In-situ LA–ICP–MS U–Pb geochronology and trace elements analysis of polygenetic titanite from the giant Beiya gold–polymetallic deposit in Yunnan Province,Southwest China

The Beiya gold–polymetallic deposit, located in the middle of the Jinshajiang–Ailaoshan alkaline porphyry metallogenic belt, is one of the largest gold deposits in China. The mineralization mainly occurs in skarn along the intrusive contacts between the alkaline porphyries and Middle Triassic limestone. In this paper, we present U–Pb age as well as major and trace element geochemistry of titanite from the Beiya deposit, and distinguish the titanite into a magmatic- and a hydrothermal suite. Our study indicates that the titanite from the ore-related porphyry and from the mineralized skarn is texturally and geochemically very different. The euhedral, envelope-shaped titanite from the ore-related porphyry has lower FeO, F, HFSEs, Nb/Ta and Lu/Hf, together with higher TiO₂ and Th/U than the subhedral titanite from the mineralized skarn. The titanite from the porphyry also displays higher LREE/HREE and more subtle negative Eu anomaly than its mineralized skarn counterpart. This suggests a magmatic- and a hydrothermal origin for, respectively, the titanite from the ore-related porphyry and from the mineralized skarn. In-situ magmatic titanite U–Pb dating has yielded an Eocene age of 36.0 ± 5.9 Ma, consistent with the porphyry zircon U–Pb age (36.07 ± 0.43 Ma) obtained in previous studies. Hydrothermal titanite has yielded a weighted average ²⁰⁶Pb/²³⁸U age of 33.1 ± 1.0 Ma (MSWD = 2.0), which represents the age of the retrograde skarn alteration and the maximum age for the gold mineralization. Together with the previous molybdenite Re–Os age, we have further constrained the Beiya gold–polymetallic metallogeny to 33.1–34.1 Ma. The mineralization age is slightly younger than the porphyry emplacement, indicating that the Beiya metallogeny was likely to be a post-magmatic hydrothermal product of the Himalayan orogenic event. The REE characteristics of hydrothermal titanite also reveal that the ore forming fluids may have been derived from a highly oxidized magma.     

The sources of ore-forming material in the low-sulfidation epithermal Wulaga gold deposit,NE China: Constraints from S,Pb isotopes and REE pattern

The Wulaga gold deposit, located in Heilongjiang province, NE China, is a subvolcanic rock-hosted, low-sulfidation epithermal gold deposit, and has an Au reserve of about 84 tons. The gold mineralization occurs in a crypto-explosive breccia, and is spatially and temporally associated with an Early Cretaceous granodioritic porphyry. Three individual stages of mineralization have been identified in the Wulaga gold deposit: an early white quartz-euhedral vein stage, a fine-grained pyrite–marcasite–stibnite–chalcedony stage, and a late calcite–pyrite stage. The sulfur isotopic values of sulfide minerals vary in a wide range from − 4 to 4.9‰, but are concentrated in the range of − 3 to 0‰, implying that sulfur in the hydrothermal fluids was derived from magmatic volatiles. Lead isotopic results of the granodioritic porphyry (²⁰⁶Pb/²⁰⁴Pb = 18.341–18.395, ²⁰⁷Pb/²⁰⁴Pb = 15.507–15.523, ²⁰⁸Pb/²⁰⁴Pb = 38.174–38.251) and sulfide minerals (²⁰⁶Pb/²⁰⁴Pb = 18.172–18.378, ²⁰⁷Pb/²⁰⁴Pb = 15.536–15.600, ²⁰⁸Pb/²⁰⁴Pb = 38.172–38.339) are comparatively consistent and clustered together between the orogenic and upper mantle lines, indicating the lead in the ores is closely related to the parent magma of the granodioritic porphyry. The REE patterns of fluid inclusions trapped in sulfides are similar to those of the granodioritic porphyry, which confirms the magmatic origin of the REE in the hydrothermal fluids. The characteristics of S and Pb isotopes and REE suggest that the ore-forming materials of the Wulaga gold deposit are partly magmatic in origin, and related to a high-level hydrous granodioritic magma.     

Geological characteristics and genesis of the Jurassic No. I porphyry Cu–Au deposit in the Xiongcun district,Gangdese porphyry copper belt,Tibet

The Xiongcun district, located in the western segment of the Gangdese porphyry copper belt (GPCB), hosts the only known Jurassic mineralization in the GPCB, Tibet, PRC. The No. I deposit in the Xiongcun district is related to the Middle Jurassic quartz diorite porphyry (167–161 Ma) and the mineralization was formed at ca. 161.5 ± 2.7 Ma. Ore-bearing Middle Jurassic quartz diorite porphyry emplaced into the Early Jurassic volcano-sedimentary rock sequences of the Xiongcun Formation. Veinlets and disseminated mineralization developed within the Middle Jurassic quartz diorite porphyry and the surrounding metamorphosed tuff, hosting a measured and indicated resource of 1.04 Mt copper, 143.31 t gold and 900.43 t silver with an average grade of 0.48% copper, 0.66 g/t gold, and 4.19 g/t silver. The mineralization can be assigned to four stages, including three main stages of hypogene mineralization and one epigenetic stage. The main alteration associated with mineralization is potassic. Seven mineralization-related hydrothermal veins have been recognized, including quartz–sulfide, biotite–sulfide, magnetite–sulfide, quartz–molybdenite–sulfide, chalcopyrite–pyrite–pyrrhotite, pyrite and polymetallic veins. The S and Pb isotopic compositions of the ore sulfides and the Re contents of the molybdenite suggest a mantle source for the ore-forming materials with minor contamination from the subducted sediments. Hydrogen and oxygen isotope compositions of quartz in the ores suggest that both magmatic and meteoric waters were involved in the ore-forming process. The ore-bearing porphyry (167–161 Ma) and ore-forming (161.5 ± 2.7 Ma) ages of the No. I deposit correspond to the time of northward subduction of Neo-Tethys oceanic slab. The geochemical data of the ore-bearing porphyry indicate that the No. I deposit formed in an intra-oceanic island arc setting and the ore-bearing porphyry originated from the partial melting of mantle with limited contribution of subducted sediments. The genesis of the ore-bearing porphyry and No. I deposit is interpreted as being related to northward intra-oceanic subduction of Neo-Tethys oceanic slab in the Middle Jurassic time (167–161 Ma).     

