Hydrothermal Fluid Sources of the Fengjia Barite–fluorite Deposit in Southeast Sichuan,China: Evidence from Fluid Inclusions and Hydrogen and Oxygen Isotopes

The Fengjia barite–fluorite deposit in southeast Sichuan is a stratabound ore deposit which occurs mainly in Lower Ordovician carbonate rocks. Here we present results from fluid inclusion and oxygen and hydrogen isotope studies to determine the nature and origin of the hydrothermal fluids that generated the deposit. The temperature of the ore‐forming fluid shows a range of 86 to 302 °C. Our detailed microthermometric data show that the temperature during mineralization of the fluorite and barite in the early ore‐forming stage was higher than that during the formation of the calcite in the late ore‐forming stage. The salinity varied substantially from 0.18% to 21.19% NaCl eqv., whereas the density was around 1.00 g/cm³. The fluid composition was mainly H₂O (>91.33%), followed by CO₂, CH₄ and traces of C₂H₆, CO, Ar, and H₂S. The dominant cation was Na⁺ and the dominant anion Cl^‐, followed by Ca²⁺, SO₄^2‐, K⁺, and Mg²⁺, indicating a mid–low‐temperature, mid‐low‐salinity, low‐density NaCl–H₂O system. Our results demonstrate that the temperature decreased during the ore‐forming process and the fluid system changed from a closed reducing environment to an open oxidizing environment. The hydrogen and oxygen isotope data demonstrate that the hydrothermal fluids in the study area had multiple sources, primarily formation water, as well as meteoric water and metamorphic water. Combined with the geological setting and mineralization features we infer that the stratabound barite–fluorite deposits originated from mid–low‐temperature hydrothermal fluids and formed vein filling in the fault zone.     

The origin of the fumaroles of La Solfatara (Campi Flegrei, South Italy)

The analysis of gaseous compositions from Solfatara (Campi Flegrei, South Italy) fumaroles since the early 1980s, clearly reveals a double thermobarometric signature. A first signature at temperatures of about 360 °C was inferred by methane-based chemical-isotopic geoindicators and by the H₂/Ar geothermometer. These high temperatures, close to the critical point of water, are representative of a deep zone where magmatic gases flash the hydrothermal liquid, forming a gas plume. A second signature was found to be at around 200-240 °C. At these temperatures, the kinetically fast reactive species (H₂ and CO) re-equilibrate in a pure vapor phase during the rise of the plume. A combination of these observations with an original interpretation of the oxygen isotopic composition of the two dominant species, i.e. H₂O and CO₂, shed light on the origin of fumarolic fluids by showing that effluents are mixture between fluids degassed from a magma body and the vapor generated at about 360 °C by the vaporization of hydrothermal liquids. A typical ‘andesitic’ water type (δD ∼ −20‰, δ¹⁸O ∼10‰) and a CO₂-rich composition (X_CO2∼0.4) has been inferred for the magmatic fluids, while for the hydrothermal component a meteoric origin and a CO₂ fugacity fixed by fluid-rock reaction at high temperatures have been estimated. In the time the fraction of magmatic fluids in the fumaroles increased (up to ∼0.5) at each seismic and ground uplift crisis (bradyseism) which occurred at Campi Flegrei, suggesting that bradyseismic crises are triggered by periodic injections of CO₂-rich magmatic fluids at the bottom of the hydrothermal system.     

Chemical,isotopic and mineralogical characteristics of volcanogenic epithermal fluorite deposits on the Permo-Mesozoic foreland of the Andean volcanic arc in Patagonia (Argentina)

Epithermal deposits mined for fluorite in Patagonia, Argentina, are closely related to late Triassic through Jurassic magmatic activity which brought about felsic to intermediate magmatic rocks. The fluorite mineralization in the Patagonian epithermal system resulted from gaseous F-and CO₂-enriched magmas which lead to an explosive phreatomagmatic volcanism, when getting in contact with groundwater near the surface. As a result of these hydrothermal processes, rapid cooling took place in the epithermal mineralization. Changes in the viscosity along with the cooling down of mineralizing fluids caused mottled mineral colors blurring the boundaries between the stages and ore textures.The fluids accountable for the main constituents fluorite, quartz, barite and silica were operative over a vertical extension of roughly 600 m. Their temperature of formation dropped from 379 °C through 64 °C, while the pH decreased from the heat center towards the paleosurface under oxidizing conditions. This steep temperature gradient conducive to the telescoping of mineral associations into each other was accompanied by a rapid loss in CO₂, and a mixing of meteoric and magmatic fluids. Even the boundary between the hypogene and supergene alteration cannot be drawn precisely within the assemblage of Mn oxides, which bridge the gap between hypogene and supergen mineralization. The physical-chemical parameters of the fluids, particularly, the redox conditions did not allow sulfides to be preserved. A classification of the epithermal system as to its degree of sulfidation is based on K-feldspar and kaolinite which are present in significant amounts, whereas APS (aluminum-phosphate-sulfate) minerals are absent. Therefore a categorization as an epithermal fluorite deposit of low- to intermediate sulfidation is justified, because the only mineral of economic interest in the system is fluorite.The data obtained during this joint study render the Patagonian fluorite district a reference type of fluorite in an epithermal system of low- to intermediate sulfidation which are widespread in Argentina, e.g., Sierras Pampeanas, and evolved on part of the stable craton, called Gondwana and which grade into epithermal Au, Ag, In, Pb and Zn deposits.     

