hydrogen diffusion through the capsule wall relative to that of fluid inclusion formation is a critical factor in f_O2-dependent solubility studies. Graphical evaluation of the solubility data suggests that Sn may have been dissolved as Sn(OH)Cl in the NaCl-bearing fluids, as Sn(OH)Cl and SnCl₂ in the HCl-bearing fluids, and as SnF₂ in the HF-bearing fluids. Experiments with NaF-bearing fluids produced an additional melt phase with an approximate composition of 53 wt% SiO₂, 25 wt% H₂O, 14 wt% NaF and 8 wt% SnO, which caused the composition of the coexisting fluid to be buffered at 0.5 wt% NaF and 150 ppm Sn. Fluorine-rich, peralkaline melts may therefore serve as important transport media for Sn in the final crystallization stages of tin granites. Based on the available cassiterite-solubility data in fluids and melts, in natural granite systems is estimated to be in the order of 0.1-4 (depending on their aluminosity), suggesting that Sn is not easily mobilized by magmatic-hydrothermal fluids. This interpretation is in accordance with the high degrees of Sn-enrichment commonly observed in highly fractionated melt inclusions. is primarily controlled by the HCl concentration in the fluid, which in turn is a function of the aluminum saturation index of the magma. Compared to HCl, the effect of fluorine on is subordinate.     

Synthesis and properties of ammoniojarosites prepared with iron-oxidizing acidophilic microorganisms at 22-65 °C

Ammoniojarosite [(NH₄,H₃O)Fe₃(OH)₆(SO₄)₂], a poorly soluble basic ferric sulfate, was produced by microbiological oxidation of ferrous sulfate at pH 2.0-3.0 over a range of concentrations (5.4-805 mM) and temperatures (22-65 °C). Ammoniojarosites were also produced by chemical (abiotic) procedures in parallel thermal (36-95 °C) experiments. At 36 °C, schwertmannite [ideally Fe₈O₈(OH)₆(SO₄)] was the only solid product formed at <10 mM concentrations. Between 11.5 and 85.4 mM , a mixed product of ammoniojarosite and schwertmannite precipitated, as identified by X-ray diffraction. In excess of 165 mM , ammoniojarosite was the only solid phase produced. An increase in the incubation temperature using thermoacidophiles at 45 and 65 °C accelerated the formation of ammoniojarosite in culture solutions containing 165 mM . Both the biogenic and chemical ammoniojarosites were yellow (2Y-4Y in Munsell hue), low surface area (<1 m²/g), well crystalline materials with average c_o and a_o unit cell parameters of 17.467 ± 0.048 Å and 7.330 ± 0.006 Å, respectively. Strong positive correlations were observed between unit cell axial ratios (c_o/a_o) and increasing synthesis temperature in both biotic and abiotic systems. All samples were N deficient compared to stoichiometric ammoniojarosite, and both chemical and X-ray data indicated partial replacement of by H₃O⁺ to form solid solutions with 0.14-0.24 mole H₃O⁺ per formula unit. The morphology of the biogenic jarosites included aggregated discs, pseudo-cubic crystals and botryoidal particles, whereas the chemical specimens prepared at 36-95 °C were composed of irregular crystals with angular edges. Morphological information may thus be useful to evaluate environmental parameters and mode of formation. The data may also have application in predicting phase boundary conditions for Fe(III) precipitation in biogeochemical processes and treatment systems involving acid sulfate waters.     

Ammonium in aqueous fluids to 600 °C, 1.3 GPa: A spectroscopic study on the effects on fluid properties, silica solubility, and K-feldspar to muscovite reactions