滇西北衙金矿床富水岩浆对成矿的制约

成矿岩浆富水(4%)是形成斑岩型矿床的关键。滇西北衙金矿床是金沙江-哀牢山新生代富碱斑岩成矿带中规模最大的金多金属矿床,目前探明金资源储量超过320吨,伴生的铅锌、银、铜、铁、硫也达到大-中型规模。本文以北衙成矿的二长花岗斑岩中角闪石斑晶和锆石为研究对象,开展岩相学和地球化学研究,厘定成矿岩浆的特征,并探讨富水岩浆对成矿的制约。研究表明,北衙二长花岗斑岩角闪石斑晶发育、轻稀土富集而重稀土亏损、具有高Sr(300×10~(-6))、低Y(10×10~(-6))和高(La/Yb)N(6.19~26.8)的地球化学特征,暗示在岩浆结晶早期有角闪石斑晶的晶出。角闪石晶出的条件是岩浆中水含量大于4.5%,因此北衙金矿床成矿岩浆演化早期角闪石的晶出显示成矿岩浆相对富水。角闪石矿物组分计算表明岩浆熔体中水含量在3.8%~4.1%之间,进一步证实北衙金矿床成矿岩浆相对富水。北衙金矿床这种具有高水含量的岩浆在源区岩石部分熔融的过程中,水的加入可以降低其熔点,促进源区含Cu、Au硫化物重熔,或萃取岩石中Cu、Au成矿元素,或聚集岩浆中分散分布的金属元素,形成富金属、富水的岩浆。含矿岩浆就位后,其通过压力的降低(岩浆房脆性破裂或岩浆向上侵位)来降低水的溶解度,或通过岩浆持续的结晶(在等压条件下晶出无水矿物)逐渐提高岩浆水含量,促使熔体中水含量大于水在熔体中溶解度,从而导致岩浆水达到饱和状态,流体开始出溶。总体而言,北衙金矿床富水岩浆不仅能促进北衙矿床成矿流体的形成与演化,也对成矿流体中Cu、Au等成矿元素的富集具有重要的作用。     

Mineralogy,fluid inclusions,and isotopes of the Cihai iron deposit,eastern Tianshan,NW China: Implication for hydrothermal evolution and genesis of subvolcanic rocks-hosted skarn-type deposits

Most skarn deposits are closely related to granitoids that intruded into carbonate rocks. The Cihai (>100 Mt at 45% Fe) is a deposit with mineral assemblages and hydrothermal features similar to many other typical skarn deposits of the world. However, the iron orebodies of Cihai are mainly hosted within the diabase and not in contact with carbonate rocks. In addition, some magnetite grains exhibit unusual relatively high TiO₂ content. These features are not consistent with the typical skarn iron deposit. Different hydrothermal and/or magmatic processes are being actively investigated for its origin. Because of a lack of systematic studies of geology, mineral compositions, fluid inclusions, and isotopes, the genetic type, ore genesis, and hydrothermal evolution of this deposit are still poorly understood and remain controversial.The skarn mineral assemblages are the alteration products of diabase. Three main paragenetic stages of skarn formation and ore deposition have been recognized based on petrographic observations, which show a prograde skarn stage (garnet-clinopyroxene-disseminated magnetite), a retrograde skarn stage (main iron ore stage, massive magnetite-amphibole-epidote ± ilvaite), and a quartz-sulfide stage (quartz-calcite-pyrite-pyrrhotite-cobaltite).Overall, the compositions of garnet, clinpyroxene, and amphibole are consistent with those of typical skarn Fe deposits worldwide. In the disseminated ores, some magnetite grains exhibit relatively high TiO₂ content (>1 wt.%), which may be inherited from the diabase protoliths. Some distinct chemical zoning in magnetite grains were observed in this study, wherein cores are enriched in Ti, and magnetite rims show a pronounced depletion in Ti. The textural and compositional data of magnetite confirm that the Cihai Fe deposit is of hydrothermal origin, rather than associated with iron rich melts as previously suggested.Fluid inclusions study reveal that, the prograde skarn (garnet and pyroxene) formed from high temperature (520–600 °C), moderate- to high-salinity (8.1–23.1 wt.% NaCl equiv, and >46 wt.% NaCl equiv) fluids. Massive iron ore and retrograde skarn assemblages (amphibole-epidote ± ilvaite) formed under hydrostatic condition after the fracturing of early skarn. Fluids in this stage had lower temperature (220°–456 °C) and salinity (8.4–16.3 wt.% NaCl equiv). Fluid inclusions in quartz-sulfide stage quartz and calcite also record similar conditions, with temperature range from 128° to 367 °C and salinity range from 0.2 to 22.9 wt.% NaCl equiv. Oxygen and hydrogen isotopic data of garnet and quartz suggest that mixing and dilution of early magmatic fluids with external fluids (e.g., meteoric waters) caused a decrease in fluid temperature and salinity in the later stages of the skarn formation and massive iron precipitation. The δ¹⁸O values of magnetite from iron ores vary between 4.1 and 8.5‰, which are similar to values reported in other skarn Fe deposits. Such values are distinct from those of other iron ore deposits such as Kiruna-type and magmatic Fe-Ti-V deposits worldwide. Taken together, these geologic, geochemical, and isotopic data confirm that Cihai is a diabase-hosted skarn deposit related to the granitoids at depth.     

Geochemistry and geochronology of porphyries from the Beiya gold–polymetallic orefield,western Yunnan,China

The Beiya gold–polymetallic orefield, with gold reserves of 305 t, is one of the most representative porphyry-skarn orefields in the Jinshajiang–Ailaoshan Cu–Au ore belt within the Sanjiang region of southwest China. The orefield contains seven deposits: the Wandongshan, Hongnitang, Dashadi, Bijiashan, Weiganpo, Matouwan, and Bailiancun deposits. In this paper we report on the geochemistry and geochronology of porphyries associated with mineralization from the seven deposits. The results show that all the porphyries have similar geochemistry, with high alkalinity, high contents of SiO₂, Al₂O₃, K₂O, and Sr, high K₂O/Na₂O ratios, low MgO, Y, and Yb contents, enrichments in Ba, K, and Pb, depletions in P, Ti, Nb, and Ta, and non-evident to weak Eu depletions (δEu = 0.42–0.99). In the SiO₂ vs. Th/Ce diagram, the porphyry samples are distributed in the area of thickened lower crust, and in the Sr/Y vs. Y and La/Yb vs. Yb diagrams, the porphyries broadly followed the batch-melting trend of amphibolite containing up to 10% garnet. LA-MC-ICP-MS zircon U–Pb dating analysis suggests that the porphyries were emplaced between 34.62 ± 0.25 and 36.72 ± 0.25 Ma. They were coeval with lamprophyres (34 to 36 Ma) in the Beiya area and with potassic–ultrapotassic intrusive rocks (40 to 35 Ma) within the Jinshajiang–Ailaoshan magmatic belt, indicating possible genetic relation between these rock types. We suggest that the porphyries in the Beiya gold–polymetallic orefield were derived from the partial melting of a K-rich mafic source in the thickened lower crust, with the melting triggered by asthenospheric upwelling following the removal of lower lithospheric mantle.     

The Lamandau IOCG deposit,southwestern Kalimantan Island,Indonesia: Evidence for its formation from geochronology,mineralogy, and petrogenesis of igneous host rocks

The Lamandau region of Kalimantan Island, Indonesia is located in Sandaland, in the southern part of the Kuching tectonic belt. A series of Cenozoic epithermal gold deposits and Fe–Cu–Au deposits are located in the Kuching belt. The Lamandau Fe–Cu–Au deposit is hosted by diorite porphyry. In-situ zircon U–Pb dating of the diorite porphyry shows that it formed between 82.1 ± 1.7 Ma and 78.7 ± 2.3 Ma. Geochemical data indicate a depletion of high field strength elements (HFSE) in the diorite porphyry and related basalt is similar to that of arc-related igneous rocks. The diorite porphyry and basalt were probably derived from typical arc magmas related to continental margin subduction and thus are characterized by light rare earth element (REE) enrichment and HFSE depletion. The sub-chondritic Nb/Ta ratios for the basalt in the Lamandau region indicate that the subducted Pacific slab began partial melting at depths where amphibole was the major residual phase, with some residual rutile. The basalt was derived from a depleted mantle source. The composition of apatite and zircon in the diorite porphyry indicates that the dioritic magma was produced from the subcontinental mantle after it was metasomatized by slab-derived fluids. The magma had a high oxygen fugacity, thus and therefore it was particularly conducive to the precipitation of Cu, Au and other ore-forming elements. The composition of magnetite indicates that it was of volcanic origin. The magnetite has a low REE content, and a high Cu–Au content. The deposit may be classified as an IOCG mineral system. In summary, the ore-related diorite porphyry in the Lamandau region might have formed in an extensional environment during rollback of the subducting western Pacific plate. The convergent velocity between the Philippine Sea and Eurasian plates was at a minimum during the rollback, so that the margin of East Asian began to undergo rifting with associated magmatism.     