Fluid inclusion studies of gold-bearing quartz veins from the Yirisen deposit,Sula Mountains greenstone belt,Masumbiri, Sierra Leone

The auriferous veins at Yirisen, Masumbiri, Sierra Leone, occurring mainly in the form of sericitic quartz-sulphide lodes and stringers, are hosted in metamorphosed volcano-sedimentary assemblages invaded by at least two generations of granitic intrusions. Detailed microthermometric studies of fluid inclusions from the veins coupled with laser Raman spectroscopic analysis show that the inclusions contain aqueous fluids of variable salinity (5 to 60 wt.% NaCl equivalent) and dense carbonic fluids (pure CO₂: 1.08>d>0.88 g/cm³). Optical observations and analysis on opened inclusions by scanning electron microscopy (SEM) reveal that some of the aqueous inclusions contain a number of daughter minerals: halite, sylvite, Ca-, Fe-, Mg- and possibly Li-bearing chlorides, and anhydrite; nahcolite occurs also in some of the CO₂ inclusions. The SEM runs also detected a small amount of electrum, suggesting that silver might be a bi-product of the mineralisation. The aqueous and carbonic fluids remained immiscible throughout the formation and evolution of the hydrothermal veins. A few mixed (H₂O+CO₂) inclusions apparently resulted from accidental trapping of both fluids in the same cavity. The wide range of salinities observed in the aqueous inclusions is attributed to the mixing of relatively hot, low-salinity aqueous fluids and colder, high-salinity brines. The CO₂-rich and low-salinity H₂O inclusions are considered to be derived from the metamorphic decarbonation/dehydration of the greenstone pile whilst the high-salinity brines are believed to be basinal in origin. Pressure–temperature (P–T) conditions of entrapment, inferred from the intersection of representative isochores of the immiscible fluids, indicate that the formation of the veins started at T=400°C and P about 4 kbar, in the presence of the high-density CO₂ and low-salinity H₂O fluids. At about 200°C, pressure fluctuations (incremental opening of the vein) correspond to the trapping of the lower-density CO₂ inclusions and high-salinity brines. It is proposed that the decarbonation/dehydration processes (possibly aided by later magmatic processes) expelled and mobilised the gold from the greenstone pile and concentrated it in the CO₂-bearing hydrothermal fluid in the form of Au–chloride complexes. High thermal gradients are believed to have caused the upward migration of this fluid from the bottom of the greenstone pile through structurally controlled conduits. We contend that phase separation of the H₂O–CO₂ metamorphic fluid, aided possibly by some wall–rock alteration, most probably triggered a decrease in ligand activity and thus, precipitation of the gold into lodes. Percolation of the basinal brines is thought to have remobilised some of the gold together with some silver.     

Fluid Inclusions,C–H–O–S Isotope and Geochronology of the Bujinhei Pb–Zn Deposit in the Southern Great Xing'an Range of Northeast China: Implication for Ore Genesis

The Bujinhei Pb–Zn deposit is located in the southern Great Xing'an Range metallogenic belt. It is a representative medium‐ to high‐temperature hydrothermal vein type deposit controlled by fractures, and orebodies hosted in the Permian Shoushangou Formation. The hydrothermal mineralization is classified into three stages: pyrite ± arsenopyrite–quartz (Stage 1), polymetallic sulfide–quartz (Stage 2), and polymetallic sulfide–calcite (Stage 3). Fluid inclusion petrography, laser Raman analyses and microthermometry indicate that the liquid‐rich aqueous inclusions (L) and vapor‐rich CO₂ ± CH₄–H₂O inclusions (C) occur in the Stage 1 and as medium‐ to high‐ temperature and low‐ to medium‐salinity NaCl–H₂O–CO₂–CH₄ hydrothermal fluids. The liquid‐rich (L) and rare vapor‐rich CO₂ ± CH₄–H₂O inclusions (C) occur in the Stage 2 with medium‐temperature and low‐salinity NaCl–H₂O ± CO₂ ± CH₄ hydrothermal fluids. The exclusively liquid‐rich (L) fluid inclusions are observed in the Stage 3, and the hydrothermal fluid belongs to medium‐temperature and low‐salinity NaCl–H₂O hydrothermal fluids. The results of hydrogen and oxygen isotope analyses indicate that ore‐forming fluids were initially derived from the magmatic water and mixed with local meteoric water in the late stage (δ¹⁸O_H2O‐SMOW = 6.0 to 2.2‰, δD_SMOW = ?103 to ?134‰). The carbon isotope compositions (?18.4‰ to ?26.5‰) indicate that the carbon in the fluid was derived from the surrounding strata. The sulfur isotope compositions (5.7 to 15.2‰) indicate that the ore sulfur was also primarily derived from the strata. The ore vein No. 1 occurs in fractures and approximately parallel to the rhyolite porphyry; orebodies have a close spatial and temporal relationship with the rhyolite porphyry. The rhyolite porphyry yielded a crystallization age of 122.9  ± 2.4 Ma, indicating that the Bujinhei deposit may be related to the Early Cretaceous magmatic event. Geochemical analyses reveal that the Bujinhei rhyolite porphyry is high in K₂O and peraluminous, and derived from an acidic liquid as a result of strong interaction with hydrothermal fluid during the late magmatic stage; it is similar to A2‐type granites, and formed in a backarc extensional environment. These results indicate that the Bujinhei Pb–Zn deposit was a vein type system that formed in Early Cretaceous and influenced by the Paleo‐Pacific tectonic system. Bujinhei deposit is a representative hydrothermal vein type deposit on the genetic types, and occurs on the western slope of the southern Great Xing'an Range. The ore‐forming fluids were medium‐ to high‐temperature and low‐to medium‐salinity NaCl–H₂O–CO₂–CH₄ hydrothermal fluids, which became medium‐temperature and low‐salinity NaCl–H₂O hydrothermal fluids in later stages, and came from magmatic water and mixed with meteoric water, whereas the ore‐forming materials were mainly derived from the surrounding strata. The LA–ICP–MS zircon U–Pb dating indicates that the Bujinhei deposit formed at the period of late Early Cretaceous, potentially in a backarc extensional environment influenced by the Paleo‐Pacific tectonic system.     

