Geology and ore genesis of the late Paleozoic Heijianshan Fe oxide–Cu (–Au) deposit in the Eastern Tianshan,NW China

The Heijianshan Fe–Cu (–Au) deposit, located in the Aqishan-Yamansu belt of the Eastern Tianshan (NW China), is hosted in the mafic–intermediate volcanic and mafic–felsic volcaniclastic rocks of the Upper Carboniferous Matoutan Formation. Based on the pervasive alteration, mineral assemblages and crosscutting relationships of veins, six magmatic–hydrothermal stages have been established, including epidote alteration (Stage I), magnetite mineralization (Stage II), pyrite alteration (Stage III), Cu (–Au) mineralization (Stage IV), late veins (Stage V) and supergene alteration (Stage VI). The Stage I epidote–calcite–tourmaline–sericite alteration assemblage indicates a pre-mineralization Ca–Mg alteration event. Stage II Fe and Stage IV Cu (–Au) mineralization stages at Heijianshan can be clearly distinguished from alteration, mineral assemblages, and nature and sources of ore-forming fluids.Homogenization temperatures of primary fluid inclusions in quartz and calcite from Stage I (189–370 °C), II (301–536 °C), III (119–262 °C) and V (46–198 °C) suggest that fluid incursion and mixing probably occurred during Stage I to II and Stage V, respectively. The Stage II magmatic–hydrothermal-derived Fe mineralization fluids were characterized by high temperature (>300 °C), medium–high salinity (21.2–56.0 wt% NaCl equiv.) and being Na–Ca–Mg–Fe-dominated. These fluids were overprinted by the external low temperature (<300 °C), medium–high salinity (19.0–34.7 wt% NaCl equiv.) and Ca–Mg-dominated basinal brines that were responsible for the subsequent pyrite alteration and Cu (–Au) mineralization, as supported by quartz CL images and H–O isotopes. Furthermore, in-situ sulfur isotopes also indicate that the sulfur sources vary in different stages, viz., Stage II (magmatic–hydrothermal), III (basinal brine-related) and IV (magmatic–hydrothermal). Stage II disseminated pyrite has δ³⁴S_fluid values of 1.7–4.3‰, comparable with sulfur from magmatic reservoirs. δ³⁴S_fluid values (24.3–29.3‰) of Stage III Type A pyrite (coexists with hematite) probably indicate external basinal brine involvement, consistent with the analytical results of fluid inclusions. With the basinal brines further interacting with volcanic/volcaniclastic rocks of the Carboniferous Matoutan Formation, Stage III Type B pyrite–chalcopyrite–pyrrhotite assemblage (with low δ³⁴S_fluid values of 4.6–10.0‰) may have formed at low fO₂ and temperature (119–262 °C). The continuous basinal brine–volcanic/volcaniclastic rock interactions during the basin inversion (∼325–300 Ma) may have leached sulfur and copper from the rocks, yielding magmatic-like δ³⁴S_fluid values (1.5–4.1‰). Such fluids may have altered pyrite and precipitated chalcopyrite with minor Au in Stage IV. Eventually, the Stage V low temperature (∼160 °C) and low salinity meteoric water may have percolated into the ore-forming fluid system and formed late-hydrothermal veins.The similar alteration and mineralization paragenetic sequences, ore-forming fluid sources and evolution, and tectonic settings of the Heijianshan deposit to the Mesozoic Central Andean IOCG deposits indicate that the former is probably the first identified Paleozoic IOCG-like deposit in the Central Asian Orogenic Belt.     

PGE geochemistry of the Eagle Ni–Cu–(PGE) deposit, Upper Michigan: constraints on ore genesis in a dynamic magma conduit

The Eagle Ni–Cu–(PGE) deposit is hosted in mafic–ultramafic intrusive rocks associated with the Marquette–Baraga dike swarm in northern Michigan. Sulfide mineralization formed in association with picritic magmatism in a dynamic magma conduit during the early stages in the development of the ~1.1?Ga Midcontinent Rift System. Four main types of sulfide mineralization have been recognized within the Eagle deposit: (1) disseminated sulfides in olivine-rich rocks; (2) rocks with semi-massive sulfides located both above and below the massive sulfide zone; (3) massive sulfides; and (4) sulfide veins in sedimentary country rocks. The disseminated, massive and lower semi-massive sulfide zones are typically composed of pyrrhotite, pentlandite and chalcopyrite, whereas the upper semi-massive sulfide ore zone also contains pyrrhotite, pentlandite, and chalcopyrite, but has higher cubanite content. Three distinct types of sulfide mineralization are present in the massive sulfide zone: IPGE-rich, PPGE-rich, and PGE-unfractioned. The lower and upper semi-massive sulfide zones have different PGE compositions. Samples from the lower semi-massive sulfide zone are characterized by unfractionated PGE patterns, whereas those from the upper semi-massive sulfide zone show moderate depletion in IPGE and moderate enrichment in PPGE. The mantle-normalized PGE patterns of unfractionated massive and lower semi-massive sulfides are subparallel to those of the disseminated sulfides. The results of numerical modeling using PGE concentrations recalculated to 100% sulfide (i.e., PGE tenors) and partition coefficients of PGE between sulfide liquid and magma indicate that the disseminated and unfractionated massive sulfide mineralization formed by the accumulation of primary sulfide liquids with similar R factors between 200 and 300. In contrast, the modeled R factor for the lower semi-massive sulfide zone is <100. The fractionated sulfide zones such as those of the IPGE-rich and PPGE-rich massive sulfides and the upper semi-massive sulfide zone can be explained by fractional crystallization of monosulfide solid solution from sulfide liquids. The results of numerical modeling indicate that the sulfide minerals in the upper semi-massive sulfide zone are the products of crystallization of fractionated sulfide liquids derived from a primary sulfide liquid with an R factor similar to that for the disseminated sulfide mineralization. Interestingly, the modeled parental sulfide liquid for the IPGE-rich and PPGE-rich massive sulfide zones has a higher R factor (~400) than that for the unfractionated massive sulfide mineralization. Except one sample which has unusually high IPGE and PPGE contents, all other samples from the Cu-rich sulfide veins in the footwall of the intrusion are highly depleted in IPGE and enriched in PPGE. These signatures are generally consistent with highly fractionated sulfide liquids expelled from crystallizing sulfide liquid. Collectively, our data suggest that at least four primary sulfide liquids with different R factors (<100, 200–300, ~400) were involved in the formation of the Eagle magmatic sulfide deposit. We envision that the immiscible sulfide liquids were transported from depth by multiple pulses of magma passing through the Eagle conduit system. The sulfide liquids were deposited in the widened part of the conduit system due to the decreasing velocity of magma flow. The presence of abundant olivine in some of the sulfide ore zones indicates that the ascending magma also carried olivine crystals. Sulfide saturation was attained in the parental magma due in large part to the assimilation of country rock sulfur at depth.     

