Copper isotopes trace the evolution of skarn ores: A case study from the Hongshan-Hongniu Cu deposit,southwest China

Transition metal isotopes are sensitive geochemical tracers of ore genesis. Here we present MC-ICP-MS analytical data of Cu isotope compositions from the Hongshan-Hongniu Cu deposit in Yunnan province. The δ⁶⁵Cu values (δ⁶⁵Cu = [(⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_NIST976 − 1] × 1000) of seven whole-rock quartz monzonite porphyries and twenty-two chalcopyrite samples from the skarn ore-bodies display relatively narrow ranges from −0.15‰ to 0.38‰ and from −0.02‰ to 0.77‰, respectively. The overlap of δ⁶⁵Cu values indicates a genetic relationship between the quartz monzonite porphyry and skarn ore-bodies. We also evaluate the spatial and temporal variations of Cu isotope compositions in the skarn ore-bodies by comparison with some well-documented porphyry deposits in the world. The quartz monzonite porphyry shows compositional zoning with the inner domain enriched in heavy Cu isotope and the skarn related to the porphyry depleted in heavy Cu isotope. The chalcopyrites that formed during the late stage of mineralization tend to be enriched in heavy Cu isotope, and this feature is analogous to porphyry deposits. The δ⁶⁵Cu values of the quartz monzonite porphyry show typical features of hypogene mineralization, suggesting a potential scope for deep exploration and development in this deposit.     

Mineral chemistry of hydrothermal biotite from the Kahang porphyry copper deposit (NE Isfahan), Central Province of Iran

The Kahang porphyry Cu deposit, located northeast of Isfahan city in central of Iran, is associated with a composite Miocene stock and ranges in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies show that the emplacement of the Kahang stock occurred in several pulses, each associated with its related hydrothermal activity. Early hydrothermal alteration started with a potassic style in the central part of the system and produced a secondary biotite–K-feldspar–magnetite assemblage accompanied by chalcopyrite and pyrite mineralization. Propylitic alteration that took place at the same time as the potassic alteration occurred in the peripheral portions of the stock. Subsequent phyllic alteration overprinted earlier potassic and propylitic alterations. Biotite grains from the potassic and phyllic zones show distinct chemical compositions. The FeO, TiO₂, MnO, K₂O, and Na₂O concentrations in biotite from the phyllic alteration zone are lower than those from the potassic alteration zone. The F and Cl contents of biotite from the potassic alteration zone display relatively high positive correlation with the X_Mg. The fluorine intercept values [IV(F)] from the potassic and phyllic alteration zones are strongly correlated with the fluorine/chlorine intercept values [IV(F/Cl)]. Biotite geothermometry for the potassic and phyllic alteration zones, based on the biotite geothermometer of Beane (1974), yields a temperature range of 422° to 437 °C (mean = 430 °C) and 329° to 336 °C (mean = 333 °C), respectively. The position of data in log (X_F/X_OH) ratio vs. X_Mg and X_Fe diagram suggests that biotite formed under dissimilar composition and temperature conditions in the potassic and phyllic alteration zones. Calculated log fugacity ratios of (fH₂O/fHF), (fH₂O/fHCl), and (fHF/fHCl) show that hydrothermal fluids associated with the potassic alteration were distinctively different from those fluids associated with the phyllic alteration zone at Kahang porphyry Cu deposit. The results of this research indicate that the chemistry of biotite is related to the chemical composition of the magma and the prevailing physical conditions during crystallization.     