Fluid inclusion study of Xihuashan tungsten deposit in the southern Jiangxi province,China

The Xihuashan tungsten deposit is closely related to a small highly evolved granitic intrusion. The fluid phases associated with the wolframite-bearing quartz veins have been investigated using microthermometry and the Raman microprobe; they are highly variable in density and composition. The earlier fluids are low-density and low-salinity CO₂-bearing aqueous solutions circulating at temperatures up to 420 °C, and low-salinity (2–3 equiv. wt% NaCl) aqueous solutions without traces of CO₂ circulating at high temperatures 280°–400 °C) involved in a specific hydrothermal fracturing event; limited unmixing occurs at 380 °C and 200–100 bar in response to a sudden pressure drop. The second types of fluids related to deposition of idiomorphic drusy quartz are typical CO₂-bearing aqueous solutions with low salinity (2.5 equiv. wt% NaCl) homogenizing at low to moderate temperatures (180°–340 °C). The late fluids characterize the sulfide deposition stage; they are aqueous fluids with variable salinities homogenizing in the liquid phase between 100° and 275 °C. The Xihuashan hydrothermal evolution resulted from a discontinuous sequence of specific events occurring between 420° and 150 °C and during a continuous hydrothermal evolution of the system during cooling. The role played by the CO₂-rich fluids in the transport and deposition of tungsten in the hydrothermal environment is discussed.     

Fluid inclusion microthermometry and the P-T evolution of gold-bearing hydrothermal fluids in the Niuxinshan gold deposit, eastern Hebei province, NE China

Niuxinshan is a typical example of the numerous mesothermal gold deposits formed during Mesozoic tectono-magmatic reactivation of the Archean North China Craton in eastern Hebei province. Gold occurs in quartz-sulfide lodes in Archean amphibolites and also in greisen zones in the Mesozoic Niuxinshan granite stock. Four mineralization stages can be recognized from early to late: (1) quartz-K-feldspar, (2) quartz-pyrite, (3) quartz-polysulfide, and (4) quartz-carbonate. Gold mineralization mainly occurs in stages 2 and 3. Fluid inclusions in quartz and fluorite from greisen zones in the Niuxinshan granite, and inclusions in vein quartz and sphalerite from stages 1 to 3 in the amphibolites, have been studied by microthermometry. Three compositional types of inclusions are recognized: type 1 (Tp1) are H₂O-CO₂-bearing inclusions and include primary (Tp1-P) and secondary (Tp1-S) inclusions. These are found in quartz and fluorite from the greisen zones as well as in vein quartz and sphalerite from stages 1 to 3. The Tp1-P inclusions are considered to represent the gold-bearing hydrothermal fluids. Type 2 (Tp2-S) are secondary H₂O-CO₂ + solid phase inclusions in fluorite from the greisen zones. Type 3 (Tp3-S) are secondary aqueous inclusions with a solid phase which coexist with the Tp2-S in fluorite from the greisen zones. The Tp1-P inclusions show variable V_CO2 (commonly 0.3 to 0.6) and X_CO2 values (mainly 0.1 to 0.4). The salinities of inclusions cluster around 3 to 11 wt.% NaCl equivalent and their homogenization temperatures to the liquid phase (Th(L)) fall dominantly in the range of 260 to 360 °C. The compositional variations of inclusions in stage 1 probably result from exsolution of magmatic fluids at various stages; immiscibility or boiling of the fluids can be ruled out. The compositional variations of inclusions in the greisen zones and in vein stages 2 and 3 are attributed to cooling, mixing (dilution), and necking-down of the fluids. The Tp1-S and Tp2-S inclusions show salinities of 3 to 6 wt.% NaCl equivalent and X_CO2 values of 0.04 to 0.17. Th(L) clusters at 240 to 260 °C. The Tp3-S inclusions have salinities of 3 to 6 wt.% NaCl equivalent and Th(L) of 170 to 240 °C. Isochoric reconstructions, combined with oxygen and sulfur isotope geothermometry of mineral pairs, give trapping P-T conditions for the gold-bearing fluids. The greisen zones formed at 310 to 460 °C and 1.3 to 3.7 kbar; stage 1 veins at 300 to 430 °C and 1.2 to 3.7 kbar; stage 2 veins at 290 to 380 °C and 1 to 3 kbar; stage 3 veins at 250 to 350 °C and 1 to 3 kbar. H₂O-CO₂ fluids with low to moderate salinities and moderate to high densities (0.66 to 1.01 g/cm³) dominated at early mineralization stages, and evolved towards H₂O-richer and CO₂- and less saline fluids through time. The retrograde P-T evolution probably resulted from regional uplift and cooling of gold-bearing hydrothermal fluids. The gold bisulfide complex was dominant in the fluids during mineralization and gold deposition was mainly induced by decreases of temperature and pressure, as well as destabilization of the bisulfide complex during sulfidization of wall rocks. Received: 16 March 1998 / Accepted: 11 January 1999     