Electron microprobe analyses of ore minerals and H–O,S isotope geochemistry of the Yuerya gold deposit,eastern Hebei,China: Implications for ore genesis and mineralization

The Yuerya gold deposit in eastern Hebei Province, China, is located on the eastern margin of the North China Craton and is hosted by Mesozoic Yanshanian granitoid rocks and adjacent Mesoproterozoic Gaoyuzhuang Formation carbonates. The auriferous quartz veins in this deposit are dominated by pyrite, with subordinate sphalerite, chalcopyrite, and galena in a quartz-dominated gangue that also contains calcite, dolomite, barite, apatite, and fluorite. Gold is present as native gold and electrum, which are generally present as micron-size infillings in microfissures within pyrite and less commonly as tiny inclusions within pyrite, quartz, and tellurobismuthite. The pyrite in this deposit has high Co/Ni ratios and contains elevated concentrations of both of these elements, suggesting that the Yuerya gold deposit has a magmato-hydrothermal origin and that the ore-forming fluids that formed the deposit leached trace elements such as Co, Ni, As, and Au during passage through Archean metamorphic rocks, Mesoproterozoic carbonates, and the Yanshanian Yuerya granitoid. Pyrite in the study area has S/Se ratios and S isotopic compositions that suggest that the sulfur (and by inference the gold) within the deposit was sourced from magmato-hydrothermal fluids that were probably originally derived from Archean metamorphic rocks and Yanshanian granitoids. Tellurobismuthite in the study area is closely intergrown with gold and was the single telluride phase identified during this study. The fineness of gold associated with tellurobismuthite is greater than the fineness of gold associated with pyrite, although the fine particle size of the gold surrounded by tellurobismuthite means that the recovery of this gold is difficult, in turn meaning that the tellurobismuthite has little significance to the economics of the Yuerya gold deposit. Only trace amounts of sulfides are associated with the tellurobismuthite within the Yuerya gold deposit, suggesting that this mineral was deposited under conditions of low fS₂ and/or high fTe₂. In addition, the presence of tellurides within the Yuerya gold deposit reflects a genetic relationship between the deposit and magmatism. Quartz from mineralized veins in the study area has δ¹⁸O values of 11.2‰–12.9‰ and the fluids that formed these veins have δD values of − 78.3‰ to − 72.1‰. The δ³⁴S values of pyrite within the deposit are rather restricted (2.3‰–3.5‰). These data, combined with the trace element geochemistry of sulfides within the deposit, suggest that the formation of the Yuerya gold deposit was closely related to both Archean metamorphic rocks and the Yanshanian Yuerya granitoid.     

Petrography and geochemistry of the Shilu Fe–Co–Cu ore district,South China: Implications for the origin of a Neoproterozoic BIF system

The Shilu Fe–Co–Cu ore district is situated in the western Hainan Province of south China. This district consists of the upper Fe-rich layers and the lower Co–Cu ores, which are mainly hosted within the Neoproterozoic Shilu Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Three facies of metamorphosed BIFs, the oxide, the silicate–oxide and the sulfide–carbonate–silicate, have been identified within the Shilu Group. The oxide banded iron formation (BIF) facies (quartz itabirites or Fe-rich ores) consists of alternating hematite-rich and quartz-rich microbands. The silicate–oxide BIF facies (amphibolitic itabirites or Fe-poor ores) comprises alternating millimeter to tens of meter scale, magnetite–hematite-rich bands with calc-silicate-rich macro- to microbands. The sulfide–carbonate–silicate BIF facies (Co–Cu ores) contain alternating cobaltiferous pyrite, cobaltiferous pyrrhotite and chalcopyrite macrobands to microbands mainly with dolomite–calcite, but also with minor sericite–quartz bands. Blasto-oolitic, pelletoidal, colloidal, psammitic, and cryptocrystalline to microcrystalline textures, and blasto-bedding structures, which likely represent primary sedimentation, are often observed in the Shilu BIF facies.The Shilu BIFs and interbedded host rocks are generally characterized by relatively low but variable ∑ REE concentrations, LREE depletion and/or MREE enrichment relative to HREE, and no Ce, Gd and Eu anomalies to strongly positive Ce, Gd and Eu anomalies in the upward-convex PAAS-normalized REY patterns, except for both the banded or impure dolostones with nil Ce anomaly to negative Ce anomalies and negative La anomalies, and the minor sulfide–carbonate–silicate BIF facies with moderately negative Eu anomalies. They also contain relatively low but variable HFSE abundances as Zr, Nb, Hf, Th and Ti, and relatively high but variable abundances of Cu, Co, Ni, Pb, As, Mn and Ba. The consistently negative ε_Nd(t) values range from − 4.8 to − 8.5, with a T_DM age of ca. 2.0 Ga. In line with the covariations between Al₂O₃ and TiO₂, Fe₂O₃ + FeO and SiO₂, Mn and Fe, Zr and Y/Ho and REE, and Sc and LREE, the geochemical and Sm–Nd isotopic features suggest that the precursors to the Shilu BIFs formed from a source dominated by seafloor-derived, high- to low temperature, acidic and reducing hydrothermal fluids but with variable input of detrital components in a seawater environment. Moreover, the involved detrital materials were sourced dominantly from an unknown, Paleoproterozoic or older crust, with lesser involvement from the Paleo- to Mesoproterozoic Baoban Group underlying the Shilu Group.The Shilu BIFs of various facies are interpreted to have formed in a shallow marine, restricted or sheltered basin near the rifted continental margin most likely associated with the break-up of Rodinia as the result of mantle superplume activity in South China. The seafloor-derived, periodically upwelling metalliferous hydrothermal plume/vent fluids under anoxic but sulfidic to anoxic but Fe^2 +-rich conditions were removed from the plume/vent and accumulated in the basin, and then variably mixed with terrigenous detrital components, which finally led to rhythmic deposition of the Shilu BIFs.     

