Sulfidic and non-sulfidic indium mineralization of the epithermal Au–Cu–Zn–Pb–Ag deposit San Roque (Provincia Rio Negro,SE Argentina) — with special reference to the “indium window” in zinc sulfide

At San Roque in Patagonia's Rio Negro Province, Argentina, an In–Au–Cu–Zn–Pb–Ag mineralization (< 0.24 wt.% In, < 7 ppm Au, < 0.45 wt.% Cu, < 14.1 wt.% Zn, < 0.55 wt.% Pb, < 60 ppm Ag) is bound to lava, and volcaniclastics of Triassic through Jurassic age. The polymetallic sulfidic and non-sulfidic indium mineralization is attributed to the low-sulfidation (LS) to intermediate sulfidation (IS) epithermal type of mineralization. Its vein-type and stockwork mineralization developed at 39.2 bars under hydrostatic conditions, corresponding to a depth of 400 m below the water level of the paleoaquifer. In the redox-controlled hypogene mineralization, the temperature increased from 130 °C up to as much as 250 °C at depth, while the pH regime changed from slightly acidic near surface to more alkaline conditions around pH 8 at a depth of approximately 150 m. The monophase mineral associations composed of sphalerite, Ag–Bi-enriched and inclusion-free galena (< 1.7 wt.% Ag, < 3.7 wt.% Bi), chalcopyrite, pyrite, gold, silver, digenite, various In–Cu- and Pb–Zn–Ag “intermediate products”, wittichenite, roquesite, sakuraiite, dzhalindite, brochantite, antlerite, cerussite, and “manganomelane” in a quartz and muscovite-rich gangue have been subdivided into three different stages: (1) Stockwork mineralization of LS to IS epithermal type (hypogene), (2) quartz vein mineralization (hypogene), and (3) salar mineralization (supergene–hypogene).Salt–mud flats controlled the youngest mineralization with Mn, Li, Ca, Mg, V, Sr, Cu, Ag and In bound to oxides, hydroxides, sulfates and subordinate carbonates. The quartz vein mineralization is made up of oxides, hydroxides prevailing over sulfides and containing W, Fe, Au, As, Pb, In, and Cu. It formed at the passage from the vadose into the phreatic zones under oxidizing to slightly reducing conditions. The level marks the boiling level of the hydrothermal solutions involved in the mineralizing process. The hypogene stockwork mineralization is exclusively made up of sulfides containing Zn, Pb, Cu, In, Ag and Bi in the phreatic zones. It developed under reducing conditions. Indium is present at all levels within the volcanic rocks and has been derived from sphalerite rich in Cd (< 1.6 wt.% Cd), In (< 7.3 wt.% In) and Cu (< 7.2 wt.% Cu) while the Fe contents are moderate in sphalerite (< 6.8 wt.% Fe). Indium reached economic grade only through the segregation of a Cu–In–S phase in the “indium window” which is defined by a Cd content of sphalerite in the range 0.2–0.6 wt.% Cd. This concentration of In is controlled by the crystal morphology and the lattice parameters of the minerals involved. It is described as a two-stage process with interdiffusion processes in an Fe-enriched system (stage I) and zoned replacement in an Fe-poor system enriched in indium (stage II). Cu-bearing sphalerite decomposed into sphalerite poor in trace elements and into Cu–In-bearing sphalerite. Further indium concentration took place, when roquesite and sakuraiite decomposed along with an increase in oxygen pressure under hypogene and supergene conditions into dzhalindite. The physical–chemical conditions of the mineralogy and chemical changes in the system In–Cu–Zn–Cd observed in nature have been approximated based upon the results obtained during laboratory studies in material sciences that were focused on solar energy.     

Evolution of hydrothermal fluids of HS and LS type epithermal Au–Ag deposits in the Seongsan hydrothermal system of the Cretaceous Haenam volcanic field,South Korea

The Haenam volcanic field was formed in the southern part of the Korean peninsula by the climactic igneous activity of the Late Cretaceous. The volcanic field hosts more than nine hydrothermal clay deposits and two epithermal Au–Ag deposits. This study focuses on the relationship between hydrothermal clay alteration and epithermal Au–Ag mineralization based on the geology, alteration mineralogy, geochronology, and mineralization characteristics.These clay and epithermal Au–Ag deposits are interpreted to have formed by the same hydrothermal event which produced two distinct types of mineral systems: 1) Au-dominant epithermal Au–Ag deposit and 2) clay-dominant hydrothermal clay deposit. The two types of mineral systems show a close genetic relationship as suggested by their temporal and spatial relationships. The Seongsan hydrothermal system progressively evolved from a low-intermediate sulfidation epithermal system with Au–Ag mineralization and phyllic alteration to an acid–sulfate high-sulfidation system with Au–Ag mineralization and/or barren advanced argillic/argillic alteration. The Seongsan system evolved during post volcanic hydrothermal activity for at least 10 Ma in the Campanian stage of the late Cretaceous.The Seongsan hydrothermal system shows the rare and unique occurrence of superimposed high to low (intermediate) sulfidation episodes, which persisted for about 10 Ma.     

Geology,mineralogy and fluid inclusion data of the Kizilcaören fluorite–barite–REE deposit,Eskisehir, Turkey