Fluid Inclusions and Metallization of the Kendekeke Polymetallic Deposit in Qinghai Province,China

The Kendekeke polymetallic deposit, located in the middle part of the magmatic arc belt of Qimantag on the southwestern margin of the Qaidam Basin, is a polygenetic compound deposit in the Qimantag metallogenic belt of Qinghai Province. Multi-periodic ore-forming processes occurred in this deposit, including early-stage iron mineralization and lead-zinc-gold-polymetallic mineralization which was controlled by later hydrothermal process. The characteristics of the ore-forming fluids and mineralization were discussed by using the fluid inclusion petrography, Laser Raman Spectrum and micro-thermometry methods. Three stages, namely, S1-stage(copper-iron-sulfide stage), S2-stage(lead-zinc-sulfide stage) and C-stage(carbonate stage) were included in the hydrothermal process as indicated by the results of this study. The fluid inclusions are in three types: aqueous inclusion(type I), CO2-aqueous inclusion(type II) and pure CO2 inclusion(type III). Type I inclusions were observed in the S1-stage, having homogenization temperature at 240–320oC, and salinities ranging from 19.8% to 25.0%(wt % NaCl equiv.). All three types of inclusions, existing as immiscible inclusion assemblages, were presented in the S2-stage, with the lowest homogenization temperature ranging from 175 oC to 295oC, which represents the metallogenic temperature of the S2-stage. The salinities of these inclusions are in the range of 1.5% to 16%. The fluid inclusions in the C-stage belong to types I, II and III, having homogenization temperatures at 120–210oC, and salinities ranging from 0.9% to 14.5%. These observations indicate that the ore-forming fluids evolved from high-temperature to lowtemperature, from high-salinity to low-salinity, from homogenization to immiscible separation. Results of Laser Raman Spectroscopy show that high density of CO2 and CH4 were found as gas compositions in the inclusions. CO2, worked as the pH buffer of ore-forming fluids, together with reduction of organic gases(i.e. CH4, etc), affected the transport and sediment of the minerals. The fluid system alternated between open and close systems, namely, between lithostatic pressure and hydrostatic pressure systems. The calculated metallogenic pressures are in the range of 30 to 87 Mpa corresponding to 3 km mineralization depth. Under the influence of tectonic movements, immiscible separation occurred in the original ore-forming fluids, which were derived from the previous highsalinity, high-temperature magmatic fluids. The separation of CO2 changed the physicochemical properties and composition of the original fluids, and then diluted by mixing with extraneous fluids such as meteoric water and groundwater, and metallogenic materials in the fluids such as lead, zinc and gold were precipitated.     

Origin and age of rift related fluorite and manganese deposits from the San Rafael Massif,Argentina

The San Rafael Massif is characterized by widespread fluorite and manganese epithermal ore deposits whose origin has been under debate to the present. Isotopic (Sm/Nd and K/Ar) and geochemical (trace elements and REE) data of fluorite and manganese ore allowed to establish the age and genesis of the deposits and to propose a regional genetic model. The fluorite deposits were formed during the Upper Triassic–Lower Jurassic as a result of the Triassic rifting that launched a hydrothermal activity at regional scale. The hydrothermal fluids had low T and high fO₂ with fluorine probably derived from a mantle source and REE scavenged from the volcanics of the Gondwanan Choiyoi Magmatic Cycle upper section. The manganese deposits were formed by oxidizing hydrothermal fluids that collected Mn from deep sources and also leached REE from the upper section of the Choiyoi Magmatic Cycle during two mineralization episodes. One episode was linked to the rift tectonic setting that remained active up to the Upper Cretaceous and the other was related to an Early Miocene back-arc extensional geodynamic setting. Both manganese and fluorite deposits were formed in extensional tectonic settings within an epithermal environment near the surface, and can be ascribed to the general model of detachment-related deposits.     

