The Sweet Home rhodochrosite specimen mine,Alma District,Central Colorado: the porphyry molybdenum–fluorine connection

Intermediate sulfidation veins containing quartz–sphalerite–tetrahedrite–rhodochrosite–fluorite in the Sweet Home Mine, Alma District, Colorado were originally mined for silver starting in 1873. For the last 13 years up until 2004, however, the mine has produced world-class rhodochrosite specimens. Some of these specimens are considered to be among the finest mineral specimens ever produced and the finest of their species with values well over $1 million US dollars. The extraction, preparation, and marketing techniques pioneered at the Sweet Home operation have revolutionized the minerals specimen industry. The Sweet Home deposit is interpreted as a single pulse variant of a Climax-type hydrothermal system. Evidence for this includes (1) an age of mineralization (25.8 ± 0.3 Ma) that coincides with the age of the end stages of mineralization of the Climax molybdenum deposit approximately 7.5 km to the northeast; (2) a geochemical (Mn, W, F) and mineralogical (topaz, fluorite, hubnerite, greisen muscovite) signature typically associated with Climax-type systems; (3) the presence of porphyry rhyolite dikes, a breccia dike, and local quartz–molybdenite veins in the nearby area; (4) a small pegmatite within the mine with an age (25.9 ± 0.3 Ma) coincident with mineralization, which also contains minor amounts of disseminated molybdenite; and (5) the presence of similar-appearing gemmy, red rhodochrosites at Climax and other high-silica rhyolite systems. A significant difference is that unlike Climax-type systems, the Sweet Home hydrothermal system appears to have consisted of a single, relatively small pulse of magmatic fluid that slowly cooled and diluted with groundwater. This is inferred to have occurred at moderate depths in the order of 1.5–2.5 km below the surface. The fluids that formed the Sweet Home veins were dilute (salinity in the order of 2–4 wt% NaCl equivalent), high-temperature (temperatures of homogenization up to 370°C), and initially of magmatic origin. Gem quality ruby-red rhodochrosite at the Sweet Home Mine is nearly pure manganese carbonate with minimal solid solution with Fe⁺², Ca, or Mg. It formed at higher temperatures and salinities in comparison to lower value, pink rhodochrosite. Gemmy, ruby-red rhodochrosite is distinctly associated with highly evolved silica-rich igneous/hydrothermal systems. The high fluorine content typical of such systems suggests that Mn was transported in solution as fluoride complexes, which, in turn, favored rhodochrosite deposition at above-average temperatures and with minimal cation contamination. An erratum to this article can be found at     

A Sr isotope study on fluorite and siderite from post-orogenic mineral veins in the eastern Harz Mountains,Germany

Rb–Sr isotope data for siderite and fluorite from sediment-hosted epithermal mineral veins in the eastern Harz Mountains (Germany) are presented. Several fluorite and siderite-bearing paragenetic stages have been proposed for these veins, with the most important mineralization being related to a quartz–sulfide and a subsequent calcite–fluorite–quartz stage, which occurred at 226±1 and 209±2 Ma, respectively. Our Rb–Sr data do not permit the identification of distinct generations of siderite and fluorite, but rather reveal straight internal mixing relations, reflecting mixing of fluids or differential fluid–rock interaction processes. This indicates merely two significant phases of mineral deposition related to the quartz–sulfide and calcite–fluorite–quartz stages. It is shown that the Paleozoic sedimentary host rocks of the veins are the most likely source for the siderite Sr, whereas fluorite displays a two-component mixture between sedimentary Sr and radiogenic Sr derived from locally occurring Permian metavolcanic rocks. Editorial handling: B. Lehmann     

Stable isotope and fluid inclusion evidence for the origin of the Brandberg West area Sn–W vein deposits, NW Namibia

The Brandberg West region of NW Namibia is dominated by poly-deformed turbidites and carbonate rocks of the Neoproterozoic Damara Supergoup, which have been regionally metamorphosed to greenschist facies and thermally metamorphosed up to mid-amphibolite facies by Neoproterozoic granite plutons. The meta-sedimentary rocks host Damaran-age hydrothermal quartz vein-hosted Sn–W mineralization at Brandberg West and numerous nearby smaller deposits. Fluid inclusion microthermometric studies of the vein quartz suggests that the ore-forming fluids at the Brandberg West mine were CO₂-bearing aqueous fluids represented by the NaCl–CaCl₂–H₂O–CO₂ system with moderate salinity (mean=8.6 wt% NaCl_equivalent).Temperatures determined using oxygen isotope thermometry are 415–521°C (quartz–muscovite), 392–447°C (quartz–cassiterite), and 444–490°C (quartz–hematite). At Brandberg West, the oxygen isotope ratios of quartz veins and siliciclastic host rocks in the mineralized area are lower than those in the rocks and veins of the surrounding areas suggesting that pervasive fluid–rock interaction occurred during mineralization. The O- and H-isotope data of quartz–muscovite veins and fluid inclusions indicate that the ore fluids were dominantly of magmatic origin, implying that mineralization occurred above a shallow granite pluton. Simple mass balance calculations suggest water/rock ratios of 1.88 (closed system) and 1.01 (open system). The CO₂ component of the fluid inclusions had similar δ ¹³C to the carbonate rocks intercalated with the turbidites. It is most likely that mineralization at Brandberg West was caused by a combination of an impermeable marble barrier and interaction of the fluids with the marble. The minor deposits in the area have quartz veins with higher δ ¹⁸O values, which is consistent with these deposits being similar geological environments exposed at higher erosion levels.     