The Kizilcaören fluorite–barite–Rare Earth Element (REE) deposit occurs as epithermal veins and breccia fillings in altered Triassic metasandstones and Oligocene–Miocene pyroclastics adjacent to alkaline porphyritic trachyte and phonolite. This deposit is the only commercial source of REE and thorium in Turkey. Most of the fluorite–barite–REE mineralisation at Kizilcaören has been formed by hydrothermal solutions, which are thought to be genetically associated with alkaline volcanism. The occurrence of the ore minerals in vuggy cavities and veins of massive and vuggy silica indicate that the ore stage postdates hydrothermal alteration. The deposit contains evidence of at least three periods of hypogene mineralisation separated by two periods of faulting. The mineral assemblage includes fluorite, barite, quartz, calcite, bastnäsite, phlogopite, pyrolusite and hematite as well as minor amounts of plagioclase feldspar, pyrite, psilomelane, braunite, monazite, fluocerite, brockite, goethite, and rutile. Fluid inclusion microthermometry indicates that the barite formed from low salinity (0.4–9.2 equiv. wt% NaCl) fluids at low temperatures, between 105 and 230 °C, but fluorite formed from slightly higher salinity (<12.4 equiv. wt% NaCl) fluids at low and moderate temperatures, between 135–354 °C. The depositional temperature of bastnäsite is between 143–286 °C. The local coexistence of liquid- and vapour-rich inclusions suggests boiling conditions. Many relatively low-salinity (<10.0 equiv. wt% NaCl), low and moderate temperature (200–300 °C) inclusions might be the result of episodic mixing of deep-saline brines with low-salinity meteoric fluids. The narrow range of δ³⁴S (pyrite and barite) values (2.89–6.92‰ CDT)suggests that the sulphur source of the hydrothermal fluids are the same and compatible with a volcanogenic sulphate field derived from a magmatic sulphur source.     

Fluorite REE-Y (REY) geochemistry of the ca. 850 Ma Tumen molybdenite–fluorite deposit,eastern Qinling,China: Constraints on ore genesis

The Tumen molybdenite–fluorite vein system is hosted by carbonate rocks of the Neoproterozoic Luanchuan Group, located on the southern margin of the North China Craton (NCC) in central China. Previous studies divided the mineralization into four stages according to the crosscutting relationships between veinlets and their mineral assemblages. In this contribution, two distinctive types of fluorite mineralization are recognized: 1) the first type (Type 1) includes colourless, white or green fluorite grains present in Stage 1 veins; and 2) the second type includes Type 2a purple fluorite present in Stage 2 veins and does not coexist with sulfides, and Type 2b purple fluorite crystals associated with sulfides in Stage 2 veins. The rare earth element (REE) content in the fluorite ranges between 13.8 and 27.9 ppm in Type 1, 16.9 and 27.2 ppm in Type 2a, and 42.5 and 75.1 ppm in Type 2b, which suggests that the fluorite was precipitated from acidic fluids (given that REEs are mobile in saline HCl-bearing fluids at high temperature (~ 400 °C)). Comparing the REE chemistry of the Stage 1 against Stage 2 fluorite, the LREE/HREE ratios decrease from 9.8 to 4.0, La/Yb ratios decrease from 16.0 to 6.9 and La/Ho ratios decrease from 10.2 to 3.0, indicating that the hydrothermal process was at high-T and low-pH conditions. The Eu/Eu* ratios in the fluorite decrease from 1.11 ± 0.35 for Type 1 through 0.89 ± 0.19 for Type 2a to 0.75 ± 0.17 for Type 2b, suggesting a gradual increase in oxygen fugacity (fO₂) and pH of the mineralising fluid. The Tb/Ca, Tb/La and Y/Ho ratios of the fluorite types indicate that they were formed from the interaction between magmatic fluids and carbonate wallrocks. The fluorite samples show similar REE + Y (REY) patterns to those of dolostone units in the Luanchuan Group and the nearby Neoproterozoic syenite, suggesting that the REY in the fluorite was mainly sourced from the host-rocks, although the syenite could be an additional minor source.     

Ore petrology,hydrothermal alteration,fluid inclusions,and sulfur stable isotopes of the Milin Kamak intermediate sulfidation epithermal Au-Ag deposit in Western Srednogorie,Bulgaria

The Milin Kamak gold-silver deposit is located in Western Srednogorie zone, 50 km west of Sofia, Bulgaria. This zone belongs to the Late Cretaceous Apuseni-Banat-Timok-Srednogorie magmatic and metallogenic belt. The deposit is hosted by altered trachybasalt to andesitic trachybasalt volcanic and volcanoclastic rocks with Upper Cretaceous age, which are considered to be products of the Breznik paleovolcano. Milin Kamak is the first gold-silver intermediate sulfidation type epithermal deposit recognized in Srednogorie zone in Bulgaria. It consists of eight ore zones with lengths ranging from 400 to 1000 m, widths from several cm to 3–4 m, rarely to 10–15 m, an average of 80–90 m depth (a maximum of 200 m) and dip steeply to the south. The average content of gold is 5.04 g/t and silver – 13.01 g/t. The styles of alteration are propylitic, sericite, argillic, and advanced argillic. Ore mineralization consists of three stages. Quartz-pyrite stage I is dominated by quartz, euhedral to subhedral pyrite, trace pyrrhotite and hematite in the upper levels of the deposit. Quartz-polymetallic stage II is represented by major anhedral pyrite, galena, Fe-poor sphalerite; minor chalcopyrite, tennantite, bournonite, tellurides and electrum; and trace pyrrhotite, arsenopyrite, marcasite. Gangue minerals are quartz and carbonates. The carbonate-gold stage III is defined by deposition of carbonate minerals and barite with native gold and stibnite.Fluid inclusions in quartz are liquid H₂O-rich with homogenization temperature (T_h) ranging from 238 to 345 °C as the majority of the measurements are in the range 238–273 °C. Ice-melting temperatures (T_m) range from −2.2 to −4.1 °C, salinity – from 3.7 to 6.6 wt.% NaCl equiv. These measurements imply an epithermal environment and low- to moderate salinity of the ore-forming fluids.δ³⁴S values of pyrite range from −0.49 to +2.44‰. The average calculated δ³⁴S values are 1.35‰. The total range of δ³⁴S values for pyrite are close to zero suggesting a magmatic source for the sulfur.     

Genesis of the Zhaxikang epithermal Pb-Zn-Sb deposit in southern Tibet,China: Evidence for a magmatic link

The Zhaxikang Pb-Zn-Sb deposit is one of the most important deposits in the Southern Tibet metallogenic belt. Based on field geology, petrography, melt- and fluid inclusions and C-H-O isotopes, we describe and discuss the mineralization, alteration, and their possible link with magmatic fluids. Our results show that the Zhaxikang deposit shares many geological and geochemical similarities with typical intermediate-sulfidation (IS) epithermal deposits. The Pb-Zn-Sb mineralization is closely related to Fe-Mn carbonate- and silicic alterations, which formed the outer rim around the greisen in the Cuonadong Dome. Orebodies occur mainly as structurally-controlled veins and breccia dikes, with major minerals include sphalerite, galena, pyrite, arsenopyrite, and Fe-Mn carbonates. Main stage ore-forming fluids were of medium temperature (214–292 °C), low salinity (2.6–5.3 wt.% NaCl eqv.) and CO₂-bearing.Melt/fluid inclusions in beryl and quartz from the pegmatite indicate that the primary magmatic fluids were derived from the melt-fluid immiscibility. The magmatic fluids were of low salinity (0.2–7.9 wt.% NaCl eqv.), high temperature (298–457 °C) and CO₂-rich, and contained minor CH₄, N₂, C₂H₆, C₃H₈ and C₆H₆. The presence of Mn-Fe carbonates and daughter gahnite minerals in the beryl-hosted inclusions indicates high Mn, Fe and Zn contents in the parental magma and related magmatic fluids. This implies a genetic link between magmatic fluids and the Pb-Zn-Sb mineralization, as also supported by Ar-Ar dating and H-O-C isotopic evidence. We suggest that the Zhaxikang is best classified as an IS epithermal deposit, and the ore-forming fluids are likely to be magma-derived. Boiling of the magmatic fluids led to high-salinity fluids and metal enrichment. High regional geothermal gradient caused by the thermal doming event may have facilitated long distance transportation of magmatic fluids, and led to the formation of a wide alteration zone and distal Pb-Zn-Sb mineralization. The temperature drop and meteoric water involvement may have precipitated the Pb-Zn-Sn minerals in the distal fault systems.     

The Nadun Cu–Au mineralization,central Tibet: Root of a high sulfidation epithermal deposit

A new high sulfidation epithermal Cu–Au occurrence (Nadun) has been discovered adjacent to the Cretaceous Duolong porphyry Cu–Au deposit within the Bangong–Nujiang metallogenic belt, central Tibet. The Nadun Cu–Au mineralization is hosted in a tectonic–hydrothermal breccia with advanced argillic alteration, which occurs above sandstone, associated with quartz–pyrite veins. The granodiorite porphyry with strong argillic alteration yields a zircon U–Pb age of 119.1 ± 1.3 Ma, whereas the weakly argillic granodiorite porphyry intruded into the breccia has a younger age of 116.1 ± 1.3 Ma. This indicates that Cu–Au epithermal mineralization likely occurred between ~ 116 Ma and ~ 119 Ma, consistent with the duration of magmatic–hydrothermal activity at Duolong (~ 115–118 Ma), and providing evidence that Nadun and Duolong were formed during the same event. Moreover, the Nadun and Duolong porphyries have similar Hf isotopic compositions (εHf(t) values ranging from − 8.8 to 8.1; mean = 5.0 ± 1.1, n = 32), likely indicating that the deposits are comagmatic. In addition, boiling assemblages in vapor-rich inclusions coexisting with brines occur in early stage quartz–pyrite veins, and likely record phase separation at a temperature of > 550–300 °C and pressure of 700–110 bars. Most liquid-rich fluid inclusions formed at the breccia stage show similar salinity (1.7–19.3 wt.% NaCl equiv) to vapor-rich inclusions from the underlying quartz–pyrite veins, likely indicating vapor contraction during cooling at elevated presssure. This suggests that quartz–pyrite veins may act as conduits for ore-forming fluid traveling from the porphyry to the epithermal hydrothermal system. O and H isotopic compositions (δ¹⁸O_fluid = 0.42–9.71‰ and δD = − 102 to − 66‰) suggest that ore-forming fluids are dominantly from a magmatic source with a minor addition of meteoric water at a later stage. The S and Fe isotope compositions of sulfides (δ³⁴S = − 5.9 to 0.5‰ and δ⁵⁷Fe = − 2.15 to 0.17‰) decrease from the quartz–pyrite vein to breccia ore, indicating that ore-forming fluids gradually become SO₄²-enriched and relatively oxidized. This body of evidence suggests that the Nadun Cu–Au mineralization may represent the root of a high sulfidation epithermal deposit.     

Paleogene magmatism and gold metallogeny of the Jinping terrane in the Ailaoshan ore belt,Sanjiang Tethyan Orogen (SW China): Geology,deposit type and tectonic setting

The Jinping terrane is situated in the southern segment of the Ailaoshan ore belt, Sanjiang Tethyan Orogen (SW China). The Paleogene intrusions in Jinping consist of syenite porphyry, fine-grained syenite and biotite granite stocks/dikes, and contain relatively low TiO₂ (0.21–0.38 wt%), P₂O₅ (0.01–0.35 wt%), and high Na₂O (2.00–4.62 wt%) and K₂O (4.48–7.06 wt%), belonging to high-K alkaline series. Paleogene gold mineralization in Jinping comprises four genetic types, i.e., orogenic, alkali-rich intrusion-related, porphyry and supergene laterite. The NW–NNW-trending faults and their subsidiaries are the major ore-controlling structures. The orogenic Au mineralization, dominated by polymetallic sulfide-quartz veins, occurs in the diorite and minor in Silurian-Devonian sedimentary rocks. It contains a CO₂-rich mesothermal fluid system generated from the mixing of mantle-derived fluids with crustal-derived metamorphic fluids, and the ore-forming materials were upper crustal- or orogenic-derived. The alkali-rich intrusion-related Au mineralization is hosted in the Ordovician-Silurian sedimentary rocks and minor in the Paleogene alkaline intrusions, and the Au orebodies occur predominantly in the alteration halos. It contains a CO₂-bearing, largely metamorphic-sourced mesothermal fluid system, and the ore-forming materials were derived from the ore-hosting rocks and minor from the alkali-rich intrusions. The porphyry Cu-Mo-Au mineralization occurs in the granite/syenite porphyries and/or along their contact skarn, with the mineralizing fluids being magmatic-hydrothermal in origin. The former two hypogene Au mineralization types in Jinping were mainly formed in the late Eocene (ca. 34–33 Ma) and slightly after the porphyry Cu-Mo-Au mineralization (ca. 35–34 Ma), which is coeval with the regional Himalayan orogenic event. Subsequent weathering produced the laterite Au mineralization above or near the hypogene Au orebodies.     

Geochemical,fluid inclusion and isotopic (O,H and S) constraints on the origin of Pb–Zn ± Au vein-type mineralizations in the Eastern Pontides Orogenic Belt (NE Turkey)

The mineralization area (Altınpınar, Torul–Gümüşhane) is situated in the Southern Zone of the Eastern Pontides Orogenic Belt (EPOB), which is one of the important metallogenic provinces in the Alpine–Himalayan belt and is intruded by the late Carboniferous granitic rocks (Gümüşhane Granitoid), an early to middle Jurassic volcano-sedimentary unit consisting mainly of basaltic–andesitic volcanic and pyroclastic rocks (Şenköy Formation) and Eocene basaltic–andesitic volcanic rocks (Alibaba Formation). The studied Pb–Zn ± Au mineralizations are related to silica veins ranging from a few millimeters to a maximum of 40 cm in thickness and are localized within fracture zones developed along the contact between the Gümüşhane Granitoid and Şenköy Formation. Silicic, sulfidic, hematitic, argillic, intense chloritic and carbonate alteration are the most common types from the fault lines toward the outer zones. Cavity filling and banded structures are widely observed. The mineral paragenesis comprises galena, sphalerite, pyrite, chalcopyrite, tennantite and quartz. Mineral chemistry studies indicate that ion exchange occurs between Zn and Fe in sphalerites, and the Zn/Cd ratio of sphalerites varies between 50.65 and 144.64. The homogenization temperatures measured from fluid inclusions vary between 170 °C and 380 °C, especially between 250 °C and 300 °C, and the wt.% NaCl eqv. salinity of ore-forming fluids is between 2.4 and 7.3 (4.7 on average), supporting an epithermal system in their origin. The values of sulfur isotopes, which are obtained from pyrite and galena minerals, range between − 8.3‰ and − 2.3‰, indicating that sulfur, which enables mineral formation, originates from magmatic genesis. The average formation temperature of the ore is 317 °C as determined with a sulfur isotope geothermometer. The values of oxygen and hydrogen isotopes vary between 8.5‰ and 10.2‰ and − 91‰ and −73‰, respectively. With regard to the compositions of oxygen and hydrogen isotopes, fluids comprising the mineralization are formed by the mixture of magmatic water and meteoric water. This situation is supported by the fact that the increase in the homogenization temperature indicates dilution with surface water but depends on the increase in the salinity of fluid inclusions. Considering all the data, it is clear that the studied mineralization is an epithermal vein-type mineralization that is related to granitic magmas.     

Sulfur-poor intense acid hydrothermal alteration: A distinctive hydrothermal environment

A fundamentally distinct, sulfide-poor variant of intense acid (advanced argillic) alteration occurs at the highest structural levels in iron oxide-rich hydrothermal systems. Understanding the mineralogy, and geochemical conditions of formation in these sulfide-poor mineral assemblages have both genetic and environmental implications. New field observations and compilation of global occurrences of low-sulfur advanced argillic alteration demonstrates that in common with the sulfide-rich variants of advanced argillic alteration, sulfide-poor examples exhibit nearly complete removal of alkalis, leaving a residuum of aluminum-silicate + quartz. In contrast, the sulfur-poor variants lack the abundant pyrite ± other sulfides, hypogene alunite, Al-leached rocks (residual “vuggy” quartz) as well as the Au-Cu-Ag ± As-rich mineralization of some sulfur-rich occurrences. Associated mineralization is dominated by magnetite and/or hematite with accessory elements such as Cu, Au, REE, and P. These observations presented here indicate there must be distinct geologic processes that result in the formation of low-sulfur advanced argillic styles of alteration.Hydrolysis of magmatic SO₂ to sulfuric acid is the most commonly recognized mechanism for generating hypogene advanced argillic alteration, but is not requisite for its formation. Low sulfur iron-oxide copper-gold systems are known to contain abundant acid-styles of alteration (e.g. sericitic, chloritic), which locally reaches advanced argillic assemblages. A compilation of mapping in four districts in northern Chile and reconnaissance observations elsewhere show systematic zoning from near surface low-sulfide advanced argillic alteration through chlorite-sericite-albite and locally potassic alteration. The latter is commonly associated with specular hematite-chalcopyrite mineralization. Present at deeper structural levels are higher-temperature styles of sodic-calcic (oligoclase/scapolite – actinolite) alteration associated with magnetite ± chalcopyrite mineralization. These patterns are in contrast to the more sulfur-rich examples which generally zone to higher pyrite and locally alunite-bearing alteration.Fluid inclusion evidence from the systems in northern Chile shows that many fluids contain 25 to >50 wt% NaCl_eq with appreciable Ca, Fe, and K contents with trapping temperatures >300 °C. These geological and geochemical observations are consistent with the origin of the low-sulfur advanced argillic assemblages from HCl generated by precipitation of iron oxides from iron chloride complexes from a high-salinity fluid by reactions such as 3FeCl₂ + 4H₂O = Fe₃O₄ + 6HCl + H₂. Such HCl-rich (and relatively HSO₄⁼-poor) fluids can then account for the intense acid, Al-silicate-rich styles of alteration observed at high levels in some iron-oxide-coppe-gold (IOCG) systems. The geochemical differences between the presence of sulfide-rich and sulfur-poor examples of advanced argillic alteration are important to distinguishing between system types and the acid-producing capacity of the system, including in the modern weathering environment. They have fundamental implications for effective mineral exploration in low-sulfur systems and provide yet another vector of exposed alteration in the enigmatic IOCG clan of mineral deposits. Furthermore, understanding the geochemistry and mineralogy of this distinct geologic environment has applications to understanding the acid generating capacity and deleterious heavy metals associated with advanced argillic alteration.     

Genesis of Luobuzhen Pb–Zn veins: Implications for porphyry Cu systems and exploration targeting at Luobuzhen-Dongshibu in western Gangdese belt,southern Tibet

Porphyry systems are known to form in magmatic arc environment and commonly include porphyry Cu, epithermal Pb–Zn–Au–Ag, skarn polymetallic mineralization, etc. The systems are rarely reported in collisional zones, such as the Gangdese belt in southern Tibet where many postcollisional porphyry copper deposits occurred. In addition, other types of mineral systems are rarely present except porphyry copper mineralization in the Gangdese belt. In this study, we present Pb–Zn-bearing quartz veins at Luobuzhen in the western Gangdese belt. The Luobuzhen Pb–Zn veins cross-cut dacite of the Linzizong Group with zircon U–Pb age of 50.1 ± 0.2 Ma and monzogranite with zircon U–Pb age of 17.1 ± 0.1 Ma. Ore minerals include sphalerite, galena, chalcopyrite, and pyrite; gangue minerals are quartz with minor chlorite and sericite. Primary fluid inclusions of quartz are liquid-rich, aqueous, and two-phase inclusions. The homogenization temperatures of these primary inclusions are moderate to high (267–400 °C), and salinities range from 8.9 to 18.4 wt.% NaCl equiv. Quartz has δ¹⁸O_SMOW values of 6.2–9.3‰, while sulfides have δ³⁴S_V-CDT values of −5.1‰ to 0.1‰, ²⁰⁶Pb/²⁰⁴Pb of 18.722–18.849, ²⁰⁷Pb/²⁰⁴Pb of 15.640–15.785, and ²⁰⁸Pb/²⁰⁴Pb of 39.068–39.560. These data suggest that magmatic fluids with contribution from meteoric water, magmatic sulfur, and lead derived from upper crust and metasomatized mantle by Indian continental materials would be critical for the Luobuzhen base metal mineralization.The Dongshibu area, located at ∼2 km east of the Luobuzhen, is characterized by high concentrations of Cu (up to 1450 ppm) and Mo (up to 130 ppm) of stream sediments, which is quite different from high concentrations in Pb, Zn, Ag, and Au shown in the Luobuzhen area. In addition, porphyry copper mineralization-related alteration and veins/veinlets occur in the Miocene monzogranite at Dongshibu. The monzogranite is characterized by high Sr/Y ratios, which are also shown on ore-forming intrusions in the Gangdese postcollisional porphyry copper deposits, and shows similar zircon Hf isotopes to the ore-related high Sr/Y intrusions from the Zhunuo porphyry copper deposit which is located ∼20 km northeast of the Luobuzhen-Dongshibu. A comprehensive analysis allows us to infer that the base metal veins at Luobuzhen are components of a porphyry Cu system with porphyry Cu mineralization likely present at Dongshibu and epithermal Au–Ag veins possibly occurring at Luobuzhen, which are indicative of the existence of porphyry copper systems in collisional zones. The potential porphyry Cu mineralization and epithermal Au–Ag veins should be targeted in future exploration at Luobuzhen-Dongshibu.     

Silver-base metal epithermal vein and listwanite hosted deposit Crnac,Rogozna Mts., Kosovo,part II: A link between magmatic rocks and epithermal mineralization

Crnac is an intermediate sulfidation Pb–Zn–Ag epithermal deposit located within the Vardar suture zone of the Central Balkan Peninsula. The epithermal Pb–Zn–Ag mineralization consists of (i) a series of steeply-dipping veins hosted within the Jurassic amphibolites, and (ii) overlying hydrothermal-explosive breccia with angular (level IV) or rounded fragments of listwanite (surface) cemented by epithermal mineralization. The mineralization is related to the Oligocene quartz latite dykes that crosscut the Crnac antiform. Quartz latite rocks predominantly display a shoshonitic character. The obtained ⁴⁰Ar/³⁹Ar age of fresh quartz latite is 28.9 ± 0.3 Ma. Fine-grained sericite from altered quartz latite is dated at 28.6 ± 0.5 Ma. Early, alteration related fluid inclusions within quartz latite show coexistence of high-density brine and a low-density vapor-saturated phase that homogenized at 280–405 °C. Phase separation occurs at a paleodepth of 0.6 to 0.9 km.Epithermal mineralization developed in three stages: (i) early pyrite–arsenopyrite–pyrrhotite–quartz–kaolinite; (ii) main sphalerite–galena–tetrahedrite–chalcopyrite and (iii) late carbonate–pyrite–arsenopyrite assemblage. The onset of mineral deposition within epithermal veins was initiated by boiling of Na–Cl ± K ± Ca ± Mg fluid at a paleodepth of 0.6 to 0.9 km. Coexisting vapor and liquid-rich inclusions display salinities and trapping temperatures of 4 wt.% NaCl equiv., 280–370 °C and 2–27 wt.% NaCl equiv., 230–375 °C, respectively. Boiling continued throughout the deposition of the sphalerite-galena-tetrahedrite-chalcopyrite assemblage. Late stage carbonate was deposited from diluted, non-boiling, low-temperature Na–Ca–Mg–Cl ± CO₂ fluid (0.2 to 4.8 wt.% NaCl equiv., 115–280 °C).About 100–150 m higher in the system, precipitation of listwanite breccia cement began as a result of boiling Na–Cl ± Ca ± Mg ± K fluid of medium salinities (2.6 to 12.1 wt.% NaCl equiv.) at temperatures of 245–370 °C. Boiling and dilution of fluids continue throughout the precipitation of the main sphalerite-galena-tetrahedrite and late, mainly carbonate assemblage. Surface listwanite breccia contain quartz phenocrysts deposited from a homogeneous fluid with a medium salinity (8–10 wt.% NaCl equiv.) and high temperatures (T_h = 295–315 °C), whereas the early and main stage of a surface listwanite breccia cement precipitated from a boiling fluid of decreasing salinity and temperature. Aqueous ± CO₂, high salinity (16 to 18 wt.% NaCl equiv.), low temperature (120 °C), homogeneously trapped fluid that precipitated late stage carbonates, is most likely a remnant of boiled off fluid. The epithermal assemblage of the surface listwanites precipitated at a paleodepth of 0.4 to 0.6 km.The δ¹³C values of the late stage ankerite range from − 4.2 to 4.1‰, whereas δ¹⁸O range from 9.6 to 17.5‰. The calculated δ¹⁸O of fluid that precipitated carbonates within epithermal veins, and listwanite breccia cement range from 6.3 to 11.3‰, indicating a contribution of magmatic water.Deposition of all mineralization types was initiated by neutralization of primary acidic magmatic fluid by water-rock reactions that caused widespread propylitization and sericitization. Extensive and long-lasting boiling combined with dilution by meteoric water increased the pH towards the final stage of hydrothermal activity.     

Fluid inclusions,muscovite Ar–Ar age,and fluorite trace elements at the Baiyanghe volcanic Be–U–Mo deposit,Xinjiang, northwest China: Implication for its genesis

The Baiyanghe Be–U–Mo deposit is located in the Late Paleozoic Xuemisitan–Kulankazi island arc of the northwestern margin of the Junggar plate, Northwest China. It is the largest Be deposit (2.2 M tons of ore with grades ranging from 0.2% to 1.4%) in Asia. Orebodies in the deposit occur as fractures along contact zones between the Yangzhuang granite porphyry intrusion and Devonian pyroclastic country rocks and within the porphyry itself. Muscovite–fluorite veins are closely associated with the Be–U–Mo mineralization. A new Ar–Ar dating of the muscovite in this study yields a plateau age of 303.0 ± 1.6 Ma, which constrains the timing of the Be–U–Mo mineralization of the deposit. Three stages of fluorite of different colors have been identified at the deposit, with the earliest dark-purple fluorite more closely associated with the mineralization. Microthermometry of fluid inclusions obtained from the three stages of fluorite suggests that the fluorites were precipitated as veins from low temperature (120–150 °C) hydrothermal fluids with salinity ranging from 4.7 to 19.7 wt.% NaCl eqv. Based on the trace elemental concentrations and REE patterns of the fluorite, the style of veining, and the low salinity and low temperature characters of the fluid inclusions, it is suggested that Be and U were most likely transported as fluoride complexes and Mo as hydroxyl complexes. Pb isotopic compositions of the ores and country rocks, as well as O and H isotopic characters of the ore-related muscovite, indicate mixing between magmatic and meteoric waters; both contributed to formation of the ore-forming fluids. Metallic Be, U, and Mo were most likely leached out from the granite porphyry by the fluids. The fluid mixing led to the reduction of U, Mo, and Be and their precipitation at the deposit.     

Mineralogical and geochemical evidence for multi-stage origin of mineral veins hosted by teschenites at Tichá, Outer Western Carpathians,Czech Republic

Numerous mineral veins are hosted in a body of teschenite which is situated within the Lower Cretaceous flysch siliciclastics of the Silesian Unit at Tichá. Mineralogy, fluid inclusions, stable isotopes and trace elements have been studied in order to assess the origin of this mineralization. Three stages of vein cementation have been recognized, each of them being characterized by distinct mineral composition and genetic conditions. The first stage is composed of titanite, aegirine-augite to aegirine, annite, analcime and strontian apatite. These minerals originated from NaCl-rich, CaCl₂-poor magmatic brine (total fluid salinities range between 47 and 57 wt%), leaving after crystallization of host teschenite in low-pressure (<1 kbar) environment. Crystallization temperatures reached ～390–510 °C for early phases, titanite and aegirine-augite. The second stage is formed by calcite, chlorite, dolomite, siderite, strontianite, quartz, pyrite and sphalerite. The parent fluids were low-salinity (0.5–4.5 wt% NaCl eq.) aqueous solutions with low content of strong REE-complexing ligands, that were progressively cooled during mineral precipitation (up to ～190 °C at the beginning, ～90 °C at the end of crystallization). These fluids are interpreted to be predominantly of external origin, derived from surrounding sedimentary sequences during diagenetic dewatering of clay minerals. The highly positive δ¹⁸O and near-zero δ¹³C values indicate an interaction of fluids with sedimentary carbonates. The third stage is formed by a dense net of calcite veinlets, which probably originated during tectonic deformations connected with orogenetic movements during the Tertiary. The source of strontium for first stage mineralization was probably related to the special conditions of magmatic evolution of the host teschenite, whereas strontium for second stage minerals could have been remobilized during hydrothermal alteration from earlier teschenite-hosted mineral phases and/or limestone.     

Base and precious metal mineralization in Middle Jurassic rocks of the Lesser Caucasus: A review of geology and metallogeny and new data from the Kapan,Alaverdi and Mehmana districts

