Hydrogen-alkali exchange between silicate melts and two-phase aqueous mixtures: an experimental investigation

Experiments were performed in the three-phase system high-silica rhyolite melt + low-salinity aqueous vapor + hydrosaline brine, to investigate the exchange equilibria for hydrogen, potassium, and sodium in magmatic-hydrothermal systems at 800 °C and 100 MPa, and 850 °C and 50 MPa. The K ^aqm/melt _H,Na and K ^aqm/melt _H,K for hydrogen-sodium exchange between a vapor + brine mixture and a silicate melt are inversely proportional to the total chloride concentration (ΣCl) in the vapor + brine mixture indicating that HCl/NaCl and HCl/KCl are higher in the low-salinity aqueous vapor relative to high-salinity brine. The equilibrium constants for vapor/melt and brine/melt exchange were extracted from regressions of K ^{a q m / m e l t} _{H , N a} and K ^{a q m / m e l t} _{H , K} versus the proportion of aqueous vapor relative to brine in the aqueous mixture (F^aqv) at P and T, expressed as a function of ΣCl. No significant pressure effect on the empirically determined exchange constants was observed for the range of pressures investigated. Model equilibrium constants are: K ^aqv/melt _H,Na(vapor/melt)=26(±1.3) at 100 MPa (800 °C), and 19( ± 7.0) at 50 MPa (850 °C); K ^aqv/melt _H,K=14(±1.1) at 100 MPa (800 °C), and 24(±12) at 50 MPa (850 °C); K ^aqb/melt _H,b(brine/melt)= 1.6(±0.7) at 100 MPa (800 °C), and 3.9(±2.3) at 50 MPa (850 °C); and K ^aqb/melt _H,K=2.7(±1.2) at 100 MPa (800 °C) and 3.8(±2.3) at 50 MPa (850 °C). Values for K ^aqv/melt _H,K and K ^aqb/melt _H,K were used to calculate KCl/HCl in the aqueous vapor and brine as a function of melt aluminum saturation index (ASI: molar Al₂O₃/(K₂O+Na₂O+CaO) and pressure. The model log KCl/HCl values show that a change in melt ASI from peraluminous (ASI = 1.04) to moderately metaluminous (ASI = 1.01) shifts the cooling pathway (in temperature-log KCl/HCl space) of the aqueous vapor toward the andalusite+muscovite+K-feldspar reaction point. Received: 22 August 1996  / Accepted: 5 February 1997     

An Experimental Study of Oxygen Isotope Fractionation in the Quartz—Wolframite—Water System

Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water system from 200 to 420 °C. The starting wolframite was synthesized in aqueous solutions of Na₂WO₄ · 2H₂O + FeCl₂ · 4H₂O or MnCl₂ · 4H₂O. The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl. Experiments were conducted in a gold-lined stainless steel autoclave, with filling degrees of about 50%. The results showed no significant difference in equilibrium isotope fractionation between water and wolframite, ferberite and huebnerite at the same temperature (310 °C ). The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370 °C, but to increase significantly with decreasing temperature below 370 °C: 1000 ln α_wf-H₂o= 1.03×10⁶T−2-4.91 (370 °C ±200 °C ) 1000 ln α_wf-H₂o = 0.21×10⁶T −2-2.91 (420 °C -370 °C ±) This projects was financially supported by the National Natural Science Foundation of China.     

H2O activity in concentrated NaCl solutions at high pressures and temperatures measured by the brucite-periclase equilibrium

