Fluid inclusion and stable isotope study of the Cobre–Babilonia polymetallic epithermal vein system, Taxco district, Guerrero, Mexico

The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ¹³C and δ¹⁸O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ³⁴S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.     

Geology, mineralogy and stable isotope geochemistry of the Kabwe carbonate-hosted Pb–Zn deposit, Central Zambia

The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu.Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ³⁴S_CDT permil (‰) values of − 17.75 ± 0.28 (1σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ³⁴S for sphalerite and of − 11.91 ± 0.71‰ δ³⁴S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur.Carbon and oxygen isotope ratios of the host dolomite have mean δ¹³C_PDB and δ¹⁸O_SMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO₂ content introduced during silicification of the host dolomite. The depletion in ¹⁸O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and ¹⁸O-rich hydrothermal solution.Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl.Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.     

Geological features and origin of gold deposits occurring in the Baotou–Bayan Obo district, south-central Inner Mongolia, People's Republic of China

Located at western portion of northern margin of North China craton, the Baotou–Bayan Obo district is one of the most important Fe–REE–Nb and Au metallogenic provinces in China. Presently, about 52 gold deposits and prospects have been discovered, explored and mined, among which Shibaqinhao, Laoyanghao, Houshihua, Saiyinwusu, Wulashan and Donghuofang are the most important ones. All these gold occurrences can be subdivided into three groups (or types) according to its host rocks: (1) hosted by Archean high-grade metamorphic rocks; (2) hosted by Proterozoic sedimentary rocks; (3) hosted by or related to Hercynian alkaline intrusive rocks. The first group contains the Shibaqinhao, Laoyanghao and Houshihua gold deposits. Gold mineralization at these three deposits occurs within Archean amphibolite, gneiss and granulite as gold-bearing quartz veins and veinlet groups containing native gold, electrum, pyrite and chalcopyrite. The Saiyinwusu deposit belongs to the second group, and occurs within Proterozoic sandstone, quartzite and carbonaceous slate as quartz veins and replacement bodies along the fracture zones. Pyrite, marcasite, arsenopyrite, native gold and electrum are identified. The third group includes the Wulashan, Donghuofang and Luchang deposits. Gold mineralization at these three deposits occurs predominantly within the Hercynian alkaline syenite or melagabbro stocks and dyke swarms or along their contacts with Archean metamorphic wall rocks as K-feldspar–quartz veins, dissemination and veinlets. Pyrite, galena, chalcopyrite, native gold and calaverite are major metallic minerals.δ³⁴S value of sulfides (pyrite, galena and pyrrhotite) separates from groups 1 and 2 varies from −4.01‰ to −0.10‰ and −3.01‰ to 2.32‰, respectively. δ³⁴S values of Archean and Proterozoic metamorphic wall rocks for groups 1 and 2 deposits range from −20.2‰ to −17.0‰ and −15.8‰ to −16.2‰, respectively. The values are much lower than their hosted gold deposits. All these pyrite separates from Hercynian alkaline intrusions associated with the gold deposits show positive δ³⁴S values of 1.3‰ to 4.8‰, which is higher than those Precambrian metamorphic wall rocks and their hosted gold deposits. δ³⁴S values of the sulfides (pyrite and galena) from the Donghuofang and Wulashan deposits (group 3) increase systematically from veins (−14.8‰ to −2.4‰) to the Hercynian alkaline igneous wall rocks (2.8‰ to 4.8 ‰). All of these deposits in groups 1, 2 and 3 show relatively radiogenic lead isotopic compositions compared to mantle or lower crust curves. Most lead isotope data of sulfides from the gold ores plot between the Hercynian alkaline intrusions and Precambrian metamorphic wall rocks. Data are interpreted as indicative of a mixing of lead from mantle-derived alkaline magma with lead from Precambrian metamorphic wall rocks.Isotopic age data, geological and geochemical evidence suggest that the ore fluids for the groups 1 and 2 deposits were generated during the emplacement of the Hercynian alkaline syenite and mafic intrusions. The Hercynian alkaline magma may provide heat, volatiles and metals for these groups 1 and 2 deposits. Evolved metamorphic fluids produced by the devolatilization, which circulated the wall rocks, were also progressively involved in the alkaline magmatic hydrothermal system, and may have dominate the ore fluids during late stage of ore-forming processes. Most of these gold deposits hosted by Archean high-grade metamorphic rocks occur at or near the intersections of the NE- and E–W-trending fracture systems. The ore fluid of the group 3 deposits may have resulted from the mixing of Hercynian alkaline magmatic fluids and evolved meteoric waters. The deposits are believed to be products of Hercynian alkaline igneous processes along deep-seated fault zones within Archean terrain.     