Geological characteristics and genesis of the Laoshankou Fe–Cu–Au deposit in Junggar,Xinjiang, Central Asian Orogenic Belt

The Laoshankou Fe–Cu–Au deposit is located at the northern margin of Junggar Terrane, Xinjiang, China. This deposit is hosted in Middle Devonian andesitic volcanic breccias, basalts, and conglomerate-bearing basaltic volcanic breccias of the Beitashan Formation. Veined and lenticular Fe–Cu–Au orebodies are spatially and temporally related to diorite porphyries in the ore district. Wall–rock alteration is dominated by skarn (epidote, chlorite, garnet, diopside, actinolite, and tremolite), with K–feldspar, carbonate, albite, sericite, and minor quartz. On the basis of field evidence and petrographic observations, three stages of mineralization can be distinguished: (1) a prograde skarn stage; (2) a retrograde stage associated with the development of Fe mineralization; and (3) a quartz–sulfide–carbonate stage associated with Cu–Au mineralization. Electron microprobe analysis shows that garnets and pyroxenes are andradite and diopside-dominated, respectively. Fluid inclusions in garnet yield homogenization temperatures (T_h) of 205–588 °C, and salinities of 8.95–17.96 wt.% NaCl equiv. In comparison, fluid inclusions in epidote and calcite yield T_h of 212–498 and 150–380 °C, and salinities of 7.02–27.04 and 13.4–18.47 wt.% NaCl equiv., respectively. Garnets yield values of 6.4‰ to 8.9‰ δ¹⁸O_fluid, whereas calcites yield values of − 2.4‰ and 4.2‰ δ¹⁸O_fluid, and − 0.9‰ to 2.4‰ δ¹³C_PDB, indicating that the ore-forming fluids were dominantly magmatic fluids in the early stage and meteoric water in the late stage. The δ³⁴S values of sulfides range from − 2.6‰ to 5.4‰, indicating that the sulfur in the deposit was probably derived from deep-seated magmas. The diorite porphyry yields LA–MC–ICP–MS zircon U–Pb age of 379.7 ± 3.0 Ma, whereas molybdenites give Re–Os weighted mean age of 383.2 ± 4.5 Ma (MSWD = 0.06). These ages suggest that the mineralization-related diorite porphyry was emplaced during the Late Devonian, coincident with the timing of mineralization within the Laoshankou Fe–Cu–Au deposit. The geological and geochemical evidence presented here suggest that the Laoshankou Fe–Cu–Au deposit is a skarn deposit.     

Geological,fluid inclusion and isotopic studies of the Yinshan Cu–Au–Pb–Zn–Ag deposit,South China: Implications for ore genesis and exploration

The Yinshan Cu–Au–Pb–Zn–Ag deposit is located in Dexing, South China. Ore bodies are primarily hosted in low-grade phyllite of the Neoproterozoic Shuangqiaoshan Group along EW- and NNW-striking fault zones. Pb–Zn–Ag mineralization is dictated by Jurassic rhyolitic quartz porphyries (ca. 172 Ma), whereas Cu–Au mineralization is associated with Jurassic dacite porphyries (ca. 170 Ma). The main ore minerals are pyrite, chalcopyrite, galena, sphalerite, tetrahedrite–tennatite, gold, silver, and silver sulphosalt, and the principal gangue minerals are quartz, sericite, calcite, and chlorite. Two-phase liquid-rich (type I), two-phase vapor-rich (type II), and halite-bearing (type III) fluid inclusions can be observed in the hydrothermal quartz-sulfides veins. Type I inclusions are widespread and have homogenization temperatures of 187–303 °C and salinities of 4.2–9.5 wt.% NaCl equivalent in the Pb–Zn–Ag mineralization, and homogenization temperatures of 196–362 °C and salinities of 3.5–9.9 wt.% NaCl equivalent in the Cu–Au mineralization. The pervasive occurrence of type I fluid inclusions with low-moderate temperatures and salinities implies that the mineralizing fluids formed in epithermal environments. The type II and coexisting type III inclusions, from deeper levels below the Cu–Au ore bodies, share similar homogenization temperatures of 317–448 °C and contrasting salinities of 0.2–4.2 and 30.9–36.8 wt.% NaCl equivalent, respectively, which indicates that boiling processes occurred. The sulfur isotopic compositions of sulfides (δ³⁴S = −1.7‰ to +3.2‰) suggest a homogeneous magmatic sulfur source. The lead isotopes of sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.01–18.07; ²⁰⁷Pb/²⁰⁴Pb = 15.55–15.57; and ²⁰⁸Pb/²⁰⁴Pb = 38.03–38.12) are consistent with those of volcanic–subvolcanic rocks (²⁰⁶Pb/²⁰⁴Pb = 18.03–18.10; ²⁰⁷Pb/²⁰⁴Pb = 15.56–15.57; and ²⁰⁸Pb/²⁰⁴Pb = 38.02–38.21), indicating a magmatic origin for lead in the ore. The oxygen and hydrogen isotope compositions (δ¹⁸O = +7.8‰ to +10.5‰, δD = −66‰ to −42‰) of inclusion water in quartz imply that ore-forming fluids were mainly derived from magmatic sources. The local boiling process beneath the epithermal Cu–Au ore-forming system indicates the possibility that porphyry-style ore bodies may exist at even deeper zones.     