Relative age of Cordilleran base metal lode and replacement deposits, and high sulfidation Au–(Ag) epithermal mineralization in the Colquijirca mining district, central Peru

At Colquijirca, central Peru, a predominantly dacitic Miocene diatreme-dome complex of 12.4 to 12.7 Ma (⁴⁰Ar/³⁹Ar biotite ages), is spatially related to two distinct mineralization types. Disseminated Au–(Ag) associated with advanced argillic alteration and local vuggy silica typical of high- sulfidation epithermal ores are hosted exclusively within the volcanic center at Marcapunta. A second economically more important mineralization type is characterized as "Cordilleran base metal lode and replacement deposits." These ores are hosted in Mesozoic and Cenozoic carbonate rocks surrounding the diatreme-dome complex and are zoned outward from pyrite–enargite–quartz–alunite to pyrite–chalcopyrite–dickite–kaolinite to pyrite–sphalerite–galena–kaolinite–siderite. Alunite samples related to the Au–(Ag) epithermal ores have been dated by the ⁴⁰Ar/³⁹Ar method at 11.3–11.6 Ma and those from the Cordilleran base metal ores in the northern part of the district (Smelter and Colquijirca) at 10.6–10.8 Ma. The significant time gap (~0.5 My) between the ages of the two mineralization types in the Colquijirca district indicates they were formed by different hydrothermal events within the same magmatic cycle. The estimated time interval between the younger mineralization event (base metal mineralization) at ~10.6 Ma and the ages of ~12.5 Ma obtained on biotites from unmineralized dacitic domes flanking the vicinity of the diatreme vent, suggest a minimum duration of the magmatic–hydrothermal cycle of around 2 Ma. This study on the Colquijirca district offers for the first time precise absolute ages indicating that the Cordilleran base metal lode and replacement deposits were formed by a late hydrothermal event in an intrusive-related district, in this case post Au–(Ag) high-sulfidation epithermal mineralization.Electronic Supplementary Material Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.Editorial handling: O. Christensen     

Origin and granite alteration effects of hydrothermal fluid: isotopic evidence from fluorite veins, Co. Galway, Ireland

The Costelloe Murvey Granite is a chemically evolved, high heat production, leucocratic component of the 400 Ma old Galway Granite batholith and is host to hydrothermal fluorite-quartz-calcite veins. A previously reported clinopyroxene ⁴⁰Ar-³⁹Ar age of 231±4 Ma obtained from a pre-mineralization dolerite dyke is reinterpreted as dating this mineralization. The hydrothermal fluid extensively altered its granite wallrocks, leading to lower Sm and Nd and higher Rb concentrations in altered granite, disturbing both its Rb-Sr and Sm-Nd isotopic systems. The ⁸⁷Sr/⁸⁶Sr ratio of the hydrothermal fluid from which fluorite and calcite precipitated ranged from 0.7101 to 0.7139. These ratios are very much lower than in the Costelloe Murvey Granite at the time of mineralization, precluding the granite as a source for more than 2% of the hydrothermal Sr. The initial ¹⁴³Nd/¹⁴⁴Nd ratio varies between fluorite in different veins due to Nd derivation from local wallrocks, and between fluorite of petrographically distinct growth phases within a single hand specimen, highlighting the difficulty of Sm-Nd isochron dating of fluorite in cases where there are multiple sources of hydrothermal Nd. It is proposed that fluorite and calcite precipitated where hot, dilute fluids rising through the granite mixed with cooler, more saline fluids of basinal origin migrating through Lower Carboniferous limestone which then overlay the granite. Received: 3 August 1995 / Accepted: 11 April 1996     

Cenozoic collisional tectonics and origin of Pb-Zn-F mineralization in the Bitlis Massif,SE Turkey

Hasbey Pb-Zn-F mineralization in the Bitlis Massif, south of Lake Van, lies within the Neotethyan suture of the Alpine orogenic belt. Mineralization occurs in two different lithologies and locations: Type-I is present in dolostone fractures and faults as veins and veinlets, whereas Type-II occupies a fault zone between black marbles and calc-schists. Sphalerite and argentiferous galena are the main ore minerals in both types. The dominant gangue minerals are quartz and dolomite in Type-I ore and calcite, quartz, and green-white fluorite in Type-II. Analysed fluid inclusion data from sphalerite, fluorite, and quartz indicate that high-temperature (>500°C) mineralization was initiated from low-salinity fluids (4.3 wt.% NaCl equiv.). As temperatures dropped from 400°C to 160°C, the salinity of solutions increased and appreciable CO₂ was contributed to the fluid system. In the absence of immiscibility, assemblages of fluid inclusions containing CO₂ indicate that the solutions were homogeneous during entrapment and that mineralization took place under pressure conditions between 5 and 2 kb.

Analysed δ³⁴S _CDT (‰) values (?1.5 and??3.8, n?=?15) of sphalerite and galena indicate that the source of the sulphur is consistent with a magmatic origin for Hasbey Pb-Zn-F mineralization. The stable isotopic compositions and fluid inclusions in fluorite are also suggestive of an origin related to high-temperature, high-salinity magmatic fluids. In the region, volcanic rocks are abundant, and they document the magmatic events associated with the closure of the neo-Tethys.

The timing of mineralization is restricted to post-early Oligocene, inasmuch as mineralization occurs in faults that cut post-Eocene–Oligocene thrust faults and because of the relationship between mineralization and wall-rock deformation.     

