The genesis of metal zonation in the Weilasituo and Bairendaba Ag–Zn–Pb–Cu–(Sn–W) deposits in the shallow part of a porphyry Sn–W–Rb system,Inner Mongolia,China

The Weilasituo and Bairendaba Zn–Pb–Ag–Cu–(Sn–W) sulphide deposits are located in the southern part of Great Xing'an Range of Inner Mongolia in China. The deposits are located at shallow depths in the newly discovered Weilasituo porphyry hosting Sn–W–Rb mineralization. The mineralization at Weilasituo and Bairendaba consist of zoned massive sulphide veins within fractures cutting the Xilinhot Metamorphic Complex and quartz diorite. The Weilasituo deposit gradually zones from the Cu-rich Zn–Cu sulphide mineralization in the west to Zn-rich Zn–Cu sulphide mineralization in the east. The Bairendaba deposit has a Cu-bearing and Zn-rich core through a transitional zone devoid of copper to an outer zone of Zn–Pb–Ag mineralization. Three main veins contain more than 50 wt.% of the contained metal in the two deposits with their metal ratios displaying a systematic and gradual increase in Zn/Cu, Pb/Zn and Ag/Zn ratios from the western part of Weilasituo to the eastern part of Bairendaba.Three stages of vein-type mineralization are recognized. Early, sub-economic mineralization consists of a variable proportion of euhedral arsenopyrite, pyrite, quartz, and rare wolframite, scheelite, cassiterite, magnetite and cobaltite. This was succeeded by main stage mineralization with economic concentration of zoned Cu, Zn, Pb and Ag sulphide minerals along strike within the veins. The zones consist of the assemblages: (1) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–quartz–fluorite) at west Weilasituo; (2) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) at east Weilasituo; (3) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) in the centre of Bairendaba; (4) pyrrhotite–Fe-rich sphalerite–galena(–chalcopyrite–tetrahedrite–quartz–fluorite) in the transition zone of Bairendaba; and (5) pyrrhotite–Fe-rich sphalerite–galena–tetrahedrite(–chalcopyrite–falkmanite–argentite–pyrargyrite–quartz–fluorite) in the outer zone at Bairendaba. Post-main ore stage is devoid of sulphides and characterized overprinting of fluorite, sericite, chlorite, illite, kaolinite and calcite.Zircon SHRIMP U–Pb dating, Zircon LA–ICP–MS U–Pb dating, molybdenite Re–Os isochron dating, and muscovite Ar–Ar dating indicate the Beidashan granitic batholith was intruded at 140 ± 3 Ma (MSWD = 3.3), the porphyritic monzogranite from marginal facies of the Beidashan batholith was intruded at 139 ± 2 Ma (MSWD = 0.75), the mineralized quartz porphyry was intruded at 135 ± 2 Ma (MSWD = 0.91), the greisen mineralization occurred at 135 ± 11 Ma (MSWD = 7.2), and the post-main ore stage muscovite deposited at 129.5 ± 0.9 Ma. The new geochronology data show the porphyry Sn–W–Rb and vein-type sulphide mineralization are contemporaneous with granitic magmatism in the region.The metal zonation at the Weilasituo and Bairendaba deposits is a result of progressive metal deposition. This was during the evolution of a metal-bearing fluid along the strike of the veins and during the main stage of ore formation at the upper part of the deep-seated porphyry Sn–W–Rb system. This progressive zonation indicates that the deposits represent end-numbers formed from one ore-forming fluid, which moved from west to east from the porphyry. The metal zonation patterns of the major veins are consistent with metal-bearing fluid entering the system with the precipitation of chalcopyrite proximally and sphalerite, galena and Ag-bearing minerals more distally. We show that the mechanism of metal deposition is therefore controlled by thermodynamic conditions resulting in the progressive separation of sulphides from the metal-bearing fluid. The temperature gradient between the inflow zone and the outflow zone appears to be one of the key parameters controlling the formation of the metal zonation pattern. The sulphide precipitation sequence is consistent with a low fS₂ and low fO₂ state of the acidic metal-bearing fluid. The metal zonation pattern provides helpful clues from which it is possible to establish the nature of fluid migration and metal deposition models to locate a possible porphyry mineralization at depth in the Great Xing'an Range, which is consistent with the geology of the newly discovered porphyry Sn–W–Rb system.     