Geology,isotope geochemistry and ore genesis of the Shanshulin carbonate-hosted Pb–Zn deposit,southwest China

The Shanshulin Pb–Zn deposit occurs in Upper Carboniferous Huanglong Formation dolomitic limestone and dolostone, and is located in the western Yangtze Block, about 270 km west of Guiyang city in southwest China. Ore bodies occur along high angle thrust faults affiliated to the Weishui regional fault zone and within the northwestern part of the Guanyinshan anticline. Sulfide ores are composed of sphalerite, pyrite, and galena that are accompanied by calcite and subordinate dolomite. Twenty-two ore bodies have been found in the Shanshulin deposit area, with a combined 2.7 million tonnes of sulfide ores grading 0.54 to 8.94 wt.% Pb and 1.09 to 26.64 wt.% Zn. Calcite samples have δ¹³C_PDB and δ¹⁸O_SMOW values ranging from − 3.1 to + 2.5‰ and + 18.8 to + 26.5‰, respectively. These values are higher than mantle and sedimentary organic matter, but are similar to marine carbonate rocks in a δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, suggesting that carbon in the hydrothermal fluid was most likely derived from the carbonate country rocks. The δ³⁴S_CDT values of sphalerite and galena samples range from + 18.9 to + 20.3‰ and + 15.6 to + 17.1‰, respectively. These values suggest that evaporites are the most probable source of sulfur. The δ³⁴S_CDT values of symbiotic sphalerite–galena mineral pairs indicate that deposition of sulfides took place under chemical equilibrium conditions. Calculated temperatures of S isotope thermodynamic equilibrium fractionation based on sphalerite–galena mineral pairs range from 135 to 292 °C, consistent with previous fluid inclusion studies. Temperatures above 100 °C preclude derivation of sulfur through bacterial sulfate reduction (BSR) and suggest that reduced sulfur in the hydrothermal fluid was most likely supplied through thermo-chemical sulfate reduction (TSR). Twelve sphalerite samples have δ⁶⁶Zn values ranging from 0.00 to + 0.55‰ (mean + 0.25‰) relative to the JMC 3-0749L zinc isotope standard. Stages I to III sphalerite samples have δ⁶⁶Zn values ranging from 0.00 to + 0.07‰, + 0.12 to + 0.23‰, and + 0.29 to + 0.55‰, respectively, showing the relatively heavier Zn isotopic compositions in later versus earlier sphalerite. The variations of Zn isotope values are likely due to kinetic Raleigh fractional crystallization. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of the sulfide samples fall in the range of 18.362 to 18.573, 15.505 to 15.769 and 38.302 to 39.223, respectively. The Pb isotopic ratios of the studied deposit plot in the field that covers the upper crust, orogenic belt and mantle Pb evolution curves and overlaps with the age-corrected Proterozoic folded basement rocks, Devonian to Lower Permian sedimentary rocks and Middle Permian Emeishan flood basalts in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram. This observation points to the derivation of Pb metal from mixed sources. Sphalerite samples have ⁸⁷Sr/⁸⁶Sr_200 Ma ratios ranging from 0.7107 to 0.7115 similar to the age-corrected Devonian to Lower Permian sedimentary rocks (0.7073 to 0.7111), higher than the age-corrected Middle Permian basalts (0.7039 to 0.7078), and lower than the age-corrected Proterozoic folded basement (0.7243 to 0.7288). Therefore, the Sr isotope data support a mixed source. Studies on the geology and isotope geochemistry suggest that the Shanshulin deposit is a carbonate-hosted, thrust fault-controlled, strata-bound, epigenetic, high grade deposit formed by fluids and metals of mixed origin.     

Tectonodynamic Adjustment of Crustal Materials in the Middle-Lower Reaches of the Yangtze River

Under the tectonodynamic process, crustal materials tend to experience two modes of adjustment: (1) structural (physical) adjustment, manifested by folding, faulting, uplifting, downwarping, etc.: (2) compositional adjustment, represented by element migration, concentration and dispersion, crystalline and dynamic differentiation of crystals, metamorphism, etc. (Yang Kaiqing. 1986; Yang Kaiqing et al., 1986). The dynamic adjustment of crustal materials in the middle-lower reaches of the Yangtze mainly occurred in the Mesozoic under the conditions of intense collision between the North China (Dabie) massif and the Yangtze massif. The structural adjustment refers to various types of deformation within the two massifs and the intensive shortening of the stratigraphic coyer of the Yangtze massif, whereas the compositional adjustment implies the structural remelting of the basement and the ore. and rock- forming processes in the two massifs.     

Mineral chemistry and H–O–S–Pb isotopic compositions of skarn type copper deposits in the Jiurui district of the Middle-Lower Yangtze River metallogenic belt,Eastern China

The skarn type copper deposits are widespread in the Jiurui district in the Middle-Lower Yangtze River metallogenic belt. This paper reports a detailed study on mineral chemistry, and H, O, S and Pb isotopic compositions on skarn silicate and sulfide minerals in the three major skarn dominant deposits (Wushan, Dongleiwan and Dengjiashan). The Wushan skarn deposit is characterized with prograde garnet-dominated and clinopyroxene limited skarns with average andradite content of 83% and hedenbergite content of 10%, whereas the Dongleiwan and Dengjiashan deposits are featured with retrograde skarn alteration with abundant hydrous minerals such as epidote and chlorite. The garnet and clinopyroxene compositions show 59% andradite and 15% hedenbergite for the Dongleiwan skarns, and 43% and 22% for the Dengjiashan skarns respectively. The pistacite components (Ps value) defined as Fe^3 +/(Fe^3 ++ Al) and Fe^3 +/Fe^2 + value of epidote are 0.12 and 1.63 for the Wushan skarns, 0.30 and 32.73 for the Dongleiwan skarns, and 0.17 and 42.85 for the Dengjiashan skarns. It is suggested that the prograde skarn mineralization in the three deposits was all formed in a relatively oxidizing environment, with the Wushan showing the highest oxidation potential and the Dengjiashan having the least oxidation potential. However, in the retrograde skarns, the Dongleiwan and Dengjiashan deposits show higher oxidation potential than that of Wushan. The three deposits show similar sulfur isotopic compositions of − 2.9 to + 1.4‰ and similar lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of 17.900 to 18.205, 15.538 to 15.649 and 38.170 to 39.025, respectively. All the three deposits should have similar magmatic origin for the ore-forming materials based on their S and Pb isotopes. The oxygen isotopic compositions of the prograde and retrograde fluids in the three deposits show some differences, with δ¹⁸O_Fluid values of + 8.13‰ and + 7.81‰ for the Wushan, + 6.47‰ and + 2.33‰ for the Dongleiwan, and + 8.27‰ and + 4.43‰ for the Dengjiashan. But the hydrogen isotopic compositions are similar for the prograde (− 65 to − 31‰) and retrograde (− 64 to − 33‰) fluids. Therefore, the fluid origins and evolution may be different in each deposit. The hydrothermal fluids for the prograde skarns in all three deposits were likely derived from magmatic–hydrothermal sources, but the Dongleiwan and Dengjiashan show a higher proportion of meteoric water input in the retrograde stage. Considering the similar average prograde temperatures (574 to 560 °C) as calculated from coexisting garnet–clinopyroxene pairs, and similar retrograde temperatures (281 to 246 °C) as calculated from chlorite chemistry for the three deposits, we suggest that the trigger for deposition of sulfide ores in the Wushan garnet-dominated skarn deposit was mainly caused by system cooling with temperature drop along with magmatic intrusion and crystallization process. The Dongleiwan and Dengjiashan skarn deposits constitute a well developed retrograde skarn system with abundant epidote, chlorite, quartz and calcite, which probably caused by fluid mixing of high-temperature saline magmatic–hydrothermal fluids with cooler, oxidizing and dilute meteoric water.     