The polymetallic Cu–Au–Ag–Zn ± Pb, Cu–Au and Cu deposits in the Kapan, Alaverdi and Mehmana mining districts of Armenia and the Nagorno–Karabakh region form part of the Tethyan belt. They are hosted by Middle Jurassic rocks of the Lesser Caucasus paleo-island arc, which can be divided into the Kapan Zone and the Somkheto–Karabakh Island Arc. Mineralization in Middle Jurassic rocks of this paleo-island arc domain formed during the first of three recognized Mesozoic to Cenozoic metallogenic epochs. The Middle Jurassic to Early Cretaceous metallogenic epoch comprises porphyry Cu, skarn and epithermal deposits related to Late Jurassic and Early Cretaceous intrusions. The second and third metallogenic epochs of the Lesser Caucasus are represented by Late Cretaceous volcanogenic massive sulfide (VMS) deposits with transitional features towards epithermal mineralization and by Eocene to Miocene world-class porphyry Mo–Cu and epithermal precious metal deposits, respectively.The ore deposits in the Kapan, Alaverdi and Mehmana mining districts are poorly understood and previous researchers named them as copper–pyrite, Cu–Au or polymetallic deposits. Different genetic origins were proposed for their formation, including VMS and porphyry-related scenarios. The ore deposits in the Kapan, Alaverdi and Mehmana mining districts are characterized by diverse mineralization styles, which include polymetallic veins, massive stratiform replacement ore bodies at lithological contacts, and stockwork style mineralization. Sericitic, argillic and advanced argillic alteration assemblages are widespread in the deposits which have intermediate to high-sulfidation state mineral parageneses that consist of tennantite–tetrahedrite plus chalcopyrite and enargite–luzonite–colusite, respectively. The ore deposits are spatially associated with differentiated calc-alkaline intrusions and pebble dykes are widespread. Published δ³⁴S values for sulfides and sulfates are in agreement with a magmatic source for the bulk sulfur whereas published δ³⁴S values of sulfate minerals partly overlap with the isotopic composition of contemporaneous seawater. Published mineralization ages demonstrate discrete ore forming pulses from Middle Jurassic to the Late Jurassic–Early Cretaceous boundary, indicating time gaps of 5 to 20 m.y. in between the partly subaqueous deposition of the host rocks and the epigenetic mineralization.Most of the described characteristics indicate an intrusion-related origin for the ore deposits in Middle Jurassic rocks of the Lesser Caucasus, whereas a hybrid VMS–epithermal–porphyry scenario might apply for deposits with both VMS- and intrusion-related features.The volcanic Middle Jurassic host rocks for mineralization and Middle to Late Jurassic intrusive rocks from the Somkheto–Karabakh Island Arc and the Kapan Zone show typical subduction-related calc-alkaline signature. They are enriched in LILE such as K, Rb and Ba and show negative anomalies in HFSE such as Nb and Ta. The ubiquitous presence of amphibole in Middle Jurassic volcanic rocks reflects magmas with high water contents. Flat REE patterns ([La/Yb]_N = 0.89–1.23) indicate a depleted mantle source, and concave-upward (listric-shaped) MREE–HREE patterns ([Dy/Yb]_N = 0.75–1.21) suggest melting from a shallow mantle reservoir. Similar trace element patterns of Middle Jurassic rocks from the Somkheto–Karabakh Island Arc and the Kapan Zone indicate that these two tectonic units form part of one discontinuous segmented arc. Similar petrogenetic and ore-forming processes operated along its axis and Middle Jurassic volcanic and volcanosedimentary rocks constitute the preferential host for polymetallic Cu–Au–Ag–Zn ± Pb, Cu–Au and Cu mineralization, both in the Somkheto–Karabakh Island Arc and the Kapan Zone.     

Constraints on the mineralization processes of the Makeng iron deposit,eastern China: Fluid inclusion,H–O isotope and magnetite trace element analysis

The Makeng iron deposit is located in the Yong’an-Meizhou depression belt in Fujian Province, eastern China. Both skarn alteration and iron mineralization are mainly hosted within middle Carboniferous-lower Permian limestone. Five paragenetic stages of skarn formation and ore deposition have been recognized: Stage 1, early skarn (andradite–grossular assemblage); Stage 2, magnetite mineralization (diopside–magnetite assemblage); Stage 3, late skarn (amphibole–chlorite–epidote–johannsenite–hedenbergite–magnetite assemblage); Stage 4, sulfide mineralization (quartz–calcite–fluorite–chlorite–pyrite–galena–sphalerite assemblage); and Stage 5, carbonate (quartz–calcite assemblage). Fluid inclusion studies were carried out on inclusions in diopside from Stage 2 and in quartz, calcite, and fluorite from Stage 4.Halite-bearing (Type 1) and coexisting two-phase vapor-rich aqueous (Type 3) inclusions in the magnetite stage display homogenization temperatures of 448–564 °C and 501–594 °C, respectively. Salinities range from 26.5 to 48.4 and 2.4 to 6.9 wt% NaCl equivalent, respectively. Two-phase liquid-rich aqueous (Type 2b) inclusions in the sulfide stage yield homogenization temperatures and salinities of 182–343 °C and 1.9–20.1 wt% NaCl equivalent. These fluid inclusion data indicate that fluid boiling occurred during the magnetite stage and that fluid mixing took place during the sulfide stage. The former triggered the precipitation of magnetite, and the latter resulted in the deposition of Pb, Zn, and Fe sulfides. The fluids related to magnetite mineralization have δ¹⁸O_fluid-VSMOW of 6.7–9.6‰ and δD of −96 to −128‰, which are interpreted to indicate residual magmatic water from magma degassing. In contrast, the fluids related to the sulfide mineralization show δ¹⁸O_fluid-VSMOW of −0.85 to −1.04‰ and δD of −110 to −124‰, indicating that they were generated by the mixing of magmatic water with meteoric water. Magnetite grains from Stage 2 exhibit oscillatory zoning with compositional variations in major elements (e.g., SiO₂, Al₂O₃, CaO, MgO, and MnO) from core to rim, which is interpreted as a self-organizing process rather than a dissolution-reprecipitation process. Magnetite from Stage 3 replaces or crosscuts early magnetite, suggesting that later hydrothermal fluid overprinted and caused dissolution and reprecipitation of Stage 2 magnetite. Trace element data (e.g., Ti, V, Ca, Al, and Mn) of magnetite from Stages 2 and 3 indicate a typical skarn origin.     