Evolution of magmatic-hydrothermal system of the Kalaxiange’er porphyry copper belt and implications for ore formation (Xinjiang,China)

The Kalaxiange’er porphyry copper ore belt is situated in the eastern part of the southern Altai of the Central Asian Orogenic Belt and forms part of a broad zone of Cu porphyry mineralization in southern Mongolia, which includes the Oyu Tolgoi ore district and other copper–gold deposits. The copper ore bodies are spatially associated with porphyry intrusions of granodiorite, quartz diorite, quartz syenite, and quartz monzonite and have a polygenetic (polychromous) origin (magmatic porphyry, hydrothermal, and supergene). The mineralized porphyries are characterized by almost identical REE and trace element patterns. The Zr/Hf and Nb/Ta ratios are similar to those of normal granite produced through the evolution of mantle magma. The low initial Sr isotope ratio I_Sr, varying within a narrow range of values (0.703790–0.704218), corresponds to that of primitive mantle, whereas the εNd(T) value of porphyry varies from 5.8 to 8.4 and is similar to that of MORB. These data testify to the upper-mantle genesis of the parental magmas of ore-bearing porphyry, which were then contaminated with crustal material in an island-arc environment. The isotopic composition of sulfur (unimodal distribution of δ34S with peak values of − 2 to − 4‰) evidences its deep magmatic origin; the few lower negative δ³⁴S values suggest that part of S was extracted from volcanic deposits later. The isotopic characteristics of Pb testify to its mixed crust–upper-mantle origin. According to SHRIMP U–Pb geochronological data for zircon from granite porphyry and granodiorite porphyry, mineralization at the Xiletekehalasu porphyry Cu deposit formed in two stages: (1) Hercynian “porphyry” stage (375.2 ± 8.7 Ma), expressed as the formation of porphyry with disseminated and vein–disseminated mineralization, and (2) Indosinian stage (217.9 ± 4.2 Ma), expressed as superposed hydrothermal mineralization. The Re–Os isotope data on molybdenite (376.9 ± 2.2 Ma) are the most consistent with the age of primary mineralization at the Xiletekehalasu porphyry Cu deposit, whereas the Ar–Ar isotopic age (230 ± 5 Ma) of K-feldspar–quartz vein corresponds to the stage of hydrothermal mineralization. The results show that mineralization at the Xiletekehalasu porphyry Cu deposit was a multistage process which resulted in the superposition of the Indosinian hydrothermal mineralization on the Hercynian porphyry Cu mineralization.     

Genesis of the Zhengguang gold deposit in the Duobaoshan ore field,Heilongjiang Province,NE China: Constraints from geology,geochronology and S-Pb isotopic compositions

The Zhengguang gold deposit in the Duobaoshan ore field, hosted in volcanic rocks of the Middle Ordovician Duobaoshan Formation, is one of the largest gold deposits in the Northeastern Great Xing’an Range of the Central Asian Orogenic Belt (CAOB). The deposit comprises the No. I, II and III ore zones with a total resource exceeding 35 tonnes of Au, 100,000 tonnes of Zn and 100 tonnes of Ag. A genetic relationship between gold mineralization and concealed tonalite porphyry is inferred based on the characteristics of cryptoexplosive breccia and hydrothermal alteration indicative of porphyry-type and epithermal mineralization. Zircon LA-ICPMS U-Pb dating reveals that the tonalite porphyry was emplaced at 462.1 ± 1.8 Ma (Middle Ordovician). The δ³⁴S_V-CDT values of sulfide minerals range from −3.0‰ to −1.7‰ with an average of −2.33‰, indicating that sulfur was mainly derived from a magmatic source. The Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb ranging from 17.572 to 17.629, ²⁰⁷Pb/²⁰⁴Pb from 15.424 to 15.486, and ²⁰⁸Pb/²⁰⁴Pb from 37.206 to 37.418) suggest a major mantle component for Pb and, by inference, for other ore metals. Therefore, we suggest that the ore-forming elements in the Zhengguang gold deposit may be related to the mantle-sourced tonalite porphyry. On the basis of the geological characteristics and geochemical signatures documented in this study, we conclude that the Zhengguang gold deposit was formed in a porphyry to epithermal transitional environment associated with the concealed tonalite porphyry, as part of the Duobaoshan porphyry-epithermal ore system that is related to the subduction of the Paleo-Asian Ocean during the Ordovician.     

Geochronology of the Xingshan molybdenum deposit,Jilin Province,NE China,and its Hf isotope significance

The Xingshan porphyry Mo deposit is located in the Lesser Xing’an Range–Zhangguangcai Range metallogenic belt, NE China. Mineralization occurred in granodioritic porphyry and monzogranite, which have zircon U–Pb ages of 171.7 ± 2.2 Ma and 170.9 ± 4.6 Ma, respectively. Molybdenite Re–Os dating indicates that Mo mineralization occurred at 167.3 ± 2.5 Ma. These geochronological data suggest that the magmatic and hydrothermal activities of the Xingshan Mo deposit happened during the Middle Jurassic in Mesozoic. Positive ε_Hf values (6.2–11.6) and young T_DM2 (473–826 Ma) of the monzogranite (XS-3) and granodioritic porphyry (XS-5) indicate that the source materials of Xingshan ore-bearing rocks are the juvenile crust, which mainly accreted on the Songnen block during the Meso-Neoproterozoic. Xingshan porphyry Mo deposits resulted from the magmatism and tectonism induced by the subduction of Paleo-Pacific Ocean.     

Chemistry of magnetite-apatite from albitite and carbonate-hosted Bhukia Gold Deposit,Rajasthan, western India – An IOCG-IOA analogue from Paleoproterozoic Aravalli Supergroup: Evidence from petrographic,LA-ICP-MS and EPMA studies

The Bhukia gold (+copper) deposit hosted by albitite and carbonates that occur within the Paleoproterozoic Aravalli-Delhi Fold Belt (ADFB) in western India consists of magnetite, graphite, apatite and tourmaline along with sulfide mineralization. Ubiquitous presence of magnetite and apatite in gold-sulfide association, alteration patterns and shear controlled mineralization suggest it to be IOCG (Iron-oxide copper gold) type deposits. The detailed mineral chemistry of magnetite and apatite are generated and interpreted in terms of their genetic significance, hydrothermal and magmatic origin vis-à-vis their affiliation with IOCG deposition. The data suggest that the magnetite has hydrothermal affiliation. The Ni/Cr ratio is greater than 1, which is explained by differences in solubility and mobility of Ni and Cr in hydrothermal fluids and is corroborated with other key evidences including that of wide ranging Mg concentration further supports a strong hydrothermal input that is envisaged for the deposition of magnetite. Concentration of vanadium in magnetite is generally <1000 ppm in case of barren hydrothermal occurrences while in the study area, it is relatively higher as it is attributed to the gold-sulfide-Cu mineralization. Ti vs Ni/Cr, Ni/(Cr+Mn) vs Ti+V, Ca+Al+Mn vs Ti+V and Al+Mn vs Ti+V variations are interpreted in terms of magnetite genesis. EPMA data suggests that apatite present in Bhukia is of fluorapatite variety with F content >1 wt% and F/Cl >1. Higher concentration of F and moderate Mn along with lower concentration of Cl attests their magmatic hydrothermal character and its derivation from meta-volcano sedimentary source. REE patterns obtained from LA-ICP-MS analysis suggest enrichment of LREE relative to MREE and HREE with negative Eu anomaly. Y/∑REE, La/Sm, Ce/Th and Eu/Eu¹ vs Ce/Ce¹ values of apatite is indicative of their origin in a highly oxidized environment. Presence of magnetite along with apatite is a common feature in IOCG-IOA (Iron-Oxide Apatite) association. Bhukia Gold Deposit has many similarities with Kiruna type Iron-Oxide Apatite (IOA) deposits particularly with respect to their similar tectonic setting, alteration patterns, mineral assemblages such as abundance of magnetite, apatite and presence of late stage sulfides based on EPMA and Laser ablation ICP-MS (LA-ICP-MS) studies. Lithological, petro-mineralogical and geochemical signatures of magnetite and apatite infer that the Bhukia is a possible IOCG-IOA type gold deposit typically associated with sulfides and graphite which may be used as petrogenetic indicators and pathfinders for exploration.     

Geology,fluid inclusion and isotope constraints on ore genesis of the post-collisional Dabu porphyry Cu–Mo deposit,southern Tibet

The Dabu Cu-Mo porphyry deposit is situated in the southern part of the Lhasa terrane within the post-collisional Gangdese porphyry copper belt (GPCB). It is one of several deposits that include the Qulong and Zhunuo porphyry deposits. The processes responsible for ore formation in the Dabu deposit can be divided into three stages of veining: stage I, quartz–K-feldspar (biotite) ± chalcopyrite ± pyrite, stage II, quartz–molybdenite ± pyrite ± chalcopyrite, and stage III, quartz–pyrite ± molybdenite. Three types of fluid inclusions (FIs) are present: liquid-rich two-phase (L-type), vapor-rich two-phase (V-type), and solid bearing multi-phase (S-type) inclusions. The homogenization temperatures for the FIs from stages I to III are in the ranges of 272–475 °C, 244–486 °C, and 299–399 °C, and their salinities vary from 2.1 to 49.1, 1.1 to 55.8, and 2.9 to 18.0 wt% NaCl equiv., respectively. The coexistence of S-type, V-type and L-type FIs in quartz of stage I and II with similar homogenization temperatures but contrasting salinities, indicate that fluid boiling is the major factor controlling metal precipitation in the Dabu deposit. The ore-forming fluids of this deposit are characterized by high temperature and high salinity, and they belong to a H₂O–NaCl magmatic–hydrothermal system. The H–O–S–Pb isotopic compositions indicate that the ore metals and fluids came primarily from a magmatic source linked to Miocene intrusions characterized by high Sr/Y ratios, similar to other porphyry deposits in the GPCB. The fluids forming the Dabu deposit were rich in Na and Cl, derived from metamorphic dehydration of subducted oceanic slab through which NaCl-brine or seawater had percolated. The inheritance of ancient subduction-associated arc chemistry, without shallow level crustal assimilation and/or input of the meteoric water, was responsible for the generation of fertile magma, as well as CO₂-poor and halite-bearing FIs associated with post-collisional porphyry deposits. The estimated mineralization depths of Qulong, Dabu and Zhunuo deposits are 1.6–4.3 km, 0.5–3.4 km and 0.2–3.0 km, respectively, displaying a gradual decrease from eastern to western Gangdese. Deep ore-forming processes accounted for the generation of giant-sized Qulong deposit, because the exsolution of aqueous fluids with large fraction of water and chlorine in deep or high pressure systems can extract more copper from melts than those formed in shallow systems. However, the formation of small-sized Dabu deposit can be explained by a single magmatic event without additional replenishment of S, metal, or thermal energy. In addition, the ore-forming conditions of porphyry Cu–Mo deposits in GPCB are comparable to those of porphyry Cu ± Au ± Mo deposits formed in oceanic subduction-related continental or island arcs, but differ from those of porphyry Mo deposit formed in the Dabie-Qinling collisional orogens. The depth of formation of the mineralization and features of primary magma source are two major controls on the metal types and ore-fluid compositions of these porphyry deposits.     

Dating the giant Zhuxi W–Cu deposit (Taqian–Fuchun Ore Belt) in South China using molybdenite Re–Os and muscovite Ar–Ar system

The recently discovered Zhuxi W–Cu ore deposit is located within the Taqian–Fuchun Ore Belt in the southeastern edge of the Yangtze Block, South China. Its inferred tungsten resources, based on new exploration data, are more than 280 Mt by 2016. At least three paragenetic stages of skarn formation and ore deposition have been recognized: prograde skarn stage; retrograde stage; and hydrothermal sulfide stage. Secondly, greisenization, marmorization and hornfels formation are also observed. Scheelite and chalcopyrite are the dominant metal minerals in the Zhuxi deposit and their formation was associated with the emplacement of granite stocks and porphyry dykes intruded into the surrounding Carboniferous carbonate sediments (Huanglong and Chuanshan formations) and the Neoproterozoic slate and phyllites. The scheelite was mostly precipitated during the retrograde stage, whereas the chalcopyrite was widely precipitated during the hydrothermal sulfide stage. A muscovite ⁴⁰Ar/³⁹Ar plateau age of about 150 Ma is interpreted as the time of tungsten mineralization and molybdenite Re–Os model ages ranging from 145.9 ± 2.0 Ma to 148.7 ± 2.2 Ma (for the subsequent hydrothermal sulfide stage of activity) as the time of the copper mineralization. Our new molybdenite Re–Os and muscovite ⁴⁰Ar/³⁹Ar dating results, along with previous zircon U–Pb age data, indicate that the hydrothermal activity from the retrograde stage to the last hydrothermal sulfide stage lasted up to 5 Myr, from 150.6 ± 1.5 to 145.9 ± 1 Ma, and is approximately coeval or slightly later than the emplacement of the associated granite porphyry and biotite granite. The new ages reported here confirm that the Zhuxi tungsten deposit represents one of the Mesozoic magmatic–hydrothermal mineralization events that took place in South China in a setting of lithospheric extension during the Late Jurassic (160–150 Ma). It is suggested that mantle material played a role in producing the Zhuxi W–Cu mineralization and associated magmatism.     

Genesis of the giant Zijinshan epithermal Cu-Au and Luoboling porphyry Cu–Mo deposits in the Zijinshan ore district,Fujian Province,SE China: A multi-isotope and trace element investigation

The Zijinshan ore district occurs as one of the largest porphyry-epithermal Cu–Au–Mo ore systems in South China, including the giant Zijinshan epithermal Cu–Au deposit and the large Luoboling porphyry Cu–Mo deposit. The mineralization is intimately related to Late Mesozoic large-scale tectono-magmatic and hydrothermal events. The Cu–Au–Mo mineralization occurs around intermediate-felsic volcanic rocks and hypabyssal porphyry intrusions. In this study, we summarize previously available Re–Os isotopes, zircon U–Pb age and trace elements, and Sr–Nd–Pb isotope data, and present new Pb–S and Re–Os isotope data and zircon trace elements data for ore-related granitoids from the Zijinshan high-sulfidation epithermal Cu–Au deposit and the Luoboling porphyry Cu–Mo deposit, in an attempt to explore the relationship between the two ore systems for a better understanding of their geneses. The ore-bearing porphyritic dacite from the Zijinshan deposit shows a zircon U-Pb age of 108–106 Ma and has higher zircon Ce⁴⁺/Ce³⁺ ratios (92–1568, average 609) but lower Ti-in-zircon temperatures (588–753 °C, average 666 °C) when compared with the barren intrusions in the Zijinshan ore district. Relative to the Zijinshan porphyritic dacite, the ore-bearing granodiorite porphyry from the Luoboling deposit show a slightly younger zircon U–Pb age of 103 Ma, but has similar or even higher zircon Ce⁴⁺/Ce³⁺ ratios (213–2621, average 786) and similar Ti-in-zircon temperatures (595–752 °C, average 675 °C). These data suggest that the ore-bearing magmatic rocks crystallized from relatively oxidized and hydrous magmas. Combined with the high rhenium contents (78.6–451 ppm) of molybdenites, the Pb and S isotopic compositions of magmatic feldspars and sulfides suggest that the porphyry and ore-forming materials in the Luoboling Cu–Mo deposit mainly originated from an enriched mantle source. In contrast, the ore-bearing porphyritic dacite in the Zijinshan Cu–Au deposit might be derived from crustal materials mixing with the Cathaysia enriched mantle. The fact that the Zijinshan Cu–Au deposit and the Luoboling Cu–Mo deposit show different origin of ore-forming materials and slightly different metallogenic timing indicates that these two deposits may have been formed from two separate magmatic-hydrothermal systems. Crustal materials might provide the dominant Cu and Au in the Zijinshan epithermal deposit. Cu and Au show vertical zoning and different fertility because the gold transports at low oxygen fugacity and precipitates during the decreasing of temperature, pressure and changing of pH conditions. It is suggested that there is a large Cu–Mo potential for the deeper part of the Zijinshan epithermal Cu–Au deposit, where further deep drilling and exploration are encouraged.     