Late Cretaceous metallogeny in the Zhongdian area: Constraints from Re–Os dating of molybdenite and pyrrhotite from the Hongshan Cu deposit,Yunnan, China

The Zhongdian area in Yunnan, southwestern China, located at the southern end of the Yidun volcano-magmatic arc that was formed during the Triassic westward subduction of the Gaze-Litang Ocean, hosts numerous Triassic large porphyry and skarn deposits. The arc suffered Jurassic to Cretaceous arc-continental orogenic collision and Cenozoic intracontinental strike-slip shearing. The Hongshan Cu (–Mo–Pb–Zn) deposit is potentially a large deposit and contains two ore types: 1) predominant layered skarn Cu–(Pb–Zn) ores along marble-hornfels contacts; and 2) minor crosscutting vein-type Cu–Mo mineralization. Previous research forwards a two-stage genetic model without sufficient dating evidence, supposing the skarn mineralization is related to the Triassic calc-alkalic intrusions and the vein-type mineralization related to Cretaceous quartz monzonite porphyries. Re–Os dating of molybdenite from vein-type ores and quartz monzonite porphyries and that of pyrrhotite from skarn ores are presented here to constrain the mineralization age and rebuild the genetic model. Analyses of eight molybdenite samples yield an isochron age of 79.7 ± 3.1 Ma (MSWD = 9.2) for the vein-type mineralization and a model age of 81.9 ± 1.1 Ma for the quartz monzonite porphyries. Isotope data on seven pyrrhotite samples from the skarn ores yield an isochron age of 79 ± 16 Ma z(MSWD = 8.4). The Re–Os ages for the two ore types are concordant within analytical errors, indicating that the Hongshan deposit was formed in the Late Cretaceous. Elevated Re contents in molybdenite (13.65 to 63.91 μg/g) and extremely radiogenic initial ¹⁸⁷Os/¹⁸⁸Os ratios in pyrrhotite (0.7673 to 0.8184; weighted average 0.796 ± 0.038), together with elevated γ_Os values in pyrrhotite (507 to 547; average 528) imply a significant crustal component in the ore-forming materials that was likely derived from a lower crustal reservoir. Combined with the tectonic evolution of the Zhongdian area and geochemical characteristics of corresponding intrusions, the ages of mineralization obtained in this study indicate that the Hongshan deposit was formed in a post-collision setting with a genetic relationship to the emplacement of the quartz monzonite porphyry. These results provide significant new information for the study and exploration of the Late Cretaceous metallogeny in the Zhongdian area.     

Zircon U-Pb geochronology and geochemistry of the intrusions associated with the Jiawula Ag-Pb-Zn deposit in the Great Xing’an Range,NE China and their implications for mineralization

Located in the eastern section of the Central Asian Orogenic Belt, the Jiawula Ag-Pb-Zn deposit is classified as a volcanic to subvolcanic related vein-type ore deposit. New U-Pb zircon geochronology, whole-rock geochemistry, mineral chemistry, and Sr-Nd isotope data are presented for the intrusions in the Jiawula deposit in order to evaluate the timing, petrogenetic type of the granitoid rocks, origin and evolution of magmatism, geodynamics, and to establish its relationship with lead-zinc mineralization. Zircon SHRIMP U-Pb analyses yield weighted mean ages of 150.1 ± 1.8 Ma for quartz porphyry, 148.8 ± 2.2 Ma for syenite porphyry, and 145.3 ± 1.9 Ma for monzonite porphyry, indicating a Late Jurassic (Yanshanian) magmatic event. An earlier magmatic event (Indosinian) occurred during the Late Permian to Early Triassic from ca. 254 Ma to ca. 247 Ma and is represented by granodiorite (254 ± 2 Ma), dacite porphyry (252.9 ± 4.8 Ma), and diorite porphyry (278 ± 4.1 Ma). Both the Indosinian and Yanshanian igneous rocks are classified as I-type granitoids. The late Jurassic intrusions are highly fractionated and characterized by negative anomalies of Eu, Sr, P, and Ti. The hypabyssal intrusions have initial ⁸⁷Sr/⁸⁶Sr values between 0.70458 and 0.70522, and ε_Nd(t) values of −3.4 to −0.2, indicating relatively older crust in Jiawula among more juvenile crust in this area. Magma generation in Jiawula is linked to juvenile lower crustal and slightly enriched mantle sources. The ∼250 Ma magmatic episode in Jiawula might be related to the subduction of the Mongol-Okhotsk oceanic plate towards the south beneath the Erguna massif. The ∼150 Ma magmatic event occurred after the closure of the Mongol-Okhotsk Ocean followed by the change in subduction direction of the Paleo-Pacific plate. Varying temperature, stronger fractionation and higher oxygen fugacity related to the magmatic-hydrothermal transition caused Pb-Zn 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.     

Influence of crude oil on the genesis of the Lanjiagou porphyry molybdenum deposit,western Liaoning Province,China