The behavior of ammonium, NH₄⁺, in aqueous systems was studied based on Raman spectroscopic experiments to 600 °C and about 1.3 GPa. Spectra obtained at ambient conditions revealed a strong reduction of the dynamic three-dimensional network of water with addition of ammonium chloride, particularly at small solute concentrations. The differential scattering cross section of the ν₁-NH₄⁺ Raman band in these solutions was found to be similar to that of salammoniac.The Raman band of silica monomers at ∼780 cm⁻¹ was present in all spectra of the fluid at high temperatures in hydrothermal diamond-anvil cell experiments with H₂O ± NH₄Cl and quartz or the assemblage quartz + kyanite + K-feldspar ± muscovite/tobelite. However, these spectra indicated that dissolved silica is less polymerized in ammonium chloride solutions than in comparable experiments with water. Quantification based on the normalized integrated intensity of the H₄SiO₄⁰ band showed that the silica solubility in experiments with H₂O + NH₄Cl was significantly lower than that in equimolal NaCl solutions. This suggests that ammonium causes a stronger decrease in the activity of water in chloridic solutions than sodium.The Raman spectra of the fluid also showed that a significant fraction of ammonium was converted to ammonia, NH₃, in all experiments at temperatures above 300 °C. This indicates a shift towards acidic conditions for experiments without a buffering mineral assemblage. The estimated pH of the fluid was ∼2 at 600 °C, 0.26 GPa, 6.6 m initial NH₄Cl, based on the ratio of the integrated ν₁-NH₃ and ν₁-NH₄⁺ intensities and the HCl⁰ dissociation constant. The NH₃/NH₄⁺ ratio increased with temperature and decreased with pressure. This implies that more ammonium should be retained in K-bearing minerals coexisting with chloridic fluids upon high-P low-T metamorphism. At 500 °C, 0.73 GPa, ammonium partitions preferentially into the fluid, as constrained from infrared spectroscopy on the muscovite and from mass balance.The conversion of K-feldspar to muscovite proceeded much faster in experiments with NH₄Cl solutions than in comparable experiments with water. This is interpreted as being caused by enhancement of the rate-limiting alumina solubility, suggesting complexation of Al with NH₄. Nucleation and growth of mica at the expense of K-feldspar and NH₄⁺/K⁺ exchange between fluid and K-feldspar occurred simultaneously, but incorporation of NH₄⁺ into K-feldspar was distinctly faster than K-feldspar consumption.     

The system H2O-NaCl. Part II: Correlations for molar volume, enthalpy, and isobaric heat capacity from 0 to 1000 °C, 1 to 5000 bar, and 0 to 1 XNaCl

A set of correlations for the volumetric properties and enthalpies of phases in the system H₂O-NaCl as a function of temperature, pressure, and composition has been developed that yields accurate values from 0 to 1000 °C, 1 to 5000 bar, and 0 to 1 X_NaCl. The volumetric properties of all fluid phases from low-density vapor to hydrous salt melts and single-phase binary fluids at high pressures and temperatures, can be described by a simple equation

     

Zinc complexation in aqueous sulfide solutions: Determination of the stoichiometry and stability of complexes via ZnS(cr) solubility measurements at 100 °C and 150 bars

The solubility of ZnS_(cr) was measured at 100 °C, 150 bars in sulfide solutions as a function of sulfur concentration (m(S_total) = 0.02-0.15) and acidity (pH_t = 2-11). The experiments were conducted using a Ti flow-through hydrothermal reactor enabling the sampling of large volumes of solutions at experimental conditions, with the subsequent concentration and determination of trace quantities of Zn. Prior to the experiments, a long-term in situ conditioning of the solid phase was performed in order to attain the reproducible Zn concentrations (i.e. solubilities). The ZnS_(cr) solubility product was monitored in the course of the experiment. The following species were found to account for Zn speciation in solution: Zn²⁺ (pH_t < 3), (pH_t 3-4.5), (pH_t 5-8), and ZnS(HS)⁻ (pH_t > 8) (pH_t predominance regions are given for m(S_total) = 0.1). Solubility data collected in this study at pH_t > 3 were combined with the ZnS_(cr) solubility product determined at lower pH to yield the following equilibrium constants (t = 100 °C, P = 150 bars):

     

Coupled phase and aqueous species equilibrium of the H2O-CO2-NaCl-CaCO3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H₂O-CO₂-NaCl-CaCO₃ system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H⁺, Na⁺, Ca²⁺, , Ca(OH)⁺, OH⁻, Cl⁻, , , CO_2(aq) and CaCO_3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO_2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T-P-m range, hence calcite solubility, CO₂ gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data.One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO₂ can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility.The functionality of pH value, alkalinity, CO₂ gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl_(aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.     