 H₂O activities in concentrated NaCl solutions were measured in the ranges 600°–900° C and 2–15 kbar and at NaCl concentrations up to halite saturation by depression of the brucite (Mg(OH)₂) – periclase (MgO) dehydration equilibrium. Experiments were made in internally heated Ar pressure apparatus at 2 and 4.2 kbar and in 1.91-cm-diameter piston-cylinder apparatus with NaCl pressure medium at 4.2, 7, 10 and 15 kbar. Fluid compositions in equilibrium with brucite and periclase were reversed to closures of less than 2 mol% by measuring weight changes after drying of punctured Pt capsules. Brucite-periclase equilibrium in the binary system was redetermined using coarsely crystalline synthetic brucite and periclase to inhibit back-reaction in quenching. These data lead to a linear expression for the standard Gibbs free energy of the brucite dehydration reaction in the experimental temperature range: ΔG° (±120J)=73418–134.95T(K). Using this function as a baseline, the experimental dehydration points in the system MgO−H₂O−NaCl lead to a simple systematic relationship of high-temperature H₂O activity in NaCl solution. At low pressure and low fluid densities near 2 kbar the H₂O activity is closely approximated by its mole fraction. At pressures of 10 kbar and greater, with fluid densities approaching those of condensed H₂O, the H₂O activity becomes nearly equal to the square of its mole fraction. Isobaric halite saturation points terminating the univariant brucite-periclase curves were determined at each experimental pressure. The five temperature-composition points in the system NaCl−H₂O are in close agreement with the halite saturation curves (liquidus curves) given by existing data from differential thermal analysis to 6 kbar. Solubility of MgO in the vapor phase near halite saturation is much less than one mole percent and could not have influenced our determinations. Activity concentration relations in the experimental P-T range may be retrieved for the binary system H₂O-NaCl from our brucite-periclase data and from halite liquidus data with minor extrapolation. At two kbar, solutions closely approach an ideal gas mixture, whereas at 10 kbar and above the solutions closely approximate an ideal fused salt mixture, where the activities of H₂O and NaCl correspond to an ideal activity formulation. This profound pressure-induced change of state may be characterized by the activity (a) – concentration (X) expression: a _{H 2}O=X _{H 2}O/(1+αX _NaCl), and a _NaCl=(1+α)^(1+α)[X _NaCl/(1+αX _NaCl)]^(1+α). The parameter α is determined by regression of the brucite-periclase H₂O activity data: α=exp[A–B/ϱ_{H 2}O ]-CP/T, where A=4.226, B=2.9605, C=164.984, and P is in kbar, T is in Kelvins, and ϱ_{H 2}O is the density of H₂O at given P and T in g/cm³. These formulas reproduce both the H₂O activity data and the NaCl activity data with a standard deviation of ±0.010. The thermodynamic behavior of concentrated NaCl solutions at high temperature and pressure is thus much simpler than portrayed by extended Debye-Hückel theory. The low H₂O activity at high pressures in concentrated supercritical NaCl solutions (or hydrosaline melts) indicates that such solutions should be feasible as chemically active fluids capable of coexisting with solid rocks and silicate liquids (and a CO₂-rich vapor) in many processes of deep crustal and upper mantle metamorphism and metasomatism. Received: 1 September 1995 / Accepted: 24 March 1996     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

H2O activity in concentrated KCl and KCl-NaCl solutions at high temperatures and pressures measured by the brucite-periclase equilibrium

H₂O activities in supercritical fluids in the system KCl-H₂O-(MgO) were measured at pressures of 1, 2, 4, 7, 10 and 15  kbar by numerous reversals of vapor compositions in equilibrium with brucite and periclase. Measurements spanned the range 550–900 °C. A change of state of solute KCl occurs as pressures increase above 2 kbar, by which H₂O activity becomes very low and, at pressures of 4 kbar and above, nearly coincident with the square of the mole fraction (x _H2O). The effect undoubtedly results primarily from ionic dissociation as H₂O density (ρ_H2O) approaches 1 gm/cm³, and is more pronounced than in the NaCl-H₂O system at the same P-T-X conditions. Six values of solute KCl activity were yielded by terminal points of the isobaric brucite-periclase T-x _H2O curves where sylvite saturation occurs. The H₂O mole fraction of the isobaric invariant assemblage brucite-periclase-sylvite-fluid is near 0.52 at all pressures, and the corresponding temperatures span only 100 °C between 1 and 15 kbar. This remarkable convergence of the isobaric equilibrium curves reflects the great influence of pressure on lowering of both KCl and H₂O activities. The H₂O and KCl activities can be expressed by the formulas: a _H2O = γ_H2O[x _H2O+(1 + (1 + α)x _KCl)], and a _KCL = γ_KCl[(1 + α)x _KCl/(x _H2O +(1 + α)x _KCl)]^(1 + α), where α is a degree of dissociation parameter which increases from zero at the lowest pressures to near one at high pressures and the γ's are activity coefficients based on an empirical regular solution parameter W: ln γ_i = (1 − x_i)²W. Least squares fitting of our H₂O and KCl activity data evaluates the parameters: α = exp(4.166 −2.709/ρ_H2O) − 212.1P/T, and W = (−589.6 − 23.10P) /T, with ρ_H2O in gm/cm³, P in kbar and T in K. The standard deviation from the measured activities is only ± 0.014. The equations define isobaric liquidus curves, which are in perfect agreement with previous DTA liquidus measurements at 0.5–2 kbar, but which depart progressively from their extrapolation to higher pressures because of the pressure-induced dissociation effect. The great similarity of the NaCl-H₂O and KCl-H₂O systems suggests that H₂O activities in the ternary NaCl-KCl-H₂O system can be described with reasonable accuracy by assuming proportionality between the binary systems. This assumption was verified by a few reconnaissance measurements at 10 kbar of the brucite-periclase equilibrium with a Na/(Na + K) ratio of 0.5 and of the saturation temperature for Na/(Na + K) of 0.35 and 0.50. At that pressure the brucite-periclase curves reach a lowest x _H2O of 0.45 and a temperature of 587 °C before salt saturation occurs, values considerably lower than in either binary. This double-salt eutectic effect may have a significant application to natural polyionic hypersaline solutions in the deep crust and upper mantle in that higher solute concentrations and very low H₂O activities may be realized in complex solutions before salt saturation occurs. Concentrated salt solutions seem, from this standpoint, and also because of high mechanical mobility and alkali-exchanging potential, feasible as metasomatic fluids for a variety of deep-crust and upper mantle processes. Received: 9 August 1996 / Accepted: 15 November 1996     

Calculation of multicomponent chemical equilibria and reaction processes in systems involving minerals,gases and an aqueous phase

The compositional characteristics of many geochemical systems which involve the interaction of natural aqueous solutions with minerals and gases are conveniently described using the following thermodynamic components: Cl^?, SO₄⁼, HS^?, CO₃⁼, H⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Fe⁺⁺, Zn⁺⁺, Cu⁺, Al⁺⁺⁺, SiO₂ and H₂O. A set of mass balance and mass action equations equal in number to the number of components plus the number of saturated minerals (and gases) is defined for a specified temperature, pressure and bulk composition. The mass balance equations include terms for minerals, gases and the molalities of aqueous complexes and dissociated species. This set of non-linear equations can be solved with the aid of a computer using'a Newton-Raphson technique. The calculation takes account of aqueous ion complexing, oxidation-reduction equilibria, activity coefficients, non-unit water activity and solid solutions. The use of H⁺, SO₄⁼, HS^? and H₂O as components allows straightforward treatment of processes involving oxidation-reduction, evaporation, boiling and changes of total aqueous H⁺ due to hydrolysis, mineral reaction or temperature change. One product of this approach is a technique for calculating pH at high temperature from measurement of pH at room temperature.By linking a series of discrete overall heterogeneous equilibrium calculations in which incremental changes of bulk composition, temperature or pressure are made, dynamic geochemical processes can be modeled. Example calculations for two such processes are given. These are the heating of seawater from 25° to 300°C and the isothermal irreversible reaction of rhyolite with an aqueous solution at 250°C.     

The partitioning of copper between silicate melts and two-phase aqueous fluids: An experimental investigation at 1 kbar, 800° C and 0.5 kbar, 850° C

 Experiments were performed in the three phase system high-silica rhyolite melt+low-salinity aqueous vapor+hydrosaline brine, to investigate the partitioning equilibria for copper in magmatic-hydrothermal systems at 800° C and 1 kbar, and 850° C and 0.5 kbar. D^aqm/mlt _Cu and apparent equilibrium constants, K^aqm/mlt _Cu,Na, between the aqueous mixture (aqm=quenched vapor+brine) and the silicate melt (mlt) are calculated. D^aqm/mlt _Cu increases with increasing aqueous chloride concentration and is a function of pressure. K^aqm/mlt _Cu,Na=215(±73) at 1 kbar and 800° C and K^aqm/mlt _Cu,Na=11(±6) at 0.5 kbar and 850°C. Decreasing pressure from 1 to 0.5 kbar lowers K^aqm/mlt _Cu,Na by a factor of approximately 20. Data revealed no difference in K^aqm/mlt _Cu,Na or D^aqm/mlt _Cu as a function of the melt aluminium saturation index. Within the 2-phase field the K^aqm/mlt _Cu,Na show no variation with total aqueous chloride, indicating that copper-sodium exchange between the vapor, brine and silicate melt is independent of the mass proportion of vapor and brine. Model copper-sodium apparent equilibrium constants for the hydrosaline brine and the silicate melt revealed a negative dependence on pressure. Model apparent equilibrium constants for copper-sodium exchange between the brine and vapor were close to unity at 1 kbar and 800° C. Received: 27 June 1994/Accepted: 30 March 1995     

Diagenesis in tertiary sandstones from Kettleman North Dome. California—II. Interstitial solutions: Distribution of aqueous species at 100°C and chemical relation to the diagenetic mineralogy

Interstitial brines from the Temblor and the McAdams sandstones at Kettleman are essentially NaCaCl solutions with subsidiary SO₄ and the total salinities are roughly 30,000 and 10,000 ppm, respectively. Activities of H⁺ and all other aqueous species have been calculated for 100°C (the in situ temperatures of the brines) from chemical analyses of the brines and 100-degree dissociation constants alone. The brine alkalinities measured at surface temperature appear to be too low when comparing them against alkalinities calculated from the measured pHs of the brines. Consequently, alkalinities calculated for 25°C were substituted for the measured ones in the calculation of the distribution of aqueous species at 100°C.Although the brines are nearly neutral (pH 6·3–d7·9) at surface temperature, their pHs calculated for 100°C range from 8·1 to 8·7 (± 0·35). These pHs and the 100-degree activities of the other aqueous species permit graphic representation of the brines on activity diagrams. Most brines fall at or near the boundaries between the stability fields of quartz, albite, microcline, mica, montmorillonite and anhydrite. Because these minerals are present as authigenic phases in the sandstones, the calculations suggest that the minerals are in stable equilibrium with the brines. By contrast, the calculations suggest that the brines are supersaturated by about three orders of magnitude with respect to calcite, also present in the sandstones. One possible explanation for this is kinetic inhibition of calcite crystallization by Mg²⁺ and SO₄^2? ions in the brines. Phosphatic pellets, glauconite and probably dolomite, pyrite and some kaolinite are early authigenic minerals preserved in the sandstones and they are not now in equilibrium with the brines, which are supersaturated with respect to dolomite and pyrite. The chemical relationship between the brines and the diagenetic minerals laumontite and sphene, also present in the Temblor Formation, cannot be assessed reliably until the thermodynamic properties of laumontite and of aqueous titanium complexes are well known.     

Experimental study of Pd hydrolysis in aqueous solutions at 25–70°C

The hydrolysis of the Pd²⁺ ion in HClO₄ solutions was examined at 25–70°C, and the thermodynamic constants of equilibrium K ₍₁₎⁰ and K ₍₂₎⁰were determined for the reactions Pd²⁺ + H₂O = PdOH⁺ + H⁺ and Pd²⁺ + 2H₂O = Pd(OH)₂⁰ + 2H⁺, respectively. The values of log K ₍₁₎⁰ = −1.66 ± 0.5 (25°C) and −0.65 ± 0.25 (50°C) and log K ₍₂₎⁰ = −4.34 ± 0.3 (25°C) and −3.80 ± 0.3 (50°C) were derived using the solubility technique at 0.95 confidence level. The values of log K ₍₁₎⁰ = −1.9 ± 0.6 (25°C), −1.0 ± 0.4 (50°C), and −0.5 ± 0.3 (70°C) were obtained by spectrophotometric techniques. The palladium ion is significantly hydrolyzed at elevated temperatures (50–70°C) even in strongly acidic solutions (pH 1–1.5), and its hydrolysis is enhanced with increasing temperature.     