Dissolution–reprecipitation process of magnetite from the Chengchao iron deposit: Insights into ore genesis and implication for in-situ chemical analysis of magnetite

Magnetite formed in different environments commonly has distinct assemblages and concentrations of trace elements that can potentially be used as a genetic indicator of this mineral and associated ore deposits. In this paper, we present textural and compositional data of magnetite from the Chengchao iron deposit, Daye district, China to provide a better understanding in the formation mechanism and genesis of the deposit and shed light on analytical protocols for in-situ chemical analysis of hydrothermal magnetite. Magnetite grains from the ore-related granitoid pluton, mineralized endoskarn, magnetite-dominated exoskarn, and vein-type iron ores hosted in marine carbonate intruded by the pluton were examined using scanning electron microscopy and analyzed for major and trace elements using electron microprobe. Back-scattered electron images reveal that primary magnetite from the mineralized skarns and vein-type ores were all partly reequilibrated with late-stage hydrothermal fluids, forming secondary magnetite domains that are featured by abundant porosity and have sharp contact with the primary magnetite. These textures are interpreted as resulting from a dissolution–reprecipitation process of magnetite, which, however, are mostly obscure under optically.Primary magnetite grains from the mineralized endoskarn and vein-type ores contain high SiO₂ (0.92–3.21 wt.%), Al₂O₃ (0.51–2.83 wt.%), and low MgO (0.15–0.67 wt.%), whereas varieties from the exoskarn ores have high MgO (2.76–3.07 wt.%) and low SiO₂ (0.03–0.23 wt.%) and Al₂O₃ (0.54–1.05 wt.%). This compositional contrast indicates that trace-element geochemical composition of magnetite is largely controlled by the compositions of magmatic fluids and host rocks of the ores that have reacted with the fluids. Compared to its precursor mineral, secondary magnetite is significantly depleted in most trace elements, with SiO₂ deceasing from 1.87 to 0.47 wt.% (on average) and Al₂O₃ from 0.89 to 0.08 wt.% in mineralized endoskarn and vein type ores, and MgO from 2.87 to 0.60 wt.% in exoskarn ores. On the contrary, average content of iron is notably increased from 69.2 wt.% to 71.9 wt.% in the secondary magnetite grains. The results suggest that the dissolution–reprecipitation process has been important in significantly removing trace elements from early-stage magnetite to form high-grade, high-quality iron ores in hydrothermal environments. The textural and compositional data confirm that the Chengchao iron deposit is of hydrothermal origin, rather than being crystallized from immiscible iron oxide melts as previously suggested. This study also highlights the importance of textural characterization using various imaging techniques before in-situ chemical analysis of magnetite, as is the case for texturally complicated UTh-bearing accessory minerals that have been widely used for UPb geochronology study.     

Geology and fluid characteristics of the Ulu Sokor gold deposit,Kelantan, Malaysia: Implications for ore genesis and classification of the deposit

The Ulu Sokor gold deposit is one of the most famous and largest gold deposits in Malaysia and is located in the Central Gold Belt. This deposit consists of three major orebodies that are related to NS- and NE-striking fractures within fault zones in Permian-Triassic meta-sedimentary and volcanic rocks of the East Malaya Block. The faulting events represent different episodes that are related to each orebody and are correlated well with the mineralogy and paragenesis. The gold mineralization consists of quartz-dominant vein systems with sulfides and carbonates. The hydrothermal alteration and mineralization occurred during three stages that were characterized by (I) silicification and brecciation; (II) carbonatization, sericitization, and chloritization; and (III) quartz–carbonate veins.Fluid inclusions in the hydrothermal quartz and calcite of the three stages were studied. The primary CO₂–CH₄–H₂O–NaCl fluid inclusions in stage I are mostly related to gold mineralization and display homogenization temperatures of 269–389 °C, salinities of 2.77–11.89 wt.% NaCl equivalent, variable CO₂ contents (typically 5–29 mol%), and up to 15 mol% CH₄. In stage II, gold was deposited at 235–398 °C from a CO₂ ± CH₄–H₂O–NaCl fluid with a salinity of 0.83–9.28 wt.% NaCl equivalent, variable CO₂ contents (typically 5–63 mol%), and up to 4 mol% CH₄. The δ¹⁸O_H2O and δD values of the ore-forming fluids from the stage II quartz veins are 4.5 to 4.8‰ and − 44 to − 42‰, respectively, and indicate a metamorphic–hydrothermal origin. Oxygen fugacities calculated for the entire range of T-P-X_CO2 conditions yielded log f_O2 values between − 28.95 and − 36.73 for stage I and between − 28.32 and − 39.18 for stage II. These values indicate reduced conditions for these fluids, which are consistent with the mineral paragenesis, fluid inclusion compositions, and isotope values.The presence of daughter mineral-bearing aqueous inclusions is interpreted to be a magmatic signature of stage IIIa. Combined with the oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 6.8 to 11.9‰, δD = − 77 to − 62‰), these inclusions indicate that the initial fluid was likely derived from a magmatic source. In stage IIIb, the gold was deposited at 263° to 347 °C from a CO₂–CH₄–H₂O–NaCl fluid with a salinity of 5.33 to 11.05 wt.% NaCl equivalent, variable CO₂ contents (typically 9–15 mol%), and little CH₄. The oxygen and hydrogen isotopic compositions of this fluid (δ¹⁸O_H2O = 8.1 to 8.8‰, δD = − 44 to − 32‰) indicate that it was mainly derived from a metamorphic–hydrothermal source. The CO₂–H₂O ± CH₄–NaCl fluids that were responsible for gold deposition in the stage IIIc veins had a wide range of temperatures (214–483 °C), salinities of 1.02 to 21.34 wt.% NaCl equivalent, variable CO₂ contents (typically 4–53 mol%), and up to 7 mol% CH₄. The oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 8.5 to 9.8‰, δD = − 70 to − 58‰) were probably acquired at the site of deposition by mixing of the metamorphic–hydrothermal fluid with deep-seated magmatic water and then evolved by degassing at the site of deposition during mineralization. The log f_O2 values from − 28.26 to − 35.51 also indicate reduced conditions for this fluid in stage IIIc. Moreover, this fluid had a near-neutral pH and δ³⁴S values of H₂S of − 2.32 to 0.83‰, which may reflect the derivation of sulfur from the subducted oceanic lithospheric materials.The three orebodies represent different gold transportation and precipitation models, and the conditions of ore formation are related to distinct events of hydrothermal alteration and gold mineralization. The gold mineralization of the Ulu Sokor deposit occurred in response to complex and concurrent processes involving fluid immiscibility, fluid–rock reactions, and fluid mixing. However, fluid immiscibility was the most important mechanism for gold deposition and occurred in these orebodies, which have corresponding fluid properties, structural controls, geologic characteristics, tectonic settings, and origins of the ore-forming matter. These characteristics of the Ulu Sokor deposit are consistent with its classification as an orogenic gold deposit, while some of the veins are genetically related to intrusions.     

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.     

Geochronology and geochemistry of porphyritic intrusions in the Duolong porphyry and epithermal Cu-Au district,central Tibet: Implications for the genesis and exploration of porphyry copper deposits

The Duolong district in central Tibet hosts a number of porphyry as well as high sulfidation epithermal copper–gold deposits and prospects, associated with voluminous calc-alkaline volcanism and plutonism. In this study, we present new geochronological, geochemical, isotopic and mineralogical data for both economically mineralized and barren porphyritic intrusions from the Duobuza and Naruo porphyry Cu–Au deposits. Zircon U–Pb analyses suggest the emplacement of economically mineralized granodiorite porphyry and barren granodiorite porphyry at Naruo deposit took place at 119.8 ± 1.4 Ma and 117.2 ± 0.5 Ma, respectively. Four molybdenite samples from the Naruo deposit yield an isochron Re–Os age of 119.5 ± 3.2 Ma, indicating mineralization occurred synchronously with the emplacement of the early granodiorite porphyry. At Duobuza deposit, the barren quartz diorite porphyry intruded at 119.5 ± 0.7 Ma, and two economically mineralized intrusions intruded at 118.5 ± 1.2 Ma (granodiorite porphyry) and 117.5 ± 1.2 Ma (quartz diorite porphyry), respectively. Petrographic investigations and geochemical data indicate that all of the porphyritic intrusions were oxidized, water rich, and subduction-related calc-alkaline magmas. Zircons from the porphyritic intrusions have a wide range in the ε_Hf (0–11.1) indicating that they were sourced from mixing of mantle-derived mafic, and crust-derived felsic melts. Moreover, the variation of trace element content of plagioclase phenocrysts indicates that the magma chambers were recharged by mafic magmas.Comparison of the composition of amphibole phenocrysts indicates the porphyry copper–gold mineralization at Duolong was generated in magma chambers at low crystallization temperatures and pressures (754° to 791 °C, 59 M to 73 MPa, n = 8), and under highly oxidizing conditions (ΔNNO 2.2 to 2.7, n = 8). In contrast, barren intrusions were sourced from the magma chambers with higher crystallization temperatures and pressures (816° to 892 °C, 111 to 232 MPa, n = 22) that were less oxidizing (ΔNNO 0.6 to 1.6, n = 22). The requirement for a thermal contrast is supported by the declining of Ti content in magnetite crystals in barren intrusions (12,550 to 34,200 ppm) versus those from economically mineralized intrusions (600 to 3400 ppm). Moreover, the V content in magnetite crystals from economically mineralized intrusions (990 to 2510 ppm) is lower than those recorded from barren intrusions (2610 to 3510 ppm), which might reflect the variation in oxidation state of the magma. The calculated water solubility of the magma forming the economically mineralized intrusions (3.2–3.7 wt%) is lower than that of magma forming the barren intrusions (4.6–6.4 wt%). Based on the chemical–physical characteristics of economically mineralized magma, our study suggests that the development of porphyry Cu–Au mineralization at Duolong was initiated by shallow-level emplacement of a magma that crystallized at lower temperatures and pressures. Experimental studies show that copper and water solubilities in silicate melts decrease with falling temperatures and pressures, indicating metals and ore-forming fluids are more likely to be released from a magma reservoir emplaced at shallow crustal levels. We propose the magnetite might be a convenient exploration tool in the search for porphyry copper mineralization because the variations in Ti and V content of mineral concentrates and rock samples are indicative of barren versus mineralized intrusions.     

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.     

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

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