Metamorphism,graphite crystallinity,and sulfide anatexis of the Rampura–Agucha massive sulfide deposit,northwestern India

Located adjacent to the Banded Gneissic Complex, Rampura–Agucha is the only sulfide ore deposit discovered to date within the Precambrian basement gneisses of Rajasthan. The massive Zn–(Pb) sulfide orebody occurs within graphite–biotite–sillimanite schist along with garnet–biotite–sillimanite gneiss, calc–silicate gneisses, amphibolites, and garnet-bearing leucosomes. Plagioclase–hornblende thermometry in amphibolites yielded a peak metamorphic temperature of 720–780°C, whereas temperatures obtained from Fe–Mg exchange between garnet and biotite (580–610°C) in the pelites correspond to postpeak resetting. Thermodynamic considerations of pertinent silicate equilibria, coupled with sphalerite geobarometry, furnished part of a clockwise P–T–t path with peak P–T of ∼6.2 kbar and 780°C, attained during granulite grade metamorphism of the major Zn-rich stratiform sedimentary exhalative deposits orebody and its host rocks. Arsenopyrite composition in the metamorphosed ore yielded a temperature [and log f(S ₂)] range of 352°C (−8.2) to 490°C (−4.64), thus indicating its retrograde nature. Contrary to earlier research on the retrogressed nature of graphite, Raman spectroscopic studies on graphite in the metamorphosed ore reveal variable degree of preservation of prograde graphite crystals (490 ± 43°C with a maximum at 593°C). The main orebody is mineralogically simple (sphalerite, pyrite, pyrrhotite, arsenopyrite, galena), deformed and metamorphosed while the Pb–Ag-rich sulfosalt-bearing veins and pods that are irregularly distributed within the hanging wall calc–silicate gneisses show no evidence of deformation and metamorphism. The sulfosalt minerals identified include freibergite, boulangerite, pyrargyrite, stephanite, diaphorite, Mn–jamesonite, Cu-free meneghinite, and semseyite; the last three are reported from Agucha for the first time. Stability relations of Cu-free meneghinite and semseyite in the Pb–Ag-rich ores constrain temperatures at >550°C and <300°C, respectively. Features such as (1) low galena–sphalerite interfacial angles, (2) presence of multiphase sulfide–sulfosalt inclusions, (3) microcracks filled with galena (±pyrargyrite) without any hydrothermal alteration, and (4) high contents of Zn, Ag (and Sb) in galena, indicate partial melting in the PbS–Fe_0.96S–ZnS–(1% Ag₂S ± CuFeS₂) system, which was critical for metamorphic remobilization of the Rampura–Agucha deposit.     

Modeling and predicting of drainage quality for sulfide mine tailings impoundments

Effluent from tailings impoundments of sulfide mine is an important environmental problem. The oxidation of sulfide minerals in tailings impoundments and consequent release of acid and contaminants, including heavy metals and arsenic, to tailings pore-water can last for decades to centuries. Pollution of water bodies including surface water and groundwater occurs when infiltration of precipitation is unhindered, bottom liners are absent and no drainage collection is installed. So there is a great need to develop reliable modeling techniques for characterizing geochemical interactions taking place within the tailings and predicting potential future environmental hazard which favor further prevention and remediation of the acidic mine drainage （AMD）. In this paper, a comprehensive dynamic model for tailings-water interaction was established on the basis of considering the coupling and feedback among many factors and processes such as sulfide oxidation, gangue dissolution, oxygen diffusion, water flow and mass transport,     

An experimental study of Fe–Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt \(X_{{{\text{Ni}}}}^{{{\text{Sulfide}}}}=\frac{{{\text{Ni}}}}{{{\text{Ni}}+{\text{Fe}}}}\) (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of \({f_{{{\text{O}}_{\text{2}}}}}\) on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0?±?1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ ??1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients \(K_{{\text{D}}}^{{}}=\frac{{(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}/X_{{{\text{Fe}}}}^{{{\text{sulfide}}}})}}{{(X_{{{\text{Ni}}}}^{{{\text{olivine}}}}/X_{{{\text{Fe}}}}^{{{\text{olivine}}}})}}\) are small, averaging 10.0?±?5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K_D (21.1–25.2). Compared to previous determinations at 100 kPa, values of K_D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.28)?>?140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.     