Metamorphic fluid origins in the Osborne Fe oxide–Cu–Au deposit,Australia: evidence from noble gases and halogens

The Osborne iron oxide–copper–gold (IOCG) deposit is hosted by amphibolite facies metasedimentary rocks and associated with pegmatite sheets formed by anatexis during peak metamorphism. Eleven samples of ore-related hydrothermal quartz and two pegmatitic quartz–feldspar samples contain similarly complex fluid inclusion assemblages that include variably saline (<12–65 wt% salts) aqueous and liquid carbon dioxide varieties that are typical of IOCG mineralisation. The diverse fluid inclusion types present in each of these different samples have been investigated by neutron-activated noble gas analysis using a combination of semi-selective thermal and mechanical decrepitation techniques. Ore-related quartz contains aqueous and carbonic fluid inclusions that have similar ⁴⁰Ar/³⁶Ar values of between 300 and 2,200. The highest-salinity fluid inclusions (47–65 wt% salts) have calculated ³⁶Ar concentrations of approximately 1–5 ppb, which are more variable than air-saturated water (ASW = 1.3–2.7 ppb). These fluid inclusions have extremely variable Br/Cl values of between 3.8 × 10⁻³ and 0.3 × 10⁻³, and I/Cl values of between 27 × 10⁻⁶ and 2.4 × 10⁻⁶ (all ratios are molar). Fluid inclusions in the two pegmatite samples have similar ⁴⁰Ar/³⁶Ar values of ≤1,700 and an overlapping range of Br/Cl and I/Cl values. High-salinity fluid inclusions in the pegmatite samples have 2.5–21 ppb ³⁶Ar, that overlap the range determined for ore-related samples in only one case. The fluid inclusions in both sample groups have ⁸⁴Kr/³⁶Ar and ¹²⁹Xe/³⁶Ar ratios that are mainly in the range of air and air-saturated water and are similar to mid-crustal rocks and fluids from other settings. The uniformly low ⁴⁰Ar/³⁶Ar values (<2,200) and extremely variable Br/Cl and I/Cl values do not favour a singular or dominant fluid origin from basement- or mantle-derived magmatic fluids related to A-type magmatism. Instead, the data are compatible with the involvement of metamorphic fluids that have interacted with anatectic melts to variable extents. The ‘metamorphic’ fluids probably represent a mixture of (1) inherited sedimentary pore fluids and (2) locally derived metamorphic volatilisation products. The lowest Br/Cl and I/Cl values and the ultra-high salinities are most easily explained by the dissolution of evaporites. The data demonstrate that externally derived magmatic fluids are not a ubiquitous component of IOCG ore-forming systems, but are compatible with models in which IOCG mineralisation is localised at sites of mixing between fluids of different origin. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorised users.     

Sr and Nd isotope data from the fluorspar district of Asturias, northern Spain

The origin and age of the hydrothermal fluids related to the precipitation of fluorite, barite and calcite in the Villabona, La Collada and Berbes localities (Asturias fluorspar district, N Spain) have been evaluated from Sr and Nd radiogenic isotopes. Sr isotope data (⁸⁷Sr / ⁸⁶Sr = 0.7081 to 0.7096) are compatible with mixing between seawater and a more evolved groundwater that interacted with the basement. From Nd isotopes in fluorite, an isochron age of 185 ± 29 Ma (Lower Jurassic) was obtained, consistent with other hydrothermal events in the Iberian Peninsula and Europe. These constraints are essential to proceed with a quantitative model for the genesis of the mineralization that includes fluid and heat flow together with reactive transport of solutes.     

Himalayan Cu–Mo–Au mineralization in the eastern Indo–Asian collision zone: constraints from Re–Os dating of molybdenite

We present new Re–Os molybdenite age data on three porphyry Cu–Mo–Au deposits (Yulong, Machangqing, and Xifanping). These deposits are associated with the Himalayan adakitic magmatism that occurred in a continental collision environment, controlled by large-scale Cenozoic strike-slip faults in the eastern Indo–Asian collision zone. Three distinct episodes of Cu–Mo–Au mineralization are recognized. At Yulong, Re–Os isotopic data of four molybdenite samples from sulfide-quartz veins in the quartz–sericite alteration zone yield an isochron with an age of 40.1±1.8 Ma (2σ), coincident to a zircon sensitive high-mass resolution ion microprobe (SHRIMP) age of 40.9±0.1 Ma for the host monzogranite. The molybdenite Re–Os dates, together with K–Ar, Rb–Sr, U–Pb, and ⁴⁰Ar/³⁹Ar dates on the pre- and intra-ore porphyries, suggest that Cu–Mo–Au mineralization formed during the late stage (∼40 Ma) of regional porphyry magmatism, but hydrothermal activity probably lasted to at least ∼36 Ma. At Machangqing, molybdenite Re–Os data from the K–silicate and quartz–sericite alteration zones yield an isochron with an age of 35.8±1.6 Ma (2σ), which is identical to the zircon SHRIMP and bulk-rock Rb–Sr ages (35∼36 Ma) of the host granite, but older than bulk-rock K–Ar dates (31∼32 Ma) for associated Au-bearing quartz syenite with advanced argillic alteration. At Xifanping, five molybdenite samples from the K–silicate alteration zone yield the youngest Re–Os isochron age in the area, at 32.1±1.6 Ma (2σ). The Re–Os molybdenite dates here are younger than K–Ar ages (33.5∼34.6) for hydrothermal biotite and actinolite. There is a positive correlation between the absolute age of the deposits and their Cu and Au reserves in the eastern Indo–Asian collisional zone. Episodic stress relaxation probably caused multiple magmatic intrusions, which most likely resulted in three episodes of Cu–Mo–Au mineralization in the eastern Indo–Asian collision zone.     