A thermodynamic model for calculating methane solubility, density and gas phase composition of methane-bearing aqueous fluids from 273 to 523 K and from 1 to 2000 bar

A thermodynamic model is presented to calculate methane solubility, liquid phase density and gas phase composition of the H₂O-CH₄ and H₂O-CH₄-NaCl systems from 273 to 523 K (possibly up to 573 K), from 1 to 2000 bar and from 0 to 6 mol kg⁻¹ of NaCl with experimental accuracy. By a more strict theoretical approach and using updated experimental data, this model made substantial improvements over previous models: (1) the accuracy of methane solubility in pure water in the temperature range between 273 and 283 K is increased from about 10% to about 5%, but confirms the accuracy of the Duan model [Duan Z., Moller N., Weare J.H., 1992a. Prediction of methane solubilities in natural waters to high ionic strength from 0 to 250 °C and from 0 to 1600 bar. Geochim. Cosmochim. Acta56, 1451-1460] above 283 K up to 2000 bar; (2) the accuracy of methane solubility in the NaCl aqueous solutions is increased from >12% to about 6% on average from 273 K and 1 bar to 523 K and 2000 bar; (3) this model is able to calculate water content in the gas phase and liquid phase density, which cannot be calculated by previous models; and (4) it covers a wider range of temperature and pressure space. With a simple approach, this model is extended to predict CH₄ solubility in other aqueous salt solutions containing Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻ and , such as seawater and geothermal brines, with excellent accuracy. This model is also able to calculate homogenization pressure of fluid inclusions (CH₄-H₂O-NaCl) and CH₄ solubility in water at gas-liquid-hydrate phase equilibrium. A computer code is developed for this model and can be downloaded from the website: www.geochem-model.org/programs.htm.     

Solubilities of corundum, wollastonite and quartz in H2O-NaCl solutions at 800 °C and 10 kbar: Interaction of simple minerals with brines at high pressure and temperature

Solubilities of corundum (Al₂O₃) and wollastonite (CaSiO₃) were measured in H₂O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H₂O and NaCl at pressure (P) and temperature (T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al₂O₃ molality (m_Al2O3) of 0.0013(1) (1σ error) in pure H₂O and then leveling off to a maximum of ∼0.015 at halite saturation (X_NaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H₂O, , passes through a maximum at X_NaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H₂O at this P and T(m_CaSiO3=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H₂O at X_NaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H₂O-NaCl-SiO₂, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from m_SiO2=1.248 in pure H₂O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H₂O reproduces the data and indicates that hydrogen bonding of molecular H₂O to dissolved silica species is thermodynamically negligible. The maxima in for corundum and wollastonite indicate that the solute products include hydrates and Na⁺ and/or Cl⁻ species produced by molar ratios of reactant H₂O to NaCl of 6:1 and 2:1, respectively. Our results imply that quite simple mechanisms may exist in the dissolution of common rock-forming minerals in saline fluids at high P and T and allow assessment of the interaction of simple, congruently soluble rock-forming minerals with brines associated with deep-crustal metamorphism.     

Oxygen isotope fractionation between apatite-bound carbonate and water determined from controlled experiments with synthetic apatites precipitated at 10-37 °C

The oxygen isotope fractionation between the structural carbonate of inorganically precipitated hydroxyapatite (HAP) and water was determined in the range 10-37 °C. Values of 1000 ln α() are linearly correlated with inverse temperature (K) according to the following equation: 1000 ln α() = 25.19 (±0.53)·T⁻¹ − 56.47 (±1.81) (R² = 0.998). This fractionation equation has a slightly steeper slope than those already established between calcite and water ( [O’Neil et al., 1969] and [Kim and O’Neil, 1997]) even though measured fractionations are of comparable amplitude in the temperature range of these experimental studies. It is consequently observed that the oxygen isotope fractionation between apatite carbonate and phosphate increases from about 7.5‰ up to 9.1‰ with decreasing temperature from 37 °C to 10 °C. A compilation of δ¹⁸O values of both phosphate and carbonate from modern mammal teeth and bones confirms that both variables are linearly correlated, despite a significant scattering up to 3.5‰, with a slope close to 1 and an intercept corresponding to a 1000 ln α() value of 8.1‰. This apparent fractionation factor is slightly higher or close to the fractionation factor expected to be in the range 7-8‰ at the body temperature of mammals.     

Carbon solubility in core melts in a shallow magma ocean environment and distribution of carbon between the Earth’s core and the mantle

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.     