Tectono-metallogenic settings of the formation and convergence of disseminated Au–sulfide mineralization

Large Au-sulfide deposits (GSDs) of disseminated ores occur worldwide in metallogenic provinces of various ages (from Precambrian to Pliocene). The studies performed showed that the great genetic diversity of GSD is determined by the similar oregenesis conditions that appear in different tectono-metallogenic settings (TMSs). A GSD is included in a certain TMS by the respective changes in the mineral and geochemical assemblages of ores. However, in the majority of cases, the GSDs of different TMSs are convergent (quasi-identical) in the texture, structure, and mineral composition of ores. All types of the above TMSs are found in Russia, which allows forecasting the discovery of new GSDs in each setting.     

Mineral systems and the thermodynamics of selenites and selenates in the oxidation zone of sulfide ores – a review

Mineralogy and Petrology - Contemporary mineralogy and geochemistry are concerned with understanding and deciphering processes that occur near the surface of the Earth. These processes are...     

Se and In minerals in the submarine oxidation zone of a massive sulfide orebody of the molodezhnoe copper–zinc massive sulfide deposit,Southern Urals

For the first time, extremely high Se and In contents were determined for the pinches of massive sulfide orebodies that are composed of small-clastic layered sulfide sediments transformed during submarine supergenesis. Se (clausthalite and naumannite) and In (roquesite) minerals were found. Hydrothermal chalcopyrite, a significant amount of which is present in the clasts of paleohydrothermal black smoker chimneys, was the source of Se. Most of the amount of In was contributed during dissolution of clasts of hydrothermal sphalerite, which is unstable in the submarine oxidation zone in the presence of oxidized pyrite.     

A laser ablation ICP-MS study of platinum-group and chalcophile elements in base metal sulfide minerals of the Jinchuan Ni–Cu sulfide deposit,NW China

The paper presents concentrations of the platinum-group and chalcophile elements in the base metal sulfides (BMS) from the Jinchuan Ni–Cu sulfide deposit determined by laser ablation-inductively coupled plasma-mass spectrometry. Mass balance calculations reveal that pentlandite hosts a large proportion of Co, Ni and Pd (> 65%), and that pentlandite and pyrrhotite accommodate significant proportions of Re, Os, Ru, Rh, and Ag (~ 35–90%), whereas chalcopyrite contains a small amount of Ag (~ 10%) but negligible platinum-group elements. Iridium and Pt are not concentrated in the BMS and mostly occur in As-rich platinum-group minerals. The enrichments of Co, Ni, Re, Os, Ru, and Rh in pentlandite and pyrrhotite, and Cu in chalcopyrite are consistent with the fractionation of sulfide liquid and exsolution of pentlandite and pyrrhotite from the mono-sulfide solid solution (MSS). The Ir-bearing minerals exsolved from the MSS, depleting pentlandite and pyrrhotite in Ir, whereas sperrylite exsolved from the residual sulfide liquid on cooling. Diffusion of Pd from residual sulfide liquid into pentlandite during its exsolution from the MSS and crystallization of Pt-bearing minerals in the residual sulfide liquid resulted in the enrichment of Pd in pentlandite and decoupling between Pd and Pt in the Jinchuan net-textured and massive ores.     

Black shales and massive sulfide deposits: causal or casual relationships? Insights from Rammelsberg, Tharsis, and Draa Sfar

Black shales and massive sulfides represent reduced lithofacies that require isolation from oxic environments to be preserved. This, together with the sedimentary affinity of both lithofacies, can explain their common concurrence in the geologic record. The present study is based on the comparison of Rammelsberg in Germany, Tharsis in Spain, and Draa Sfar in Morocco, three massive sulfide deposits closely associated with black shales that are distributed along the European and North African Variscan orogen. The study entails geochemical, biostratigraphic, and stratigraphic analyses of the black shale sequences hosting the three deposits and mineralogical and textural analyses of the sulfides. All three deposits were formed in immature, tectonically unstable basins within an active continental margin or continental magmatic arc. Their stratigraphic records consist of a sequence of black shales enclosing massive sulfides and variable proportions of bimodal volcanic and subvolcanic rocks. The major differences among the three deposits concern the size, composition, and mineralogy. Regarding age, they are diachronous and younger southward: Rammelsberg is middle Eifelian, Tharsis latest Famennian, and Draa Sfar late Viséan. The study of redox conditions of the paleoenvironment using organic and inorganic proxies highlights similarities and significant differences among the three ore-hosting basins during massive sulfide and black shale deposition. The black shales generally display low C_org and high S_tot contents. At Rammelsberg, the S_tot/C_tot ratios provide values typical for normal Middle Devonian marine environments, which suggests that the original reactive organic C is now fixed in carbonates. At Tharsis, most of the samples have C_org >1 and S_tot/C_org values equivalent to those of Devonian?CCarboniferous normal marine sediments. However, some pyritic hanging-wall samples have C_org <1 and S_tot up to 5?wt.%, suggesting the epigenetic addition of HS^?. The S_tot/C_org ratio for the Draa Sfar samples resembles that of Middle Carboniferous normal marine environments. Geochemical inorganic proxies used to define the environmental conditions include the enrichment factors of U (U_EF) and Mo (Mo_EF) together with V/Cr and V/(V?+?Ni) ratios. Footwall shales at Filón Norte (Tharsis) show positive and eventually elevated U_EF and Mo_EF values, which suggests anoxic conditions, whereas at Rammelsberg and Draa Sfar oxic bottom water is indicated. The relations V/Cr and V/(V + Ni) in all three cases point to a redox boundary near the sediment?Cwater interface, although at Tharsis some samples indicate anoxic/euxinic conditions (i.e., V/(V + Ni) >0.9). Regarding the environmental conditions of the source areas, feldspar illitization and selective depletion in Na and Ca occurred at the three studies sites. Available sulfur isotopic data from the Rammelsberg and Tharsis sulfide ore indicate that biogenic reduction of marine sulfate was a major sulfur source during massive sulfide generation. Nevertheless, a hydrothermal sulfur source has also been detected. At Rammelsberg, this is indicated from the polymetallic sulfides that replace sedimentary and diagenetic pyrite. At Tharsis, the bacteriogenic sulfur signature is also restricted to sulfide with less evolved textures, whereas a hydrothermal source is more evident in sulfides showing evidence of recrystallization. Both geochemical and isotopic data suggest that the bacteriogenic reduction process was inhibited by rapid burial. The sedimentation rates calculated for Rammelsberg, Tharsis, and Draa Sfar were in the range 7?C13, 8?C14, and 19?C27?cm/ka, respectively. Continuous sedimentation of black shale favored the isolation of the massive sulfides and organic material from bottom waters and hence favored their preservation. Accordingly, the relationships between black shales and massive sulfides are considered to be casual. Nevertheless, the tectono-sedimentary evolution of each basin controlled the deposition of both black shales and massive sulfides and the parameters that favored their coeval deposition.     

Distribution of indium in ores of some base metal and tin–sulfide deposits in Siberia and the Russian Far East

The study of base-metal massive sulfide and tin–sulfide deposits in Siberia and the Russian Far East has revealed that the indium content in ores exceeding the average statistical value at similar deposits worldwide could be economically important. Sphalerite and chalcopyrite and chalcopyrite, bornite, and sphalerite are the major indium carriers in the base-metal massive sulfide and tin–sulfide ores, respectively. In addition, base-metal massive sulfide ores have high Cd, Ag, and Te contents, whereas tin–sulfide ores have elevated Ge, Ga, and Nb contents. This has stimulated the investment attractiveness of these deposits.     

The development of volcanic hosted massive sulfide and barite–gold orebodies on Wetar Island, Indonesia

Wetar Island is composed of Neogene volcanic rocks and minor oceanic sediments and forms part of the Inner Banda Arc. The island preserves precious metal-rich volcanogenic massive sulfide and barite deposits, which produced approximately 17 metric tonnes of gold. The polymetallic massive sulfides are dominantly pyrite (locally arsenian), with minor chalcopyrite which are cut by late fractures infilled with covellite, chalcocite, tennantite–tetrahedrite, enargite, bornite and Fe-poor sphalerite. Barite orebodies are developed on the flanks and locally overly the massive sulfides. These orebodies comprise friable barite and minor sulfides, cemented by a series of complex arsenates, oxides, hydroxides and sulfate, with gold present as <10 m free grains. Linear and pipe-like structures comprising barite and iron-oxides beneath the barite deposits are interpreted as feeder structures to the barite mineralization. Hydrothermal alteration around the orebodies is zoned and dominated by illite–kaolinite–smectite assemblages; however, local alunite and pyrophyllite are indicative of late acidic, oxidizing hydrothermal fluids proximal to mineralization. Altered footwall volcanic rocks give an illite K–Ar age of 4.7±0.16 Ma and a ⁴⁰Ar/³⁹Ar age of 4.93±0.21 Ma. Fluid inclusion data suggest that hydrothermal fluid temperatures were around 250–270°C, showed no evidence of boiling, with a mean salinity of 3.2 wt% equivalent NaCl. The ³⁴S composition of sulfides ranges between +3.3 and +11.7 and suggests a significant contribution of sulfur from the underlying volcanic edifice. The ³⁴S barite data vary between +22.4 and +31.0, close to Miocene seawater sulfate. Whole rock ⁸⁷Sr/⁸⁶Sr analyses of unaltered volcanic rocks (0.70748–0.71106) reflect contributions from subducted continental material in their source region. The ⁸⁷Sr/⁸⁶Sr barite data (0.7076–0.7088) indicate a dominant Miocene seawater component to the hydrothermal system. The mineral deposits formed on the flanks of a volcanic edifice at depths of ~2 km. Spectacular sulfide mounds showing talus textures are localized onto faults, which provided the main pathways for high-temperature hydrothermal fluids and the development of associated stockworks. The orebodies were covered and preserved by post-mineralization chert, gypsum, Globigerina-bearing limestone, lahars, subaqueous debris flows and pyroclastics rocks.     

Fractionation of platinum, palladium, nickel, and copper in sulfide–arsenide systems at magmatic temperature

Experimentally derived phase relations of arsenide in sulfide melt are presented to quantify the fractionation paths of As-bearing sulfide melts. When a natural sulfide melt reaches arsenide saturation, a separate Ni–PGE-rich arsenide melt exsolves. The arsenic saturation concentration in an Fe–Ni–Cu sulfide melt is between 0.5 and 1.5 wt%. The affinities of the chalcophile metals for an immiscible arsenide melt follow the order Pt > Pd > Ni ? Fe ≈ Cu. In natural systems, arsenide exsolution will be triggered by the activity of the nickel arsenide components dissolved in sulfide melt, Ni being the most common base metal with strong affinity to the As^n? anionic species. Arsenic may have a major effect on the fractionation paths of sulfide melts even if no separate arsenide phase forms. Arsenic, and probably many other chalcogens and metalloids in magmatic melts, may undergo associations with Pt and Pd well before discrete PGE minerals become stable phases.     

Mineralogical,petrological, and geochemical studies of the Limahe mafic–ultramatic intrusion and associated Ni–Cu sulfide ores,SW China

The Limahe Ni–Cu sulfide deposit is hosted by a small mafic–ultramafic intrusion (800 × 200 × 300 m) that is temporally associated with the voluminous Permian flood basalts in SW China. The objective of this study is to better understand the origin of the deposit in the context of regional magmatism which is important for the ongoing mineral exploration in the region. The Limahe intrusion is a multiphase intrusion with an ultramafic unit at the base and a mafic unit at the top. The two rock units have intrusive contacts and exhibit similar mantle-normalized trace element patterns and Sr–Nd isotopic compositions but significantly different cumulus mineralogy and major element compositions. The similarities suggest that they are related to a common parental liquid, whereas the differences point to magma differentiation by olivine crystallization at depth. Sulfide mineralization is restricted to the ultramafic unit. The abundances of sulfides in the ultramafic unit generally increase towards the basal contacts with sedimentary footwall. The δ ³⁴S values of sulfide minerals from the Limahe deposit are elevated, ranging from +2.4 to +5.4‰. These values suggest the involvement of external S with elevated δ ³⁴S values. The mantle-normalized platinum-group element (PGE) patterns of bulk sulfide ores are similar to those of picrites associated with flood basalts in the region. The abundances of PGE in the sulfide ores, however, are significantly lower than that of sulfide liquid expected to segregate from undepleted picrite magma. Cr-spinel and olivine are present in the Limahe ultramafic rocks as well as in the picrites. Mantle-normalized trace element patterns of the Limahe intrusion generally resemble those of the picrites. However, negative Nb–Ta anomalies, common features of contamination with the lower or middle crust, are present in the intrusion but absent in the picrites. Sr–Nd isotopes suggest that the Limahe intrusion experienced higher degrees of contamination with the upper crust than did the picrites. The results of this study permit us to suggest that the parental magma of the Limahe intrusion was derived from picritic magma by olivine fractionation and contamination in a staging chamber at mid-crustal levels. Depletion of PGE in the sulfide ores in the Limahe intrusion is likely due to previous sulfide segregation of the parental magmas in the staging chamber. Sulfide mineralization in the Limahe intrusion is related to second-stage sulfide segregation after the fractionated magmas acquired external S from pyrite-bearing country rocks during magma ascent to the Limahe chamber. The abrupt change in mineralogical and chemical compositions between the ultramafic unit and the overlying unit suggests that at least two separate pulses of magma were involved in the development of the Limahe intrusion. We propose that the Limahe intrusion was once a wider part of a dynamic conduit that fed magma to the overlying subvolcanic dykes/sills or lavas. The ultramafic unit formed by the first, relatively more primitive magma, and the mafic unit formed by the second, relatively more fractionated magma. Immiscible sulfide droplets that segregated from the first magma settled down with olivine crystals to form the sulfide-bearing, olivine-rich rocks in the base of the intrusion. The overlying residual liquids were then pushed out of the chamber by the second magma. Critical factors for the formation of an economic Ni–Cu sulfide deposit in such a small intrusion include the dynamic petrologic processes involved and the availability of external sulfur. The Limahe deposit reminds us that small, multiphase, mafic–ultramafic intrusions in the region should not be overlooked for the potential of economic Ni–Cu sulfide deposits.     

Diamond formation in sulfide pyrrhotite-carbon melts: Experiments at 6.0–7.1 GPa and application to natural conditions

