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1.
The coupled solubility of Au(cr) and Pt(cr) has been measured in acidic chloride solutions at 350–450°С and 0.5 and 1 kb using the autoclave technique with determination of dissolved metal contents after quenching. The constants of the reaction combining the dominant species of Au and Pt in high-temperature hydrothermal fluids (K(Au–Pt)) have been determined: 2 Au(cr) + PtCl42- = Pt(cr) + 2AuCl2-; log K(Au–Pt) =–1.02 ± 0.25 (450°С, 1 kb), 0.09 ± 0.15 (450°С, 0.5 kb), and –1.31 ± 0.20 (350°С, 1 kb). It has been established that the factors affecting the Au/Pt concentration ratio in hydrothermal fluids and precipitated ores are temperature, pressure, redox potential, and sulfur fugacity. An increase in temperature results in an increase in the Au/Pt concentration ratio (up to ~550°С at P = 1 kb). A decrease in pressure and redox potential leads to enrichment of fluid in Au. An increase in sulfur fugacity in the stability field of Pt sulfides results in increase in the Au/Pt concentration ratio. Native platinum is replaced by sulfide mineral in low-temperature systems enriched in Pt (relative to Au).  相似文献   

2.
Gold mass transfer with chloride and carbonate-chloride solutions was examined at the 300 and 400°C isotherms and P tot = 1 kbar by means of experimental modeling and theoretical simulations. CO2 was confirmed to suppress Au solubility in fluids. The low Au solubility (mAu < 10?8) determined in the experiments explains the mechanism of its precipitation when serpentinites and listwanites interact with acidic mineralized solutions. Listwanitization, which was genetically related with the emplacement of orogenic granitoids, was determined to have overprinted serpentinites and rodingites and strongly affected Au transport in the oregeochemical system. The characteristics of the metasomatic processes in the Ust’-Dep ophiolites and the gold concentration in the rocks produced by these processes confirm this conclusion.  相似文献   

3.
Using the methods of electron spectroscopy of the surface and SEM–EDS, it is shown that native gold of the deposit related to the epithermal Au–Ag ore formation contains oxidized gold with an oxidation degree of Au (I) or higher on the surface. A thin layer (~15 nm) with high concentrations of Ag and S and an underlying SiO2-bearing layer with a thickness of ~30–60 nm play a protective role providing preservation of Ag and Au sulfides in the surface parts of the Au–Ag grains under the oxidizing conditions. S-rich marginal parts of native gold particles may be represented by solid solutions Ag2–xAu x S or (with a lack of S) by agglomerates of Ag n Au m S clusters. The formation of surface zoning in the nanoscale on the surface of native Au is abundant in nature and may be applied in prospecting.  相似文献   

4.
The thermodynamic simulation of the geochemical mobility of Au and Ag during their hydrothermal transfer and precipitation was conducted with regard for the formation of continuous nonideal Au-Ag solid solutions (or AuXAg1?X) alloys) and with the analysis of the effects of principal physicochemical parameters (temperature, pH, redox potential, and the concentrations of sulfide sulfur and chloride ions) on the solubility of Au-Ag alloys of various composition. Predominant Au and Ag complexes and the types of solutions were identified, which are characterized by different extractive ability with respect to these metals. A tendency in the variations in the Au/Ag ratio in the solid phase during the evolution of the hydrothermal process was revealed with regard for various conditions under which Ag sulfides can occur. The possible effect of the AuXAg1?X/solution ratio on the composition of the Au-Ag mineralization was demonstrated, and tendencies in the variations in the composition (fineness) of the alloys during their redeposition were identified.  相似文献   