Geochemical constraints on Cu–Fe and Fe skarn deposits in the Edong district,Middle–Lower Yangtze River metallogenic belt,China

Copper and iron skarn deposits are economically important types of skarn deposits throughout the world, especially in China, but the differences between Cu and Fe skarn deposits are poorly constrained. The Edong ore district in southeastern Hubei Province, Middle–Lower Yangtze River metallogenic belt, China, contains numerous Fe and Cu–Fe skarn deposits. In this contribution, variations in skarn mineralogy, mineralization-related intrusions and sulfur isotope values between these Cu–Fe and Fe skarn deposits are discussed.The garnets and pyroxenes of the Cu–Fe and Fe skarn deposits in the Edong ore district share similar compositions, i.e., dominantly andradite (Ad_29–100Gr_0–68) and diopside (Di_54–100Hd_0–38), respectively. This feature indicates that the mineral compositions of skarn silicate mineral assemblages were not the critical controlling factors for variations between the Cu–Fe and Fe skarn deposits. Intrusions associated with skarn Fe deposits in the Edong ore district differ from those Cu–Fe skarn deposits in petrology, geochemistry and Sr–Nd isotope. Intrusions associated with Fe deposits have large variations in their (La/Yb)_N ratios (3.84–24.6) and Eu anomalies (δEu = 0.32–1.65), and have relatively low Sr/Y ratios (4.2–44.0) and high Yb contents (1.20–11.8 ppm), as well as radiogenic Sr–Nd isotopes (εNd(t) = − 12.5 to − 9.2) and (⁸⁷Sr/⁸⁶Sr)_i = 0.7067 to 0.7086. In contrast, intrusions associated with Cu–Fe deposits are characterized by relatively high Sr/Y (35.0–81.3) and (La/Yb)_N (15.0–31.6) ratios, low Yb contents (1.00–1.62 ppm) without obvious Eu anomalies (δEu = 0.67–0.97), as well as (⁸⁷Sr/⁸⁶Sr)_i = 0.7055 to 0.7068 and εNd(t) = − 7.9 to − 3.4. Geochemical evidence indicates a greater contribution from the crust in intrusions associated with Fe skarn deposits than in intrusions associated with Cu–Fe skarn deposits. In the Edong ore district, the sulfides and sulfates in the Cu–Fe skarn deposits have sulfur isotope signatures that differ from those of Fe skarn deposits. The Cu–Fe skarn deposits have a narrow range of δ³⁴S values from − 6.2‰ to + 8.7‰ in sulfides, and + 13.2‰ to + 15.2‰ in anhydrite, while the Fe skarn deposits have a wide range of δ³⁴S values from + 10.3‰ to + 20.0‰ in pyrite and + 18.9‰ to + 30.8‰ in anhydrite. Sulfur isotope data for anhydrite and sedimentary country rocks suggest that the formation of skarns in the Edong district involved the interaction between magmatic fluids and variable amounts of evaporites in host rocks.     

Compositional variations of olivine from the Jinchuan Ni–Cu sulfide deposit,western China: implications for ore genesis

The Jinchuan Ni–Cu sulfide deposit is hosted by an elongated, olivine-rich ultramafic body that is divided by subvertical strike-slip faults into three segments (central, eastern, and western). The central segment is characterized by concentric enrichments of cumulus olivine crystals and interstitial sulfides (pyrrhotite–pentlandite–chalcopyrite intergrowth), whereas the eastern and western segments are characterized by an increase of sulfides toward the lower contacts. In all segments sulfides are concentrated at the expense of intercumulus silicates. Olivine re-crystallization is found to be associated with actinolite alteration in some samples. The compositional variations of primary olivine from the sulfide-poor samples can be explained by a small degree of olivine crystallization (<5%) from a basaltic magma followed by local re-equilibration of the olivine with up to 30% trapped silicate liquid. In the sulfide-bearing samples the compositions of primary olivine record the results of olivine-sulfide Fe–Ni exchange that occurred after the trapped silicate liquid crystallized. Our olivine data indicate that Ni in the original sulfide liquids increased inward in the central segment and laterally away from the lower contact in the eastern segment. Variations in the compositions of sulfide liquids are thought to result from fractional segregation of immiscible sulfide liquid from a basaltic magma in a staging chamber instead of in situ differentiation. High concentrations of olivine crystals (mostly >50 modal%) and sulfide (averaging ~5 wt%) in the rocks are consistent with the interpretation that the Jinchuan deposit was formed by olivine- and sulfide-laden magma successively ascending through a conduit to a higher, now-eroded, level. Sulfide enrichment toward the center in the central segment and toward the lower contact in the eastern and western segments may have, in part, resulted from flow differentiation and gravitational settling during magma ascent, respectively.Editorial handling: P. Lightfoot     

Geochemistry,mineralogy and genesis of the Ayazmant Fe–Cu skarn deposit in Ayvalik, (Balikesir), Turkey

The Ayazmant Fe–Cu skarn deposit is located approximately 20 km SE of Ayval?k or 140 km N of Izmir in western Turkey. The skarn occurs at the contact between metapelites and the metabasites of the Early Triassic K?n?k Formation and the porphyritic hypabyssal intrusive rocks of the Late Oligocene Kozak Intrusive Complex. The major, trace, and rare earth-element geochemical analysis of the igneous rocks indicate that they are I-type, subalkaline, calc-alkaline, metaluminous, I-type products of a high-level magma chamber, generated in a continental arc setting. The ⁴⁰Ar–³⁹Ar isochron age obtained from biotite of hornfels is 20.3 ± 0.1 Ma, probably reflecting the age of metamorphic–bimetasomatic alteration which commenced shortly after intrusion into impure carbonates. Three stages of skarn formation and ore development are recognized: (1) Early skarn stage (Stage I) consisting mainly of garnet with grossular-rich (Gr_75–79) cores and andradite-rich (Gr_36–38) rims, diopside (Di_94–97), scapolite and magnetite; (2) sulfide-rich skarn (Stage II), dominated by chalcopyrite with magnetite, andraditic garnet (Ad₈₄–₈₉), diopside (Di₆₅–₇₅) and actinolite; and (3) retrograde alteration (Stage III) dominated by actinolite, epidote, orthoclase, phlogopite and chlorite in which sulfides are the main ore phases. ⁴⁰Ar–³⁹Ar age data indicate that potassic alteration, synchronous or postdating magnetite–pyroxene–amphibole skarn, occurred at 20.0 ± 0.1 Ma. The high pyroxene/garnet ratio, plus the presence of scapolite in calc-silicate and associated ore paragenesis characterized by magnetite (± hematite), chalcopyrite and bornite, suggests that the bulk of the Ayazmant skarns were formed under oxidized conditions. Oxygen isotope compositions of pyroxene, magnetite and garnet of prograde skarn alteration indicate a magmatic fluid with δ¹⁸O values between 5.4 and 9.5‰. On the basis of oxygen isotope data from mineral pairs, the early stage of prograde skarn formation is characterized by pyroxene (Di_94–97)-magnetite assemblage formed at an upper temperature limit of 576 °C. The lower temperature limit for magnetite precipitation is estimated below 300 °C, on the basis of magnetite–calcite pairs either as fracture-fillings or massive ore in recrystallized limestone-marble. The sulfide assemblage is dominated by chalcopyrite with subordinate molybdenite, pyrite, cubanite, bornite, pyrrhotite, galena, sphalerite and idaite. Gold–copper mineralization formed adjacent to andradite-dominated skarn which occurs in close proximity to the intrusion contacts. Native gold and electrum are most abundant in sulfides, as fine-grained inclusions; grain size with varying from 5 to 20 µm. Sulfur isotope compositions obtained from pyrrhotite, pyrite, chalcopyrite, sphalerite and galena form a narrow range between ? 4.8 and 1.6‰, suggesting the sulfur was probably mantle-derived or leached from magmatic rocks. Geochemical data from Ayazmant shows that Cu is strongly associated with Au, Bi, Te, Se, Cd, Zn, Pb, Ni and Co. The Ayazmant mineralizing system possesses all the ingredients of a skarn system either cogenetic with, or formed prior to a porphyry Cu(Au–Mo) system. The results of this study indicate that the Aegean Region of Turkey has considerable exploration potential for both porphyry-related skarns and porphyry Cu and Au mineralization.     

Trace element composition of magnetite from the Xinqiao Fe–S(–Cu–Au) deposit,Tongling, Eastern China: constraints on fluid evolution and ore genesis

The Xinqiao deposit is one of several polymetallic deposits in the Tongling ore district. There are two types of mineralization in the Xinqiao: skarn-type and stratiform-type. The skarn-type mineralization is characterized by iron oxides such as magnetite and hematite, whereas stratiform-type mineralization is characterized by massive sulfides with small amounts of magnetite and hematite. We defined three types of ores within the stratiform-type mineralization by the mineral assemblages and ore structures. Type I ore is represented by magnetite crosscut by minor calcite veins. Type II is a network ore composed of magnetite and crosscutting pyrite. Type III is a massive ore containing calcite and hematite. Type I magnetite is characterized by highly variable trace element content, whereas Type II magnetite has consistently higher Si, Ti, V, and Nb. Type III magnetite contains more In, Sn, and As than the other two types. Fluid–rock interaction, oxygen fugacity (fO₂), and temperature (T) are the main factors controlling element variation between the different magnetite types. Type I magnetite was formed by more extensive fluid–rock interaction than the other two types at moderate fO₂ and T conditions. Type II magnetite is thought to have formed in relatively low fO₂ and high-T environments, and Type III in relatively high fO₂ and moderate-T environments. Ca?+?Al?+?Mn and Ti?+?V discrimination diagrams show that magnetite in the Xinqiao deposit is hydrothermal in origin and is possibly linked with skarn.     

In situ zircon U–Pb dating and O isotopes of the Neoarchean Hongtoushan VMS Cu–Zn deposit in the North China Craton: Implication for the ore genesis

