Sources and composition of fluids associated with fluorite deposits of Asturias (N Spain)

The fluorite deposits of Asturias (northern Iberian Peninsula) are hosted by rocks of Permo‐Triassic and Palaeozoic age. Fluid inclusions in ore and gangue minerals show homogenization temperatures from 80 to 170°C and the presence of two types of fluids: an H₂O–NaCl low‐salinity fluid (<8 eq. wt% NaCl) and an H₂O–NaCl–CaCl₂ fluid (7–13 wt% NaCl and 11–14 wt% CaCl₂). The low salinity and the Cl/Br and Na/Br ratios (Cl/Br_molar 100–700 and Na/Br_molar 20–700) are consistent with an evaporated sea water origin of this fluid. The other end‐member of the mixture was highly saline brine with high Cl/Br and Na/Br ratios (Cl/Br_molar 700–13 000 and Na/Br_molar 700–11 000) generated after dissolution of Triassic age evaporites. LA‐ICP‐MS analyses of fluid inclusions in fluorite reveal higher Zn, Pb and Ba contents in the high‐salinity fluids (160–500, 90–170, 320–480 p.p.m. respectively) than in the low‐salinity fluid (75–230, 25–150 and 100–300 p.p.m. respectively). The metal content of the fluids appears to decrease from E to W, from Berbes to La Collada and to Villabona. The source of F is probably related to leaching of volcanic rocks of Permian age. Brines circulated along faults into the Palaeozoic basement. Evaporated sea water was present in permeable rocks and faults along or above the unconformity between the Permo‐Triassic sediments and the Palaeozoic basement. Mineralization formed when the deep brines mixed with the surficial fluids in carbonates, breccias and fractures resulting in the formation of veins and stratabound bodies of fluorite, barite, calcite, dolomite and quartz and minor amounts of sulphides. Fluid movement and mineralization occurred between Late Triassic and Late Jurassic times, probably associated with rifting events related to the opening of the Atlantic Ocean. This model is also consistent with the geodynamic setting of other fluorite‐rich districts in Europe.     

Fluid inclusion and stable isotope constraints on the genesis of the Jian copper deposit,Sanandaj–Sirjan metamorphic zone,Iran

The Jian copper deposit, located on the eastern edge of the Sanandaj–Sirjan metamorphic zone, southwest of Iran, is contained within the Surian Permo‐Triassic volcano‐sedimentary complex. Retrograde metamorphism resulted in three stages of mineralization (quartz ± sulfide veins) during exhumation of the Surian metamorphic complex (Middle Jurassic time; 159–167 Ma), and after the peak of the metamorphism (Middle to Late Triassic time; approximately 187 Ma). The early stage of mineralization (stage 1) is related to a homogeneous H₂O–CO₂ (XCO₂ > 0.1) fluid characterized by moderate salinity (<10 wt.% NaCl equivalent) at high temperature and pressure (>370°C, >3 kbar). Early quartz was followed by small amounts of disseminated fine‐grained pyrite and chalcopyrite. Most of the main‐ore‐stage (stage 2) minerals, including chalcopyrite, pyrite and minor sphalerite, pyrrhotite, and galena, precipitated from an aqueous‐carbonic fluid (8–18 wt.% NaCl equivalent) at temperatures ranging between 241 and 388°C during fluid unmixing process (CO₂ effervescence). Fluid unmixing in the primary carbonaceous fluid at pressures of 1.5–3 kbar produced a high XCO₂ (>0.05) and a low XCO₂ (<0.01) aqueous fluid in ore‐bearing quartz veins. Oxygen and hydrogen isotope compositions suggest mineralization by fluids derived from metamorphic dehydration (δ¹⁸O_fluid = +7.6 to +10.7‰ and δD = ?33.1 to ?38.5‰) during stage 2. The late stage (stage 3) is related to a distinct low salinity (1.5–8 wt.% NaCl equivalent) and temperatures of (120–230°C) aqueous fluid at pressures below 1.5 kbar and the deposition of post‐ore barren quartz veins. These fluids probably derived from meteoric waters, which circulated through the metamorphic pile at sufficiently high temperatures and acquire the characteristics of metamorphic fluids (δ¹⁸O_fluid = +4.7 to +5.1‰ and δD = ?52.3 to ?53.9‰) during waning stages of the postearly Cimmerian orogeny in Surian complex. The sulfide‐bearing quartz veins are interpreted as a small‐scale example of redistribution of mineral deposits by metamorphic fluids. This study suggests that mineralization at the Jian deposit is metamorphogenic in style, probably related to a deep‐seated mesothermal system.     