An experimental study of the solubility of molybdenum in H2O and KCl-H2O solutions from 500 °C to 800 °C, and 150 to 300 MPa

The solubility of molybdenum (Mo) was determined at temperatures from 500 °C to 800 °C and 150 to 300 MPa in KCl-H₂O and pure H₂O solutions in cold-seal experiments. The solutions were trapped as synthetic fluid inclusions in quartz at experimental conditions, and analyzed by laser ablation inductively coupled plasma mass spectrometry (LA ICPMS).Mo solubilities of 1.6 wt% in the case of KCl-bearing aqueous solutions and up to 0.8 wt% in pure H₂O were found. Mo solubility is temperature dependent, but not pressure dependent over the investigated range, and correlates positively with salinity (KCl concentration). Molar ratios of ∼1 for Mo/Cl and Mo/K are derived based on our data. In combination with results of synchrotron X-ray absorption spectroscopy of individual fluid inclusions, it is suggested that Mo-oxo-chloride complexes are present at high salinity (>20 wt% KCl) and ion pairs at moderate to low salinity (<11 wt% KCl) in KCl-H₂O aqueous solutions. Similarly, in the pure H₂O experiments molybdic acid is the dominant species in aqueous solution. The results of these hydrothermal Mo experiments fit with earlier studies conducted at lower temperatures and indicate that high Mo concentrations can be transported in aqueous solutions. Therefore, the Mo concentration in aqueous fluids seems not to be the limiting factor for ore formation, whereas precipitation processes and the availability of sulfur appear to be the main controlling factors in the formation of molybdenite (MoS₂).     

Iron control by equilibria between hydroxy-Green Rusts and solutions in hydromorphic soils

In order to verify Fe control by solution - mineral equilibria, soil solutions were sampled in hydromorphic soils on granites and shales, where the occurrence of Green Rusts had been demonstrated by Mössbauer and Raman spectroscopies. Eh and pH were measured in situ, and Fe(II) analyzed by colorimetry. Ionic Activity Products were computed from aqueous Fe(II) rather than total Fe in an attempt to avoid overestimation by including colloidal particles. Solid phases considered are Fe(II) and Fe(III) hydroxides and oxides, and the Green Rusts whose general formula is [Fe^II_1−xFe^III_x(OH)₂]^+x· [x/z A^−z]^−x, where compensating interlayer anions, A⁻, can be Cl⁻, SO₄²⁻, CO₃²⁻ or OH⁻, and where x ranges a priori from 0 to 1. In large ranges of variation of pH, pe and Fe(II) concentration, soil solutions are (i) oversaturated with respect to Fe(III) oxides; (ii) undersaturated with respect to Fe(II) oxides, chloride-, sulphate- and carbonate-Green Rusts; (iii) in equilibrium with hydroxy-Green Rusts, i.e., Fe(II)-Fe(III) mixed hydroxides. The ratios, x = Fe(III)/Fe_t, derived from the best fits for equilibrium between minerals and soil solutions are 1/3, 1/2 and 2/3, depending on the sampling site, and are in every case identical to the same ratios directly measured by Mössbauer spectroscopy. This implies reversible equilibrium between Green Rust and solution. Solubility products are proposed for the various hydroxy-Green Rusts as follows: log K_sp = 28.2 ± 0.8 for the reaction Fe₃(OH)₇ + e⁻ + 7 H⁺ = 3 Fe²⁺ + 7 H₂O; log K_sp = 25.4 ± 0.7 for the reaction Fe₂(OH)₅ + e⁻ + 5 H⁺ = 2 Fe²⁺ + 5 H₂O; log K_sp = 45.8 ± 0.9 for the reaction Fe₃(OH)₈ + 2e⁻ + 8 H⁺ = 3 Fe²⁺ + 8 H₂O at an average temperature of 9 ± 1°C, and 1 atm. pressure. Tentative values for the Gibbs free energies of formation of hydroxy-Green Rusts obtained are: Δ_fG° (Fe₃(OH)₇, cr, 282.15 K) = −1799.7 ± 6 kJ mol⁻¹, Δ_fG° (Fe₂(OH)₅, cr, 282.15 K) = −1244.1 ± 6 kJ mol⁻¹ and Δ_fG° (Fe₃(OH)₈, cr, 282.15 K) = −1944.3 ± 6 kJ mol⁻¹.     

Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

Geochemical interactions resulting from carbon dioxide disposal on the seafloor

The storage of CO_2(liquid) on the seafloor has been proposed as a method of mitigating the accumulation of greenhouse gases in the Earth's atmosphere. Storage is possible below 3000 m water depth because the density of CO_2(liquid) exceeds that of seawater and, thus, injected CO_2(liquid) will remain as a stable, density stratified layer on the seafloor. The geochemical consequences of the storage of CO_2(liquid) on the seafloor have been investigated using calculations of chemical equilibrium among complex aqueous solutions, gases, and minerals. At 3000 m water depth and 4°C, the stable phases are CO_2(hydrate) and a brine. The hydrate composition is CO₂·6.3H₂O. The equilibrium composition of the brine is a 1.3 molal sodium-calcium-carbonate solution with pH ranging from 3.5 to 5.0. This acidified brine has a density of 1.04 g cm⁻³ and will displace normal seawater and react with underlying sediments. Seafloor sediment has an intrinsic capacity to neutralize the acid brine by dissolution of calcite and clay minerals and by incorporation of CO₂ into carbonates including magnesite and dawsonite. Large volumes of acidified brine, however, can deplete the sediments buffer capacity, resulting in growth of additional CO_2(hydrates) in the sediment. Volcanic sediments have the greatest buffer capacity whereas calcareous and siliceous oozes have the least capacity. The conditions that favor carbonate mineral stability and CO_2(hydrates) stability are, in general, mutually exclusive although the two phases may coexist under restricted conditions.The brine is likely to cause mortality in both plant and animal comunities: it is acidic, it does not resemble seawater in composition, and it will have reduced capacity to hold oxygen because of the high solute content. Lack of oxygen will, consequently, produce anoxic conditions, however, the reduction of CO₂ to CH₄ is slow and redox disequilibrium mixtures of CO₂ and CH₄ are likely. Seismic or volcanic activity may cause conversion of CO_2(liquid) to gas with potentially catastrophic release in a Lake Nyos-like event. The long term stability of the CO_2(hydrate) may be limited: once isolated from the CO_2(liquid) pool, either through burial or through depletion of the CO₂ pool, the hydrate will decopose, releasing CO₂ back into the sediment-water system.     

Experimental Study of the SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O–KF–KCl–NaF System at 700–800°C and 1–2 kbar Based on Synthetic Fluid Inclusions in Quartz

The phase state of the fluid in the H₂O–KF ± KCl ± NaF system is studied in the presence of quartz for an experimental assay of the mutual influence of various salts of the fluid-forming mixture on heterogeneous fluid equilibria. The fluid inclusions were synthesized in quartz by the fracture healing method from solutions with KF + KCl and KF + NaF mixtures at 1 or 2 kbar and 700, 750, or 800°C. The results of the fluid inclusion study indicate a heterogeneous state of the fluid and variation in the fluid composition during experiments as a result of its interaction with quartz. The increase in temperature and pressure, as well as variation in the proportions of the salt contents in the fluid-forming mixture, changed the course of chemical reactions. After all the experiments, a glassy phase was observed in some types of inclusions. It is known that aqueous KF or KCl solutions, the solubility of which increases during heating, are characterized by phase equilibria of systems of the first type (Valyashko, 1990), when liquid and vapor are equilibrated for a heterogeneous state of the fluid. In this case, some inclusions should homogenize to vapor. However, no similar inclusions were observed in contrast to denser fluid phases (liquids), which are typical of the upper heterogeneous area of systems of the second (P–Q) type. Some inclusions host solid phases, the solubility of which decreases as the temperature increases. The results of experiments in the presence of KF + NaF solutions showed that the amount of inclusions of heterogeneous entrapment increases at higher temperatures simultaneously with a decrease in the H₂O content of the glassy phase.     