Geology,geochronology, fluid inclusion and H–O isotope geochemistry of the Luoboling Porphyry Cu–Mo deposit,Zijinshan Orefield,Fujian Province,China

The Luoboling Cu–Mo deposit in the Zijinshan Orefield, Fujian province, southeastern China, is a large porphyry deposit hosted by the Sifang granodiorite and the Luoboling granodiorite porphyry. The largest Cu–Mo orebody is saddle-shaped with various types of hydrothermal veinlets. Intensive hydrothermal alteration in the deposit is characterized by outward zoning from potassic, overprinted by phyllic alteration, to phyllic and alunite–dickite alteration. Based on the mineral assemblages and crosscutting relationships of veins, the ore-forming process can be divided into three stages, namely: an early-stage K-feldspar + quartz ± magnetite ± molybdenite veins associated with potassic alteration; a middle-stage quartz + molybdenite + chalcopyrite + pyrite veins in phyllic zone; and a late-stage quartz ± gypsum veins in the phyllic and alunite–dickite alteration zones. Six molybdenite separates yield a Re−Os isochron age 104.6 ± 1.0 Ma, which is identical to the age of emplacement of the Sifang and Luoboling granodiorite porphyries. Three types of fluid inclusions (FIs) were observed at the Luoboling deposit: 1) NaCl–H₂O (aqueous), 2) daughter mineral-bearing and 3) CO₂–H₂O fluid inclusions. FIs of the early and middle stages are predominantly vapor-rich aqueous and daughter mineral-bearing inclusions, together with minor CO₂-rich and liquid-rich aqueous inclusions; whereas the late-stage minerals only contain liquid-rich aqueous inclusions. Homogenization temperatures and salinities of FIs trapped in the early-stage minerals range from 420 to 540 °C and 0.4 to 62.9 wt.% NaCl equiv., respectively. FIs of the middle-stage yield homogenization temperatures of 340 to 480 °C and salinities of 0.5 to 56.0 wt.% NaCl equiv. CO₂ content and the oxygen fugacity (indicated by daughter minerals) of FIs trapped in middle-stage minerals are lower than those in the early stage. The liquid-rich aqueous inclusions of the late-stage homogenize at temperatures of 140 to 280 °C, yielding salinities of 0.4 to 8.4 wt.% NaCl equiv. The minimum estimated pressures of the three stages are 30–70 MPa, 10–40 MPa and 1–10 MPa, respectively, corresponding to minimum ore-forming depths of 1–2.8 km. Fluids trapped in early, middle and late stages yield δD values of − 67‰ to − 54‰, − 54‰ to − 70‰, and − 62‰, and δ¹⁸O values of 5.4‰ to 6.7‰, 2.8‰ to 4.2‰, and − 2.1‰, respectively. Fluid boiling, which resulted in the formation of stockworks and the precipitation of sulfides, occurred in the early and middle stages. The fluids subsequently evolved into a low temperature, low salinity system in the late stage, along with an input of meteoric water. The Luoboling porphyry Cu–Mo system was developed in a transition from continental arc to back-arc extension region, which was related to the westward subduction of the paleo-Pacific plate beneath the Huanan Orogen.     

Boron,sulphur and copper isotope systematics in the orogenic gold deposits of the Archaean Hattu schist belt,eastern Finland

The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe^3 +–Al^3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ¹¹B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe^3 +–Al^3 + substitution) and δ¹¹B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ¹¹B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ¹¹B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ³⁴S_VCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ³⁴S_VCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ³⁴S_VCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ³⁴S_VCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ⁶⁵Cu_NBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ⁶⁵Cu_NBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ³⁴S_VCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.     