The use of vein fluorite as probe for paleofluid REE and Sr-Nd isotope geochemistry: The Santa Catarina Fluorite District, Southern Brazil

Fluorite can be used as a probe for the source of Sr and REE, as well as for the Sr and Nd isotope systematics of mineralizing solutions, allowing characterization of the composition, oxidation state and sources of the fluids. The ⁸⁷Sr / ⁸⁶Sr ratios in vein fluorite from the Santa Catarina Fluorite District, southern Brazil, are low (0.720 to 0.745) relative to those of the majority of host granites at the time of mineralization (90 Ma), but are similar to those of less abundant and less evolved Sr- and Ca-rich granites and plagioclases of the heterogeneous Pedras Grandes granite association. Major contributions of Sr from the unradiogenic Parana Basin rocks (⁸⁷Sr / ⁸⁶Sr_{90 Ma} = 0.705 to 0.718) are unlikely, considering the radiogenic character of the lower ⁸⁷Sr / ⁸⁶Sr end-member in fluorite mixing lines. Estimated fluorite fluid partition coefficients (K_d^Sr-Ca = 0.019 and D^Sr ≈ 600) indicate a Sr / Ca ratio in the fluorite-forming solution of 0.012, and Sr contents of 0.05 to 0.25 ppm, which are similar to those of present-day granitic geothermal waters. Initial Nd isotopic compositions of the vein fluorites (0.5120 to 0.512) are similar to those of the Pedras Grandes granites. The ¹⁴³Nd / ¹⁴⁴Nd_{90 Ma} of the evolved granites of the Tabuleiro granite association, their accessory fluorites and the Parana Basin rocks are considerably more radiogenic (0.5120 to 0.5127) and these are thus considered to be unlikely sources of the fluids. The REE patterns of vein fluorites, normalized to upper continental crust, show a range of LREE-depleted patterns, with highly variable positive and negative Eu anomalies. The host Pedras Grandes granites show flat to slightly depleted UCC normalized LREE patterns with strong negative Eu anomalies. Depletion of the LREE in fluorites resulted from the mobility of HREE fluoride complexes during fluid migration. A REE fractionation model based on ionic potential ratios indicates that Eu³⁺ was stable during fluid migration and fluorite precipitation. The coexistence of pyrite and Eu³⁺ in the mineralizing fluids is consistent with low pH and oxygen fugacities near the hematite-magnetite buffer.     

Timing of Uralian orogenic gold mineralization at Kochkar in the evolution of the East Uralian granite-gneiss terrane

Gold mineralization at Kochkar (Urals, Russia) is hosted mainly by quartz lodes, which developed at lithological contacts between mafic dikes and granitoids of the Plast massif during late Carboniferous to early Permian, regional E–W compression in the East Uralian Zone (EUZ). The alteration mineralogy in mafic dikes comprises biotite, actinolite, albite, K-feldspar, quartz, epidote, tourmaline, sericite, pyrite, arsenopyrite, chalcopyrite, sphalerite, fahlores, galena, bismuthinite, and gold, and in Plast granitoids quartz, sericite, calcite, epidote, and ore minerals. Geochemically, an enrichment of Si, K, Rb, Ba, S, base metals, W, and Au can be observed. The ore fluid had δ¹⁸O values between 8.2‰ and 9.5‰ typical for metamorphic or deep magmatic fluids. The tectonometamorphic evolution of the EUZ is marked by peak metamorphic conditions at 635±40°C and 5–6 kbar through 500±20°C during gold mineralization, and 300–350°C and 2–3 kbar. The last event was dated on a late, barren quartz vein formed during greenschist facies metamorphism at 265±3 Ma by the Rb–Sr method. Fluids related to this overprint had a δ¹⁸O value of 5.2‰ and an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.70685 indicating that they are largely equilibrated with metamorphic lithologies of the EUZ. The Plast granitoids and the adjacent Borisov granite, which was dated at 358±23 Ma (U–Pb zircon age), have an adakitic character. This, together with the arc-signature of the mafic dikes, supports the setting of the EUZ within the Valerianovsky continental arc. Eastward subduction of the Uralian Ocean below this arc began during the late Devonian to early Carboniferous. Between 320 and 265 Ma, the oblique closure of the ocean resulted in doming of granitoid massifs in a sinistral transpressional regime, subsequent retrograde gold mineralization during E–W compression and a later greenschist facies overprint. This long-lasting retrograde evolution of the EUZ was caused by the lack of postcollisional collapse. Heat for a “deep-later" type of metamorphism and triggering the auriferous fluid system was supplied by radiogenic heating of an overthickened crust. The greenschist facies overprint at Kochkar and coeval crustal melting in the EUZ was additionally initiated by local external heating of the terrane. This could have been caused by syn- to postcollisional slab rollback or delamination resulting in magmatic underplating of the EUZ, which postdates orogenic gold mineralization at Kochkar. The tectonic interpretation of the EUZ indicates that gold mineralization at Kochkar formed in a mid-crustal environment of a continental magmatic arc at the cessation of active subduction predating post orogenic plutonism.     