Geological setting, nature of ore fluids and sulphur isotope geochemistry of the Fu Ning Carlin-type gold deposits, Yunnan Province, China

Carlin‐type gold deposits in southern China are present in Palaeozoic to Mesozoic siliciclastic and carbonate rocks. The border region of Yunnan, Guizhou and Guangxi Provinces contains gold deposits on the south‐western margin of the Pre‐Cambrian South China Craton in south‐eastern Yunnan Province. The Fu Ning gold deposits host epigenetic, micron‐sized disseminated gold in: (i) Middle Devonian (D₁p) black carbonaceous mudstone at the Kuzhubao gold deposit and (ii) fault breccia zones at the contact between Triassic gabbro (β ) and the Devonian mudstone (D₁p) at the Bashishan gold deposit. The deposits are associated with zones of intense deformation with enhanced permeability and porosity that focused hydrothermal fluid flow, especially where low‐angle N‐S striking thrust faults are cut by NW striking strike‐slip and/or NE striking normal faults. Major sulphide ore minerals in the Fu Ning gold deposits are pyrite, arsenopyrite, arsenic‐rich pyrite, stibnite and minor iron‐poor sphalerite. Gangue minerals are quartz, sericite, calcite, ankerite and chlorite. Hypogene ore grades range from 1 to 7 g t^?1 Au and up to 18 g t^?1 Au at the Kuzhubao gold deposit and are generally less than 3 g t^?1 Au at the Bashishan gold deposit. Sub‐microscopic gold mineralization is associated with finely disseminated arsenic‐rich pyrite in the Stage III mineral assemblage. Two types of primary fluid inclusions have been recorded: Type I liquid–vapour inclusions with moderate‐to‐high liquid/vapour ratios, and Type II inclusions containing moderate liquid/vapour ratios with CO₂ as determined from laser Raman analysis. Temperature of homogenization (T_h) data collected from these primary fluid inclusions in gold‐ore Stage III quartz ranged from 180 to 275°C at the Kuzhubao gold deposit and 210 to 330°C at the Bashishan gold deposit. Salinity results indicate that there were possibly two fluids present during gold deposition, including: (i) an early fluid with 0.8–6.5 wt.% NaCl equivalent, similar to salinity in shear‐zone‐hosted gold deposits with metamorphic derived fluids; and (ii) a late fluid with 11.8–13.4 wt.% NaCl equivalent, indicating possible derivation from connate waters and/or brine sources. CO₂ and trace CH₄ were only detected by laser Raman spectrometry in gold‐ore‐stage primary fluid inclusions. Results of sulphur isotope studies showed that δ³⁴S values for pyrite and arsenopyrite associated with gold‐ore mineralization during Stage III at the Kuzhubao and Bashishan gold deposits are isotopically similar and moderately heavy with a range from +9 to +15 per mil, and also fall into the range of δ³⁴S values reported for Carlin‐type gold deposits. Sulphur isotopes suggest that the Fu Ning gold deposits were formed from connate waters and/or basinal brines. Fluid geochemistry data from the Fu Ning gold deposits suggest a Carlin‐type genetic model, involving fluid mixing between: (i) deep CO₂‐rich metamorphic fluids, (ii) moderately saline, reduced connate waters and/or basinal brines; and (iii) evolved meteoric waters.     

Retrograde P–T evolution and high temperature–low pressure fluid circulation in relation to late Hercynian intrusions: a mineralogical and fluid inclusion study of the Charroux-Civray plutonic complex (north-western Massif Central, France)

The calc‐alkaline plutonic complex from Charroux‐Civray (north‐western part of the French Massif Central) displays multiphase hydrothermal alteration. Plutonic rocks, as well as early retrograde Ca–Al silicate assemblages, which have crystallized during cooling and uplifting of the plutonic series, are affected by multiphase chlorite–phengite–illite–carbonate alteration linked to intense pervasive fluid circulation through microfractures. The petrographic study of alteration sequences and their associated fluid inclusions in microfissures of the plutonic rocks, as well as in mineral fillings of the veins, yields a reconstruction of the P–T–X evolution of the Hercynian basement after the crystallization of the main calc‐alkaline plutonic bodies. This reconstruction covers the uplift of the basement to its exposure and the subsequent burial by Mesozoic sediments. Cooling of the calc‐alkaline plutonic series started at solidus temperatures (～650°C), at a pressure of about 4 kbar (1 bar = 10⁵ N m^?2), as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data. Cooling continued under slightly decreasing pressure during uplift down to 2–3 kbar at 200–280°C (prehnite–pumpellyite paragenesis). Then, a hot geothermal circulation of CO₂‐bearing fluids was induced within the calc‐alkaline rocks leading to the formation of greisen‐like mineralizations. During this stage, temperatures around 400–450°C were still high for the inferred depths (～2 kbar). They imply abnormal heat flows and thermal gradients of 60–80°C km^?1. The hypothesis of the existence of one large or a succession of smaller peraluminous plutons at depth, supported by geophysical data, suggests that localized heat flows were linked to concealed leucogranite intrusions. As uplift continued, greisen mineralization was subsequently affected by the chlorite–phengite–dolomite assemblage, correlated with aqueous and nitrogen‐bearing fluid circulations in the temperature range of 400–450°C. In a later stage, a continuous temperature decrease at constant pressure (～0.5 kbar) led to the alteration of the dolomite–illite–chlorite type in the 130–250°C temperature range.     