Fluid flow, alteration and polysulphide mineralisation associated with a low-angle reverse shear zone in the Lower Palaeozoic of the Anglo-Brabant fold belt, Belgium

In the Lower Palaeozoic rocks of the Brabant Massif (Belgium), a recently discovered polysulphide mineralisation is related to a low-angle reverse shear zone. This shear zone has been attributed to the main early Devonian deformation event. Data from boreholes and outcrops allow a detailed investigation of the alteration pattern and palaeofluid flow along this shear zone. Macroscopic observations of the mineralogy and quantitative changes in the phyllosilicate mineralogy indicate that this shear zone is characterised by an envelope of intense sericitisation and silicification. In addition, chloritisation is associated with this alteration. The alteration zone may reach a thickness of 250 m. Ore mineralisation occurred synkinematically and is spatially related to the shear zone. The mineralisation consists of pyrite, marcasite, arsenopyrite, pyrrhotite, chalcopyrite, sphalerite, galena, stibnite and smaller amounts of tetrahedrite and other sulphosalts. It is concentrated in quartz–sulphide veins or occurs diffusely in the host rock. The mineralising fluids have a low-salinity H₂O–CO₂–CH₄–NaCl–(KCl) composition and a minimum temperature of 250–320 °C. The δ¹⁸O values of quartz vary between +12.3‰ and +14.5‰ SMOW, and δD compositions of the fluid inclusions in the quartz crystals range from −65‰ to −35‰ V-SMOW. The δD and the calculated δ¹⁸O values of the mineralising fluids fall in the range typical for metamorphic fluids and partly overlap with that for primary magmatic fluids. The δ³⁴S values, between +4.7‰ and +10.6‰ CDT, fall outside the interval typical for I-type magmas. Important migration of likely metamorphic fluids, causing a widespread alteration and a polysulphide mineralisation along a low-angle shear zone, has, thus, been identified for the first time in the Caledonian Anglo-Brabant fold belt.     

Emarat carbonate-hosted Zn–Pb deposit, Markazi Province, Iran: A geological, mineralogical and isotopic (S, Pb) study

The Emarat deposit, with a total proved reserve of 10 Mt ore grading 6% Zn and 2.26% Pb, is one of the largest Zn–Pb deposits in the Malayer–Esfahan belt. The mineralization is stratabound and restricted to Early Cretaceous limestones and dolomites. The ore consists mainly of sphalerite and galena with small amounts of pyrite, chalcopyrite, calcite, quartz, and dolomite. Textural evidence shows that the ore has replaced the host rocks and thus is epigenetic.Sulfur isotopes indicate that the sulfur in sphalerite and galena has been derived from Cretaceous seawater through thermochemical sulfate reduction. Sulfur isotope compositions of four apparently coprecipitated sphalerite–galena pairs suggest their precipitation was under equilibrium conditions. The sulfur isotopic fractionation observed for the sphalerite–galena pairs corresponds to formation temperatures between 77 °C and 168 °C, which agree with homogenization temperatures of fluid inclusions.Lead-isotope studies indicate that the lead in galena has been derived from heterogeneous sources including orogenic and crustal reservoirs with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios. Ages derived from the Pb-isotope model give meaningless ages, ranging from Early Carboniferous to future. It is probable that the Pb-isotope model ages that point to an earlier origin than the Early Cretaceous host rocks are derived from older reservoirs in the underlying Carboniferous or Jurassic units, either from the host rocks or from earlier-formed ore deposits within these units.This research and other available data show that the Emarat Zn–Pb deposit has many important features of Mississippi Valley-type (MVT) lead–zinc deposits and thus we argue that it is an MVT-type ore deposit.     