O,H, and Sr isotope evidences of mixing processes in two geothermal fluid reservoirs at Yangbajing,Tibet, China

The Yangbajing geothermal field with the highest reservoir temperature among Chinese hydrothermal systems is located about 90 km northwest to Lhasa City, capital of Tibet, where high temperature geothermal fluids occur in two reservoirs: a shallow one at a depth of 180–280 m and a deep one at 950–1,850 m. In this study, Oxygen-18 and deuterium isotope compositions as well as ⁸⁷Sr/⁸⁶Sr ratios of water samples collected from geothermal wells, cold springs and surface water bodies were characterized to understand the genesis of geothermal fluids at Yangbajing. The results show that the deep geothermal fluid is the mixing product of both magmatic and infiltrating snow-melt water, whereas the shallow geothermal fluid is formed by the mixing of deep geothermal fluid with cold groundwater. Using a binary mixing model with deep geothermal fluid and cold groundwater as two endmembers, the mixing ratios of the latter in most shallow geothermal water samples were calculated to be between 40 and 50%. The combined use of O, H, and Sr isotopes proves to be an effective approach to depict the major sources of geothermal fluids and the mixing processes occurring in two reservoirs at Yangbajing.     

Sulfur isotopic zonation in the Cadia district,southeastern Australia: exploration significance and implications for the genesis of alkalic porphyry gold–copper deposits

The alkalic porphyry gold–copper deposits of the Cadia district occur in the eastern Lachlan Fold Belt of New South Wales, Australia. The district comprises four porphyry deposits (Ridgeway, Cadia Quarry, Cadia Hill, and Cadia East) and two iron–copper–gold skarn deposits (Big Cadia and Little Cadia). Almost 1,000 tonnes of contained gold and more than four million tonnes of copper have been discovered in these systems, making Cadia the world’s largest known alkalic porphyry district, in terms of contained gold. Porphyry gold–copper ore at Cadia is associated with quartz monzonite intrusive complexes, and is hosted by central stockwork and sheeted quartz–sulfide–(carbonate) vein systems. The Cadia porphyry deposits are characterized by cores of potassic and/or calc–potassic alteration assemblages, and peripheral halos of propylitic alteration, with late-stage phyllic alteration mostly restricted to fault zones. Hematite dusting is an important component of the propylitic alteration assemblage, and has produced a distinctive reddening of feldspar minerals in the volcanic wall rocks around the mineralized centers. Sulfide mineralization is strongly zoned at Ridgeway and Cadia East, with bornite-rich cores surrounded by chalcopyrite-rich halos and peripheral zones of pyrite mineralization. The Cadia Hill and Cadia Quarry deposits have chalcopyrite-rich cores and pyrite-rich halos, and Cadia Hill contains a high-level bornite-rich zone. Distinctive sulfur isotopic zonation patterns have been identified at Ridgeway, Cadia Hill, and Cadia East. The deposit cores are characterized by low δ³⁴S_sulfide values (−10 to −4‰), consistent with sulfide precipitation from an oxidized (sulfate-predominant) magmatic fluid at 450 to 400°C. Pyrite grains that occur in the propylitic alteration halos typically have δ³⁴S_sulfide values near 0‰. There is a gradual increase in δ³⁴S_sulfide values outwards from the deposit cores through the propylitic halos. Water–rock interaction during propylitic alteration caused magmatic sulfate reduction and concomitant oxidation of ferrous iron-bearing minerals, resulting in enrichment of ³⁴S in pyrite and also producing the distinctive reddened, hematite-rich alteration halos to the Cadia deposits. These results show that sulfur isotope analyses have potential applications in the exploration of alkalic porphyry-style deposits, with zones of depleted δ³⁴S_sulfide values most prospective for high-grade mineralization.     

Formation of the Vysoká–Zlatno Cu–Au skarn–porphyry deposit, Slovakia

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu–Au skarn–porphyry mineralisation, related to granodiorite/quartz–diorite porphyry dyke clusters and stocks. Vysoká–Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg–Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na–Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31–70 wt.% NaCl eq. and temperatures of liquid–vapour homogenization (Th) of 186–575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1–31 wt.% NaCl eq. and Th of 320–360°C. Quartz–chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0–3 wt.% NaCl eq. and Th of 323–364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ¹⁸O_fluid 2.5–12.3‰) with a minor meteoric component. Corresponding low δD_fluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile–brittle transition. The magma chamber at ∼5–6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid–vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.     

Multi-stage Ag–Bi–Co–Ni–U and Cu–Bi vein mineralization at Wittichen,Schwarzwald, SW Germany: geological setting,ore mineralogy,and fluid evolution

The Wittichen Co–Ag–Bi–U mining area (Schwarzwald ore district, SW Germany) hosts several unconformity-related vein-type mineralizations within Variscan leucogranite and Permian to Triassic redbeds. The multistage mineralization formed at the intersection of two fault systems in the last 250 Ma. A Permo-Triassic ore stage I with minor U–Bi–quartz–fluorite mineralization is followed by a Jurassic to Cretaceous ore stage II with the main Ag and Co mineralization consisting of several generations of gangue minerals that host the sub-stages of U–Bi, Bi–Ag, Ni–As–Bi and Co–As–Bi. Important ore minerals are native elements, Co and Ni arsenides, and pitchblende; sulphides are absent. The Miocene ore stage III comprises barite with the Cu–Bi sulfosalts emplectite, wittichenite and aikinite, and the sulphides anilite and djurleite besides native Bi, chalcopyrite, sphalerite, galena and tennantite. The mineral-forming fluid system changed from low salinity (<5 wt.% NaCl) at high temperature (around 300°C) in Permian to highly saline (around 25 wt.% NaCl + CaCl₂) at lower temperatures (50–150°C) in Triassic to Cretaceous times. Thermodynamic calculations and comparison with similar mineralizations worldwide show that the Mesozoic ore-forming fluid was alkaline with redox conditions above the hematite–magnetite buffer. We suggest that the precipitation mechanism for native elements, pitchblende and arsenides is a decrease in pH during fluid mixing processes. REE patterns in fluorite and the occurrence of Bi in all stages suggest a granitic source of some ore-forming elements, whereas, e.g. Ag, Co and Ni probably have been leached from the redbeds. The greater importance of Cu and isotope data indicates that the Miocene ore stage III is more influenced by fluids from the overlying redbeds and limestones than the earlier mineralization stages.     