Hydrology of the Western Arkoma basin and Ozark platform during the Ouachita orogeny: implications for Mississippi Valley-type ore formation in the Tri-State Zn–Pb district

Numerical groundwater modeling was used to investigate the role of fluid flow associated with uplift of the Arkoma basin during the closing stages of the Ouachita orogeny in forming the Mississippi Valley‐type Zn–Pb ores of the Tri‐State district. The model hydrostratigraphy was flexurally compensated to account for the restoration of Pennsylvanian–Permian sediments removed since the close of the orogeny in estimating the regional paleotopographic gradient. Estimates of the amount of Pennsylvanian–Permian sediment that has been removed by erosion vary widely. A thick and a thin endmember case were considered, and in both cases topographydriven fluid flow was shown to have been an important mechanism for groundwater motion, with a lesser component contributed during the early stages of uplift by overpressuring created by compaction in the deep portion of the Arkoma basin. The Pennsylvanian–Permian sediments and underlying Western Interior Plains confining system acted as thick capping aquitards that caused slow rates of groundwater flow over much of the profile. As a result, meteoric water infiltration initiated during uplift was slow to flush saline formation waters, allowing MVT ore‐forming salinities to persist at Tri‐State on the order of at least 10⁰ Myr. The slow groundwater flow rates also caused heat transport to occur primarily by conduction rather than advection. Despite this, MVT ore‐forming temperatures were still reached at Tri‐State for both endmember cases of Pennsylvanian–Permian aquitard thickness, though much more readily in the thick aquitard case. Faults within the Tri‐State district served as a regional fluid focusing mechanism and probably played a more important role in localizing mineralization than the window in the Ozark confining unit that occurs in the district. Fluids rising along these faults could have cooled by about 8–10°C and as much as another 0.3°C km^?1 as they flowed laterally northward. This temperature change alone however would not have been sufficient to precipitate the total mass of metal sulfide ore occurring at Tri‐State.     

Precipitation of lead–zinc ores in the Mississippi Valley‐type deposit at Trèves,Cévennes region of southern France

The Trèves zinc–lead deposit is one of several Mississippi Valley‐type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ³⁴S values determined for the minerals in the deposit (12.2–19.2‰ for barite, 3.8–13.8‰ for sphalerite and galena, and 8.7 to ?21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur‐rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced sulfur concentration on the Zn and Pb transport capacity of the ore fluid and the volumes of fluid required to form the deposit. The studies of the Trèves ores provide insights into the ore‐forming processes of a typical MVT deposit in the Cévennes region. However, the extent to which these processes can be extrapolated to other MVT deposits in the Cévennes region is problematic. Nevertheless, the evidence for the extensive migration of fluids in the basement and sedimentary cover rocks in the Cévennes region suggests that the ore forming processes for the Trèves deposit must be considered equally viable possibilities for the numerous fault‐controlled and mineralogically similar MVT deposits in the Cévennes region.     

Contrasting paleofluid systems in the continental basement: a fluid inclusion and stable isotope study of hydrothermal vein mineralization,Schwarzwald district,Germany

An integrated fluid inclusion and stable isotope study was carried out on hydrothermal veins (Sb‐bearing quartz veins, metal‐bearing fluorite–barite–quartz veins) from the Schwarzwald district, Germany. A total number of 106 Variscan (quartz veins related to Variscan orogenic processes) and post‐Variscan deposits were studied by microthermometry, Raman spectroscopy, and stable isotope analysis. The fluid inclusions in Variscan quartz veins are of the H₂O–NaCl–(KCl) type, have low salinities (0–10 wt.% eqv. NaCl) and high T_h values (150–350°C). Oxygen isotope data for quartz range from +2.8‰ to +12.2‰ and calculated δ¹⁸O_H2O values of the fluid are between ?12.5‰ and +4.4‰. The δD values of water extracted from fluid inclusions vary between ?49‰ and +4‰. The geological framework, fluid inclusion and stable isotope characteristics of the Variscan veins suggest an origin from regional metamorphic devolatilization processes. By contrast, the fluid inclusions in post‐Variscan fluorite, calcite, barite, quartz, and sphalerite belong to the H₂O–NaCl–CaCl₂ type, have high salinities (22–25 wt.% eqv. NaCl) and lower T_h values of 90–200°C. A low‐salinity fluid (0–15 wt.% eqv. NaCl) was observed in late‐stage fluorite, calcite, and quartz, which was trapped at similar temperatures. The δ¹⁸O values of quartz range between +11.1‰ and +20.9‰, which translates into calculated δ¹⁸O_H2O values between ?11.0‰ and +4.4‰. This range is consistent with δ¹⁸O_H2O values of fluid inclusion water extracted from fluorite (?11.6‰ to +1.1‰). The δD values of directly measured fluid inclusion water range between ?29‰ and ?1‰, ?26‰ and ?15‰, and ?63‰ and +9‰ for fluorite, quartz, and calcite, respectively. Calculations using the fluid inclusion and isotope data point to formation of the fluorite–barite–quartz veins under near‐hydrostatic conditions. The δ¹⁸O_H2O and δD data, particularly the observed wide range in δD, indicate that the mineralization formed through large‐scale mixing of a basement‐derived saline NaCl–CaCl₂ brine with meteoric water. Our comprehensive study provides evidence for two fundamentally different fluid systems in the crystalline basement. The Variscan fluid regime is dominated by fluids generated through metamorphic devolatilization and fluid expulsion driven by compressional nappe tectonics. The onset of post‐Variscan extensional tectonics resulted in replacement of the orogenic fluid regime by fluids which have distinct compositional characteristics and are related to a change in the principal fluid sources and the general fluid flow patterns. This younger system shows remarkably persistent geochemical and isotopic features over a prolonged period of more than 100 Ma.     