The sources and evolution of mineralising fluids in iron oxide–copper–gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide–apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10⁻³ and δ³⁷Cl values from −3.1‰ to −1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu–Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10⁻³ and δ³⁷Cl values from −5.6‰ to −1.3‰. Finally, the Cu–Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10⁻³ and δ³⁷Cl values that range from −2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰.The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide–apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ³⁷Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ³⁷Cl values would be significantly larger.The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.     

Nature of fluids and regional implications for Lesser Himalayan carbonates and associated mineralization

Fluid inclusion data are presented for the successive stages of limestone, dolomite, magnesite and sulphide-bearing quartz veins in Proterozoic carbonate rocks of the Lesser Himalaya. Subsurface fluids were H₂O–NaCl–KCl ± MgCl₂ ± CaCl₂ and showed successive increase in salinity and temperature. The salinity of the pore fluid during limestone diagenesis was in the range of 7.5–15 eq wt.% NaCl and the magnesite-forming fluids had a salinity of about 9 to 19 eq wt.% NaCl. This progressive rise in salinity is attributed to a more saline fluid in the deeper zones. The inverse relation between homogenization temperatures and final melting temperatures suggests mixing of the fluids during diagenesis, and highly depleted δ¹⁸O values rule out participation of magmatic fluid in the mixing. A late stage carbonic fluid is linked with talc formation. The low temperature of sulphide-forming epigenetic solutions, as obtained from fluid inclusions, is also substantiated by the chemical data from these sulphides. δ³⁴S values in galena infer that magmatic sulphur was probably not involved, and the sulphur of the galena is derived from an isotopically heavy source.     

The Daduhe gold field at the eastern margin of the Tibetan Plateau: He, Ar, S, O, and H isotopic data and their metallogenic implications

The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have ³He/⁴He ratios of 0.16 to 0.86 R_a, whereas their ⁴⁰Ar/³⁶Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ³⁴S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ¹⁸O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.     

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondônia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondônia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Bárbara deposit (Rondônia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sn (±W, ±Ta, ±Nb), and base-metal suite (Zn–Cu–Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0–19 wt.% NaCl eq.) CO₂-bearing aqueous fluids homogenizing at 245–450 °C, and (2) aqueous solutions with low CO₂, low to moderate salinity (0–14 wt.% NaCl eq.), which homogenize between 100 and 340 °C. In the Santa Bárbara deposit, the early inclusions are represented by (1) low-salinity (5–12 wt.% NaCl eq.) aqueous fluids with variable CO₂ contents, homogenizing at 340 to 390 °C, and (2) low-salinity (0–3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320–380 °C. Cassiterite, wolframite, columbite–tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0–6 wt.% NaCl eq.) CO₂-free aqueous solution, which homogenizes at (100–260 °C) and characterizes the sulfide–fluorite–sericite association in the Correas deposit. The late fluid in the Santa Bárbara deposit has lower salinity (0–3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240–450 °C, and 1.0–2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (δ¹⁸O_quartz from 9.9‰ to 10.9‰, δD_H2O from 4.13‰ to 6.95‰) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 °C. In the Santa Bárbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 °C, respectively), and that for the cassiterite-quartz-veins is 415 °C. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (δ¹⁸O_qtz-H2O=5.5–6.1‰) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (δ¹⁸O_mica-H2O=3.3–9.8‰) suggest mixing with meteoric water. Late muscovite veins (δ¹⁸O_qtz-H2O=−6.4‰) and late quartz (δ¹⁸O_mica-H2O=−3.8‰) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor columbite–tantalite precipitation. Change in the redox conditions related to mixing of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit.     

Fluid–rock interaction at the roots of an Eopaleozoic epithermal system, Sierra Norte de Córdoba, Argentina: Paragenesis, thermometry and fluid sources