西藏冈底斯斑岩型铜钼矿床的Cu、Mo同位素组成及其意义

选取西藏冈底斯成矿带的驱龙、达布斑岩型铜钼矿及鸡公村石英脉型钼矿为研究对象,分别挑选含矿斑岩和石英脉中的黄铜矿、辉钼矿进行Cu、Mo同位素测定.结果表明,西藏冈底斯斑岩型黄铜矿的δ^65/63Cu介于0.01‰~0.98‰,辉钼矿的δ^97/95Mo介于-0.34‰^-0.15‰,热液脉型矿床中辉钼矿的δ^97/95Mo介于-0.35‰^-0.23‰.形成于陆-陆碰撞造山后的冈底斯斑岩型铜钼矿床的Cu同位素与俯冲带产出的斑岩型矿床中的Cu同位素组成具有一定的相似性,均表现为单峰分布的特征.驱龙斑岩型矿床中热液脉与含矿斑岩中的δ^65/63Cu具有一致性,可能反映了二者在来源上具有一致性.在冈底斯斑岩型铜钼矿床中,不同蚀变带具有不同的Cu、Mo同位素组成,自蚀变中心向外,δ^65/63Cu与δ^97/95Mo表现出负相关趋势,可能与成矿流体的性质密切相关.冈底斯石英脉型钼矿较斑岩型铜钼矿δ^97/95Mo相对偏负,结合两类矿床的成矿年代,可能暗示两类矿床的成矿物质是同一源区连续演化的结果.     

Yandong porphyry Cu deposit,Xinjiang, China—Geology,geochemistry and SIMS U–Pb zircon geochronology of host porphyries and associated alteration and mineralization

The Yandong porphyry copper deposit, located in the Eastern Tianshan Mountains, Xinjiang, China, is part of the Central Asian Orogenic Belt. The Yandong deposit is hosted by a volcanic complex in the Early Carboniferous Qi’eshan Group and a felsic intrusion. The complex consists of andesite, basalt, diorite porphyry, and porphyritic quartz diorite. The felsic intrusion is a plagiogranite porphyry emplaced within the complex. The diorite porphyry and plagiogranite porphyry yield SIMS zircon U–Pb ages of 340.0 ± 3 and 332.2 ± 2.3 Ma, respectively. Element geochemistry shows that both the complex and plagiogranite porphyry formed in the Dananhu–Tousuquan island arc, a Carboniferous magmatic arc.The diorite porphyry and plagiogranite porphyry are host porphyries, but the plagiogranite porphyry is a productive porphyry. It caused the porphyry-style Cu mineralization and associated alteration. The alteration assemblages include early potassic and propylitic assemblages. These were overprinted by a chlorite–sericite assemblage, which in turn was overprinted by a late phyllic assemblage. The phyllic alteration is associated with the highest Cu grades. The mineralization is recognized to include three stages, from early to late: stage 1, a potassic alteration associated with a chalcopyrite + pyrite assemblage; stage 2, represented by chlorite–sericite alteration with a chalcopyrite + pyrite assemblage; and stage 3, the main-ore stage that is marked by phyllic alteration with chalcopyrite + pyrite ± molybdenite and producing more than 70% of the total copper production at Yandong. Yandong may represent a common scenario for Paleozoic porphyry Cu systems in the Central Asian Orogenic Belt.     

The Sarcheshmeh porphyry copper deposit,Kerman, Iran: A mineralogical analysis of the igneous rocks and alteration zones including halogen element systematics related to Cu mineralization processes

The giant Sarcheshmeh porphyry Copper deposit is located 65 km southwest of Kerman City, southeastern Iran. Numerous Miocene porphyry stocks and dykes intruded thick sequences of Upper Cretaceous sedimentary and Eocene volcanic rocks. Hypogene and supergene porphyry Cu mineralization occurs within the granodioritic porphyry and host rock sequence, which was extensively altered to a dominantly potassic, phyllic, and argillic assemblage with interstitial to distal propylitic types.Biotite-bearing assemblages occur as both primary phenocrysts and secondary replacements showing variable size, colour, and shape. Fluorine contents (0.22 to 1.33 wt.%) and X_Mg (0.54 to 0.71) in biotites from the potassic and phyllic zones are higher than those of non-mineralized granitoids (F = 0.09 to 0.56 wt.%, X_Mg = 0.43 to 0.54), whereas their Cl contents (Cl = 0.05 to 0.24 wt.%) are lower than those of the non-mineralized granitoids (Cl = .0.11 to 0.45). The biotites from the phyllic zone have higher log (fH₂O/fHF) and log (fH₂O/fHCl) values than those of the potassic zone, as well as the granitoid and andesitic dykes. The log (fHF/fHCl) values determined for the granitoid, potassic and phyllic zones are similar, though more negative than those of the andesitic dykes. The log (fHF/fHCl) values have a similar range for biotite from the granitoid, and potassic and phyllic zones. The halogen fugacity ratios established for fluids associated with the Sarcheshmeh deposit from their F and Cl contents in biotite show that the granitoid, potassic zone and phyllic zone are increasingly affected by meteoric waters. The fluids that circulated in the phyllic zone are predominantly of meteoric origin, possibly overprinting original phyllic zone halogen contents.The Cl intercept values of biotite in the granitoid, and phyllic and potassic are similar to other ore-forming systems and tend to be more Cl-rich than Cl-intercept values of biotites in common igneous rocks. Calculated F/Cl intercept values for biotite in the granitoid and potassic zone are also consistent with many other porphyry copper forming systems.     

S,O and Pb isotopic evidence on the origin of the İnkaya (Simav-Kütahya) Cu–Pb–Zn–(Ag) Prospect,NW Turkey

The İnkaya Cu–Pb–Zn–(Ag) prospect is a typical example of the hydrothermal mineralization occurring in the Menderes Massif, which crop out in Western Anatolia. The prospect located approximately 20 km west of Simav (Kütahya-Turkey) in northern part of the Menderes Massif have been characterized through the detailed examinations involving geological, mineralogical, whole-rock geochemistry, fluid inclusion, stable isotope and lead isotope.The İnkaya Cu–Pb–Zn–(Ag) prospect is located along an E–W-trending fault in the Cambrian Simav Metamorphics, which consist of quartz–muscovite schist, quartz–biotite schist, muscovite schist, biotite schist and the Arıkayası Formation, which is composed of marbles. Galena, sphalerite, chalcopyrite, pyrite and fahlore are the main minerals, and they are accompanied by small amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, and Fe-oxides with gangue quartz. In addition to Pb, Zn, Cu, Ag, the ore samples contain substantial quantities of As, Cd and Bi and small amount of Au. Average contents of Cu, Pb, Zn and Ag are 77,400 ppm, 102,600 ppm, 6843 ppm and 203 ppm, respectively.The δ³⁴S values for galena, chalcopyrite and pyrite formed in the same stage vary in the range from − 1.7 to − 2.1‰ (average − 2.0), 0.1 to 0.3‰ (average 0.2) and − 1.5 to 2.6‰ (average + 1.5), respectively.δ³⁴S values for H₂S, representing the composition of the fluids responsible for the sulfide mineral formations and calculated from the δ³⁴S value are between − 2.77 and 1.33‰; it is consistent with the sulfur in sulfide minerals. δ¹⁸O_quartz values range from 11.3 to 16.4‰ and estimated δ¹⁸O_fluid values range from 5.4 to 10.6‰.Pyrite–galena and pyrite–chalcopyrite pairs calculated to determine equilibrium isotope temperatures based on δ³⁴S values are between 254.6 and 277.4 °C for pyrite–galena and 274.7 °C for pyrite–chalcopyrite. Sulfur and oxygen isotope values similar to the values for fluid equilibrated with an felsic magmatic source.Fluid inclusion studies on quartz of the same silicification stage coexisting with galena, sphalerite and chalcopyrite collected from the mineralized vein indicate that the temperature range of the fluids is 235 °C to 340 °C and that the salinities are 0.7 to 4.49 wt.% NaCl equivalent. The wide range of homogenization temperatures and relatively lower salinities of the fluid inclusions indicate that at least two different fluid generations were trapped in the quartz from only one fluid type. Also, lower salinities of fluid inclusion probably indicate mixing of meteoric water and magmatic fluid.The galena has ²⁰⁶Pb/²⁰⁴Pb values of 18.862–18.865, ²⁰⁷Pb/²⁰⁴Pb values of 15.707–15.711, and ²⁰⁸Pb/²⁰⁴Pb values of 39.033–39.042. The lead isotope values show a similarity with upper crustal values.     

Copper and iron isotope fractionation in mine tailings at the Laver and Kristineberg mines,northern Sweden

Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (⁶⁵Cu/⁶³Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (⁵⁶Fe/⁵⁴Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ⁶⁵Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ⁵⁶Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ⁵⁶Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural 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.     

The Cu isotopic signature of granites from the Lachlan Fold Belt,SE Australia

This contribution reports our preliminary work to determine Cu isotope ratios for various granite rocks and examine the Cu isotope systematics within granite suites. A chemical procedure, modified from Maréchal [Maréchal, C.N., Télouk, P. and Albarède, F., 1999. Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chemical Geology, 156(1–4): 251–273.], was used to separate Cu from rock matrix. Quantitative recovery (100.6 ± 1.6%), with a low total procedural blank (2.65 ± 0.66 ng) for Cu, has been achieved, allowing Cu isotopic measurements on samples with as little as 10 ppm Cu. The Cu isotope ratios (δ⁶⁵Cu relative to NIST SRM 976) of 32 rock samples, ranging from mafic to felsic compositions, from 3 batholiths (2 I-type, 1 S-type) from the Lachlan Fold Belt in southeastern Australia, vary from ? 0.46‰ to 1.51‰. Most of them cluster around zero, with mean values for the I-type and S-type granites of 0.03 ± 0.15‰ and ? 0.03 ± 0.42‰ (2 sigma) respectively. These data, together with Cu isotope ratios of two loess samples, provide preliminary evidence that the baseline Cu isotopic composition of the crystalline part of upper continental crust is close to zero. The tight clustering of Cu isotope ratios of rocks from the I-type suites suggests that high-temperature magmatic processes do not produce significant Cu isotope fractionation. However, two granites with abnormally heavy Cu isotope signatures (up to 1.51‰) appears to be the result of localized hydrothermal alteration. Measurable variation in Cu isotopic composition of the S-type granite may reflect isotopic heterogeneity in the sedimentary source region as a result of redox processes or may be due to hydrothermal overprinting. Thus, Cu isotope geochemistry may be a useful tracer for studying hydrothermal alteration and source heterogeneity of granitic rocks.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

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.     

Hydrothermal Alteration and Mineralization of Middle Jurassic Dexing Porphyry Cu-Mo Deposit, Southeast China

The Dexing deposit is located in a NE‐trending magmatic belt along the southeastern margin of the Yangtze Craton. It is the largest porphyry copper deposit in China, consisting of three porphyry copper orebodies of Zhushahong, Tongchang and Fujiawu from northwest to southeast. It contains 1168 Mt of ores with 0.5% Cu and 0.01% Mo. The Dexing deposit is hosted by Middle Jurassic granodiorite porphyries and pelitic schist of Proterozoic age. The Tongchang granodiorite porphyry has a medium K cal‐alkaline series, with medium K₂O content (1.94–2.07 wt%), and low K₂O/(Na₂O + K₂O) (0.33–0.84) ratios. They have high large‐ion lithophile elements, high light rare‐earth elements, and low high‐field‐strength elements. The hydrothermal alteration at Tongchang is divided into four alteration mineral assemblages and related vein systems. They are early K‐feldspar alteration and A vein; transitional (chlorite + illite) alteration and B vein; late phyllic (quartz + muscovite) alteration and D vein; and latest carbonate, sulfate and oxide alteration and hematite veins. Primary fluid inclusions in quartz from phyllic alteration assemblage include liquid‐rich (type 1), vapor‐rich (type 2) and halite‐bearing ones (type 3). These provide trapping pressures of 20–400 ´ 10⁵ Pa of fluids responsible for the formation of D veins. Igneous biotite from least altered granochiorite porphyry and hydrothermal muscovite in mineralized granodiorite porphyry possess δ¹⁸O and δD values of 4.6‰ and ?87‰ for biotite and 7.1–8.9‰, ?71 to ?73‰ for muscovite. Stable isotopic composition of the hydrothermal water suggests a magmatic origin. The carbon and oxygen isotope for hydrothermal calcite are ?4.8 to ?6.2‰ and 6.8–18.8‰, respectively. The δ³⁴S of pyrite in quartz vein ranges from ?0.1 to 3‰, whereas δ³⁴S for chalcopyrite in calcite veins ranges from 4 to 5‰. These are similar to the results of previous studies, and suggest a magmatic origin for sulfur. Results from alteration assemblages and vein system observation, as well as geochemical, fluid inclusion, stable isotope studies indicate that the involvement of hydrothermal fluids exsolved from a crystallizing melt are responsible for the formation of Tongchang porphyry Cu‐Mo orebodies in Dexing porphyry deposit.     

Alteration and mineralization at the Zhibula Cu skarn deposit,Gangdese belt,Tibet

The Zhibula Cu skarn deposit contains 0.32 Mt. Cu metal with an average grade of 1.64% and is located in the Gangdese porphyry copper belt in southern Tibet. The deposit is a typical metasomatic skarn that is related to the interaction of magmatic–hydrothermal fluids and calcareous host rock. Stratiform skarn orebodies occur at the contact between tuff and marble in the Lower Jurassic Yeba Formation. Alteration zones generally grade from a fresh tuff to a garnet-bearing tuff, a garnet pyroxene skarn, and finally to a wollastonite marble. Minor endoskarn alteration zonations are also observed in the causative intrusion, which grade from a fresh granodiorite to a weakly chlorite-altered granodiorite, a green diopside-bearing granodiorite, and to a dark red-brown garnet-bearing granodiorite. Prograde minerals, which were identified by electron probe microanalysis include andradite–grossularite of various colors (e.g., red, green, and yellow) and green diopside. Retrograde metamorphic minerals overprint the prograde skarn, and are mainly composed of epidote, quartz, and chlorite. The ore minerals consist of chalcopyrite and bornite, followed by magnetite, molybdenite, pyrite, pyrrhotite, galena, and sphalerite. Three types of fluid inclusions are recognized in the Zhibula deposit, including liquid-rich two-phase inclusions (type L), vapor-rich two-phase inclusions (type V), and daughter mineral-bearing three-phase inclusions (type S). As the skarn formation evolved from prograde (stage I) to early retrograde (stage II) and later retrograde (stage III), the ore-forming fluids correspondingly evolved from high temperature (405–667 °C), high salinity (up to 44.0 wt.% NaCl equiv.), and high pressure (500–600 bar) to low-moderate temperature (194–420 °C), moderate-high salinity (10.1–18.3 and 30.0–44.2 wt.% NaCl equiv.), and low-moderate pressure (250–350 bar). Isotopic data of δ³⁴S (− 0.1‰ to − 6.8‰, estimated δ³⁴S_fluids = − 0.7‰), δD_H2O (− 91‰ to − 159‰), and δ¹⁸O_H2O (1.5‰ to 9.2‰) suggest that the ore-forming fluid and material came from magmatic–hydrothermal fluids that were associated with Miocene Zhibula intrusions. Fluid immiscibility likely occurred at the stage I and stage II during the formation of the skarn and mineralization. Fluid boiling occurred during the stage III, which is the most important Cu deposition mechanism for the Zhibula deposit.     

Geologic and geochemical insights into the formation of the Taiyangshan porphyry copper–molybdenum deposit,Western Qinling Orogenic Belt,China

Taiyangshan is a poorly studied copper–molybdenum deposit located in the Triassic Western Qinling collisional belt of northwest China. The intrusions exposed in the vicinity of the Taiyangshan deposit record episodic magmatism over 20–30 million years. Pre-mineralization quartz diorite porphyries, which host some of the deposit, were emplaced at 226.6 ± 6.2 Ma. Syn-collisional monzonite and quartz monzonite porphyries, which also host mineralization, were emplaced at 218.0 ± 6.1 Ma and 215.0 ± 5.8 Ma, respectively. Mineralization occurred during the transition from a syn-collisional to a post-collisional setting at ca. 208 Ma. A barren post-mineralization granite porphyry marked the end of post-collisional magmatism at 200.7 ± 5.1 Ma. The ore-bearing monzonite and quartz monzonite porphyries have a ε_Hf(t) range from − 2.0 to + 12.5, which is much more variable than that of the slightly older quartz diorite porphyries, with T_DM2 of 1.15–1.23 Ga corresponding to the positive ε_Hf(t) values and T_DM1 of 0.62–0.90 Ga corresponding to the negative ε_Hf(t) values. Molybdenite in the Taiyangshan deposit with 27.70 to 38.43 ppm Re suggests metal sourced from a mantle–crust mixture or from mafic and ultramafic rocks in the lower crust. The δ³⁴S values obtained for pyrite, chalcopyrite, and molybdenite from the deposit range from + 1.3‰ to + 4.0‰, + 0.2‰ to + 1.1‰, and + 5.3‰ to + 5.9‰, respectively, suggesting a magmatic source for the sulfur. Calculated δ¹⁸O_fluid values for magmatic K-feldspar from porphyries (+ 13.3‰), hydrothermal K-feldspar from stockwork veins related to potassic alteration (+ 11.6‰), and hydrothermal sericite from quartz–pyrite veins (+ 8.6 to + 10.6‰) indicate the Taiyangshan deposit formed dominantly from magmatic water. Hydrogen isotope values for hydrothermal sericite ranging from − 85 to − 50‰ may indicate that magma degassing progressively depleted residual liquid in deuterium during the life of the magmatic–hydrothermal system. Alternatively, δD variability may have been caused by a minor amount of mixing with meteoric waters. We propose that the ore-related magma was derived from partial melting of the ancient Mesoproterozoic to Neoproterozoic middle to lower continental crust. This crust was likely metasomatized during earlier subduction, and the crustal magmas may have been contaminated with lithospheric mantle derived magma triggered by MASH (e.g., melting, assimilation, storage, and homogenization) processes during collisional orogeny. In addition, a significant proportion of the metals and sulfur supplied from mafic magma were simultaneously incorporated into the resultant hybrid magmas.     

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.     

Hydrothermal evolution of the Sar-Cheshmeh porphyry Cu–Mo deposit,Iran: Evidence from fluid inclusions

The Sar-Cheshmeh porphyry Cu–Mo deposit is located in Southwestern Iran (∼65 km southwest of Kerman City) and is associated with a composite Miocene stock, ranging in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies demonstrate that the emplacement of the Sar-Cheshmeh stock took place in several pulses, each with associated hydrothermal activity. Molybdenum was concentrated at a very early stage in the evolution of the hydrothermal system and copper was concentrated later. Four main vein Groups have been identified: (I) quartz+molybdenite+anhydrite±K-feldspar with minor pyrite, chalcopyrite and bornite; (II) quartz+chalcopyrite+pyrite±molybdenite±calcite; (III) quartz+pyrite+calcite±chalcopyrite±anhydrite (gypsum)±molybdenite; (IV) quartz±calcite±gypsum±pyrite±dolomite. Early hydrothermal alteration produced a potassic assemblage (orthoclase-biotite) in the central part of the stock, propylitic alteration occurred in the peripheral parts of the stock, contemporaneously with potassic alteration, and phyllic alteration occurred later, overprinting earlier alteration. The early hydrothermal fluids are represented by high temperature (350–520 °C), high salinity (up to 61 wt% NaCl equivalent) liquid-rich fluid inclusions, and high temperature (340–570 °C), low-salinity, vapor-rich inclusions. These fluids are interpreted to represent an orthomagmatic fluid, which cooled episodically; the brines are interpreted to have caused potassic alteration and deposition of Group I and II quartz veins containing molybdenite and chalcopyrite. Propylitic alteration is attributed to a liquid-rich, lower temperature (220–310 °C), Ca-rich, evolved meteoric fluid. Influx of meteoric water into the central part of the system and mixing with magmatic fluid produced albitization at depth and shallow phyllic alteration. This influx also caused the dissolution of early-formed copper sulphides and the remobilization of Cu into the sericitic zone, the main zone of the copper deposition in Sar-Cheshmeh, where it was redeposited in response to a decrease in temperature.     

The δ18O of UST Quartz in Two Porphyry Deposits,China

The unidirectional solidification textures (UST) quartz is generally thought to form from fluids exsolved from shallow intrusions and/or magma chambers, but such an idea is still poorly constrained from the evidence of stable isotopes. In this study, we report for the first time the δ¹⁸O of quartz that shows UST from the Qulong Cu–Mo and the Yechangping Mo porphyry deposits in China. The analysis results show that the UST quartz samples from the Qulong deposit have δ¹⁸O values ranging from +6.2 ‰ to +7.6 ‰, which are similar to that of quartz phenocrysts (+6.7 ‰ to +7.8 ‰). In contrast, the UST quartz samples from the Yechangping porphyry Mo deposit yield a high δ¹⁸O value (+10.0 ‰). The δ¹⁸O_water value of Yechangping UST quartz (+8.5 ‰) is also higher than that of Qulong (+4.6 ‰ to +5.8 ‰). Hydrothermal biotite from potassic alteration and sericite from early phyllic alteration at Qulong have similar δ¹⁸O values to UST quartz, suggesting the involvement of magmatic fluids during this stage of deposit evolution.     

Geological,geochronological, and H–O isotopic constraints on the genesis of the Tongjing Cu–Au deposit in the Ningwu basin,east China

The Tongjing Cu–Au deposit is a medium-sized deposit within the Ningwu volcanic basin, east China, and is hosted by Cretaceous volcanic rocks of the Dawangshan and Niangniangshan Formations. The veined and lenticular Cu–Au orebodies are spatially and temporally related to the volcanic and subvolcanic rocks of the Niangniangshan Formation in the ore district. The wall-rock alteration is dominated by silicification, siderite alteration, carbonation, sericitization, chloritization, and kaolinization. On the basis of field evidence and petrographic observations, two stages of mineralization are recognized: (1) a siderite–quartz–sulfide stage (Stage 1) associated with the formation of chalcopyrite and pyrite in a quartz and siderite gangue; and (2) a quartz–bornite stage (Stage 2) cutting the Stage 1 phases. Stage 1 is the main mineralization stage. Quartz that formed in Stage 1 has δ¹⁸O_H2O values of − 4.3‰ to 3.5‰ with δD values of fluid inclusion waters of − 97.1‰ to − 49.9‰, indicating that the ore-forming fluids were derived from early magmatic fluids and may have experienced oxygen isotopic exchange with meteoric water during Stage 1 mineralization.LA–MC–ICP–MS zircon U–Pb dating of the mineralization-related nosean-bearing phonolite and nosean-bearing phonolitic brecciated tuff at Tongjing yields ages of 129.8 ± 0.5 Ma and 128.9 ± 1.1 Ma, respectively. These results are interpreted as the crystallization age of the volcanic rocks of the Niangniangshan Formation. A hydrothermal sericite sample associated with Cu–Au mineralization at Tongjing yields a plateau ⁴⁰Ar–³⁹Ar age of 131.3 ± 1.3 Ma. These results confirm a genetic link between the volcanism and associated Cu–Au mineralization. The Tongjing Cu–Au deposit in the Ningwu basin is genetically and possibly tectonically similar to alkaline intrusion-related gold deposits elsewhere in the world.