Fluid systems and mineralization in the north German and Polish basin

The North European Basin hosts mineral deposits like the Kupferschiefer and the Mississippi Valley Type deposits in the Silesian sub‐basin in Poland. The basement to this basin, exposed in the Harz Mts and in the Flechtingen and Calvörde Blocks, contains Mesozoic Pb–Zn vein mineralization and barite–fluorite deposits as well as massive hematite veins in the Rotliegend volcanics. A comparison of the mineralizing models of these deposits with results from a basin‐wide petrographic, fluid inclusion and stable isotope study shows that the genesis of the mineral deposits can be explained by fluid systems that were active during different stages of basin evolution. These comprise syn‐ to post‐magmatic fluids derived from or mobilized in the course of the Rotliegend magmatism, fluids convecting in the Rotliegend units during the extensional basin subsidence in the Permo‐Triassic and originating from progressive devolatilization of the basin sequence and fluids derived from the overlying Zechstein evaporites. Deep‐reaching fault systems developing during the Cretaceous tectonic reactivation enhanced fluid percolation from the surface to the deep sections of the basin sequence. Identification and correlation of these fluids across the basin and in the mineralizations provide the base for a basin‐wide metallogenetic model.     

Hydrothermal palaeofluid circulation in the fracture network of the Baksa Gneiss Complex of SW Pannonian Basin,Hungary

A well‐developed fracture‐filling network is filled by dominantly Ca‐Al‐silicate minerals that can be found in the polymetamorphic rock body of the Baksa Gneiss Complex (SW Hungary). Detailed investigation of this vein network revealed a characteristic diopside→epidote→sphalerite→albite ± kfeldspar→chlorite1 ± prehnite ± adularia→chlorite2→chlorite3→pyrite→calcite1→calcite2→calcite3 fracture‐filling mineral succession. Thermobarometric calculations (two feldspar: 230–336°C; chlorites: approximately 130–300°C) indicate low‐temperature vein formation conditions. The relative succession of chlorites in the mineral sequence combined with the calculated formation temperatures reveals a cooling trend during precipitation of the different chlorite phases (T_chlorite1: 260 ± 32°C →T_chlorite2: 222 ± 20°C →T_chlorite3: 154 ± 13°C). This cooling trend can be supported by the microthermometry data of primary fluid inclusions in diopside (T_h: 276–362°C) and epidote (T_h: 181–359°C) phases. The identical chemical character (0.2–1.5 eq. wt% NaCl) of these inclusions mean that vein mineralization occurred in a same fluid environment. The high trace element content (e.g. As, Cu, Zn, Mn) and Co/Ni ratio approximately 1–5 of pyrite grains support the postmagmatic hydrothermal origin of the veins. The vein microstructure and identical fluid composition indicate that vein mineralization occurred in an interconnected fracture system where crystals grew in fluid filled cracks. Vein system formed at approximately <200 MPa pressure conditions during cooling from approximately 480°C to around 150°C. The rather different fluid characteristics (T_h: 75–124°C; 17.5–22.6 eq. wt% CaCl₂) of primary inclusions of calcite1 combining with the special δ¹⁸O signature of fluid from which this mineral phase precipitated refer to hydrological connection between the crystalline basement and the sedimentary cover.     

Comparing closed system, flow-through and fluid infiltration geochemical modelling: examples from K-alteration in the Ernest Henry Fe-oxide–Cu–Au system

Potassic alteration of rocks adjacent to, and within the Ernest Henry Fe‐oxide–Cu–Au deposit is used here as a test case to investigate fluid–rock interactions using various equilibrium dynamic geochemical modelling approaches available in the HCh code. Reaction of a simple K–Fe–(Na,Ca) brine (constrained by published fluid inclusion analysis) with an albite‐bearing felsic volcanic rock, resulted in predicted assemblages defined by (i) K‐feldspar–muscovite–magnetite, (ii) biotite–K‐feldspar–magnetite, (iii) biotite–quartz–albite and (iv) albite–biotite–actinolite–pyroxene with increasing rock buffering (decreasing log w/r). Models for isothermal–isobaric conditions (450°C and 2500 bars) were compared with models run over a T–P gradient (450 to 200°C and 2500 to 500 bars). Three principal equilibrium dynamic simulation methods have been used: (i) static closed system, where individual steps are independent of all others, (ii) flow‐through and flush, where a part of the result is passed as input further along the flow line, and (iii) fluid infiltration models that simulate fluid moving through a rock column. Each type is best suited to a specific geological fluid–rock scenario, with increasing complexity, computation requirements and approximation to different parts of the natural system. Static closed system models can be used to quickly ascertain the broad alteration assemblages related to changes in the water/rock ratio, while flow‐through models are better suited to simulating outflow of reacted fluid into fresh rock. The fluid infiltration model can be used to simulate spatially controlled fluid metasomatism of rock, and we show that, given assumptions of porosity relationships and spatial dimensions, this model is a first‐order approximation to full reactive transport, without requiring significant computational time. This work presents an overview of the current state of equilibrium dynamic modelling technology using the HCh code with a view to applying these techniques to predictive modelling in exploration for mineral deposits. Application to the Ernest Henry Fe‐oxide–Cu–Au deposit demonstrates that isothermal fluid–rock reaction can account for some of the alteration zonation around the deposit.     

Hydrothermal fluid flow models of stratiform ore genesis in the McArthur Basin, Northern Territory, Australia

This paper explores the role of basin‐scale fluid migration in stratiform Pb–Zn ore formation in the southern McArthur Basin, Australia. Mathematical models are presented for coupled brine migration and heat transport in the basin. The models account for: (i) topographically driven flow (forced convection) during periods when parts of the McArthur Basin were subaerial and elevated above the central Batten Fault Zone; (ii) density‐driven flow (free convection) during periods when the basin was mostly submarine; and (iii) transient flows associated with fault rupture during periods of transpression. These hydrologic models help to compare and contrast a variety of hypotheses concerning deep fluid migration and the origin of base metal ores in the McArthur Basin. The numerical results exhibit a strong structural control on fluid flow caused by the north‐trending fault systems that characterize the Batten Fault Zone. As a result, fluids descend to depths of a few kilometers along the western side, migrate laterally to the east through the clastic and volcanic aquifers of the upper Tawallah and lowest McArthur Groups, and then ascend along the eastern side of the fault zone. This recharge–discharge pattern dominates all of the hydrogeologic models. The basin‐wide flow pattern suggests that Na–Ca–Cl brines acquired base metals in the deepest levels of the basin stratigraphy as the fluids migrated eastwards through the aquifer system. Upward flow was relatively rapid along the Emu Fault Zone, so much so that fluid temperatures likely approached 130°C in the muddy sediments near the sea floor due to upward flow and venting at the HYC (‘Here’s Your Chance'). Transient pulses of flow characterized periods of transpressional stress and subsequent faulting may have punctuated the basin history. Large‐scale free convection, however, characterized notably long periods of diagenesis and ore mineralization during the Proterozoic in the McArthur Basin.     

High‐temperature magmatic fluid exsolved from magma at the Duobuza porphyry copper–gold deposit,Northern Tibet

The Duobuza porphyry copper–gold deposit (proven Cu resources of 2.7 Mt, 0.94% Cu and 13 t gold, 0.21 g t^?1 Au) is located at the northern margin of the Bangong‐Nujiang suture zone separating the Qiangtang and Lhasa Terranes. The major ore‐bearing porphyry consists of granodiorite. The alteration zone extends from silicification and potassic alteration close to the porphyry stock to moderate argillic alteration and propylitization further out. Phyllic alteration is not well developed. Sericite‐quartz veins only occur locally. High‐temperature, high‐salinity fluid inclusions were observed in quartz phenocrysts and various quartz veins. These fluid inclusions are characterized by sylvite dissolution between 180 and 360°C and halite dissolution between 240 and 540°C, followed by homogenization through vapor disappearance between 620 and 960°C. Daughter minerals were identified by SEM as chalcopyrite, halite, sylvite, rutile, K–feldspar, and Fe–Mn‐chloride. They indicate that the fluid is rich in ore‐forming elements and of high oxidation state. The fluid belongs to a complex hydrothermal system containing H₂O – NaCl – KCl ± FeCl₂ ± CaCl₂ ± MnCl₂. With decreasing homogenization temperature, the fluid salinity tends to increase from 34 to 82 wt% NaCl equiv., possibly suggesting a pressure or Cl/H₂O increase in the original magma. No coexisting vapor‐rich fluid inclusions with similar homogenization temperatures were found, so the brines are interpreted to have formed by direct exsolution from magma rather than trough boiling off of a low‐salinity vapor. Estimated minimum pressure of 160 MPa imply approximately 7‐km depth. This indicates that the deposit represents an orthomagmatic end member of the porphyry copper deposit continuum. Two key factors are proposed for the fluid evolution responsible for the large size of the gold‐rich porphyry copper deposit of Duobuza: (i) ore‐forming fluids separated early from the magma, and (ii) the hydrothermal fluid system was of magmatic origin and highly oxidized.     

Numerical modeling of the origin of calcite mineralization in the Refugio‐Carneros fault,Santa Barbara Basin,California

Many faults in active and exhumed hydrocarbon‐generating basins are characterized by thick deposits of carbonate fault cement of limited vertical and horizontal extent. Based on fluid inclusion and stable isotope characteristics, these deposits have been attributed to upward flow of formation water and hydrocarbons. The present study sought to test this hypothesis by using numerical reactive transport modeling to investigate the origin of calcite cements in the Refugio‐Carneros fault located on the northern flank of the Santa Barbara Basin of southern California. Previous research has shown this calcite to have low δ¹³C values of about ?40 to ?30‰PDB, suggesting that methane‐rich fluids ascended the fault and contributed carbon for the mineralization. Fluid inclusion homogenization temperatures of 80–125°C in the calcite indicate that the fluids also transported significant quantities of heat. Fluid inclusion salinities ranging from fresh water to seawater values and the proximity of the Refugio‐Carneros fault to a zone of groundwater recharge in the Santa Ynez Mountains suggest that calcite precipitation in the fault may have been induced by the oxidation of methane‐rich basinal fluids by infiltrating meteoric fluids descending steeply dipping sedimentary layers on the northern basin flank. This oxidation could have occurred via at least two different mixing scenarios. In the first, overpressures in the central part of the basin may have driven methane‐rich formation waters derived from the Monterey Formation northward toward the basin flanks where they mixed with meteoric water descending from the Santa Ynez Mountains and diverted upward through the Refugio‐Carneros fault. In the second scenario, methane‐rich fluids sourced from deeper Paleogene sediments would have been driven upward by overpressures generated in the fault zones because of deformation, pressure solution, and flow, and released during fault rupture, ultimately mixing with meteoric water at shallow depth. The models in the present study were designed to test this second scenario, and show that in order for the observed fluid inclusion temperatures to be reached within 200 m of the surface, moderate overpressures and high permeabilities were required in the fault zone. Sudden release of overpressure may have been triggered by earthquakes and led to transient pulses of accelerated fluid flow and heat transport along faults, most likely on the order of tens to hundreds of years in duration. While the models also showed that methane‐rich fluids ascending the Refugio‐Carneros fault could be oxidized by meteoric water traversing the Vaqueros Sandstone to form calcite, they raised doubts about whether the length of time and the number of fault pulses needed for mineralization by the fault overpressuring mechanism were too high given existing geologic constraints.     

Fluid inclusion constraints on the origin of the brines responsible for Pb–Zn mineralization at Pine Point and coarse non‐saddle and saddle dolomite formation in southern Northwest Territories

The Pine Point region is a classic metallogenic mining camp that produced over 58 million short tons of Zn–Pb ore from approximately 40 base‐metal mineralized deposits hosted by Middle Devonian carbonates. The ore deposits are localized in paleokarstic features found in the epigenetic ‘Presqu'ile’ dolomite that preferentially replaced some of the upper barrier limestones. The main ore‐stage sulfides include galena, sphalerite, marcasite, and pyrite. A bulk fluid inclusion chemistry study was carried out on sulfide, coarse non‐saddle and saddle dolomite and calcite samples from the Pine Point and Great Slave Reef deposits, and unmineralized coarse non‐saddle and saddle dolomite samples from Hay West, Windy Point and Qito areas. Molar Cl/Br ratio data from Pine Point indicate the presence of four fluids at different stages of the paragenesis. The fluids trapped in sulfides and ore‐stage dolomites predominately consist of a Br‐rich fluid with a composition similar to that of evaporated seawater (fluid A), and a very Br‐enriched fluid of unknown origin (fluid B). Both these fluids are CaCl₂–NaCl (Na to Ca ratios of 1:10)‐rich brines and have compositions unlike the modern formation waters in the Devonian aquifers in the basin today. A third, relatively Cl‐rich (or Br‐poor), fluid (fluid C) was identified in two samples and may have acquired some chlorinity by dissolving halide minerals. Mixing between the Br‐rich fluid A and a dilute fluid also occurred in the later stages of the paragenesis, resulting in the formation of calcite and native sulfur. Saddle and coarse dolomites not associated with significant sulfide mineralization have a narrow range of halogen compositions similar to fluid A. There is no evidence of fluid B or C in the unmineralized samples. Relative to a modern‐day seawater compositions all the fluids have had some modification of their cation compositions. There is some weak evidence for interactions with clastic units or crystalline basement rocks. It is also possible however, that the evaporative brines could have formed from a relatively CaCl₂‐rich, NaCl‐depleted Devonian seawater, unlike the composition of modern‐day seawater.     

Sulfosalt melts and heavy metal (As‐Sb‐Bi‐Sn‐Pb‐Tl) fractionation during volcanic gas expansion: the El Indio (Chile) paleo‐fumarole

High‐sulfidation vein gold deposits such as El Indio, Chile, formed in fracture arrays <1000 m beneath paleo‐solfatara in volcanic terranes. Stable isotope data have confirmed a predominance of magmatic vapor during the deposition of arsenic‐rich sulfide–sulfosalt assemblages in this deposit. These provide a unique opportunity to analyze the processes and products of high‐temperature volcanic gas expansion in fractures that form the otherwise inaccessible infrastructure deep inside equivalent present‐day fumaroles. We provide field emission scanning electron microscope and LA‐ICP‐MS micro‐analytical data for the wide range of heavy, semi‐metals and metalloids (arsenic, antimony, bismuth, tin, silver, gold, tellurium and selenium) in the complex pyrite‐enargite‐Fe‐tennantite assemblages from Copper Stage mineralization in the El Indio deposit. These data document the progressive fractionation of antimony and other heavy metals, such as bismuth, during crystallization from a sulfosalt melt that condensed from expanding vapor at about 15 MPa (150 bars) and >650°C following higher temperature vapor deposition of crystalline pyrite and enargite. The sulfosalt melt aggressively corroded the earlier enargite and pyrite and hosts clusters of distinctive euhedral quartz crystals. The crystallizing sulfosalt melt also trapped an abundance of vugs within which heavy metal sulfide and sulfosalt crystals grew together with K‐Al silicates and fluorapatite. These data and their geologic context suggest that, in high‐temperature fumaroles on modern active volcanoes, over 90% of the arsenic content of the primary magmatic vapor (perhaps 2000 mg kg^?1) was precipitated subsurface as sulfosalt. Subsurface fractionation may also account for the range of exotic Pb‐Sn‐Bi‐Se sulfosalts observed in fumarole sublimates on active volcanoes such as Vulcano, Italy, as well as on extra‐terrestrial volcanoes such as Maxwell Montes, Venus.     

MINERALOGICAL AND PETROLOGICAL INVESTIGATIONS OF EARLY BRONZE AGE COPPER‐SMELTING REMAINS FROM THE KIECHLBERG (TYROL,AUSTRIA)

The prehistoric settlement on the Kiechlberg hilltop is located a few kilometres to the north‐east of Innsbruck, in the Tyrolean Inn Valley. Despite its rather isolated location, a multiphase settlement between the fifth and the second millennium bc was confirmed by archaeological investigations in 2007 and 2008. Metallurgical artefacts, such as copper ore fragments, copper slag and raw copper, as well as finished copper and bronze artefacts, are concentrated mainly in Late Copper Age to Middle Bronze Age layers. The chemical compositions of the slag and raw metals confirm Fe—Zn tetrahedrite–tennantite (fahlore) smelting. The ore was most probably imported from the 30–50 km distant copper ore deposits (mainly fahlore) of Schwaz–Brixlegg, in the Lower Inn Valley. The small amount of slag and the presence of slagged and thermally altered ceramic fragments suggest copper production in small‐scale workshops. Most probably, sulphide‐rich ores were smelted in crucibles in a hearth fire. The process was relatively reducing below the 2Sb + 1.5O₂ → Sb₂O₃ reaction (?8.5 log fO₂ at 1100°C), producing Sb‐rich (>10 wt% Sb in metal) raw copper. Inhomogeneous slag remains containing high amounts of sulphide and metal inclusions suggest a poor separation of the metal, matte (copper sulphide) and silicate/oxide melt during the smelting process.     

Fluids,basin analysis,and mineral deposits

Sedimentary basins are the largest structures on the surface of our planet and the most significant sources of energy‐related commodities. With time, sedimentary successions in basins normally are subjected to increasingly intense diagenesis that results in differential evolution of basin hydrology. This hydrologic structure is in turn vitally important in determining how and where deposition of metals may occur. Fluids in all basins originate and flow as a result of sedimentological and tectonic events, so that fluid histories should reflect the control of both lithology and tectonism on ore deposition. Sandstone lithologies, in particular, reflect fluid‐flow events because they are normally the major aquifers in basins. However, early cementation results in occlusion of primary permeability in some facies (diagenetic aquitards) whereas in others, permeability develops due to the dissolution of unstable grains (diagenetic aquifers). Particularly for ore deposits in Precambrian basins, identification of paleohydrologic systems during basin evolution requires the integration of data derived from tectonics, sedimentology, stratigraphy, diagenesis, geochemistry and geology. Assessment of all these data is a prerequisite for the ‘holistic basin analysis’ needed to guide the search for basin‐hosted ores. Recent results from the Paleoproterozoic Mt Isa and McArthur basins in northern Australia serve as a template for exploring for mineral deposits in basins. Basinal fluids were saline, 200–300°C and evolved primarily from meteoric water in the Mt Isa Basin and from seawater in the McArthur Basin during burial to depths of 4–12 km. The δD_fluid and δ¹⁸O_fluid values in these brines were isotopically identical to those in the Zn‐Pb, Cu and U deposits. Geochemical changes of various lithologies during alteration support detrital minerals as the major source of the U, and volcanic units proximal to diagenetic aquifers as a source for the transition metals. Ages of diagenetic phases extracted from aquifer lithologies reveal that fluid migration from the diagenetic aquifers effectively covers the period of formation for U, Zn‐Pb and Cu mineralization, and that the deposits formed in response to tectonic events reflected in the apparent polar wandering path for the area. Sequence stratigraphic analysis and models of fluid flow also indicate that basinal reservoirs were likely sources for the mineralizing fluids. Thus, diagenetic aquifer lithologies were being drained of fluids at the same time as the deposits were forming from fluids that were chemically and isotopically similar, linking diagenesis and fluid events within the basin to the formation of the deposits.     

A comprehensive review of hydrocarbons and genetic model of the sandstone‐hosted Dongsheng uranium deposit,Ordos Basin,China

The Dongsheng uranium deposit, the largest in situ leach uranium mine in the Ordos Basin, geometrically forms a roll‐front type deposit that is hosted in the Middle Jurassic Zhiluo Formation. The genesis of the mineralization, however, has long been a topic of great debate. Regional faults, epigenetic alterations in surface outcrops, natural oil seeps, and experimental findings support a reducing microenvironment during ore genesis. The bulk of the mineralization is coffinite. Based on thin‐section petrography, some of the coffinite is intimately intergrown with authigenic pyrite (ore‐stage pyrite) and is commonly juxtaposed with some late diagenetic sparry calcite (ore‐stage calcite) in primary pores, suggesting simultaneous precipitation. Measured homogenization temperatures of greater than 100°C from fluid inclusions indicate circulation of low‐temperature hydrothermal fluids in the ore zone. The carbon isotopic compositions of late calcite cement (δ¹³C_VPDB = ?31.0 to ?1.4‰) suggest that they were partly derived from sedimentary organic carbon, possibly from deep‐seated petroleum fluids emanating from nearby faults. Hydrogen and oxygen isotope data from kaolinite cement (δD = ?133 to ?116‰ and δ¹⁸O_SMOW = 12.6–13.8‰) indicate that the mineralizing fluids differed from magmatic and metamorphic fluids and were more depleted in D (²H) than modern regional meteoric waters. Such a strongly negative hydrogen isotopic signature suggests that there has been selective modification of δD by CH₄±H₂S±H₂ fluids. Ore‐stage pyrite lies within a very wide range of δ³⁴S (?39.2 to 26.9‰), suggesting that the pyrite has a complex origin and that bacterially mediated sulfate reduction cannot be precluded. Hydrocarbon migration and its role in uranium reduction and precipitation have here been unequivocally defined. Thus, a unifying model for uranium mineralization can be established: Early coupled bacterial uranium mineralization and hydrocarbon oxidation were followed by later recrystallization of ore phases in association with low‐temperature hydrothermal solutions under hydrocarbon‐induced reducing conditions.     

Mobilization of ore fluids during Alpine metamorphism: evidence from hydrothermal veins in the Variscan basement of Western Carpathians,Slovakia

Hydrothermal polymetallic veins of the Gemeric unit of the Western Carpathians are oriented coherently with the foliation of their low‐grade Variscan basement host. Early siderite precipitated from homogeneous NaCl‐KCl‐CaCl₂‐H₂O brines with minor CO₂, while immiscible gas–brine mixtures are indicative of the superimposed barite, quartz–tourmaline and quartz–sulphide stages. The high‐salinity aqueous fluid (18–35 wt%) found in all mineralization stages corresponds to formation water modified by interaction with crystalline basement rocks at temperatures between 140 and 300°C. High brominity (around 1000 ppm in average) resulted from evaporation and anhydrite precipitation in a Permo‐Triassic marine basin, and from secondary enrichment by dissolution of organic matter in the marine sediments at diagenetic temperatures. Sulphate depletion reflects thermogenic reduction during infiltration of the formation waters into the Variscan crystalline basement. Crystallization temperatures of the siderite fill (140–300°C) and oxygen isotope ratios of the parental fluids (4–10‰) increase towards the centre of the Gemeric cleavage fan, probably as a consequence of decreasing water/rock ratios in rock‐buffered hydrothermal systems operating during the initial stages of vein evolution. In contrast, buoyant gas–water mixtures, variable salinities and strongly fluctuating P–T parameters in the successive mineralization stages reflect transition from a closed to an open hydrothermal system and mixing of fluids from various sources. Depths of burial were 6–14 km (1.7–4.4 kbar, in a predominantly lithostatic fluid regime) during the siderite and barite sub‐stages of the north‐Gemeric veins, and up to 16 km (1.6–4.5 kbar, in a hydrostatic to lithostatic fluid regime) in the quartz–tourmaline stage of the south‐Gemeric veins. The fluid pressure decreased down to approximately 0.6 kbar during crystallization of sulphides. U‐Pb‐Th, ⁴⁰Ar/³⁹Ar and K/Ar geochronology applied to hydrothermal muscovite–phengite and monazite, as well as cleavage phyllosilicates in the adjacent basement rocks and deformed Permian conglomerates corroborated the opening of hydrothermal veins during Lower Cretaceous thrusting and their rejuvenation during Late Cretaceous sinistral transpressive shearing and extension.     

Polyphasic hydrothermal and meteoric fluid regimes during the growth of a segmented fault involving crystalline and carbonate rocks (Barcelona Plain,NE Spain)

A polyphasic tectonic‐fluid system of a fault that involves crystalline and carbonate rocks (Hospital fault, Barcelona Plain) has been inferred from regional to thin section scale observations combined with geochemical analyses. Cathodoluminescence, microprobe analyses and stable isotopy in fracture‐related cements record the circulation of successive alternations of hydrothermal and low‐temperature meteoric fluids linked with three main regional tectonic events. The first event corresponds to the Mesozoic extension, which had two rifting stages, and it is characterized by the independent tectonic activity of two fault segments, namely southern and northern Hospital fault segments. During the Late Permian‐Middle Jurassic rifting, these segments controlled the thickness and distribution of the Triassic sediments. Also, dolomitization was produced in an early stage by Triassic seawater at shallow conditions. During increasing burial, formation of fractures and their dolomite‐related cements took place. Fault activity during the Middle Jurassic–Late Cretaceous rifting was localized in the southern segment, and it was characterized by hydrothermal brines, with temperatures over 180°C, which ascended through this fault segment precipitating quartz, chlorite, and calcite. The second event corresponds to the Paleogene compression (Chattian), which produced exhumation, folding and erosion, favouring the percolation of low‐temperature meteoric fluids which produced the calcitization of the dolostones and of the dolomite cements. The third event is linked with the Neogene extension, where three stages have been identified. During the syn‐rift stage, the southern segment of the Hospital fault grew by tip propagation. In the relay zone, hydrothermal brines with temperature around 140°C upflowed. During the late postrift, the Hospital fault acted as a unique segment and deformation occurred at shallow conditions and under a low‐temperature meteoric regime. Finally, and possibly during the Messinian compression, NW‐SE strike‐slip faults offset the Hospital fault to its current configuration.