A fluid inclusion and light element stable isotope study of the gold-bearing quartz vein system,Falun, Sweden

The Falun gold quartz vein mineralization is located ca 230 km NW of Stockholm, Sweden, within the Early Proterozoic volcano-sedimentary sequence of Bergslagen. The mineralization consists of a system with subparallel quartz veins that crosscut the alteration zone to the Falun massive sulphide deposit. Early barren and late gold-bearing quartz veins follow tectonic structures postdating the formation of the massive sulphide ore. Both generations of veins are epigenetic to the massive sulphide ore and were formed by hydrothermal processes. Fluid inclusion study of the gold-bearing quartz veins indicates a low-moderately saline fluid (0.3 to 17.4 equiv wt% NaCl). Heterogeneous trapping is indicated by coexisting inclusions showing a variable CO₂ content from 100% CO₂ ± CH₄ to 100% aqueous fluid. Temperatures of total homogenization also show a wide spread from 116–350°C with a slightly bimodal distribution with peaks at ca 180°C and 280°C. MeasuredδD values — 69 to — 63%0 (SMOW), of inclusion fluid and calculatedδ ¹⁸O values of hydrothermal fluids — 7.5 to — 1.4%0 (SMOW), strongly suggest a meteoric origin for the fluids. The quite consistentδD values and the range inδ ¹⁸O values indicate that major water-rock interaction led to the evolution inδ18O of the hydrothermal fluids.     

Geological and geochemical characteristics of the Baogudi Carlin-type gold district (Southwest Guizhou,China) and their geological implications

The newly discovered Baogudi gold district is located in the southwestern Guizhou Province, China, where there are numerous Carlin-type gold deposits. To better understand the geological and geochemical characteristics of the Baogudi gold district, we carried out petrographic observations, elemental analyses, and fluid inclusion and isotopic composition studies. We also compared the results with those of typical Carlin-type gold deposits in southwestern Guizhou. Three mineralization stages, namely, the sedimentation diagenesis, hydrothermal (main-ore and late-ore substages), and supergene stages, were identified based on field and petrographic observations. The main-ore and late-ore stages correspond to Au and Sb mineralization, respectively, which are similar to typical Carlin-type mineralization. The mass transfer associated with alteration and mineralization shows that a significant amount of Au, As, Sb, Hg, Tl, Mo, and S were added to mineralized rocks during the main-ore stage. Remarkably, arsenic, Sb, and S were added to the mineralized rocks during the late-ore stage. Element migration indicates that the sulfidation process was responsible for ore formation. Four types of fluid inclusions were identified in ore-related quartz and fluorite. The main-ore stage fluids are characterized by an H₂O–NaCl–CO₂–CH₄ ± N₂ system, with medium to low temperatures (180–260 °C) and low salinity (0–9.08% NaCl equivalent). The late-ore stage fluids featured H₂O–NaCl ± CO₂ ± CH₄, with low temperature (120–200 °C) and low salinity (0–7.48% NaCl equivalent). The temperature, salinity, and CO₂ and CH₄ concentrations of ore-forming fluids decreased from the main-ore stage to the late-ore stage. The calculated δ¹³C, δD, and δ¹⁸O values of the ore-forming fluids range from − 14.3 to − 7.0‰, −76 to −55.7‰, and 4.5–15.0‰, respectively. Late-ore-stage stibnite had δ³⁴S values ranging from − 0.6 to 1.9‰. These stable isotopic compositions indicate that the ore-forming fluids originated mainly from deep magmatic hydrothermal fluids, with minor contributions from strata. Collectively, the Baogudi metallogenic district has geological and geochemical characteristics that are typical of Carlin-type gold deposits in southwest Guizhou. It is likely that the Baogudi gold district, together with other Carlin-type gold deposits in southwestern Guizhou, was formed in response to a single widespread metallogenic event.

     

Recurrent hydrothermal activity induced by successive extensional episodes: the case of the Berta F–(Pb–Zn) vein system (NE Spain)

A mineralogical and geochemical (fluid inclusion, stable and radiogenic isotopes) study of the Berta F–(Pb–Zn) vein system has identified the source and temperature of the fluid reservoirs involved and proved the existence of two separate hydrothermal events at the mine scale, which reflect distinct periods of regional fluid circulation. Main stage minerals (fluorite I, sulphides, calcite I and barite I) precipitated by mixing between a polysaline H₂S bearing (δ³⁴S=11‰) brine (up to 23% NaCl eq salinity) and a more dilute fluid (δ¹⁸O from −3.2‰ to 0‰), at temperatures between 80 and 150°C. The progressive increase in ⁸⁷Sr/⁸⁶Sr ratio from the early precipitated minerals (0.71242 in calcite I) to the late ones (0.71894 in fluorite II) is mainly (but not exclusively) due to a difference in age separating the two hydrothermal events. The assumed genetic model for the main stage fluorite (I) is based on a convective circulation of surficial waters leaching the crystalline basement rocks acquiring a high salinity, high ⁸⁷Sr/⁸⁶Sr ratios and a high temperature. These fluids then mixed with low salinity–low temperature waters, having a low ⁸⁷Sr/⁸⁶Sr ratio. An at least Jurassic age is suggested for the main period of vein filling, contemporaneous with the extensional regime during the Mesozoic, when fluid circulation was probably enhanced by crustal thinning. During the early Burdigalian (lower Miocene), a new period of important extension in this area took place. Hydrothermal activity related to this new and younger extensional regime is geochemically different and produced a distinctive mineralogical record, developing a set of veinlets filled with green octahedral fluorite (fluorite II), calcite (II) and barite (II). The Sr isotope compositions of these late stage vein minerals are compatible with leaching the granodiorite host-rocks during recent times. The existence of successive hydrothermal events in the same area is not surprising as geothermal systems, like La Garriga–Samalus, are still active and currently precipitating fluorite.     