Metamorphic fluid flow in the northeastern part of the 3.8-3.7 Ga Isua Greenstone Belt (SW Greenland): A re-evalution of fluid inclusion evidence for early Archean seafloor-hydrothermal systems

Fluid inclusions in quartz globules and quartz veins of a 3.8-3.7 Ga old, well-preserved pillow lava breccia in the northeastern Isua Greenstone Belt (IGB) were studied using microthermometry, Raman spectrometry and SEM Cathodoluminescence Imaging. Petrographic study of the different quartz segregations showed that they were affected by variable recrystallization which controlled their fluid inclusion content. The oldest unaltered fluid inclusions found are present in vein crystals that survived dynamic and static recrystallization. These crystals contain a cogenetic, immiscible assemblage of CO₂-rich (+H₂O, +graphite) and brine-rich (+CO₂, +halite, +carbonate) inclusions. The gas-rich inclusions have molar volumes between 44.8 and 47.5 cm³/mol, while the brine inclusions have a salinity of ∼33 eq. wt% NaCl. Modeling equilibrium immiscibility using volumetric and compositional properties of the endmember fluids indicates that fluid unmixing occurred at or near peak-metamorphic conditions of ∼460 °C and ∼4 kbar. Carbonate and graphite were precipitated cogenetically from the physically separated endmember fluids and were trapped in fluid inclusions.In most quartz crystals, however, recrystallization obliterated such early fluid inclusion assemblages and left graphite and carbonate as solid inclusions in recrystallized grains. Intragranular fluid inclusion trails in the recrystallized grains of breccia cementing and crosscutting quartz veins have CO₂-rich assemblages, with distinctly different molar volumes (either between 43.7 and 47.5 cm³/mol or between 53.5 and 74.1 cm³/mol), and immiscible, halite-saturated H₂O-CO₂-NaCl(-other salt) inclusions. Later intergranular trails have CH₄-H₂ (X_H2 up to ∼0.3) inclusions of variable density (ranging from 48.0 to >105.3 cm³/mol) and metastable H₂O-NaCl(-other salt?) brines (∼28 eq. wt% NaCl). Finally, the youngest fluid inclusion assemblages are found in non-luminescent secondary quartz and contain low-density CH₄ (molar volume > 105.33 cm³/mol) and low-salinity H₂O-NaCl (0.2-3.7 eq. wt% NaCl). These successive fluid inclusion assemblages record a retrograde P-T evolution close to a geothermal gradient of ∼30 °C/km, but also indicate fluid pressure variations and the introduction of highly reducing fluids at ∼200-300 °C and 0.5-2 kbar. The quartz globules in the pillow fragments only contain sporadic CH₄(+H₂) and brine inclusions, corresponding with the late generations present in the cementing and crosscutting veins. We argue that due to the large extent of static recrystallization in quartz globules in the pillow breccia fragments, only these relatively late fluid inclusions have been preserved, and that they do not represent remnants of an early, seafloor-hydrothermal system as was previously proposed.Modeling the oxidation state of the fluids indicates a rock buffered system at peak-metamorphic conditions, but suggests a change towards fluid-graphite disequilibrium and a logf_H2/f_H2O above the Quartz-Fayalite-Magnetite buffer during retrograde evolution. Most likely, this indicates a control on redox conditions and on fluid speciation by ultramafic rocks in the IGB.Finally, this study shows that microscopic solid graphite in recrystallized metamorphic rocks from Isua can be deposited inorganically from a fluid phase, adding to the complexity of processes that formed reduced carbon in the oldest, well-preserved supracrustal rocks on Earth.     

The solubility of platinum and gold in NaCl brines at 1.5 kbar, 600 to 800°C: A laser ablation ICP-MS pilot study of synthetic fluid inclusions

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:

     

A simple predictive model of quartz solubility in water-salt-CO2 systems at temperatures up to 1000 °C and pressures up to 1000 MPa

Knowledge of the solubility of quartz over a broad spectrum of aqueous fluid compositions and T-P conditions is essential to our understanding of water-rock interaction in the Earth’s crust. We propose an equation to compute the molality of aqueous silica, m_SiO2(aq), mol·(kg H₂O)⁻¹, in equilibrium with quartz and water-salt-CO₂ fluids, as follows: