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1.
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   

2.
Despite the common belief that AuI complexes with hydrogen sulfide ligands (H2S/HS−) are the major carriers of gold in natural hydrothermal fluids, their identity, structure and stability are still subjects of debate. Here we present the first in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of the stability and structure of aqueous AuI–S complexes at temperatures and pressures (T–P) typical of natural sulfur-rich ore-forming fluids. The solubility of native gold and the local atomic structure around the dissolved metal in S–NaOH–Na2SO4–H2SO4 aqueous solutions were characterized at temperatures 200–450 °C and pressures 300–600 bar using an X-ray cell that allows simultaneous measurement of the absolute concentration of the absorbing atom (Au) and its local atomic environment in the fluid phase. Structural and solubility data obtained from XAFS spectra, combined with quantum-chemical calculations of species geometries, show that gold bis(hydrogensulfide) Au(HS)2− is the dominant Au species in neutral-to-basic solutions (5.5  pH  8.5; H2O–S–NaOH) over a wide range of sulfur concentrations (0.2 < ΣS < 3.6 mol/kg), in agreement with previous solubility studies. Our results provide the first direct determination of this species structure, in which two sulfur atoms are in a linear geometry around AuI at an average distance of 2.29 ± 0.01 Å. At acidic conditions (1.5  pH  5.0; H2O–S–Na2SO4–H2SO4), the Au atomic environment determined by XAFS is similar to that in neutral solutions. These findings, together with measured high Au solubilities, are inconsistent with the predominance of the gold hydrogensulfide Au(HS)0 complex suggested by recent solubility studies. Our spectroscopic data and quantum-chemical calculations imply the formation of species composed of linear S–Au–S moieties, like the neutral [H2S–Au–SH] complex. This species may account for the elevated Au solubilities in acidic fluids and vapors with H2S concentrations higher than 0.1–0.2 mol/kg. However, because of the complex sulfur speciation in acidic solutions that involves sulfite, thiosulfate and polysulfide species, the formation of AuI complexes with these ligands (e.g., AuHS(SO2)0, Au(HS2O3)2−, Au(HSn)2−) cannot be ruled out. The existence of such species may significantly enhance Au transport by high T–P acidic ore-forming fluids and vapors, responsible for the formation of a major part of the gold resources on Earth.  相似文献   

3.
The solubility of gold in hydrogen sulfide gas: An experimental study   总被引：1，自引：0，他引：1  
The solubility of gold in H2S gas has been investigated at temperatures of 300, 350 and 400 °C and pressures up to 230 bars. Experimentally determined values of the solubility of Au are 0.4-1.4 ppb at 300 °C, 1-8 ppb at 350 °C and 8.6-95 ppb at 400 °C. Owing to a positive dependence of the logarithm of the fugacity of gold on the logarithm of the fugacity of H2S, it is proposed that the solubility of Au can be attributed to formation of a solvated gaseous sulfide or bisulfide complex through reactions of the type:
(A)  相似文献   

4.
The solubility of calcite in NaCl-H2O and in HCl-H2O fluids was measured using an extraction-quench hydrothermal apparatus. Experiments were conducted at 2 kbar, between 400° C and 600° C. Measurements in NaCl-H2O were conducted in two ways: 1) at constant pressure and NaCl concentration, as a function of temperature; and 2) at constant pressure and temperature, as a function of NaCl concentration. In both the NaCl-H2O and the HCl-H2O systems, the solubility of calcite increases with increasing chlorine concentrations. For example, the log calcium molality in equilibrium with calcite increases from –3.75 at 2 kbar and 500° C, in pure H2O to –3.10 at 2 kbar and 500° C at log NaCl molality=–1.67. At fixed pressure and NaCl molality, the solubility of calcite is almost constant from 400° C to 550° C, but increases somewhat at higher temperatures. The results can be used to determine the dominant calcium species in the experimental solutions as a function of NaCl concentration and to obtain values for the second dissociation constant of CaCl2(aq). At 2 kbar, 400° C, 500° C, and 600° C, we calculate values for the log of the dissociation constant of CaCl+ of –2.1, –3.2, and –4.3, respectively. The 400° C and 500° C values are consistent with those obtained by Frantz and Marshall (1982) using electrical conductance techniques. However, our 600° C value is 0.8 log units higher than that reported by Frantz and Marshall. The calcite solubilities in the NaCl-H2O and HCl-H2O systems are inconsistent with the solubilities of calcite in pure H2O reported by Walther and Long (1986). They are, however, consistent with the measurements of calcite solubilities in pure H2O presented in this study. These results allow for the calculation of the solubilities of calcium silicates and carbonates in fluids that contain CO2 and NaCl.  相似文献   

5.
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   

6.
The Xigaze ophiolite in the central part of the Yarlung–Zangbo suture zone, southern Tibet, has a well-preserved sequence of sheeted dykes, basalts, cumulates and mantle peridotites at Jiding and Luqu. Both the basalts and diabases at Jiding have similar compositions with SiO2 ranging from 45.9 to 53.5 wt%, MgO from 3.1 to 6.8 wt% and TiO2 from 0.87 to 1.21 wt%. Their Mg#s [100Mg/(Mg + Fe)] range from 40 to 60, indicating crystallization from relatively evolved magmas. They have LREE-depleted, chondrite-normalized REE diagrams, suggesting a depleted mantle source. These basaltic rocks have slightly negative Nb- and Ti-anomalies, suggesting that the Xigaze ophiolite represents a fragment of mature MORB lithosphere modified in a suprasubduction zone environment. The mantle peridotites at Luqu are high depleted with low CaO (0.3–1.2 wt%) and Al2O3 (0.04–0.42 wt%). They display V-shaped, chondrite-normalized REE patterns with (La/Gd)N ratios ranging from 3.17 to 64.6 and (Gd/Yb)N from 0.02 to 0.20, features reflecting secondary metasomatism by melts derived from the underlying subducted slab. Thus, the geochemistry of both the basaltic rocks and mantle peridotites suggests that the Xigaze ophiolite formed in a suprasubduction zone.Both the diabases and basalts have Pd/Ir ratios ranging from 7 to 77, similar to MORB. However, they have very low PGE abundances, closely approximating the predicted concentration in a silicate melt that has fully equilibrated with a fractionated immiscible sulfide melt, indicating that the rocks originated from magmas that were S-saturated before eruption. Moderate degrees of partial melting and early precipitation of PGE alloys explain their high Pd/Ir ratios and negative Pt-anomalies. The mantle peridotites contain variable amounts of Pd (5.99–13.5 ppb) and Pt (7.92–20.5 ppb), and have a relatively narrow range of Ir (3.47–5.01 ppb). In the mantle-normalized Ni, PGE, Au and Cu diagram, they are relatively rich in Pd and depleted in Cu. There is a positive correlation between CaO and Pd. The Pd enrichment is possibly due to secondary enrichment by metasomatism. Al2O3 and Hf do not correlate with Ir, but show positive variations with Pt, Pd and Au, indicating that some noble metals can be enriched by metasomatic fluids or melts carrying a little Al and Hf. We propose a model in which the low PGE contents and high Pd/Ir ratios of the basaltic rocks reflect precipitation of sulfides and moderate degrees of partial melting. The high Pd mantle peridotites of Xigaze ophiolites were formed by secondary metasomatism by a boninitic melt above a subduction zone.  相似文献   

7.
In order to (1) explain the worldwide association between epithermal gold-copper-molybdenum deposits and arc magmas and (2) test the hypothesis that adakitic magmas would be Au-specialized, we have determined the solubility of Au at 4 kbar and 1000 °C for three intermediate magmas (two adakites and one calc-alkaline composition) from the Philippines. The experiments were performed over a fO2 range corresponding to reducing (∼NNO−1), moderately oxidizing (∼NNO+1.5) and strongly oxidizing (∼NNO+3) conditions as measured by solid Ni-Pd-O sensors. They were carried out in gold containers, the latter serving also as the source of gold, in presence of variable amounts of H2O and, in a few additional experiments, of S. Concentrations of Au in glasses were determined by LA-ICPMS. Gold solubility in melt is very low (30-240 ppb) but increases with fO2 in a way consistent with the dissolution of gold as both Au1+ and Au3+ species. In the S-bearing experiments performed at ∼NNO−1, gold solubility reaches much higher values, from ∼1200 to 4300 ppb, and seems to correlate with melt S content. No systematic difference in gold solubility is observed between the adakitic and the non-adakitic compositions investigated. Oxygen fugacity and the sulfur concentration in melt are the main parameters controlling the incorporation and concentration of gold in magmas. Certain adakitic and non-adakitic magmas have high fO2 and magmatic S concentrations favorable to the incorporation and transport of gold. Therefore, the cause of a particular association between some arc magmas and Au-Cu-Mo deposits needs to be searched in the origin of those specialized magmas by involvement of Au- and S-rich protoliths. The subducted slab, which contains metal-rich massive sulfides, may constitute a potentially favorable protolith for the genesis of magmas specialized with respect to gold.  相似文献   

8.
The solubility of gold has been measured in aqueous solutions at temperatures between 300 and 600°C and pressures from 500 to 1500 bar to determine the stability and stoichiometry of the hydroxy complexes of gold(I) in hydrothermal solutions. The experiments were carried out using a flow-through autoclave system. The solubilities, measured as total dissolved gold, were in the range 1.2 × 10−8 to 2.0 × 10−6 mol kg−1 (0.002 to 0.40 mg kg−1), in solutions of total dissolved sodium between 0.0 and 0.5 mol kg−1, and total dissolved hydrogen between 4.0 × 10−6 and 4.0 × 10−4 mol kg−1. At constant hydrogen molality, the solubility of gold increases with increasing temperature and decreases with increasing pressure. The solubilities were found to be independent of pH but increased with decreasing hydrogen molality at constant temperature and pressure. Consequently, gold dissolves in aqueous solutions of acidic to alkaline pH according to the reactionAu(s)+H2O(l)=AuOH(aq)+0.5H2(g) Ks,1The solubility constant, logKs,1, increases with increasing temperature from a minimum of −8.76 (±0.18) at 300°C and 500 bar to a maximum of −7.50 (±0.11) at 500°C and 1500 bar and decreases to −7.61 (±0.08) at 600°C and 1500 bar. From the equilibrium solubility constant and the redox potential of gold, the formation constant to form AuOH(aq) was calculated. At 25°C the complex formation is characterised by an exothermic enthalpy and a positive entropy. With increasing temperature and decreasing pressure, the formation reaction becomes endothermic and is accompanied by a large positive entropy, indicating a greater electrostatic interaction between Au+ and OH−.  相似文献   

9.
Platinum-Group Minerals from the Durance River Alluvium,France   总被引：2，自引：2，他引：0  
Summary Platinum-group minerals were discovered, during gold recovery, in the Durance river alluvium, near Peyrolles (Bouches-du-Rhône). The PGM grains (average size 130 microns) are strongly flattened (average thickness 64 microns). The PGM concentrate consists primarily of (Pt, Fe) alloys (92%), (Os, Ir, Ru) alloys (3.5%), and native gold and (Au, Cu, Ag) alloys (4.5%). The following minerals were observed: isoferroplatinum, ferroan platinum, native osmium, native iridium, iridosmine, rutheniridosmine, osmiridium, ruthenian osmium, osmian ruthenium, cuprorhodsite, guanglinite, shandite, tetrauricupride, native gold, bornite, heazlewoodite, (Pt, Pd)2Cu3, Pt(Cu, Au), (Ni, Pt)Sn, (Cu, Fe)1–x (Pd, Rh, Pt)2+xS2, (Pt, Pd)4–xCu2As1–x. Isoferroplatinum contains numerous inclusions of alloys, sulphides, arsenides, Pd-tellurides, and partly devitrified silicate glass droplets. Most of the non-silicate inclusions also exhibit a drop-like shape indicating their original entrapment in a liquid state.Cuprorhodsite crystals (up to 20 microns) are associated with bornite included in Pt3Fe. Rarely, Pd- and Cu-sulphides, and Pd-tellurides appear in this association. Complex droplet-like arsenide inclusions in isoferroplatinum are composed of Pt bearing guanglinite and (Pt,Pd)4+xCu2As1–x. Native iridium shows exsolutions of Ir-bearing isoferroplatinum and (Pt,Pd)2Cu3. In places, concentrations of Sn (up to 3 wt.%) were observed in (Au, Cu) alloys. Shandite and (Ni, Pt)Sn inclusions occur in (Au, Cu, Ag) alloys. Silicate-glass inclusions are TiO2-poor and occasionally K-rich (plotting in the shoshonitic field). Taking into account mineralogical and chemical pecularities of the PGM association occurring in the studied concentrate, it seems highly probable that its primary source should be an Alaskan-type intrusion.
Platingruppen Minerale aus dem Alluvium der Durance, Frankreich
Zusammenfassung Minerale der Platingruppe wurden im Zuge von Goldgewinnung im Alluvium der Durance in der Nähe von Peyrolles (Bouches-du-Rhône) entdeckt. Die PGM Körner (durchschnittliche Korngröße 130m) sind flach gepreßt (durchschnittliche Dicke 64m). Die PGM Konzentrate bestehen vorwiegend aus (Pt, Fe) Legierungen (92%); (Os, Ir, Ru) Legierungen (3,5%), sowie gediegen Gold und (Au, Cu, Ag) Legierungen (4,5%). Folgende Minerale wurden beobachtet:Isoferro-Platin, Fe-Platin, gediegen Osmium, gediegen Iridium, Iridosmium, Rutheniridosmium, Osmiridium, Ru-Osmium, Os-Ruthenium, Cuprorhodsit, Guanglinit, Shandit, Tetrauricuprit, gediegen Gold, Bornit, HeazIewoodit, (Pt, Pd)2 Cu3, Pt(Cu, Au), (Ni, Pt)Sn, (Cu, Fe), (Pd, Rh, Pt)2+xS2, (Pt, Pd)4+xCu2As1–x.Isoferro-Platin enthält zahlreiche Einschlüsse von Legierungen, Sulfiden, Arseniden, Pd-Telluriden und teilweise devitrifzierte Silikatglaströpfchen. Die meisten nichtsili katischen Einschlüsse sind ebenfalls tröpfchenförmig. Dies weist darauf hin, daß sie in flüssigem Zustand eingeschlossen wurden.Cuprorhodsitkristalle (bis zu 20m) sind gemeinsam mit Bornit in Pt3 Fe einge schlossen. Selten sind Pd- und Cu-Sulfide, sowie Pd-Telluride mit diesen vergesellschaftet. Bei den komplexen tröpfehenförmigen Arsenideinschlüssen im Isoferro-Platin handelt es sich um Pt-führenden Guanglinit und (Pt, Pd)4+xCu2 As1–x. Gediegen Iridium zeigt Entmischung von Ir-führendem Isoferro-Platin und (Pt, Pd)2Cu3. Stellenweise wurden Konzentrationen von Sn (bis zu 3%) in den (Au, Cu) Legierungen beobachtet. Shandit und (Ni, Pt) Sn Einschlüsse kommen in (Au, Cu, Ag) Legierungen vor. Silikatische Glaseinschlüsse sind TiO2-arm und manchmal K-reich (im Shoshonitfeld liegend).Auf Grund der mineralogischen und chemischen Eigenheiten der untersuchten PGM Konzentrate ist eine Intrusion des Alaska-Typs als primäre Quelle sehr wahrscheinlich.

With 4 Figures and 2 Plates  相似文献   

10.
The solubility of platinum and palladium in a silicate melt of the composition Di 55 An 35 Ab 10 was determined at 1200°C and 2 kbar pressure in the presence of H2O-H2 fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H2O and H2 were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.  相似文献   

11.
Summary Au-and PGE-bearing samples1 from organogenic limestone located in the western part of the Lubin mine have been investigated. They contain: Au–Ag–Pt–Hg alloys, native Pd, sobolevskite (PdBi), native lead and plumbian gold which is related to an admixture of AuPb2, electrum (Ag2Au). Clausthalite also occurs in this association and contains up to 1% Ir. Kerogen is an important member of the association and contains, among others, 700 ppm Pt, 400 ppm Pd, 600 ppm Ir and 1100 ppm Au.These alloys are closely associated with nests of secondary calcite with dark brown internal reflections due to admixture of organic compounds. Organic matter colouring calcite II contains: ketones (chiefly diketones), nitrogen derivatives, phenols, probably tertiary alcohols and aromatic hydrocarbons. Metal carbonyls were also recorded. The organic substances investigated contain oxidation retarding derivatives.
Edelmetall-Legierungen und organische Substanz in den Kupferlagerstätten des Zechstein (Kupferschiefer), Polen
Zusammenfassung Gold und PGE-führende Proben von organogenem Kalkstein aus dem Westteil der Grube Lubin enthalten Au–Ag–Pt–Hg-Legierungen, gediegen Pd, Sobolevskit (PdBi), gediegen Blei und bleireiches Gold. Letzteres ist mit einer AuPb2–Ag2Au-Verwachsung assoziiert. Außerdem konnte Clausthalit (PbSe) mit 1% Ir nachgewiesen werden.Kerogen ist ein wichtiges Glied der Edelmetall-Paragenese und enthält selbst u.a. 700 ppm Pt, 400 ppm Pd, 600 ppm Ir und 1100 ppm Au. Die Edelmetall-Legierungen sind eng mit «Nestern» von sekundärem Calcit vergesellschaftet, dessen dunkelbraune Innenreflexe auf Beimischung organischer Verbindungen zurückgehen.Letztere umfassen: Ketone (vorwiegend -Diketone), Stickstoff-Derivate, Phenole, und wohl auch tertiäre Alkohole und aromatische Kohlenwasserstoffe. Metall-Karbonyl-Verbindungen konnten ebenso nachgewiesen werden. Die untersuchten organischen Verbindungen enthalten Oxydations-verzögernde Derivate.

With 6 Figures  相似文献   

12.
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   

13.
The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10−7 to 1.30 × 10−4 mol kg−1 (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg−1 and pHT,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag2S(s) + 0.5H2S(aq) = AgHS(aq) Ks,1110.5Ag2S(s) + 0.5H2S(aq) + HS− = Ag(HS)2− Ks,122Ag2S(s) + 2HS− = Ag2S(HS)22− Ks,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag2S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H2S(aq). Consequently, Ag2S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logKs,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logKs,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logKs,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag+ and HS− at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag+ and AgClOH− are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.  相似文献   

14.
In order to asses the contribution of sorption by complexation to the concentration of noble metals at early stages of the formation of their deposits in black shales, the sorption of Au(III), Pt(IV), Rd(II), Rh(III), Ru(IV), and Os(IV) ions was studied on ash-free preparations of humic acids (HA) separated from peat of the Tver region and marine sediment samples taken on the Peruvian shelf. Data on the nature and protolytic characteristics of oxygen-containing HA functional groups were obtained. It has been shown that carboxyl groups and phenol oxygroups, which ensure the HA complexation with ions of noble metals, are present in the HA structure. The dissociation constant values for HA carboxyl groups (pKa) and the distribution function of these groups in their pKa values have been established. It has been revealed that the pKa value for both of the HA groups varies within two orders of magnitude: the average value is equal to 6.1 for HA from peat and 7.0 for HA from marine sediments. A fairly high and similar for both of the HA groups sorption capacity with respect to Au(III), Rd(II), Rh(III), Ru(IV), and Os(IV) ions was established in model experiments. It is equal to 320–350 mg g–1 for Au, 100–110 mg g–1 for Pd, 11–12 mg g–1 for Rh, 16–19 mg g–1 for Ru, and 23 mg g–1 for Os. The study of platinum(IV) sorption revealed that humic acids from peat and marine sediments do not virtually sorb Pt(IV), and this observation is important for understanding genetic features of the formation of noble metal deposits in black shales. Based on sorption isotherms for Au(III), Pd(II), Rh(III), and Ru(IV), the conditional affinity constant values for HA sorption centers with respect to ions of these metals were calculated by the method of quantitative physicochemical analysis. These values prove that complex compounds forming at the HA surface possess a high strength: the log values for the Au(III)–HA, Pd(II)–HA, Rh(III)–HA, and Ru(IV)–HA compounds are equal to 6.0, 5.0, 3.2, and 3.5, respectively.  相似文献   

15.
Arsenian pyrite in the Shuiyindong Carlin-type gold deposit in Guizhou, China, is the major host for gold with 300 to 4,000 ppm Au and 0.65 to 14.1 wt.% As. Electron miroprobe data show a negative correlation of As and S in arsenian pyrite, which is consistent with the substitution of As for S in the pyrite structure. The relatively homogeneous distribution of gold in arsenian pyrite and a positive correlation of As and Au, with Au/As ratios below the solubility limit of gold in arsenian pyrite, suggest that invisible gold is likely present as Au1+ in a structurally bound Au complex in arsenian pyrite. Geochemical modeling using the laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of fluid inclusions for the major ore forming stage shows that the dominant Au species were Au(HS)2− (77%) and AuHS(aq)0 (23%). Gold-hydroxyl and Gold-chloride complexes were negligible. The ore fluid was undersaturated with respect to native Au, with a saturation index of −3.8. The predominant As species was H3AsO30 (aq). Pyrite in the Shuiyindong deposit shows chemical zonation with rims richer in As and Au than cores, reflecting the chemical evolution of the ore-bearing fluids. The early ore fluids had relatively high activities of As and Au, to deposit unzoned and zoned arsenian pyrite that host most gold in the deposit. The ore fluids then became depleted in Au and As and formed As-poor pyrite overgrowth rims on gold-bearing arsenian pyrite. Arsenopyrite overgrowth aggregates on arsenian pyrite indicate a late fluid with relatively high activity of As. The lack of evidence of boiling and the low iron content of fluid inclusions in quartz, suggest that iron in arsenian pyrite was most likely derived from dissolution of ferroan minerals in the host rocks, with sulfidation of the dissolved iron by H2S-rich ore fluids being the most important mechanism of gold deposition in the Shuiyindong Carlin-type deposit.  相似文献   

16.
We studied primary ore samples from Kalmakyr, a giant Cu–Au–Mo porphyry deposit in eastern Uzbekistan. Disseminated and stockwork-type high-grade Cu–Au–Mo mineralization showed average concentrations of 55 ppb Pd, 5.5 ppb Pt, 0.95 ppb Rh, 0.49 ppb Ir, and 4.1 ppm Au (n = 8). This type of mineralization is characterized by the presence of pyrite, chalcopyrite, molybdenite, and gold. A peak Pd content of 292 ppb was determined in a base-metal-rich quartz vein in granodiorite porphyry, which contains galena, sphalerite, chalcopyrite, tetrahedrite, and gold. Palladium correlates with Cu, Ag, Se, and S. Mineralogical and laser ablation ICP-MS study confirmed that Pd is homogeneously distributed in chalcopyrite, which contains up to 110 ppm Pd, and tetrahedrite, containing up to 20 ppm Pd. An assessment of the Pd and Pt budget at Kalmakyr showed the potential of approximately 17 t of Pd and 1.7 t of Pt.  相似文献   

17.
Mineralized quartz diorites of the Santo Tomas II porphyry copper-gold deposit, carry high Au contents (average: 1.8 ppm) as well as 160 ppb Pd and 38 ppb Pt. Values of other platinum-group elements (PGE) and rhenium are below the analytical detection limits. There is a significant positive correlation between Au and Cu. The highest Pd values were detected in the most Au- and Cu-rich rocks. Platinum-group minerals (PGM) occur exclusively as inclusions in chalcopyrite and bornite. Potential Pd and Pt contents in sulphide concentrates are estimated at 1.5 g/t and 0.4 g/t, respectively. The precious metal assemblages consist of merenskyite (main PGM), kotulskite, moncheite, native gold, electrum, hessite and petzite. Polyphase fluid inclusions in quartz veinlets, associated with a PGM-bearing bornite-chalcopyrite-magnetite assemblage, are characterized by high salinity (35 to > 60 eq. wt% NaCl) and high trapping temperatures (between 380 and 520 °C). They may represent primary magmatic-hydrothermal fluids, which have been responsible for the transport of Pd, Pt and Au as chloride complexes.  相似文献   

18.
Summary We report here new data on the solubility of Au in silicate melts of anorthite-diopside eutectic composition at a wide range of oxygen fugacities, from pure oxygen to 10–8 atm, and at a temperature range of 1300 °C to 1480 °C. Because experiments were done with metal loops at temperatures above the Au-melting temperature, PdAu-metal-alloys had to be used. Pd-solubility data derived from the same set of experiments agree with earlier data obtained from experiments with pure Pd-metal (Borisov et al., 1994a). The results of the present experiments show that Pd-solubilities are by a factor of 2 to 6 higher than Au-solubilities. Both, Au and Pd solubilities decrease with decreasing oxygen fugacity. At oxygen fugacities below the iron-wiistite buffer (IW) Au solubility increases with decreasing fO2 probably reflecting formation of Au-silicides at such reducing conditions. Compared to Pd, Au has higher activity coefficients in Fe-metal and lower solubility in silicate melts. This leads to similar metal-silicate partition coefficients for both elements. At a temperature of 1350 °C and an oxygen fugacity corresponding to IW-2 DAu (met/sil) is about 2.5 · 107 and DPd (met/sil) about 1.6 · 107. Thus similar behavior is expected during metal separation in planetary bodies including core formation in the Earth. The metal/silicate partition coefficient of Ir is, however, by several orders of magnitudes higher (Borisov and Palme, 1995a). Equilibration with chondritic metal will therefore lead to grossly non-chondritic Pd/Ir or Au/Ir ratios in coexisting silicate phases. Chondritic ratios are thus indicative of the presence of unfractionated meteoritic components. Samples from the upper mantle of the Earth, for example, reflect the admixture of a late unfractionated (chondritic) veneer (e.g.,Kimura et al., 1974;Jagoutz et al., 1979).Solubilities of Pd and Au in silicate melts are much higher than the contents in terrestrial basalts implying that the abundances of these two elements are not buffered by residual PGE- and Au-containing alloys. The most likely process for fractionating PGEs in terrestrial magmas are mineral-melt (e.g., olivine/melt) equilibria.
Experimentelle Bestimmung der Löslichkeit von Au in Silikatschmelzen
Zusammenfassung In der vorliegenden Arbeit wird über die Ergebnisse der Bestimmung der Löslichkeit von Au in Silikatschmelzen mit der Zusammensetzung des Anorthit-Diopsid Eutektikums berichtet. Die Versuche wurden mittels Metallschlaufe über einen weiten Sauerstoffpartialdruckbereich, von reinem Sauerstoff bis zu 10–8 atm und in einem Temperaturbereich von 1300 °C bis 1480 °C, durchgeführt. Da diese Temperaturen jedoch den Au-Schmelzpunkt überschreiten, wurde mit AuPd-Legierungen gearbeitet. Die Ergebnisse der dadurch zusätzlich erhaltenen Pd-Versuche stimmen mit früher bestimmten, mit reinen Pd-Schlaufen durchgeführten Pd-Löslichkkeiten überein (Borisov et al., 1994a). Die auf reine Metalle zurückgerechneten Löslichkeiten von Pd sind um einen Faktor 2 bis 6 mal höher als die entsprechenden Au-Löslichkeiten. Die Löslichkeiten beider Metalle nehmen mit abnehmendem Sauerstoffpartialdruck ab. Unter noch stärker reduzierenden Bedingungen (Eisen-Wüstit Gleichgewicht) nimmt die Löslichkeit von Au jedoch zu. Dies könnte auf die Bildung von Au-Siliziden zurückzuführen sein.Im Vergleich zu Pd sind die Aktivitätskoeffizienten von Au in metallischem Eisen höher, die Löslichkeiten in Silikatschmelzen jedoch niedriger. Das führt zu ähnlichen Metall/Silikat Verteilungskoeffizienten von Au und Pd. Bei einer Temperatur von 1350 °C und einer Sauerstoffugazität von IW-2 ergeben sich für DAu (met/sil) 2.5 · 107 und für DPd (met/sil) 1.6* 107. Der Metall/Silikat-Verteilungskoeffizient von Ir ist jedoch unter den gleichen Bedingungen um mehrere Größenordnungen höher (Borisov andPalme, 1995a). Ein chondritisches Pd/Ir- oder Au/Ir-Verhältnis kann also auf die Anwesenheit einer unfraktionierten chondritischen Komponente zurückgeführt werden. Dies gilt beispielsweise für Proben aus dem oberen Erdmantel. Hier handelt es sich vermutlich um Zumischung einer späten chondritischen Akkretionskomponente, die sich nicht mehr mit einer metallischen Phase (Kern) ins Gleichgewicht gesetzt hat (z.B.Kimura et al., 1974,Jagoutz et al., 1979).Die Löslichkeiten von Pd und Au in Silikatschmelzen sind wesentlich höher als ihre Gehalte in basaltischen und komatiitischen Laven. Dies bedeutet, daß Au und Pd in Schmelzen aus dem Erdmantel nicht durch residuale Au- und/oder Pd-haltige Metall phasen bestimmt sind. Gleichgewichte zwischen Schmelze und Mineralen (z.B. Olivin) sind die wahrscheinlichsten Fraktionierungsmechanismen für Platingruppenelemente in terrestrischen Magmen.

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19.
The Shizishan ore field is the largest gold–copper ore field in the Tongling ore district of Anhui Province, China. Copper and gold deposits in the district are present as one-commodity deposits or as deposits with both commodities. Copper and gold mineralization are either cogenetic or are temporally and spatially distinct. We present the results of systematic geochemical analysis of fluid inclusions from typical Au–Cu deposits in the Shizishan ore field; these data are used to determine the solubility of Cu and Au in the ore-forming fluids and to ascertain the mechanisms and factors that controlled variations in the association and separation of copper and gold mineralization. Our results indicate that copper in the ore-forming fluids was transported as CuCl2− and CuCl0 complexes and that the solubility of copper was controlled by variations in Cl− concentration. In addition, the precipitation of copper was controlled by changes in temperature, pH, fO2, and fO2. In comparison, gold in the ore-forming fluids was transported as Au(HS)2− and Au2S(HS)22− complexes, and the solubility of gold was controlled by variations in total sulfur concentration; the precipitation of gold was controlled by temperature, pH, fO2, and fO2. These differences between the two elements meant that copper and gold in the ore-forming fluids responded in different ways to changes in physicochemical conditions. Copper precipitated under relatively acidic conditions at high temperatures, while gold precipitated under weakly alkaline conditions at relatively low temperatures; this dissociation resulted in the temporal and spatial separation and zonation of copper and gold mineralization in the Shizishan ore field.  相似文献   

20.
Platinum-group elements in porphyry copper deposits: a reconnaissance study   总被引：1，自引：0，他引：1  
Summary Sulphide and flotation concentrates from 33 porphyry copper deposits have been investigated for platinum-group elements (PGE), Au, Cu and platinum-group minerals (PGM). The major sulphides in the samples studied are chalcopyrite and pyrite. Bornite is less frequent and molybdenite occurs in traces only. PGM (merenskyite, sperrylite and an unidentified Pd-Sb telluride) have been found as inclusions in chalcopyrite.Pd and Pt are present in concentrations above the analytical detection limit (> 8 ppb) in 70% respectively 30% of the deposits studied. The contents of Os, Ir, Ru and Rh are below detection limits in all samples. The analytical results show that 7 deposits (six of island arc and one of continental margin setting) reveal relatively high Pd contents (130–1900 ppb) which are associated with high Au contents (1–28 ppm). In five of them discrete PGM can be identified in accordance with elevated levels of Pd. Correlations of Au, Pd and Pt point towards a common origin.Even though the data base is relatively small, a trend is obvious, suggesting that Au-rich island arc porphyry copper deposits might host more Pd and Pt than the continental margin type ones. Other aspects of intrusive rocks, such as geological age, chemical composition and magma type do not seem to influence PGE contents.
Platingruppen-Elemente in porphyrischen Kupfer Lagerstätten: eine Überblicksstudie
Zusammenfassung Es wurden Sulfid- und Flotationskonzentrate aus 33 Porphyry Kupfer Lagerstätten: auf Platingruppenelemente (PGE), Au, Cu and Platingruppenminerale (PGM) untersucht. Die Hauptsulfide im untersuchten Probenmaterial sind Chalkopyrit und Pyrit. Bornit ist weniger häufig and Molybdänit tritt nur in Spuren auf. An PGM wurden Merenskyit (in den Lagerstätten: Elacite, Majdanpek and Skouries), Sperrylith und ein nicht näher identifizierbares Pd-Sb- Tellurid (in der Lagerstätte Mamut) als Einschlüsse in Chalkopyrit festgestellt.Pd ist in 70% and Pt in 30% der untersuchten Lagerstätten: nachweisbar (> 8 ppb), während die Gehalte von Os, Ir, Ru and Rh in allen Proben unterhalb der Nachweisgrenze liegen. In 7 Lagerstätten: (davon sechs vom Inselbogen- und eine vom Kontinentalrandtyp) wurden relativ hohe Pd-Konzentrationen (130–1900 ppb) festgestellt, die auch durch hohe Au-Gehalte (1–28 ppm) gekennzeichnet sind. In 5 Lagerstätten: sind entsprechend den hohen Pd-Gehalten PGM nachweisbar.Geochemische Korrelationen zwischen Au, Pd and Pt weisen auf eine gemeinsame Herkunft dieser Metalle hin. Obwohl der Datenbestand noch relativ klein ist, ist ein Trend bereits sichtbar, daß Au-reiche Inselbogenporphyries Where Pd- und Pt- Gehalte erwarten lassen als der Kontinentalrand-Typ. Andere Aspekte wie geologisches Alter, Magmentyp and Chemismus der betreffenden Intrusivgesteine spielen bei der PGEFührung offensichtlich keine Rolle.

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