The Laal-Kan fluorite deposit,Zanjan Province,NW Iran: constraints on REE geochemistry and fluid inclusions

The Laal-Kan fluorite deposit (west of Zanjan city, NW Iran) mainly occurred as some open-space filling and vein/veinlet in the schist of the Paleozoic age. Mineralogically, calcite, fluorite types (white, smoky, and violet), and quartz are the principal constituents accompanied by a number of minor accessory minerals such as hemimorphite, hematite, barite, and clays. Based on chemical analyses, fluorites of various colors were found to have low rare earth element (REE) concentrations (4.16–25.67 ppm). The chondrite-normalized REE patterns indicated that early fluorites were enriched in LREE, relative to HREE, whereas late fluorites were enriched in HREE relative to LREE. This study, therefore, indicated that fugacity of oxygen likely played a significant role in the occurrence of positive Ce and negative anomaly in the late fluorite. Furthermore, the Gd behavior of the fluorite samples could be attributed to the Gd-F complex in ore-forming fluids. On the other hand, low pH hydrothermal fluids under alkaline conditions were probably the main mechanism responsible for the deposition of the early fluorites in this district. Fluorite-hosted fluid inclusion analyses also indicated that fluorite-forming fluids consisted of NaCl, MgCl₂, CaCl₂, and LiCl with a narrow T_H (118–151 °C) and high salinities (18.96–23.47 wt.% NaCl equiv.). Further, the diagram of Tb/La-Tb/Ca ratios revealed that fluorites were predominantly deposited in the hydrothermal environment and the late stage fluorites could be considered as the product of the secondary mineralization of the early fluorites due to the interaction of the fluid with the early fluorites.     

Thermal and chemical evolution of fluids during fluorite deposition in the Zaghouan province, north-eastern Tunisia

Several F, Pb, Zn and Ba deposits are located in the province of Zaghouan in north-eastern Tunisia. They are hosted in Lower Liassic or Upper Jurassic reef limestones, and the overlying condensed Carixian phosphatic limestones and Campanian marls, respectively. The mineralization occurs in three types of orebodies: stratiform replacement heaps and lenses (Jebel Stah and Hammam Zriba), breccia fillings and dissolution void fillings (Sidi Taya) and lodes (Jebel Oust). More than one generation of fluorite is observed in the stratiform deposits. Microthermometric analyses of the inclusion fluids observed in fluorite and quartz show that the economic concentrations of fluorite have deposited from moderate to highly saline (12–22.5 wt% NaCl equivalents) hydrothermal (110–160 °C) mineralizing fluids at the center (Jebel Stah, Sidi Taya) and to the east of the province (Hammam Zriba). Late remobilizations, observed in the stratiform deposits, are related to the circulation of a warmer (up to 185 °C) but less saline (10 wt% NaCl equivalents) fluid (Jebel Stah) and more saline (12–22 wt% NaCl equivalents) fluid (Hammam Zriba). The highest temperature (up to 250 °C) and salinity (32–34 wt% NaCl equivalents) are observed to the west of the province of Zaghouan (Jebel Oust). Less saline (3–6 wt% NaCl equivalents) and moderately hot to hot fluids (up to 220 ± 20 °C) and rich in gaseous CO₂ invade most of the ore deposits in later stages and give rise to the massive quartz within fractures at Jebel Stah. Chemical analyses of the fluids extracted from the inclusions occuring in fluorite show compositions dominated by the presence of Na⁺, Ca²⁺ and Cl⁻ ionic species and allow the mean temperature of the fluids in the source reservoir to be estimated as 275 ± 25 °C. The circulation of the ore-forming fluids is triggered by a regional tectonic extensional phase which occurs within the post-Jurassic to ante-Miocene time interval. The deposition of the economic concentrations of fluorite resulted from the decrease in pressure and temperature of the hydrothermal brines (Jebel Oust), along with the increase in the dissolved calcium activity (Jebel Stah and Sidi Taya), or a decrease in salinity due to the mixing with a hot, less saline and Na-poor, Ca-rich fluid (Hammam Zriba). The mineralogical associations (CaF₂, PbS, ZnS, BaSO₄) hosted within carbonate rocks, the temperatures and the salinities of the fluids that gave rise to the more important ore deposits (110–160 °C and 12–22.5 wt% NaCl equivalents), their composition (Na, Ca, Cl) and the molar ratios between the major ionic species, as well as the presence of liquid hydrocarbons in the mineralizing fluids, show that the ore deposits of the province of Zaghouan belong to the carbonate-hosted F, Pb, Zn, Ba Mississippi Valley-type deposits. Received: 23 June 1995 / Accepted: 18 November 1996     

Mesothermal Gold Vein Mineralization of the Seolhwa Mine,Asan Mining District,Korea

Gold mineralization of the Seolhwa mine occurs in a single stage of massive quartz veins which filled the north‐east‐trending fault shear zones in the Jurassic granitoid of 161 Ma within the Gyeonggi Massif. The vein quartz contains three main types of fluid inclusions at 25°C: (i) aqueous type I inclusions (0–15 wt.% NaCl) containing small amounts of CO₂; (ii) gas‐rich (more than 70 vol. %), vapor‐homogenizing, aqueous type II inclusions; and (iii) low‐salinity (less than 5 wt.% NaCl), liquid CO₂‐bearing, type III inclusions. The H₂O‐CO₂‐CH₄‐N₂‐NaCl inclusions represent immiscible fluids trapped earlier along the solvus curve in the temperature range 250–430°C at pressures of ～1 kb. Detailed fluid inclusion chronologies suggest a progressive decrease in pressure during the mineralization. Aqueous inclusion fluids represent either later fluids evolved through extensive fluid unmixing from a homogeneous H₂O‐CO₂‐CH₄‐N₂‐NaCl fluid due to decreases in temperature and pressure, or the influence of deep circulated meteoric waters. Initial fluids were homogeneous H₂O‐CO₂‐CH₄‐N₂‐NaCl fluids as follows: 250° to 430°C, 16–62 mol% CO₂, 5–14 mol% CH₄, 0.06–0.31 mol% N₂ and salinities of 0.4–4.9 wt.% NaCl. The T‐X data for the Seolhwa mine suggest that the hydrothermal system has been probably located nearer to the granitic melt, which facilitated the CH₄ formation and resulted in a reduced fluid state indicated by the predominance of pyrrhotite. Measured and calculated isotopic compositions of the hydrothermal fluids [δ¹⁸O = 5.3–6.5‰; δD =?69 to ?84‰] provide evidence of the CH₄‐H₂O equilibria and further indicate that the auriferous fluids were magmatically derived. Both the dominance of δ³⁴S values of sulfides close to the meteoric reference (?0.6–1.4‰; δ³⁴S_ΣS values of 0.3–1.1‰) and the available δ¹³C data (?4‰) are consistent with their deep igneous source. The Seolhwa mine was probably formed by extensive fracturing and veining due to the thermal expansion of water derived from the Jurassic granitoid melt.     

The pink topaz-bearing calcite, quartz, white mica veins from Ghundao Hill (North West Frontier Province, Pakistan): K/Ar age, stable isotope and REE data

Summary In the area of the Ghundao Hill (Northern Frontier Province, Pakistan) an orange-yellow to cherry-red topaz is found in calcite, quartz, white mica veins crosscutting the schistosity of probably Silurian to Devonian gray limestones. Topaz with such a range of colours is traded as Imperial Topaz. Low fluorine contents of about 15 wt.%, oxygen isotope thermometry, K/Ar age determination on white mica, fluid inclusion data and mineral textures indicate that the topaz from Ghundao Hill crystallized at temperatures of about 230 °C during the Eocene Himalayan tectonothermal event and not from a late to postmagmatic granite-related fluid. The pink Topaz from Ghundao Hill shares the coexistence with carbonates, low fluorine content and a crystallization at low temperature and pressure during a regional tectonothermal event with the Imperial Topaz from Ouro Preto (Brazil) and from the Sanarka/Kamenka rivers (South Urals, Russia). The efficiency of topaz to remove fluorine from fluids at low temperature explains how topaz can be formed from metamorphic fluids that are typically poor in fluorine. High CO₂ activity produced in the fluids by metamorphic decarbonatisation reactions and Al buffering by white mica prevented fluorination of carbonates stabilising topaz relative to fluorite.     

Micrometallogeny and hydrothermal fluid evolution of the Iju porphyry Cu deposit,NW Kerman,Iran: Evidence from fluid inclusions,Laser Raman spectroscopy,and SO isotope systematics

The Iju Cu porphyry is located in the NW part of the Kerman Magmatic Copper Belt (KMCB). It is related to a ~ 9 Ma granodiorite porphyry intrusion, with three main stages of hydrothermal activity. The homogenization temperatures for the fluid inclusions are in the ranges of 200–494 °C, and their salinities vary from 4.0 to 42.8 wt% NaCl equiv., which are typical magmatic-hydrothermal fluids. The δ³⁴S values of sulfides range from −0.4 to +3.2 ‰ (V-CDT), and the δ³⁴S values of anhydrite samples range from +11.6 to +16.8 ‰. The δ³⁴S values of sulfides show a narrow range, implying a homogeneous sulfur source. The oxygen isotopic composition of hydrothermal water in equilibrium with quartz samples ranges from +3.4 to +6.0 ‰ (V-SMOW) consistent with the hydrothermal fluids having a magmatic signature, but diluted with meteoric waters in the main mineralizing stage. The most important factors responsible for metal precipitation in the Iju porphyry deposit are fluid boiling, oxygen fugacity decrease and cooling followed by dilution with meteoric water. The primary fluids of the Iju Cu deposit are characterized by relatively high temperature and moderate salinity, and are CO₂-rich, indicating a typical post-collisional porphyry system.     

Fluid evolution of the Yuchiling porphyry Mo deposit,East Qinling,China

The Yuchiling Mo deposit, East Qinling, China, belongs to a typical porphyry Mo system associated with high-K calc-alkaline intrusions. The pure CO₂ (PC), CO₂-bearing (C), aqueous H₂O-NaCl (W), and daughter mineral-bearing (S) fluid inclusions were observed in the hydrothermal quartz. Based on field investigations, petrographic, microthermometric and LA-ICP-MS studies of fluid inclusions, we develop a five-stage fluid evolution model to understand the ore-forming processes of the Yuchiling deposit. The earliest barren quartz ± potassic feldspar veins, developed in intensively potassic alteration, were crystallized from carbonic-dominant fluids at high temperature (> 416 °C) and high pressure (> 133 MPa). Following the barren quartz ± potassic feldspar veins are quartz-pyrite veins occasionally containing minor K-feldspar and molybdenite, which were formed by immiscible fluids at pressures of 47–159 MPa and temperatures of 360–400 °C. The fluids were characterized by high CO₂ contents (approximately 8 mol%) and variable salinities, as well as the highest Mo contents that resulted in the development of quartz-molybdenite veins. The quartz-molybdenite veins, accounting for > 90% Mo in the orebody, were also formed by immiscible fluids with lower salinity and lower CO₂ content of 7 mol%, at temperatures of 340–380 °C and pressures of 39–137 MPa, as constrained by fluid inclusion assemblages. After the main Mo-mineralization, the uneconomic Cu-Pb-Zn mineralization occurred, as represented by quartz-polymetallic sulfides veins consisting of pyrite, molybdenite, chalcopyrite, digenite, galena, sphalerite and quartz. The quartz-polymetallic sulfide veins were formed by fluids containing 5 mol% CO₂, with minimum pressures of 32–110 MPa and temperatures of 260–300 °C. Finally, the fluids became dilute (5 wt.% NaCl equiv) and CO₂-poor, which caused the formation of late barren quartz ± carbonate ± fluorite veins at 140–180 °C and 18–82 MPa.It is clear that the fluids became more dilute, CO₂-poor, and less fertile, with decreasing temperature and pressure from quartz-pyrite to late barren veins. Molybdenite and other sulfides can only be observed in the middle three stages, i.e., quartz-pyrite, quartz-molybdenite and quartz-polymetallic sulfide veins. These three kinds of veins are generally hosted in potassic altered rocks with remarkable K-feldspathization, but always partly overprinted by phyllic alteration. The traditional porphyry-style potassic–phyllic–propylitic alteration zoning is not conspicuous at Yuchiling, which may be related to, and characteristic of, the CO₂-rich fluids derived from the magmas generated in intercontinental collision orogens.Among the fluid inclusions at Yuchiling, only the C-type contains maximum detectable Mo that gradationally decreases from 73 ppm in quartz-pyrite veins, through 19 ppm in quartz-molybdenite veins, and to 13 ppm in quartz-polymetallic sulfide veins, coinciding well with the decreasing CO₂ contents from 8 mol%, through 7 mol%, to 5 mol%, respectively. Hence it is suggested that decreasing CO₂ possibly results in decreasing Mo concentration in the fluids, as well as the precipitation of molybdenite from the fluids. This direct relationship might be a common characteristic for other porphyry Mo systems in the world.The Yuchiling Mo deposit represents a new type Mo mineralization, with features of collision-related setting, high-K calc-alkaline intrusion, CO₂-rich fluid, and unique wall-rock alterations characterized by strong K-feldspathization and fluoritization.     

Multi-stage rodingitization of ophiolitic bodies from Northern Apennines (Italy): Constraints from petrography,geochemistry and thermodynamic modelling

The investigated mantle bodies from the External Ligurians (Groppo di Gorro and Mt. Rocchetta) show evidences of a complex evolution determined by an early high temperature metasomatism, due to percolating melts of asthenospheric origin, and a later metasomatism at relatively high temperature by hydrothermal fluids, with formation of rodingites. At Groppo di Gorro, the serpentinization and chloritization processes obliterated totally the pyroxenite protolith, whereas at Mt. Rocchetta relics of peridotite and pyroxenite protoliths were preserved from serpentinization. The rodingite parageneses consist of diopside ​+ ​vesuvianite ​+ ​garnet ​+ ​calcite ​+ ​chlorite at Groppo di Gorro and garnet ​+ ​diopside ​+ ​serpentine ​± ​vesuvianite ​± ​prehnite ​± ​chlorite ​± ​pumpellyite at Mt. Rocchetta. Fluid inclusion measurements show that rodingitization occurred at relatively high temperatures (264–334 ​°C at 500 ​bar and 300–380 ​°C at 1 ​kbar). Garnet, the first phase of rodingite to form, consists of abundant hydrogarnet component at Groppo di Gorro, whereas it is mainly composed of grossular and andradite at Mt. Rocchetta. The last stage of rodingitization is characterized by the vesuvianite formation. Hydrogarnet nucleation requires high Ca and low silica fluids, whereas the formation of vesuvianite does not need CO₂-poor fluids. The formation of calcite at Groppo di Gorro points to mildly oxidizing conditions compatible with hydrothermal fluids; the presence of andradite associated with serpentine and magnetite at Mt. Rocchetta suggests Fe³⁺-bearing fluids with fO₂ slightly higher than iron-magnetite buffer. We propose that the formation of the studied rodingite could be related to different pulses of hydrothermal fluids mainly occurring in an ocean-continent transitional setting and, locally, in an accretionary prism associated with intra-oceanic subduction.