Siderite mineralization of the Gemericum superunit (Western Carpathians, Slovakia): review and a revised genetic model

The Gemericum is a segment of the Variscan orogen subsequently deformed by the Alpine–Carpathian orogeny. The unit contains abundant siderite–sulphide and quartz–antimony veins together with stratabound siderite replacement deposits in limestones and stratiform sulphide mineralization in volcano-sedimentary sequences. The siderite–sulphide veins and siderite replacement deposits of the Gemericum represent one of the largest accumulations of siderite in the world, with about 160 million tonnes of mineable FeCO₃. More than 1200 steeply dipping hydrothermal veins are arranged in a regional tectonic and compositional pattern, reflecting the distribution of regional metamorphic zones. Siderite–sulphide veins are typically contained in low-grade (chlorite zone) sedimentary, volcano-sedimentary or volcanic Lower and Upper Paleozoic rocks. Quartz–antimony veins are hosted by higher-grade units (biotite zone). Siderite–sulphide veins are dominated by early siderite followed by a complex set of stages, including quartz–sulphide (chalcopyrite, tetrahedrite), barite, tourmaline–quartz, and sulphide-remobilization stages. The temporal evolution of these stages is difficult to study because of the widespread and repeated tectonic processes, within-vein replacement and recrystallization. Siderite–sulphide veins show considerable vertical (up to 1200 m) and lateral (up to 15 km) extent, and a thickness typically reaching several metres. Carbonate-replacement siderite deposits of the Gemericum are hosted by a Silurian limestone belt and are similar to stratabound siderite deposits of the Eastern Alps (e.g., Erzberg, Austria).Based on a review of geological, petrological and geochronological data for the Gemericum, and extensive stable and radiogenic isotope data and fluid inclusion data on hydrothermal minerals, the siderite–sulphide veins and siderite replacement deposits are classified as metamorphogenic in a broad sense. The deposits were formed during several stages of regional crustal-scale fluid flow. Isotope (S, C, Sr, Pb) fingerprinting identifies the metamorphosed rock complexes of the Gemericum as a source of most components of hydrothermal fluids. Fluid inclusion and stable isotope data evidence the participation of several contrasting fluid types, and the existence of contrasting P–T conditions during vein evolution. A high-δ¹⁸O, medium- to high-salinity, H₂O-type fluid is the most important component during siderite deposition, whereas H₂O–CO₂-type fluid inclusion containing dense liquid CO₂ and corresponding to minimal pressures between 1 and 3 kbar were found in a younger tourmaline–quartz stage. Younger quartz–ankerite(±siderite)–sulphide stages are characterized by high-salinity (17 to 35 wt.% NaCl equivalent) and low-temperature (T_h=90 to 180 °C) H₂O-type fluids.The vein deposits are interpreted as a result of multistage hydrothermal circulation, with Variscan and Alpine mineralization phases. Based on available indirect data, the most important mineralization phase was related to regional fluid flow during the uplift of a Variscan metamorphic core complex, producing siderite–sulphide (±barite) mineralization, while tourmaline–quartz stage and sulphide remobilization stages are related to Alpine processes. Two phases of vein evolution are evident from two groups of ⁸⁷Sr/⁸⁶Sr isotope ratios of Sr-rich, Rb-poor hydrothermal minerals: 0.71042–0.71541 in older barite and 0.7190–0.7220 in late-stage celestine and strontianite.     

Himalayan magmatism and porphyry copper–molybdenum mineralization in the Yulong ore belt, East Tibet