The Hongtoushan volcanogenic massive sulfide (VMS) deposit is the largest Archean Cu–Zn deposit in China, located in the Qingyuan greenstone belt on the northern margin of the North China Craton. The Cu–Zn mineralization was stratigraphically controlled by the interbeds (~ 100 m in thickness) of mafic–felsic volcanic sets and overlain by banded iron layers. However, the relationship between VMS deposits and associated volcanics has not been examined. This study ultimately clarifies the times and sources of the volcanics and mineralization. Based on in situ zircon U–Pb and O isotope on VMS-hosting mafic, felsic volcanic rocks, banded and massive sulfide ores and postmineralization pegmatite vein, we considered that there were two main formation stages for the Qingyuan Cu–Zn deposits; one was exhalative-hydrothermal sedimentation and another was further Cu–Zn enriched by later hydrothermal processes. The timing of the first stage occurred at 2571 ± 6 Ma based on the magmatic zircons in the VMS-hosting mafic volcanic rocks, from which the inherited zircons also indicate the existence of 2.65–3.12 Ga ancient supercrustal rocks in the Qingyuan district. A modern mantle-like δ¹⁸Ozircon value of 5.5 ± 0.1‰ (2SD) for this volcanism was well preserved in the inherited core domains of ore samples. It suggests that the mafic volcanics was most likely sourced from partial melting of juvenile crust, e.g., TTG granites. A large-scale metamorphic or hydrothermal event is documented by the recrystallized zircons in sulfide ores. The timing is tightly constrained by the hydrothermal zircon U–Pb ages. They are 2508 ± 4 Ma for the banded ore, 2507 ± 4 Ma for the massive ore and 2508 ± 2 Ma for the postmineralization pegmatite vein. These indistinguishable ages indicate that the 2507 Ma hydrothermal systems played a significant role in the upgrading of the VMS Cu–Zn orebodies. The weighted δ¹⁸O values of hydrothermal zircons show a successively increasing trend from 6.0 ± 0.1‰ (2σ) for the banded ore, 6.6 ± 0.2‰ (2σ) for the massive ore to 7.3 ± 0.2‰ (2σ) for the later pegmatite vein. This variation might be induced by gradual inputting of the δ¹⁸O-rich oceanic crust and/or oceanic sediment during the hydrothermal cycling system. Considering its modern mantle-like oxygen isotope composition of 2571 Ma volcanism, a submarine volcanic hydrothermal system involving mantle plumes is a preferred setting for the Neoarchean VMS Cu–Zn deposits in the Qingyuan greenstone belt.     

Re–Os pseudo-isochron of disseminated ore from the Kalatongke Cu–Ni sulfide deposit,Xinjiang, Northwest China: Implications for Re–Os dating of magmatic Cu–Ni sulfide deposits

Re–Os dating of disseminated ore from the Kalatongke Cu–Ni sulfide mineral deposit, Xinjiang, Northwest (NW) China, yields an apparent isochron age of 433 ± 31 Ma with an apparent initial ¹⁸⁷Os/¹⁸⁸Os (433 Ma) ratio of 0.197 ± 0.027. This apparent age is older than not only the zircon U–Pb age of the host intrusion (287 ± 5 Ma, Han et al., 2004) but also the stratigraphic age of the intruded country rock. Thus, the regression line is a pseudo-isochron. However, previous Re–Os dating of massive ores of the same deposit yielded an age that is consistent, within analytical uncertainty, with the zircon U–Pb age (Zhang et al., 2008). This relationship is similar to that observed in the Jinchuan deposit, NW China. Therefore, we suggested that the same mechanism, post-segregation diffusion of Os (Yang et al., 2008), is applicable to the Kalatongke deposit.Re–Os isotopic studies of Kalatongke, Jinchuan and representative magmatic Cu–Ni sulfide deposits suggest that the massive ores of mafic–ultramafic-rock-associated Cu–Ni sulfide deposits would yield geologically meaningful Re–Os age, whereas a pseudo-isochron would be obtained for the disseminated ores. Therefore, to obtain a geologically meaningful Re–Os age, the type of the deposit, the type of the ore and the ore-forming process should be taken into account.     

Zircon and molybdenite geochronology and geochemistry of the Kalmakyr porphyry Cu–Au deposit,Almalyk district,Uzbekistan: Implications for mineralization processes

Copper, gold and molybdenum mineralization of the Kalmakyr porphyry deposit in Uzbek Tien Shan occurs as stockworks, veinlets and disseminations in the phyllic and K-silicate alteration zones developed predominantly in a middle to late Carboniferous intrusive complex composed of monzonite and granodiorite porphyry. Zircon U–Pb dating yielded an age of 327.2 ± 5.6 Ma for the ore-hosting monzonite and an age of 313.6 ± 2.8 Ma for the ore-bearing granodiorite porphyry. Re–Os dating of seven molybdenite samples from stockwork and veinlet ores yielded model ages from 313.2 to 306.3 Ma, with two well-constrained isochron ages of 307.6 ± 2.5 Ma (five stockwork ores) and 309.1 ± 2.2 Ma (five stockwork ores and two veinlet ores), respectively. These results indicate that Cu–Au mineralization post-dated the emplacement of the monzonite, started right after the emplacement of the granodiorite porphyry, and lasted for ca. 7 Ma afterward. The geochronological and geochemical data suggest that the Kalmakyr deposit was formed in a late Carboniferous mature magmatic arc setting, probably related to the latest subduction process of the Turkestan Ocean beneath the Middle Tien Shan. The ε_Hf(t) values of zircon grains from the monzonite vary from +11 to +1.7, with an average of +5.1, and those of zircon grains from the granodiorite porphyry range from +5.7 to −1.8, with an average of +2.4. These data indicate that the magma of both monzonite and granodiorite porphyry was derived from partial melting of a thickened lower crust with input of mantle components and variable crustal contamination, and that there was more mantle contribution to the formation of the monzonite than the granodiorite porphyry. The high rhenium concentrations of molybdenite (98–899 ppm) also indicate major mantle contribution of rhenium and by inference ore metals. The relatively high Eu_N/Eu_N¹ values (average 0.68), Ce⁴⁺/Ce³ values (average 890) and Ce/Nd values (average 36.8) for zircon grains from the granodiorite porphyry than those from the monzonite (average Eu_N/Eu_N¹ = 0.33, average Ce⁴⁺/Ce³ = 624, average Ce/Nd = 3.9) suggest that the magma for the syn-mineralization granodiorite porphyry has higher oxygen fugacity than that for the pre-mineralization monzonite. Based on these data, it is proposed that while the monzonite was emplaced, the oxygen fugacity and volatile contents in the magma were relatively low, and ore metals might disperse in the intrusive rock, whereas when the granodiorite porphyry was emplaced, the oxygen fugacity and volatile contents in the magma were increased, favoring copper and gold enrichment in the magmatic fluids. The Kalmakyr deposit formed from a long-lived magmatic-hydrothermal system connected with fertile magmatic sources in relation to the subduction of the Turkestan Ocean beneath the Middle Tien Shan.     