A deep epithermal vein system hosted in Late Proterozoic to Cambrian granodiorite has been identified in the Sierra Norte de Córdoba, the easternmost range of the Sierras Pampeanas Orientales of Argentina. The vein swarm extends over an area of 3 km² parallel to a mylonitic belt and formed in fractured granodiorite. Thicknesses of veins are less than 0.5 m and their visible strike length is less than 100 m. Veins are either barren or weakly mineralized in base-metal sulfides. Most veins have mineral associations dominated by calcite and quartz with lesser amounts of chlorite, sericite, pyrite, and minor illite. In other less exposed albite-rich, adularia-bearing veins, chalcopyrite, bornite, galena, sphalerite, chalcocite and covellite may occur. The widespread occurrence of bladed calcite without any petrographic or microthermometric evidence of boiling implies that this particular habit of calcite may also develop under sub-near boiling fluid conditions. Thermometric calculations based on fluid inclusion data, chlorite composition and oxygen isotopes in the quartz–calcite pair, constrain the formation of the system between 300 and 350 °C, at pressures between 42 and 64 MPa (1.5–2.3 km). Stable isotope data suggest that W/R interaction might have been the most probable mechanism of alteration, involving the participation of meteoric fluids; nevertheless, the metallic signature of some weakly mineralized veins as well as intermediate fluid inclusion salinities favor a magmatic input and a mixed origin for the fluids. Textures and mineral associations, as well as the absence of evidence of boiling in fluid inclusions, all suggest that the silica–carbonate vein system formed deeper than typically shallow Au and Ag-bearing boiling solutions. A 485 (±25) Ma lamprophyre dike crosscuts some of these veins locally producing metasomatic reactions and skarn formation, which constrains the age of the hydrothermal system to the Cambrian-Early Ordovician time span.     

Geology and geochemistry of the adjacent Changkeng gold and Fuwang silver deposits, Guangdong Province, South China

The Changkeng Au and Fuwang Ag deposits represent an economically significant and distinct member of the Au–Ag deposit association in China. The two deposits are immediately adjacent, but the Au and Ag orebodies separated from each other. Ores in the Au deposit, located at the upper stratigraphic section and in the southern parts of the orefield, contain low Ag contents (< 11 ppm); the Ag orebodies, in the lower stratigraphic section, are Au-poor (< 0.2 ppm). Changkeng is hosted in brecciated cherts and jasperoidal quartz and is characterized by disseminated ore minerals. Fuwang, hosted in the Lower Carboniferous Zimenqiao group bioclastic limestone, has vein and veinlet mineralization associated with alteration comprised of quartz, carbonate, sericite, and sulfides. Homogenization temperatures of fluid inclusions from quartz veinlets in the Changkeng and Fuwang deposits are in the range of 210 ± 80 °C and 230 ± 50 °C, respectively. Salinities of fluid inclusions from the two deposits range from 1.6 to 7.3 wt.% and 1.6 to 2.6 wt.% equiv. NaCl, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions from the Changkeng deposit range from − 80‰ to − 30‰, − 7.8‰ to − 3.0‰, − 16.6‰ to − 17.0‰ and 0.0100 to 0.0054 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of fluid inclusions from the Fuwang deposit range from − 59‰ to − 45‰, − 0.9‰ to 4.1‰, − 6.7‰ to − 0.6‰ and 0.5930 to 0.8357 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions suggest the ore fluids of the Changkeng Au-ore come from the meteoric water and the ore fluids of the Fuwang Ag-ore are derived from mixing of magmatic water and meteoric water. The two deposits also show different Pb-isotopic signatures. The Changkeng deposit has Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb: 18.580 to 19.251, ²⁰⁷Pb/²⁰⁴Pb: 15.672 to 15.801, ²⁰⁸Pb/²⁰⁴Pb: 38.700 to 39.104) similar to those (²⁰⁶Pb/²⁰⁴Pb: 18.578 to 19.433, ²⁰⁷Pb/²⁰⁴Pb: 15.640 to 15.775, ²⁰⁸Pb/²⁰⁴Pb: 38.925 to 39.920) of its host rocks and different from those (²⁰⁶Pb/²⁰⁴Pb: 18.820 to 18.891, ²⁰⁷Pb/²⁰⁴Pb: 15.848 to 15.914, ²⁰⁸Pb/²⁰⁴Pb: 39.579 to 39.786) of the Fuwang deposit. The different signatures indicate different sources of ore-forming material. Rb–Sr isochron age (68 ± 6 Ma) and ⁴⁰Ar–³⁹Ar age (64.3 ± 0.1 Ma) of the ore-related quartz veins from the Ag deposit indicate that the Fuwang deposit formed during the Cenozoic Himalayan tectonomagmatic event. Crosscutting relationships suggests that Au-ore predates Ag-ore. The adjacent Changkeng and Fuwang deposits could, however, represent a single evolved hydrothermal system. The ore fluids initially deposited Au in the brecciated siliceous rocks, and then mixing with the magmatic water resulted in Ag deposition within fracture zones in the limestone. The deposits are alternatively the product of the superposition of two different geological events. Age evidence for the Fuwang deposit, together with the Xiqiaoshan Tertiary volcanic-hosted Ag deposit in the same area, indicates that the Pacific Coastal Volcanic Belt in the South China Fold Belt has greater potential for Himalayan precious metal mineralization than previous realized.     

Hydrothermal evolution of the Sar-Cheshmeh porphyry Cu–Mo deposit, Iran: Evidence from fluid inclusions

The Sar-Cheshmeh porphyry Cu–Mo deposit is located in Southwestern Iran (65 km southwest of Kerman City) and is associated with a composite Miocene stock, ranging in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies demonstrate that the emplacement of the Sar-Cheshmeh stock took place in several pulses, each with associated hydrothermal activity. Molybdenum was concentrated at a very early stage in the evolution of the hydrothermal system and copper was concentrated later. Four main vein Groups have been identified: (I) quartz+molybdenite+anhydrite±K-feldspar with minor pyrite, chalcopyrite and bornite; (II) quartz+chalcopyrite+pyrite±molybdenite±calcite; (III) quartz+pyrite+calcite±chalcopyrite±anhydrite (gypsum)±molybdenite; (IV) quartz±calcite±gypsum±pyrite±dolomite. Early hydrothermal alteration produced a potassic assemblage (orthoclase-biotite) in the central part of the stock, propylitic alteration occurred in the peripheral parts of the stock, contemporaneously with potassic alteration, and phyllic alteration occurred later, overprinting earlier alteration. The early hydrothermal fluids are represented by high temperature (350–520 °C), high salinity (up to 61 wt% NaCl equivalent) liquid-rich fluid inclusions, and high temperature (340–570 °C), low-salinity, vapor-rich inclusions. These fluids are interpreted to represent an orthomagmatic fluid, which cooled episodically; the brines are interpreted to have caused potassic alteration and deposition of Group I and II quartz veins containing molybdenite and chalcopyrite. Propylitic alteration is attributed to a liquid-rich, lower temperature (220–310 °C), Ca-rich, evolved meteoric fluid. Influx of meteoric water into the central part of the system and mixing with magmatic fluid produced albitization at depth and shallow phyllic alteration. This influx also caused the dissolution of early-formed copper sulphides and the remobilization of Cu into the sericitic zone, the main zone of the copper deposition in Sar-Cheshmeh, where it was redeposited in response to a decrease in temperature.     

A three stage fluid flow model for Variscan gold metallogenesis in northern Portugal

Mineralogical, fluid inclusion and geochemical studies were made on two intra-granitic gold deposits (Grovelas and Penedono), together with a deposit linked to sub-vertical structures in silicified metasediments at Três-Minas, and several intra-metamorphic occurrences at Vila Pouca de Aguiar. They all possess similar mineral assemblages, deformational state, fluid flow characteristics, ore fluid composition and have comparable P–T conditions. Three successive crystallisation stages are recorded during the formation of gold-bearing structures independent of their location or host rocks (granites or metasediments). They are:Stage 1 — the development of milky quartz veins that formed primarily after the emplacement of peraluminous two-mica granites (315–310 Ma) at P–T conditions reflecting high temperature and low pressure. They are similar to those from pluton induced metamorphism (P=300–350 MPa and T=500–550°C). No clear evidence was found for gold deposition during this stage.Stage 2 — during orogenic uplift and repeated tectonic reactivation a clear quartz was deposited in the early milky quartz veins (Stage 1) at P–T conditions between 100 and 300 MPa and 300 and 450°C. Local sulphide deposition (arsenopyrite II and pyrite II) occurred in clear quartz, but was never massive. The fluids percolating within the granite were mainly aqueous-carbonic and reflect equilibrium with the metamorphic host rocks. They are very similar to those found in metamorphic environments. No evidence for the involvement of magmatic fluids was found.Stage 3 — intense microfissuring of the earlier vein infillings occurred, associated with the main episode of gold deposition. The P–T conditions were <100 MPa and <300°C based on aqueous fluid inclusions. Native gold and electrum crystallised together with sulphides (galena, chalcopyrite and bismuthinite), native Bi and sulphosalts (Pb–Bi–Ag dominated). The fractures frequently contain chlorite (± sericite) especially where they crosscut earlier sulphides (arsenopyrite).These processes and fluid types are similar in both the granites and metamorphic host rocks. Therefore, the gold ores appear to be the result of successive periods of fluid circulation, in this case related to the uplift of the Variscan basement in response to high heat flow and the intrusion of granites. Without exception, these fluids have been re-equilibrated with the metamorphic rocks. However magmatic fluids are absent; the granites thus act passively as heat engines for fluid circulation.     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.     

Experimental constraints on Pt, Pd and Au partitioning and fractionation in silicate melt–sulfide–oxide–aqueous fluid systems at 800 °C, 150 MPa and variable sulfur fugacity

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.     

Role of fluid mixing and wallrock sulfidation in gold mineralization at the Semna mine area, central Eastern Desert of Egypt: Evidence from hydrothermal alteration, fluid inclusions and stable isotope data

The Semna gold deposit is one of several vein-type gold occurrences in the central Eastern Desert of Egypt, where gold-bearing quartz veins are confined to shear zones close to the boundaries of small granitoid stocks. The Semna gold deposit is related to a series of sub-parallel quartz veins along steeply dipping WNW-trending shear zones, which cut through tectonized metagabbro and granodiorite rocks. The orebodies exhibit a complex structure of massive and brecciated quartz consistent with a change of the paleostress field from tensional to simple shear regimes along the pre-existing fault segments. Textural, structural and mineralogical evidence, including open space structures, quartz stockwork and alteration assemblages, constrain on vein development during an active fault system. The ore mineral assemblage includes pyrite, chalcopyrite, subordinate arsenopyrite, galena, sphalerite and gold. Hydrothermal chlorite, carbonate, pyrite, chalcopyrite and kaolinite are dominant in the altered metaggabro; whereas, quartz, sericite, pyrite, kaolinite and alunite characterize the granodiorite rocks in the alteration zones. Mixtures of alunite, vuggy silica and disseminated sulfides occupy the interstitial open spaces, common at fracture intersections. Partial recrystallization has rendered the brecciation and open space textures suggesting that the auriferous quartz veins were formed at moderately shallow depths in the transition zone between mesothermal and epithermal veins.Petrographic and microthermometric studies aided recognition of CO₂-rich, H₂O-rich and mixed H₂O–CO₂ fluid inclusions in the gold-bearing quartz veins. The H₂O–CO₂ inclusions are dominant over the other two types and are characterized by variable vapor: liquid ratios. These inclusions are interpreted as products of partial mixing of two immiscible carbonic and aqueous fluids. The generally light δ³⁴S of pyrite and chalcopyrite may suggest a magmatic source of sulfur. Spread in the final homogenization temperatures and bulk inclusion densities are likely due to trapping under pressure fluctuation through repeated fracture opening and sealing. Conditions of gold deposition are estimated on basis of the fluid inclusions and sulfur isotope data as 226–267 °C and 350–1100 bar, under conditions transitional between mesothermal and epithermal systems.The Semna gold deposit can be attributed to interplay of protracted volcanic activity (Dokhan Volcanics?), fluid mixing, wallrock sulfidation and a structural setting favoring gold deposition. Gold was transported as Au-bisulfide complexes under weak acid conditions concomitant with quartz–sericite–pyrite alteration, and precipitated through a decrease in gold solubility due to fluid cooling, mixing with meteoric waters and variations in pH and fO₂.     

Fluid geochemistry in the Ivigtut cryolite deposit, South Greenland

The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na₃AlF₆] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO₂, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO₂ and H₂O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ¹³C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ¹⁸O of CO₂ (+ 21 to + 42‰ VSMOW) and δ¹⁸O of H₂O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H₂O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.     

Sulfur isotopic compositions of the Huize super-large Pb–Zn deposit, Yunnan Province, China: Implications for the source of sulfur in the ore-forming fluids

The Huize Pb–Zn deposit of Yunnan Province, China, is located in the center of the Sichuan–Yunnan–Guizhou Pb–Zn–Ag district. Four primary orebodies (orebody No. 1, No. 6, No. 8 and No. 10), with Pb + Zn reserves from 0.5 Mt to 1 Mt, have been found at depth in this deposit. This paper provides new data on the sulfur isotopic compositions of the four orebodies. The data show that the principal sulfide minerals (galena, sphalerite and pyrite) in the four orebodies are enriched in heavy sulfur, the δ³⁴S values between 10.9‰ and 17.7‰ and where δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena. The δ³⁴S values of sulfide are close to that of the sulfates from the carbonate strata within the region. The similarity in sulfur isotope composition between sulfides and sulfates indicates the sulfur in the ore-forming fluids was likely derived by thermochemical sulfate reduction of sulfates contained within carbonate units.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

Geochemistry and evolution of ore-forming fluids of the Yueshan Cu–Au skarn- and vein-type deposits, Anhui Province, South China

The Yueshan mineral belt is geotectonically located at the centre of the Changjiang deep fracture zone or depression of the lower Yangtze platform. Two main types of ore deposits occur in the Yueshan orefield: Cu–Au–(Fe) skarn deposits and Cu–Mo–Au–(Pb–Zn) hydrothermal vein-type deposits. Almost all deposits of economic interest are concentrated within and around the eastern and northern branches of the Yueshan dioritic intrusion. In the vicinity of the Zongpu and Wuhen intrusions, there are many Cu–Pb–Zn–Au–(S) vein-type and a few Cu–Fe–(Au) skarn-type occurrences.Fluid inclusion studies show that the ore-forming fluids are characterised by a Cl⁻(S)–Na⁺–K⁺ chemical association. Hydrothermal activity associated with the above two deposit types was related to the Yueshan intrusion. The fluid salinity was high during the mineralisation processes and the fluid also underwent boiling and mixed with meteoric water. In comparison, the hydrothermal activity related to the Zongpu and Wuhen intrusions was characterised by low salinity fluids. Chlorine and sulphur species played an important role in the transport of ore-forming components.Hydrogen- and oxygen-isotope data also suggest that the ore-forming fluids in the Yueshan mineral belt consisted of magmatic water, mixed in various proportions with meteoric water. The enrichment of ore-forming components in the magmatic waters resulted from fluid–melt partitioning. The ore fluids of magmatic origin formed large Cu–Au deposits, whereas ore fluids of mixed magmatic-meteoric origin formed small- to medium-sized deposits.The sulphur isotopic composition of the skarn- and vein-type deposits varies from − 11.3‰ to + 19.2‰ and from + 4.2‰ to + 10.0‰, respectively. These variations do not appear to have been resulted from changes of physicochemical conditions, rather due to compositional variation of sulphur at the source(s) and by water–rock interaction. Complex water–rock interaction between the ore-bearing magmatic fluids and sedimentary wall rocks was responsible for sulphur mixing. Lead and silicon isotopic compositions of the two deposit types and host rocks provide similar indications for the sources and evolution of the ore-forming fluids.Hydrodynamic calculations show that magmatic ore-forming fluids were channelled upwards into faults, fractures and porous media with velocities of 1.4 m/s, 9.8 × 10^− 1 to 9.8 × 10^− 7 m/s and 3.6 × 10^− 7 to 4.6 × 10^− 7 m/s, respectively. A decrease of fluid migration velocity in porous media or tiny fractures in the contact zones between the intrusive rocks and the Triassic sedimentary rocks led to the deposition of the ore-forming components. The major species responsible for Cu transport are deduced to have been CuCl, CuCl₂⁻, CuCl₃²⁻ and CuClOH, whereas Au was transported as Au₂(HS)₂S²⁻, Au(HS)₂⁻, AuHS and AuH₃SiO₄ complexes. Cooling and a decrease in chloride ion concentration caused by fluid boiling and mixing were the principal causes of Cu deposition. Gold deposition was related to decrease of pH, total sulphur concentration and fO₂, which resulted from fluid boiling and mixing.Geological and geochemical characteristics of the two deposit types in the Yueshan mineral belt suggest that there is a close genetic relationship with the dioritic magmatism. Geochronological data show that the magmatic activity and the mineralisation took place between 130 and 136 Ma and represent a continuous process during the Yanshanian time. The cooling of the intrusions and the mineralisation event might have lasted about 6 Ma. The cooling rate of the magmatic intrusions was 80 to 120 °C my^− 1, which permitted sufficient heat supply by magma to the ore-forming system.