Summary ?The NW–SE-trending Yulong porphyry Cu–Mo ore belt, situated in the Sanjiang0 area of eastern Tibet, is approximately 400 km long and 35 to 70 km wide. Complex tectonic and magmatic processes during the Himalayan epoch have given rise to favorable conditions for porphyry-type Cu–Mo mineralization. Porphyry masses of the Himalayan epoch in the Yulong ore belt are distributed in groups along regional NW–SE striking tectonic lineaments. They were emplaced mainly into Triassic and Lower Permian sedimentary-volcanic rocks. K–Ar und U–Pb isotopic datings give an intrusion age range of 57–26 Ma. The porphyries are mainly of biotite monzogranitic and biotite syenogranitic compositions. Geological and geochemical data indicate that the various porphyritic intrusions in the belt had a common or similar magma source, are metaluminous to peraluminous, Nb–Y–Ba-depleted, I-type granitoids, and belong to the high-K calc-alkaline series. Within the Yulong subvolcanic belt a number of porphyry stocks bear typical porphyry type Cu–Mo alteration and mineralization. The most prominent porphyry Co–Mo deposits include Yulong, Malasongduo, Duoxiasongduo, Mangzong and Zhanaga, of which Yulong is one of the largest porphyry Cu (Mo) deposits in China with approximately 8 × 10⁶ tons of contained Cu metal. Hydrothermal alteration at Yulong developed around a biotite–monzogranitic porphyry stock that was emplaced within Upper Triassic limestone, siltstone and mudstone. The earliest alteration was due to the effects of contact metamorphism of the country rocks and alkali metasomatism (potassic alteration) within and around the porphyry body. The alteration of this stage was accompanied by a small amount of disseminated and veinlet Cu–Mo sulfide mineralization. Later alteration–mineralization zones form more or less concentric shells around the potassic zone, around which are distributed a phyllic or quartz–sericite–pyrite zone, a silicification and argillic zone, and a propylitic zone. Fluid inclusion data indicate that three types of fluids were involved in the alteration–mineralization processes: (1) early high temperature (660–420 °C) and high salinity (30–51 wt% NaCl equiv) fluids responsible for the potassic alteration and the earliest disseminated and/or veinlet Cu–Mo sulfide mineralization; (2) intermediate unmixed fluids corresponding to phyllic alteration and most Cu–Mo sulfide mineralization, with salinities of 30–50 wt% NaCl equiv and homogenization temperatures of 460–280 °C; and (3) late low to moderate temperature (300–160 °C) and low salinity (6–13 wt% NaCl equiv) fluids responsible for argillic and propylitic alteration. Hydrogen and oxygen isotopic studies show that the early hydrothermal fluids are of magmatic origin and were succeeded by increasing amounts of meteoric-derived convective waters. Sulfur isotopes also indicate a magmatic source for the sulfur in the early sulfide mineralization, with the increasing addition of sedimentary sulfur outward from the porphyry stock. Received August 29, 2001; revised version accepted May 1, 2002 Published online: November 29, 2002     

Hydrocarbon- and ore-bearing basinal fluids: a possible link between gold mineralization and hydrocarbon accumulation in the Youjiang basin,South China

The Youjiang basin, which flanks the southwest edge of the Yangtze craton in South China, contains many Carlin-type gold deposits and abundant paleo-oil reservoirs. The gold deposits and paleo-oil reservoirs are restricted to the same tectonic units, commonly at the basinal margins and within the intrabasinal isolated platforms and/or bioherms. The gold deposits are hosted by Permian to Triassic carbonate and siliciclastic rocks that typically contain high contents of organic carbon. Paragenetic relationships indicate that most of the deposits exhibit an early stage of barren quartz ± pyrite (stage I), a main stage of auriferous quartz + arsenian pyrite + arsenopyrite + marcasite (stage II), and a late stage of quartz + calcite + realgar ± orpiment ± native arsenic ± stibnite ± cinnabar ± dolomite (stage III). Bitumen in the gold deposits is commonly present as a migrated hydrocarbon product in mineralized host rocks, particularly close to high grade ores, but is absent in barren sedimentary rocks. Bitumen dispersed in the mineralized rocks is closely associated and/or intergrown with the main stage jasperoidal quartz, arsenian pyrite, and arsenopyrite. Bitumen occurring in hydrothermal veins and veinlets is paragenetically associated with stages II and III mineral assemblages. These observations suggest an intimate relationship between bitumen precipitation and gold mineralization. In the paleo-petroleum reservoirs that typically occur in Permian reef limestones, bitumen is most commonly observed in open spaces, either alone or associated with calcite. Where bitumen occurs with calcite, it is typically concentrated along pore/vein centers as well as along the wall of pores and fractures, indicating approximately coeval precipitation. In the gold deposits, aqueous fluid inclusions are dominant in the early stage barren quartz veins (stage I), with a homogenization temperature range typically of 230°C to 270°C and a salinity range of 2.6 to 7.2 wt% NaCl eq. Fluid inclusions in the main and late-stage quartz and calcite are dominated by aqueous inclusions as well as hydrocarbon- and CO₂-rich inclusions. The presence of abundant hydrocarbon fluid inclusions in the gold deposits provides evidence that at least during main periods of the hydrothermal activity responsible for gold mineralization, the ore fluids consisted of an aqueous solution and an immiscible hydrocarbon phase. Aqueous inclusions in the main stage quartz associated with gold mineralization (stage II) typically have a homogenization temperature range of 200–230°C and a modal salinity around 5.3 wt% NaCl eq. Homogenization temperatures and salinities of aqueous inclusions in the late-stage drusy quartz and calcite (stage III) typically range from 120°C to 160°C and from 2.0 to 5.6 wt% NaCl eq., respectively. In the paleo-oil reservoirs, aqueous fluid inclusions with an average homogenization temperature of 80°C are dominant in early diagenetic calcite. Fluid inclusions in late diagenetic pore- and fissure-filling calcite associated with bitumen are dominated by liquid C₂H₆, vapor CH₄, CH₄–H₂O, and aqueous inclusions, with a typical homogenization temperature range of 90°C to 180°C and a salinity range of 2–8 wt% NaCl eq. It is suggested that the hydrocarbons may have been trapped at relatively low temperatures, while the formation of gold deposits could have occurred under a wider and higher range of temperatures. The timing of gold mineralization in the Youjiang basin is still in dispute and a wide range of ages has been reported for individual deposits. Among the limited isotopic data, the Rb–Sr date of 206 ± 12 Ma for Au-bearing hydrothermal sericite at Jinya as well as the Re–Os date of 193 ± 13 Ma on auriferous arsenian pyrite and ⁴⁰Ar/³⁹Ar date of 194.6 ± 2 Ma on vein-filling sericite at Lannigou may provide the most reliable age constraints on gold mineralization. This age range is comparable with the estimated petroleum charging age range of 238–185 Ma and the Sm–Nd date of 182 ± 21 Ma for the pore- and fissure-filling calcite associated with bitumen at the Shitouzhai paleo-oil reservoir, corresponding to the late Indosinian to early Yanshanian orogenies in South China. The close association of Carlin-type gold deposits and paleo-oil reservoirs, the paragenetic coexistence of bitumens with ore-stage minerals, the presence of abundant hydrocarbons in the ore fluids, and the temporal coincidence of gold mineralization and hydrocarbon accumulation all support a coeval model in which the gold originated, migrated, and precipitated along with the hydrocarbons in an immiscible, gold- and hydrocarbon-bearing, basinal fluid system.     