Experiments at 6.0–7.1 GPa and 1500–1700°C were carried out to explore the boundary conditions of diamond nucleation and growth in pyrrhotite-carbon melt-solutions. Pyrrhotite is one of the main sulfide minerals of the pyrrhotite-pentlandite-chalcopyrite assemblage of mantle rocks and primary inclusions in diamond. Solutions of carbon in sulfide melts oversaturated with respect to diamond at the expense of the dissolution of starting graphite (thermodynamically unstable phase) are formed owing to the difference between the solubilities of graphite and diamond, which increases under the influence of temperature gradients in experimental samples. We determined the fields of carbon solutions in pyrrhotite melt showing labile and metastable oversaturation with respect to diamond, which correspond to the spontaneous nucleation of the diamond phase and diamond growth on seeds, respectively. The linear growth rate of diamond in sulfide-carbon melts is rather high (on average, 10 μ/min during the first 1–2 min from the onset of spontaneous crystallization). The nucleation density is estimated as 180 grains per cubic centimeter. Diamonds crystallized from sulfide melts show octahedral and spinel twin shapes. Diamond polycrystals were synthesized for the first time from a sulfide medium as intergrowths of skeletal (edge) or “cryptocrystalline” microdiamonds, from 1 to 100 μm in size, their spinel twins and, occasionally, polysynthetic (star-shaped) twins. During diamond growth from sulfidecarbon melts on smooth faces of cuboctahedral diamond seeds synthesized in metal systems, smooth-faced layer-by-layer step-like growth was observed on their octahedral (111) faces, whereas growth on the (100) cubic faces produced rough-surfaced layers of intergrown micropyramids, whose axes were oriented normal to the (100) face. The obtained experimental results were applied to the problem of diamond genesis under the conditions of the Earth’s mantle in the framework of the model of carbonate-silicate parental melts with blebs of immiscible sulfide melts.     

Hydrosulfide/sulfide complexes of zinc to 250 °C and the thermodynamic properties of sphalerite

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)₄^2?, 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(S_total) = 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)₄^2? 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)₄^2? become less important in high temperature solutions. At 25 °C and m(S_total) = 0.1, these species dominate Zn speciation at pH > 7. At 100 °C and m(S_total) = 0.1, the maximum fraction of Zn(HS)₄^2? is only 20% of the total Zn concentration (i.e. at pH_t ~ 7.5), whereas at 350 °C and 3 <pH_t <10, the fraction of Zn(HS)₄^2? 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 Δ_fG° (β-ZnS_(cr)) = ? 198.6 ± 0.2 kJ/mol at 25 °C was determined via solubility measurements of natural low-iron Santander (Spain) sphalerite.     

Significance of ancient sulfide PGE and Re–Os signatures in the mantle beneath Calatrava,Central Spain

Spinel lherzolite and wehrlite xenoliths from the Cenozoic Calatrava volcanic field carry the geochemical imprint of metasomatic agents that have affected the subcontinental lithospheric mantle beneath Central Iberia. Some xenoliths (mainly wehrlites) were enriched in REE, Sr, P, and CO₂ by silicic-carbonate-rich metasomatic melts/fluids, while others record the effects of subduction-related hydrous silicate fluids that have precipitated amphibole and induced high Ti/Eu in primary clinopyroxene. The petrographic observations and geochemical data suggest that interstitial glass in the xenoliths represent the quenched products of Si-rich melts that infiltrated the mantle peridotite shortly before the entrainment of the xenoliths in the host magmas that erupted ca 2 million years ago. During their infiltration, the metasomatic melts reacted with peridotite, resulting in silica enrichment, while remobilizing grains of iron-rich monosulfide solid solution (Fe-rich Mss) initially enclosed in, or intergranular to, primary olivine and pyroxenes. In situ laser ablation inductively coupled plasma-mass spectrometry analysis of single sulfide grains reveals that the Fe-rich Mss in glass shows platinum-group element (PGE) patterns and ¹⁸⁷Os/¹⁸⁸Os compositions identical to the Fe-rich Mss occurring as inclusions in, or at grain boundaries of primary silicates. Moreover, independent of its microstructural position, Fe-rich Mss exhibits PGE and ¹⁸⁷Os/¹⁸⁸Os signatures typical of Mss either residual after partial melting or crystallized directly from sulfide melts. Our findings reveal that young metasomatic melt(s)/fluid(s) may carry remobilized sulfides with PGE and Os-isotopic signatures identical to those of texturally older sulfides in the peridotite xenolith. These sulfides thus still provide useful information about the timing and nature of older magmatic events in the subcontinental mantle.