Geochronology,geochemistry, and mineralization of the granodiorite porphyry hosting the Matou Cu–Mo (±W) deposit,Lower Yangtze River metallogenic belt,eastern China

Porphyry and skarn Cu–Fe–Au–Mo deposits are widespread in the Middle and Lower Yangtze River metallogenic belt (MLYMB), eastern China. The Matou deposit has long been regarded as a typical Cu–Mo porphyry deposit within Lower Yangtze part of the belt. Recently, we identified scheelite and wolframite in quartz veins in the Matou deposit, which is uncommon in other porphyry and skarn deposits in the MLYMB. We carried out detailed zircon U–Pb dating and geochemical and Sr–Nd–Hf isotopic studies of the granodiorite porphyry at Matou to define any differences from other ore-related granitoids. The porphyry shows a SiO₂ content ranging from 61.85 wt.% to 65.74 wt.%, K₂O from 1.99 wt.% to 3.74 wt.%, and MgO from 1.74 wt.% to 2.19 wt.% (Mg^# value ranging from 45 to 55). It is enriched in light rare earth elements and large ion lithophile elements, but relatively depleted in Nb, Ta, Y, Yb and compatible trace elements (such as Cr, Ni, and V), with slight negative Eu anomalies (Eu/Eu^* = 0.88–0.98) and almost no negative Sr anomalies. Results of electron microprobe analysis of rock-forming silicate minerals indicate that the Matou porphyry has been altered by an oxidized fluid that is rich in Mg, Cl, and K. The samples show relatively low ε_Nd(t) values from −7.4 to −7.1, slightly high initial ⁸⁷Sr/⁸⁶Sr values from 0.708223 to 0.709088, and low ε_Hf(t) values of zircon from −9.0 to −6.5, when compared with the other Cu–Mo porphyry deposits in the MLYMB. Zircon U–Pb dating suggests the Matou granodiorite porphyry was emplaced at 139.5 ± 1.5 Ma (MSWD = 1.8, n = 15), which is within the age range of the other porphyries in the MLYMB. Although geochemical characteristics of the Matou and other porphyries in the MLYMB are similar and all adakitic, the detrital zircons in the samples from Matou suggest that Archean lower crust (2543 ± 29 Ma, MSWD = 0.25, n = 5) was involved with the generation of Matou magma, which is different from the other porphyries in the belt. Our study suggests that the Matou granodiorite porphyry originated from partial melting of thickened lower crust that was delaminated into the mantle, similar to the other porphyries in the MLYMB, but it has a higher proportion of lower crustal material, including Archean rocks, which contributed to the formation of the porphyry and related W-rich magmatic-hydrothermal system.     

Geological Fluid Mapping in the Tongling Area： Implications for the Paleozoic Submarine Hydrothermal System in the Middle-Lower Yangtze Metallogenic Belt, East China

The Tongling area is one of the 7 ore-cluster areas in the Middle-Lower Yangtze metallogenic belt,East China,and has tectonically undergone a long-term geologic history from the late Paleozoic continental rifting,through the Middle Triassic continent-continent collision to the Jurassic-Cretaceous intracontinental tectono-magmatic activation.The Carboniferous sedimentary-exhalative processes in the area produced widespread massive sulfides with ages of 303-321 Ma,which partly formed massive pyrite-Cu deposits,but mostly provided significant sulfur and metals to the skarn Cu mineralization associated with the Yanshanian felsic intrusions. To understand the Carboniferous submarine hydrothermal system,an area of about 1046 km~2 was chosen to carry out the geological fluid mapping.Associated with massive sulfide formation,footwall sequences 948 m to 1146m thick,composed of the Lower Silurian-Upper Devonian sandstone,siltstone and thin-layered shale,were widely altered.This hydrothermal alteration is interpreted to reflect large- scale hydrothermal fluid flow associated with the late Paleozoic crustal rifting and subsidence.Three hydrothermal alteration types,i.e.,deep-level semiconformable silicification(S_1),fracture-controlled quartz-sericite-pyrite alteration(S_(2-3)),and upper-level sub-discordant quartz-sericite-chlorite alteration(D_3),were developed to form distinct zones in the mapped area.About 50-m thick semiconformable silicification zones are located at～1-km depth below massive sulfides and developed between an impermeable shale caprock(S_1)and the underlying Ordovician unaltered limestone. Comparisons with modern geothermal systems suggest that the alteration zones record a sub-seafloor aquifer with the most productive hydrothermal fluid flow.Fracture-controlled quartz-sericite-pyrite alteration formed transgressive zones,which downward crosscut the semiconformable alteration zones, and upwards grade into sub-discordant alteration zones that enveloped no economic stringer- stockwork zones beneath massive sulfides.This transgressive zone likely marks an upflow path of high- flux fluids from the hydrothermal aquifer.Lateral zonation of the sub-discordant alteration zones and their relationship to overlying massive sulfide lenses suggest lateral flows and diffusive discharging of the hydrothermal fluids in a permeable sandstone sequence.Three large-sized,14 middle-small massive sulfide deposits,and 40 massive sulfide sites have been mapped in detail.They show regional strata- bound characters and two major styles,i.e.,the layered sheet plus strata-bound stringer-style and the mound-style.Associated exhalite and chemical sedimentary rock suites include(1)anhydrite-barite,(2) jasper-chert,(3)Mg-rich mudstone-pyrite shale,(4)barite lens,(5)siderite-Fe-bearing dolomite,and (6)Mn-rich shale-mudstone,which usually comprise three sulfide-exhalite cyclic units in the area. The spatial distribution of these alteration zones(minerals)and associated massive sulfides and exhalites,and regional variation inδ~(34)S of hydrothermal pyrite and inδ~(18)O-δ~(34)C of hanging wall carbonates,suggest three WNW-extending domains of fluid flow,controlled by the basement faults and syn-depositional faults.Each fluid domain appears to have at least two upflow zones,with estimated even spacing of about 5-8 km in the mapped area.The repeated appearance of sulfide-sulfate or sulfide-carbonate rhythmic units in the area suggests episodically venting of fluids through the upflow conduits by breaking the overlying seals of the hydrothermal aquifer.