Concordant ages for the giant Kipushi base metal deposit (DR Congo) from direct Rb–Sr and Re–Os dating of sulfides

We report concordant ages of 451.1 ± 6.0 and 450.5 ± 3.4 Ma from direct Rb–Sr and Re–Os isochron dating, respectively, of ore-stage Zn–Cu–Ge sulfides, including sphalerite for the giant carbonate-hosted Kipushi base metal (+Ge) deposit in the Neoproterozoic Lufilian Arc, DR Congo. This is the first example of a world-class sulfide deposit being directly dated by two independent isotopic methods. The 451 Ma age for Kipushi suggests that the ore-forming solutions did not evolve from metamorphogenic fluids mobilized syntectonically during the Pan-African-Lufilian orogeny but rather were generated in a Late Ordovician postorogenic, extensional setting. The homogeneous Pb isotopic composition of the sulfides indicates that both Cu–Ge- and Zn-rich orebodies of the Kipushi deposit formed contemporaneously from the same fluid system. The sulfide Pb isotope signatures in combination with initial ⁸⁷Sr/⁸⁶Sr and ¹⁸⁷Os/¹⁸⁸Os ratios defined by the isochrons point to metal sources located in the (upper) crust. The concordant Re–Os and Rb–Sr ages obtained in this study provide independent proof of the geological significance of direct Rb–Sr dating of sphalerite.     

Petrology,geochemistry and U–Pb geochronology of magmatic rocks from the high-sulfidation epithermal Au–Cu Chelopech deposit,Srednogorie zone,Bulgaria

The Chelopech deposit is one of the largest European gold deposits and is located 60 km east of Sofia, within the northern part of the Panagyurishte mineral district. It lies within the Banat–Srednegorie metallogenic belt, which extends from Romania through Serbia to Bulgaria. The magmatic rocks define a typical calc-alkaline suite. The magmatic rocks surrounding the Chelopech deposit have been affected by propylitic, quartz–sericite, and advanced argillic alteration, but the igneous textures have been preserved. Alteration processes have resulted in leaching of Na₂O, CaO, P₂O₅, and Sr and enrichment in K₂O and Rb. Trace element variation diagrams are typical of subduction-related volcanism, with negative anomalies in high field strength elements (HFSE) and light element, lithophile elements. HFSE and rare earth elements were relatively immobile during the hydrothermal alteration related to ore formation. Based on immobile element classification diagrams, the magmatic rocks are andesitic to dacitic in compositions. Single zircon grains, from three different magmatic rocks spanning the time of the Chelopech magmatism, were dated by high-precision U–Pb geochronology. Zircons of an altered andesitic body, which has been thrust over the deposit, yield a concordant ²⁰⁶Pb/²³⁸U age of 92.21 ± 0.21 Ma. This age is interpreted as the crystallization age and the maximum age for magmatism at Chelopech. Zircon analyses of a dacitic dome-like body, which crops out to the north of the Chelopech deposit, give a mean ²⁰⁶Pb/²³⁸U age of 91.95 ± 0.28 Ma. Zircons of the andesitic hypabyssal body hosting the high-sulfidation mineralization and overprinted by hydrothermal alteration give a concordant ²⁰⁶Pb/²³⁸U age of 91.45 ± 0.15 Ma. This age is interpreted as the intrusion age of the andesite and as the maximum age of the Chelopech epithermal high-sulfidation deposit. ¹⁷⁶Hf/¹⁷⁷Hf isotope ratios of zircons from the Chelopech magmatic rocks, together with published data on the Chelopech area and the about 92-Ma-old Elatsite porphyry–Cu deposit, suggest two different magma sources in the Chelopech–Elatsite magmatic area. Magmatic rocks associated with the Elatsite porphyry–Cu deposit and the dacitic dome-like body north of Chelopech are characterized by zircons with ɛHf_T90 values of ∼5, which suggest an important input of mantle-derived magma. Some zircons display lower ɛHf_T90 values, as low as −6, and correlate with increasing ²⁰⁶Pb/²³⁸U ages up to about 350 Ma, suggesting assimilation of basement rocks during magmatism. In contrast, zircon grains in andesitic rocks from Chelopech are characterized by homogeneous ¹⁷⁶Hf/¹⁷⁷Hf isotope ratios with ɛHf_T90 values of ∼1 and suggest a homogeneous mixed crust–mantle magma source. We conclude that the Elatsite porphyry–Cu and the Chelopech high-sulfidation epithermal deposits were formed within a very short time span and could be partly contemporaneous. However, they are related to two distinct upper crustal magmatic reservoirs, and they cannot be considered as a genetically paired porphyry–Cu and high-sulfidation epithermal related to a single magmatic–hydrothermal system centered on the same intrusion.