Ore geology,fluid inclusions and four-stage hydrothermal mineralization of the Shangfanggou giant Mo–Fe deposit in Eastern Qinling,central China

The Eastern Qinling, Central China, containing more than 20 Mesozoic porphyry ± skarn systems, is the most important Mo province in the world. The Shangfanggou giant Mo deposit, Luanchuan County, Henan Province, is a porphyry-skarn system hosted in a lithologic association comprising carbonaceous sandstone, shale, carbonate and chert within the Neoproterozoic Luanchuan Group. Mo ores are mainly altered porphyry, skarn and hornfels, with minor altered gabbro. The mineralization process includes four stages, potassic alteration of the porphyry and skarnization of dolomite marble in stage 1, stockworks of quartz + molybdenite ± sulfide (stage 2), pyrite + quartz ± sulfides (stage 3), and carbonate ± quartz ± fluorite (stage 4), respectively. Mo mineralization was generally associated with strong silicification and/or phyllic alteration. The fluid inclusions in minerals include three compositional types, i.e., CO₂-bearing (C-type), aqueous (W-type) and daughter mineral-bearing (S-type). Minerals formed in stages 1 to 3 contain all the three types of FIs, but the stage 4 minerals only contain the W-type FIs. Oxides and Cu-phosphate are recognized as daughter minerals in S-type inclusions in minerals of stage 1, whereas the daughter sulfide and reducing gases such as CO, CH₄, H₂S and C₂H₆ can be observed in quartz of stages 2 and 3, suggesting that the ore-forming fluids were initially oxidizing and then evolved to reducing. Boiling fluid inclusion assemblages can be observed in minerals formed in stage 2 or earlier, but not in stage 3 or later. Fluid boiling caused CO₂ escape, oxygen fugacity decrease and rapid precipitation of ore minerals, and was a key factor causing Mo-mineralization at Shangfanggou. Data and interpretations presented in this contribution show that the fluids forming the Shangfanggou Mo deposit evolved from CO₂-rich, high-salinity hypothermal, to CO₂-poor, low-salinity epithermal (low-T). The Mo mineralization at the Shangfanggou deposit mainly occurred at depth of 6.6–7.0 km, deeper than the majority of porphyry systems in volcanic arcs, which resulted from a CO₂-rich magma–fluid system originating from partial melting of thickened lower crust. The Shangfanggou mineral system developed during 158–134 Ma when the Yangtze–North China continental collision began to evolve from compression to extension. Magmatic hydrothermal deposits developed in a continental collision regime are generally formed by CO₂-rich, high-salinity fluids.     

The Late Paleozoic porphyry–epithermal spectrum of the Birgilda–Tomino ore cluster in the South Urals,Russia

The Birgilda–Tomino ore cluster in the East Uralian zone, South Urals, Russia, hosts a variety of Late Paleozoic porphyry copper deposits (Birgilda, Tomino, Kalinovskoe, etc.), high- and low sulfidation epithermal deposits (Bereznyakovskoe, Michurino), and skarn-related base metal mineralization (Biksizak) in carbonate rocks. The deposits are related to quartz diorite and andesite porphyry intrusions of the K–Na calc-alkaline series, associated to a subduction-related volcanic arc. We report microprobe analyses of ore minerals (tetrahedrite–tennantite, sphalerite, Bi tellurides and sulfosalts, Au and Ag tellurides), as well as fluid inclusion data and mineral geothermometry. On the basis of these data we propose that the Birgilda–Tomino ore cluster represents a porphyry–epithermal continuum, with a vertical extent of about 2–3 km, controlled by temperature decreases and fS₂ and fTe₂ increase from deeper to shallow levels.     

Epithermal deposits in South China: Geology,geochemistry, geochronology and tectonic setting

South China Block (SCB) is the broad area including the Yangtze Craton in the northwest and Huanan Orogen in the southeast. It is an important epithermal metallogenic province in China, containing at least 1 high-sulfidation (HS) and 42 low-sulfidation (LS) Au-Ag ± Cu ± Pb-Zn ± Sb epithermal deposits. Porphyry-type mineralization was recognized in four of the LS deposits, and thus they were regarded as LS–P type. These 43 deposits are mainly located in: (1) the Lower Yangtze River Belt and (2) the Northeastern Jiangnan Orogenic Belt in the Yangtze Craton, (3) the Wuyi-Yunkai Orogenic Belt and (4) the Southeast Coastal Volcanic Belt in the Huanan Orogen. They are mostly located in Mesozoic volcanic basins, especially where the regional faults and their subsidiaries occurred. The host rocks include Jurassic–Cretaceous volcanic-sedimentary rocks, coeval or slightly older subvolcanic, granitoids and breccias, and metamorphic basement rocks. The alteration of the HS epithermal deposit (Zijinshan Cu-Au) zoned from silicic (vuggy quartz), through alunite, to dickite and phyllic alteration zones, from the ore veins outwards. The alteration of the LS deposits is zoned from adularia-chalcedony-bladed calcite (or quartz pseudomorphs after bladed calcite) in ore veins to distal illite-sericite-chlorite-kaolinite assemblages. For those LS–P systems, besides the dominated LS alteration assemblages, phyllic and potassium silicate alteration related to porphyry mineralization were identified. Acid leaching textures and vein, stockwork and breccia structures are common in HS deposit, while the LS epithermal deposits are characterized by open-space filling, crustifications, colloform banding and comb structures. The ore-forming fluids are low-temperature, low-salinity meteoric water-dominated in most epithermal deposits in SCB, with variable input of magmatic water. The ore components were derived from both the deep magma and host rocks, and transported upwards or laterally and precipitated in the fracture systems by fluid boiling, mixing and cooling. Most of the epithermal deposits are formed at depth of < 1.5 km and < 300 °C, with few exceptions containing porphyry-type mineralization, such as the Zhilingtou, Yinshan and Longtoushan deposits. Deep drilling is suggested in these deposits as more epithermal and/or porphyry mineralization could be expected. The mineral systems were formed in Early Yanshanian (180–130 Ma) and Late Yanshanian (120–90 Ma) periods. The Early Yanshanian epithermal ore systems are mainly located in a series of E–W-trending metallogenic belts to the west of the Lishui–Haifeng Fault, which were formed in a syn- or post-collision tectonic setting by the collision between the SCB and its surrounding plates. The Late Yanshanian epithermal deposits are mainly located in Southeast Coastal Volcanic Belt, genetically related to the westward subduction of the paleo-Pacific plate.