Phase Equilibria in the Ternary Systems KBr–K2B4O7–H2O and KCl–K2B4O7–H2O at 373 K

According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide （KBr） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）,and those in the ternary system KCl-K2B4O7-H2O are potassium chloride （KCl） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）.Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.     

Interaction of model peridotite with H2O-KCl fluid: Experiment at 1.9 GPa and its implications for upper mantle metasomatism

Mineralogical and geochemical data suggest that chloride components play an important role in the transformation and partial melting of upper mantle peridotites. The effect of KCl on the transformation of hydrous peridotite rich in Al₂O₃, CaO, and Na₂O was examined in experiments aimed at studying interaction between model NCMAS peridotite with H₂O-KCl fluid under a pressure of 1.9 GPa, temperatures of 900–1200°C, and various initial H₂O/KCl ratios. The experimental results indicate that KCl depresses the solidus temperature of the hydrous peridotite: this temperature is <900°C at 1.9 GPa, which is more than 100°C lower than the solidus temperature (1000–1025°C) of hydrous peridotite in equilibrium with KCl-free fluid. The reason for the decrease in the melting temperature is that the interaction of KCl with silicates prevails over the effect of chloride on the water activity in the fluid. Experimental data highlight the key role of Al₂O₃ as a component controlling the whole interaction process between peridotite and H₂O-KCl fluid. Garnet, spinel, and pargasite-edenite amphibole in association with aluminous orthopyroxene are unstable in the presence of H₂O-KCl fluid at a chloride concentration in the fluid as low as approximately 2 wt % and are replaced by Cl-bearing phlogopite (0.4–1.1 wt % Cl). Interaction with H₂O-KCl fluid does not, however, affect clinopyroxene and forsterite, which are the Al poorest phases of the system. Chlorine stabilizes phlogopite at relatively high temperatures in equilibrium with melt at temperatures much higher than the solidus (>1200°C). The compositional evolution of melt generated during the melting of model peridotite in the presence of H₂O-KCl fluid is controlled, on the one hand, by the solubility of the H₂O-KCl fluid in the melt and, on the other hand, by phlogopite stability above the solidus. At temperatures below 1050°C, at which phlogopite does not actively participate in melting reactions, fluid dissolution results in SiO₂-undersaturated (35–40 wt %) and MgO-enriched (up to 45 wt %) melts containing up to 4–5 wt % K₂O and 2–3 wt % Cl. At higher temperatures, active phlogopite dissolution and, perhaps, also the separation of immiscible aqueous chloride liquid give rise to melts containing >10 wt % K₂O and 0.3–0.5 wt % Cl. Our experimental results corroborate literature data on the transformation of upper mantle peridotites into phlogopite-bearing associations and the formation of ultrapotassic and highly magnesian melts.     

Activity-composition relationship in Tschermak's substituted Fe biotites at 700°C, 2 kbar