5.
The Sandaowanzi gold-telluride deposit, with a total reserve of ?≥?25 t of Au and an average grade of 15 g/t, is located in the Great Hinggan Range Metallogenic Belt in NE China. This deposit is the first reported case of a dominantly Au (±Ag)-telluride deposit in this area and it reveals highly economic bonanza Au- and Ag-telluride ores. Ore bodies principally occur in quartz veins and stockworks and minor in disseminations hosted by trachyandesites and andesitic breccias. Four paragenetic stages of mineralization are identified, demonstrating an early deposition of sulfides and subsequent precipitation of tellurides, which are mainly composed by petzite, sylvanite and to a lesser extent, hessite, calaverite, altaite, unnamed telluride (Au1.8Ag0.2Te), krennerite, empressite, stützite and coloradoite. Abundant telluride assemblages identified from Sandaowanzi ores are mostly attributed to breakdown of early tellurium-bearing phases (i.e., γ- and χ-phases) during cooling. The deposition of substantial Au-Ag-Te minerals are constructed under physicochemical conditions of T?=?240 to 280 °C, pH?=?4.39 to 5.64, logfO2?=–44.8 to –41.8, logfTe2?=–9.75 to –9.43, logαAu+ (aq)/αAg+ (aq)?=??6.87 to –6.56, and gold is mostly scavenged from a HTe?-dominant ore-forming fluid. The unusually high Te concentrations in the Sandaowanzi epithermal system are likely attributed to alkaline to calc-alkaline magmatic degassing.  相似文献   

6.
The solubility of gold in aqueous sulphide solutions has been determined from pH20°C ≈ 4 to pH20°C ≈ 9.5 in the presence of a pyrite-pyrrhotite redox buffer at temperatures from 160 to 300°C and 1000 bar pressure. Maximum solubilities were obtained in the neutral region of pH as, for example, with mNaHS = 0.15 m, pH20°C = 5.96, T = 309°C, P = 1000 bar where a gold solubility of 225 mg/kg was obtained. It was concluded that three thio gold complexes contributed to the solubility. The complex Au2(HS)2S2? predominated in alkaline solution, the Au(HS)2? complex occurred in the neutral pH region, and in the acid pH region, it was concluded with less certainty that the Au(HS)° complex was present. Formation constants calculated forAu2(HS)2S2? and Au (HS)2? emphasize their high stability. In the temperature range from 175 to 250°C, values of pβ for Au2(HS)2S2? vary from ?53.0 to 47.9 (±1.6) and from ?23.1 to ?19.5 ( ± 1.5) for Au(HS)2?. Equilibrium constante for the dissolution reactions, Au° + H2S + HS? ? Au(HS)2? + 12H2 and 2Au° + H2S + 2H8? ? Au(HS)2? + H2 vary from pKm = +2.4 to +2.55 (±0.10) for Au2(HS)2S2? and from pKn = + 1.29 to + 1.19 (±0.10) for Au(HS)2? over the temperature range 175 to 250°C. Enthalpies of these dissolution reactions were calculated to be ΔHm° = ?5.2 ±2.0 kcal/mol and ΔHn° = +1.7 ±2.0 kcal/mol respectively. It was concluded that gold is probably transported in hydrothermal ore solutions as both thio and chloro complexes and may be deposited in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration.  相似文献   

7.
The behavior of Pt was studied in the Pt-Fe-S-Cl-H2O, Pt-Fe(Ni)-As-S-Cl-H2O, and Pt-Ni-As-Cl-H2O systems. Kinetic experiments showed that the addition of As and S to the system changes the character of Pt complexing and results in a decrease in the bulk Pt content in the solutions. The intermediate complexes that formed during this process disproportionated to produce cooperite and sperrylite. Under the experimental P-T-μ i conditions, the hydrothermal mobility of Pt was mainly provided by its hydrosulfide complexes with a definite participation of chloride complexes. The presence of Ni in the system lowers the redox potential and Pt solubility and prevents the formation of Pt phases, while Ni sulfides and arsenides crystallize copiously. The behavior of Pt and Au in hydrothermal systems and mechanisms of hydrothermal formation of noble metal minerals were considered.  相似文献   

8.
The solubility of gold was measured in KCl solutions (0.001-0.1 m) at near-neutral to weakly acidic pH in the presence of the K-feldspar-muscovite-quartz, andalusite-muscovite-quartz, and pyrite-pyrrhotite-magnetite buffers at temperatures 350 to 500°C and pressures 0.5 and 1 kbar. These mineral buffers were used to simultaneously constrain pH, f(S2), and f(H2). The experiments were performed using a CORETEST flexible Ti-cell rocking hydrothermal reactor enabling solution sampling at experimental conditions. Measured log m(Au) (mol/kg H2O) ranges from −7.5 at weakly acid pH to −5.9 in near-neutral solutions, and increases slightly with temperature. Gold solubility in weakly basic and near-neutral solutions decreases with decreasing pH at all temperatures, which implies that Au(HS)2 is the dominant Au species in solution. In more acidic solutions, solubility is independent of pH. Comparison of the experimentally measured solubilities with literature values for Au hydrolysis constants demonstrates that at 350°C dominates Au aqueous speciation at the weakly acidic pH and f(S2)/f(H2) conditions imposed by the pyrite-pyrrhotite-magnetite buffer. In contrast, at temperatures >400°C becomes less important and predominates in weakly acid solutions. Solubility data collected in this study were used to calculate the following equilibrium reaction constants:
  相似文献   

9.
Chalcopyrite and bornite are the main Au-bearing minerals at Cu porphyry deposits, volcanogenic massive sulfide (VMS) deposits, Cu-Ni deposits of the mafic magmatic complexes, and ores of submarine sulfide edifices. Bornite and intermediate solid solutions with wide compositional variations (bnss and iss – high-temperature chalcopyrite, correspondingly), which can scavenge economic concentrations of Au, appear in the Cu-Fe-S system at ore-forming conditions. However, the state of Au in bnss and iss is yet unknown. To solve this conundrum, we synthesized samples with net chemical composition of bnss and iss, studied them by in situ X–ray absorption spectroscopy (XAS), and used the experimental data to explain the Au distribution among natural ore-forming minerals. The sulfide samples were obtained at 495–700 °C in Au-saturated system by means of salt flux method. The bnss contained ～1.2–1.6 log units more Au than iss: up to 18 wt.% Au in bnss vs 0.4 wt.% Au in iss at 700 °C. An increase of temperature resulted in the sharp increase of Au concentration in both phases, ～1 log unit per 100 °C at f(S2) close to S(l) saturation. Analysis of Au L3-edge spectra recorded at 25–675 °C revealed that at 25 °C Au exists mainly in the metallic state. At t > 500 °C the spectral features of Au° disappear, and “chemically bound” Au predominates. The Au form of occurrence in the iss field is interpreted as Au-bearing clusters with a stromeyerite-like (CuAgS) structure. Digenite Cu2–xS and bnss contain Au in a mixture of stromeyerite-like and petrovskaite-like (Au0.8Ag1.2S) clusters. The chemical composition of both forms is close to CuAuS, where the nearest Au neighbors are two S atoms at RAu-S = 2.34–2.36 Å. Results of the present study allow to determine the state of Au and its concentration in the main Cu-bearing minerals of sulfide ores as a function of the T-f(S2)-compositional parameters. Due to the sharp increase of the CuAuS clusters stability with increasing temperature, in high-temperature ores formed at t > 350 °C Au enriches Cu-bearing minerals in comparison with Cu-free or Cu-deficient ones. As a result, in these ores native gold, being a product of decomposition of the Au-bearing clusters, is associated with Cu-rich minerals – chalcopyrite, bornite, digenite, chalcocite.  相似文献   

10.
We have performed experiments to constrain the effect of sulfur fugacity (fS2) and sulfide saturation on the fractionation and partitioning behavior of Pt, Pd and Au in a silicate melt–sulfide crystal/melt–oxide–supercritical aqueous fluid phase–Pt–Pd–Au system. Experiments were performed at 800 °C, 150 MPa, with oxygen fugacity (fO2) fixed at approximately the nickel–nickel oxide buffer (NNO). Sulfur fugacity in the experiments was varied five orders of magnitude from approximately log fS2 = 0 to log fS2 = −5 by using two different sulfide phase assemblages. Assemblage one consisted initially of chalcopyrite plus pyrrhotite and assemblage two was loaded with chalcopyrite plus bornite. At run conditions pyrrhotite transformed compositionally to monosulfide solid solution (mss), chalcopyrite to intermediate solid solution (iss), and in assemblage two chalcopyrite and bornite formed a sulfide melt. Run-product silicate glass (i.e., quenched silicate melt) and crystalline materials were analyzed by using both electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. The measured concentrations of Pt, Pd and Au in quenched silicate melt in runs with log fS2 values ranging from approximately 0.0 to −5.0 do not exhibit any apparent dependence on fS2. The measured Pt, Pd and Au concentrations in mss do vary as a function of fS2. The measured Pt, Pd and Au concentrations in iss do not appear dependent on fS2. The data suggest that fS2, working in concert with fO2, via the determinant role that these variables play in controlling the magmatic sulfide phase assemblage and the solubility of Pt, Pd and Au as lattice bound components in magmatic sulfide phases, is a controlling factor on the budgets of Pt, Pd and Au during the evolution of magmatic systems.  相似文献   

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

12.
The concentration and temperature dependences of pyrochlore and Nb oxide solubility in Na2CO3 and Na2СO3 + NaF aqueous solutions with concentrations from 0.01 to 2.0 m at 300–550°C and 50 and 100 MPa (the Co–CoO buffer) are studied. It is established that the Nb equilibrium content in the solution increases at 550°C and 100 MPa with an increase in mNa2CO3 and reaches the value of 10–4 m. The Nb2O5 solubility almost does not change as the concentration of Na2CO3 increases and is found within 10–6 to 10–5.5 m.  相似文献   

13.
An experimental study of the solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions was conducted at temperatures from 200° to 350 °C and at saturated vapor pressure. A 500-mL Bridgemantype pressure vessel constructed of titanium, and equipped with a motor-driven magnetic stirrer was employed. The pH and the oxidation state were buffered by the coexistence of H2S/HS–/SO inf4 sup2– . The pH at temperature was calculated to be in the range 5.91–9.43, and S was 0.3–2.2 m. Under the experimental conditions, the measured solubility of gold is about two to three orders of magnitude greater than that of either platinum and palladium, and the measured solubility of platinum is, in general, approximately equal to that of palladium, in molal units. The solubilities are found to be in the range: platinum 4–800 ppb, palladium 1–400 ppb, and gold 2–300 ppm. The solubility data can be modeled adequately using the following reactions: Au+H2S+HH–=Au(HS) 2 – +1/2H2 (K14); PtS+HS–+H+=Pt (HS) 2 0 (K15); PdS+HS–+H+=Pd (HS) 2 0 (K16); PtS2+H2=Pt (HS) 2 0 (K21).With equilibrium constants determined as follows (errors represent two standard deviations): Preliminary measurements of the solubilities of metallic Pt, Pd and Au as hydroxide complexes were also conducted using a second titanium pressure vessel, at temperatures of 200° to 350 °C and vapor saturation pressure, with pH and the oxidation state controlled or buffered by adding known amounts of NaOH and H2 gas. The concentration of NaOH was in the range 0.01–1.3 m, and the partial pressure of H2 at 200 °C was 62–275 bars, initially. Under the temperature and pressure conditions of these experiments, the solubility of platinum in 1 m NaOH solution is less than 100 ppb, that of palladium is less than 10 ppb and that of gold is less than 0.2 ppm; and in 0.01 m NaOH solutions, both Pt and Pd solubilities are less than 1 ppb. These data indicate that the contributions of hydroxide complexes to the total solubilities in the bisulfide runs, where the pH was in the range of 5.9–9.4, are negligible. The concentrations of both Pt and Pd as bisulfide complexes in the Salton Sea geothermal system predicted using the stability constants determined in this work agree very well with those values measured by McKibben et al. (1990). This calculation strongly suggests that the PGE are transported in moderately reducing, near neutral hydrothermal fluids as bisulfide complexes, as is gold. However, the much lower maximum solubility of the PGE relative to gold severely constrains models of re genesis, and may explain the relative rarity of hydrothermal PGE deposits compared to the relative abundance of hydrothermal Au deposits.  相似文献   

14.
The intermetallic compound Ni3Au and Au-Ni solid solutions (native nickel Au and Au-bearing native Ni) were found in the contact metamorphosed metalliferous sediments of the Triassic chert formation in Sikhote-Alin. The metalliferous rocks are characterized by high contents of Au, Ag, and PGE, as well as the presence of diverse minerals of precious metals. Nickel gold (Au0.91-0.88 Ni0.09-0.12) is found as grains and crystals (3 to 4 im in size) in Au-bearing cherts with hematite, which are conventionally defined as “itabir-ites” and in the altered siliceous rocks of the Dal’nerechensky district (the upper reaches of the Gornya River). The nickel gold is associated with copper Au, pure native Au (Au1.00), and Au-Ag and Au-Ag-Pb solid solutions (Au0.86/0.84Ag0.14_0.16 and Au0.78Ag0.19Pb0.03, respectively). The Au-bearing Ni is found in the metamorphosed carbonaceous mudstones and Au-bearing “itabirites” of the Shirokopadninsky area (Olgin-sky district). The Au content varies from 6.09 wt % (Ni0.98Au0.02) to 11.30 wt % (Ni0.96Au0.04) in some Au-bearing Ni grains (about 10—15 im in diameter) taken from the metamorphosed mudstones. The grains of Au-bearing Ni (Co0.001_0.00Au00.2 - 0.17 Ni 0.98_0.83) in the “itabirites” are also characterized by their heterogeneous composition and the fine impregnation of the Ni3 Au intermetallic compound (Ni2.99Au1.01 based on the microprobe analysis).  相似文献   

15.
The solubility of rhodonite, represented by the reaction MnSiO3 (rhodonite) + 2HCl0 = MnCl20 + SiO2 (quartz) + H2O, was investigated experimentally in the temperature range 400°–700°C at 1 and 2 kbar by rapid-quench hydrothermal techniques and the Ag-AgCl buffer methods. Variations in the molalities of associated hydrogen chloride (mHCl0) as a function of the molalities of total Mn indicate that Mn in the fluid in equilibrium with the assemblage rhodonite + quartz is predominantly associated as MnCl20. The Mn:Cl in the fluid ?2, indicating that Mn+2 is the dominant oxidation state.The solubility data were used to calculate the equilibrium constant of the above reaction as a function of temperature, pressure, and the difference in Gibbs free energy of formation between MnCl20 and HCl0. The equilibrium constants of solubility for Mn minerals for which thermochemical data are available were also calculated. Calculated mineral solubilities were used in conjunction with the data of Frantz et al. (1981) to calculate the composition of supercritical fluids in equilibrium with Mn-bearing phases and assemblages. At 400°C and 1000 bars, supercritical fluids in equilibrium with olivines of compositions similar to those present in MORB tend to be enriched in Mn, despite the low mole fraction of tephroite in the olivine. Supercritical fluids in equilibrium with the assemblage quartz-hematite-rhodonite at 500° and 400°C and 1000 bars show high concentrations of Mn relative to Fe. Manganese concentrations in the fluids increase with decrease in the mole fraction of H, whereas Fe concentrations decrease. The data indicate that H fugacity plays a significant role in the separation of Mn from Fe in chloride-bearing hydrothermal fluids at supercritical temperatures.  相似文献   

16.
In the design of hydrothermal solubility studies it is important that the system be completely defined chemically. If the solubilities of minerals containing m metallic elements are to be determined in hydrothermal NaCl solutions, the phase rule requires that a total of m + 6 independent intensive parameters be controlled or measured in order to determine completely the system.In this study the solubility of the univariant assemblage pyrite + pyrrhotite + magnetite has been determined in vapor saturated hydrothermal solutions from 200 to 350°C for NaCl concentrations ranging from 0.0 to 5.0 molal. At any temperature, oxygen and sulfur fugacities were buffered by the chosen assemblage. System pH was determined from excess CO2 partial pressures and computed ionic equilibria. Equilibrium constants were calculated by regression analysis of solubility data. The results show that more than 10 ppm of each mineral can dissolve in typical hydrothermal solutions under geologically realistic conditions. Solubilities were best represented by the species Fe2+ and FeCl+ at 200 and 250°C; Fe2+, FeCl+ and FeCl20 at 300°C; and Fe2+ and FeCl20 at 350°C. Ore deposition would occur by lowering temperature, diluting chloride concentration, or by raising pH through wall rock alteration reactions.  相似文献   

17.
A vapor-undersaturated synthetic brine was equilibrated with metallic gold and a haplogranitic melt at 800°C and 100 MPa to examine the solubility, speciation and partitioning of gold in the silicate melt-brine-metallic gold system. The starting composition of the NaCl-KCl-HCl-H2O brine was 70 wt.% NaCl (equivalent) with starting KCl/NaCl ranging from 0.5 to 1. KCl/HCl was varied from 3.2 to 104 to evaluate the solubility and partitioning of gold as a function of the concentration of HCl in the brine. Inclusions of brine were trapped in a silicate glass during quench. Inclusion-poor and inclusion-rich portions of glass were analyzed for gold and chloride by using neutron activation analysis. The inclusion-poor glass yielded an estimate of the solubility of gold and chloride in the silicate melt. The solubility of gold in the melt, at gold metal saturation, was estimated as ≈1 ppm. The solubility of gold in the brine was estimated by mass balance, given the concentration of gold and chloride in the inclusion-poor and inclusion-rich glasses. The solubility of gold metal at low-HCl concentrations in the brine, CHClb, (3 × 103 to 1.1 × 104 ppm) is ≈40 ppm (by weight) and is independent of the HCl concentration under those conditions. For CHClb of 1.1 × 104 to 4.0 × 104 ppm, the solubility of gold increased from 40 to 840 ppm, and the solubility is given by: log CAub = [2.2 · log CHClb] − 7.2(1) These data suggest that a significant amount of gold is not chloride complexed in brines at low-HCl concentrations (< 1.1 × 104 ppm), but that gold-chloride complexes, possibly AuCl2H, are important at elevated concentrations of HCl (> 1.1 × 104 ppm). The calculated Nernst partition coefficient (DAub/m) for gold between a brine and melt varied from 40 to 830 over a range of brine HCl concentrations of 3 × 103 to 1.1 × 104 ppm. Our results indicate a significant amount of gold can be transported by a brine in the magmatic-hydrothermal environment independent of the fugacity of sulfur in the system. Thus brines provide an effective mechanism for the scavenging of gold from a crystallizing melt and transport into an associated magmatic-hydrothermal system, regardless of their sulfur contents.  相似文献   

18.
Two sets of measurements of the solubility of Pt and Pd in bisulfide solutions have been carried out at low temperatures. The first involved the equilibration of Pt metal with bisulfide solutions at 25 °C and pH = 6–12 for periods up to five years. These experiments yielded Pt concentrations on the order of tens of g/L at sulfide concentrations as low as 0.001 molal under conditions too reducing to permit significant contributions from hydroxide complexes. The second set of experiments consisted of reacting PtS, PdS and Au with H2S-saturated solutions having pH values of 3–4 at 25°, 50° and 90 °C. These experiments showed that the solubilities of all three metals increased with temperature. The observed order of solubility was Au > Pt Pd. Solubilities ranged from 10 to 75 g/L Au, 4 to 20 g/L Pt and 0.5 to 10 g/L Pd. The data do not permit definitive identification of the Pt and Pd species present in either set of experiments, but do strongly suggest that the species present under acidic and basic conditions are different. The measured solubility of gold at 25° and 50 °C is consistent with that measured in previous studies.Although the measured Pt and Pd solubilities are not as high as those estimated by theoretical methods, it is nevertheless evident that bisulfide complexation can lead to the remobilization of Pt and Pd over a wide range of pH under reducing conditions at geologically reasonable sulfide concentrations, at low as well as high temperatures. Such conditions are characteristic of a wide variety of geological environments where Pt and Pd have been inferred to have been affected by hydrothermal transport. In these cases, bisulfide complexation is far more effective than chloride or hydroxide complexes in transporting the PGE. On leave from: Shenyang Laboratory of Rock and Mineral Resources, Ministry of Geology and Mineral Resources, People's Republic of China  相似文献   

19.
The solubility of synthetic ZnS(cr) was measured at 25–250 °C and P = 150 bars as a function of pH in aqueous sulfide solutions (~ 0.015–0.15 m of total reduced sulfur). The solubility determinations were performed using a Ti flow-through hydrothermal reactor. The solubility of ZnS(cr) was found to increase slowly with temperature over the whole pH range from 2 to ~ 10. The values of the Zn–S–HS complex stability constant, β, were determined for Zn(HS)20(aq), Zn(HS)3?, Zn(HS)42?, and ZnS(HS)?. Based on the experimental values the Ryzhenko–Bryzgalin electrostatic model parameters for these stability constants were calculated, and the ZnS(cr) solubility and the speciation of Zn in sulfide-containing hydrothermal solutions were evaluated. The most pronounced solubility increase, about 3 log units at m(Stotal) = 0.1 for the temperatures from 25 to 250 °C, was found in acidic solutions (pH ~ 3 to 4) in the Zn(HS)20(aq) predominance field. In weakly alkaline solutions, where Zn(HS)3? and Zn(HS)42? are the dominant Zn–S–HS complexes, the ZnS(cr) solubility increases by 1 log unit at the same conditions. It was found that ZnS(HS)? and especially Zn(HS)42? become less important in high temperature solutions. At 25 °C and m(Stotal) = 0.1, these species dominate Zn speciation at pH > 7. At 100 °C and m(Stotal) = 0.1, the maximum fraction of Zn(HS)42? is only 20% of the total Zn concentration (i.e. at pHt ~ 7.5), whereas at 350 °C and 3 <pHt <10, the fraction of Zn(HS)42? and ZnS(HS)? is less than 0.05% and 2.5% respectively, of the total Zn concentration and Zn(HS)20 and Zn(HS)3? predominate. The measured equilibrium formation constants were combined with the literature data on the stability of Zn–Cl complexes in order to evaluate the concentration and speciation of Zn in chloride solutions. It was found that at acidic pH, and in more saline fluids having total chloride > 0.05 m, Zn–Cl complexes are responsible for hydrothermal Zn transport with no significant contribution of Zn–S–HS complexes. The hydrosulfide/sulfide complexes will play a more important role in lower salinity (< 0.05 m chloride) hydrothermal solutions which are characteristic of many epithermal ore depositing environments. The value of ΔfG° (β-ZnS(cr)) = ? 198.6 ± 0.2 kJ/mol at 25 °C was determined via solubility measurements of natural low-iron Santander (Spain) sphalerite.  相似文献   

20.
Copper transport and deposition in highly saline hydrothermal fluids are controlled by the stability of copper(I) complexes with ligands such as chloride and hydrosulphide. However, our understanding of the behavior of copper(I)-chloride complexes at elevated temperatures and in highly saline brines is limited by the conditions of existing experimental studies where the maximum chloride concentration is 2 m. This paper presents the results of a study of copper(I)-chloride complexes at much higher chloride concentrations, 1.5 m to 9.1 m, using a UV spectrophotometric method. The UV spectra of copper(I)-bearing LiCl solutions were measured at temperatures between 100 °C and 250 °C at vapor-saturated pressures and quantitative interpretation of the spectra shows that CuCl2−, CuCl32−, and CuCl43− were present in the experimental solutions. The fitted logarithms of formation constants (log K) for CuCl2− are in good agreement with the previous results of solubility experiments reported by Xiao et al. (1998) and Liu et al. (2001). The log K values for CuCl32− also agree with those of Liu et al. (2001) and theoretical estimates of Sverjensky et al. (1997). This study presents the first experimentally determined formation constants for CuCl43−, at temperatures greater than 25 °C, and indicates that this complex predominates at chloride concentrations greater than 5 m. Based on the new log K values generated from this study, the calculated chalcopyrite solubility in NaCl solutions indicates that in addition to cooling, fluid mixing (dilution of saline fluids) may be an important factor controlling the deposition of copper minerals from hydrothermal solutions.  相似文献   

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