The reaction-displacement technique was applied to the end-member reaction annite = sanidine + magnetite + H₂ in order to determine the activity of the annite component (a _Ann) in iron biotites with variable degrees of the Tschermak's substitution (^[6]Fe + ^[4]Si = ^[6]Al + ^[4]Al). Based on the simplified relation a _Ann = f _{H 2}/foH₂ (foH₂ = hydrogen fugacity of the end-member reaction at P, T), two types of experiments were performed at 700°C / 2 kbar: Type I used Fe-Al biotites of known starting composition together with sanidine + magnetite + H₂O. This assemblage was exposed to various f _{H 2} conditions (f _{H 2} < foH₂) produced in the pressure vessel either by using different ratios of water/oil as pressure medium (f _{H 2} in this case was measured by the hydrogen sensor technique), or by the Ni′NiO buffer. The composition of the Fe-Al biotites changed through incorporation or release of the annite component in response to the externally imposed f _{H 2}. By using opposite biotite starting compositions, the equilibrium composition as a function of f _H2 was bracketed. For type II, f _{H 2} in equilibrium with a specific combination of fine-grained Fe-Al biotite (+ sanidine + magnetite + H₂O) was measured internally by application of the hydrogen sensor technique. Both type I and type II experiments yield consistent results demonstrating that a fine-grained assemblage of Fe-Al biotite (+ sanidine + magnetite + H₂O) is able to act as a sliding-scale buffer. The final chemical composition of the Fe-Al biotite after the experiments was determined by electron microprobe and Mössbauer spectroscopy. The ^[4]Al and ^[6]Al in the biotites are coupled according to the Tschermak's substitution. In the tetrahedral sheet 0.1 Al-atoms per formula unit are present in excess to the amount required to balance ^[6]Al, and all Fe-Al biotites contain 8–10% Fe³⁺. Therefore, they are not members of the pure annite - siderophyllite join, but have an almost constant amount (15 Mol%) of two additional Fe³⁺-bearing components (ferri-siderophyllite and a vacancy end-member). The volume - composition relationship obtained does not indicate excess molar volumes of mixing for the annite (Ann) - siderophyllite (Sid) binary. The data are consistent with a molar volume of annite of 15.46 ± 0.02 Jbar^–1 and of 15.06 ± 0.02 Jbar^–1 for siderophyllite. The experimentally determined activity - composition relation shows that biotites on the join annite - siderophyllite deviate negatively from ideality. A symmetric interaction parameter W_AnnSid is sufficient to represent the data within error. This was constrained as: W _AnnSid = –29 ± 4 kJmol^–1. This is in contradiction to empirical interaction parameters derived from natural assemblages for this binary that predict positive deviation from ideality. Reasons for this discrepancy are discussed.     

Experimental metasomatism of monazite and xenotime: mineral stability, REE mobility and fluid composition

In this study a Th-bearing monazite from a Brazil beach sand, a low Th monazite from a Malawi carbonatite, and a xenotime from a pegmatite in northern Pakistan were experimentally metasomatised in a series of common metamorphic and igneous fluids at 600°C/500 MPa and 900°C/1000 MPa. Fluids included H₂O, NaCl, and KCl brines, CaF₂?+?H₂O, 1m and 2m HCl, 1m and 2m H₂SO₄, 1m NaOH, and Na₂Si₂O₅?+?H₂O. The monazite show a variety of responses to the fluids ranging from no reaction (KCl?+?H₂O) to small compositional changes and partial replacement of the monazite grain rim by Th-enriched monazite in the NaOH and (Na₂Si₂O₅?+?H₂O) experiments respectively. The other acid and brine fluids induced varying degrees of partial dissolution in the monazite and xenotime, but no compositional alteration. Partial replacement of monazite grain rims by Th-enriched monazite occurred only in the alkaline fluids as the result of a coupled dissolution-reprecipitation process.     

Experimental determination of the solubility of the assemblage paragonite,albite, and quartz in supercritical H2O

The concentrations of Na, Al, and Si in an aqueous fluid in equilibrium with natural albite, paragonite, and quartz have been measured between 350°C and 500°C and 1 to 2.5 kbar. Si is the dominant solute in solution and is near values reported for quartz solubility in pure H₂O. At 1 kbar the concentrations of Na and Al remain fairly constant from 350°C to 425°C but then decrease at 450°C. At 2 kbar, Na increases slightly with increasing temperature while Al remains nearly constant. Concentrations of Si, Na, and Al all increase with increasing pressure at constant temperature.The molality of Al is close to that of Na and is nearly a log unit greater than calculated molalities assuming Al(OH)⁰₃ is the dominant Al species. This indicates a Na-Al complex is the dominant Al species in solution as shown by Anderson and Burnham (1983) at higher temperature and pressure. The complex can be written as NaAl(OH)⁰₄ ± nSiO₂ where n is the number of Si atoms in the complex. The value of n is not well constrained but appears to be less than or equal to 3.The results indicate Al can be readily transported in pure H₂O solutions at temperatures and pressures as low as 350°C and 1 kbar.