The Lanjiagou porphyry molybdenum deposit in western Liaoning Province, China, is hosted in fine-grained Jurassic granites. LA-ICP-MS zircon U–Pb analyses indicate that the crystallization of the ore-hosting granites took place 185.0 ± 1.8 Ma (MSWD = 1.4). Molybdenum mineralization in the deposit can be divided into three stages: the stockwork quartz vein stage, the planar quartz vein stage, and the fissure-filling quartz vein stage. Re–Os isotopic ages for the molybdenite from the stockwork quartz vein-type ores yielded an isochron age of 188.8 ± 9.9 Ma (MSWD = 3.0), while six samples from the planar quartz vein-type ores yielded a similar isochron age of 185.6 ± 1.2 Ma (MSWD = 0.5). Re–Os isotopic ages for the molybdenite identical, within error, to zircon U–Pb isotopic ages indicate that the molybdenum mineralization is related to the host intrusions. Apart from primary inorganic fluid inclusions (IFIs), a large number of primary organic fluid inclusions (OFIs) are found in the latter two stages of vein quartz, and minors found in the first stage. The components and characteristics of OFIs in the three stages of vein quartz differ from each other, which is also true for the IFIs. OFIs in stockwork vein quartz are characterized by halite-bearing inclusions, and organic liquids in the inclusions are brown and do not fluoresce under ultraviolet (UV) light. Homogenization temperatures (T_h) for the primary IFIs coeval with OFIs of this stage ranges from 300 °C to > 450 °C, while the salinity varies from 10 to 53 wt.% NaCl equiv.. In planar vein quartz, OFIs are predominately two-phased (liquid and gas), and salt daughter minerals (halite) are absent. Organic liquids are light brown to colorless and show blue fluorescence under UV light; The T_h range for the IFIs of this stage is 250–360 °C, and the salinity range is 3–17 wt.% NaCl equiv. Finally, OFIs in fissure-filling vein quartz are marked by liquid–gas inclusions. Organic liquids are generally colorless and show yellow fluorescence under UV light. The T_h range for the primary IFIs is 180–240 °C and the salinity range is 4–11 wt.% NaCl equiv. Organic geochemical analyses indicate that organic matter in the Lanjiagou deposit was derived from mature crude oil. We suggest that large volumes of crude-oil-bearing non-magmatic fluids were flushed into the Lanjiagou porphyry hydrothermal system during all phases of ore formation and likely played important roles in mineralization.     

Geochronology of the Hongniu-Hongshan porphyry and skarn Cu deposit,northwestern Yunnan province,China: Implications for mineralization of the Zhongdian arc

The Hongniu-Hongshan porphyry and skarn copper deposit is located in the Triassic Zhongdian island arc, northwestern Yunnan province, China. Single-zircon laser ablation inductively coupled plasma mass spectrometry U–Pb dating suggests that the diorite porphyry and the quartz monzonite porphyry in the deposit area formed at 200 Ma and 77 Ma, respectively. A Re–Os isotopic date of molybdenite from the ore is 78.9 Ma, which indicates that in addition to the known Triassic Cu–(Au) porphyry systems, a Late Cretaceous porphyry Cu–Mo mineralization event also exists in the Zhongdian arc. The quartz monzonite porphyry shows characteristics of a magnetite series intrusion, with a high concentration of Al, K, Rb, Ba, and Pb, low amount of Ta, Ti, Y, and Yb, and a high ratio of Sr/Y (average 26.42). The Cretaceous porphyry also shows a strong fractionation between light and heavy rare earth elements (average (La/Yb)_N 37.9), which is similar to those of the Triassic subduction-related diorite porphyry in the Hongniu-Hongshan deposit and the porphyry hosting the Pulang copper deposit. However, in contrast to the older intrusions, the quartz monzonite porphyry contains higher concentrations of large ion lithophile elements and Co, and lesser Sr and Zr. Therefore, whereas the Triassic porphyry Cu–(Au) mineralization is related to slab subduction slab in an arc setting, the quartz monzonite porphyry in the Hongniu-Hongshan deposit formed by the remelting of the residual oceanic slab combined with contributions from subduction-modified arc lithosphere and continental crust, which provided the metals for the Late Cretaceous mineralization.     

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).     

Jurassic magmatism related Pb-Zn-W-Mo polymetallic mineralization in the central Nanling Range,South China: Geochronologic,geochemical, and isotopic evidence from the Huangshaping deposit

The Nanling Range in South China is characterized by extensive Mesozoic magmatism and coeval nonferrous and rare metal mineralization. Huangshaping is a world-class Pb-Zn-W-Mo polymetallic skarn deposit in the central Nanling Range. Magmatic rocks occurring in this ore district include quartz porphyry, granite porphyry, granophyre, dacite porphyry, and aplite, with only the first three granitoids genetically associated with polymetallic mineralization. Most of the orebodies are constrained within the contact zones as skarn and veins between these granitic stocks and the carbonate wall rocks.Since the age of the quartz porphyry is still controversial, and studies of the dacite porphyry and aplite are absent, we focus on these magmatic rocks first. LA-ICP-MS zircon U-Pb dating suggests that the crystallization ages of the quartz porphyry, dacite porphyry, and aplite are 154.3 ± 1.9 Ma, 158.1 ± 0.8 Ma, and 148.4 ± 3.4 Ma, respectively. Combined with previously published age data, we infer the evolutionary sequence of magmatic rocks should be dacite porphyry → quartz porphyry → granite porphyry (granophyre) → aplite. The quartz porphyry, dacite porphyry, and aplite yield high contents of high field strength elements (Zr + Nb + Ce + Y = 255–440 ppm), high ratios of 10,000 × Ga/Al (2.6–3.2), and prominent depletions in Ba, Sr, Eu, P, and Ti, indicating their crustal affinities to A-type granites. They have negative ε_Nd(t) values (−9.4 to −7.0) and high initial Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb_i = 18.307–18.644, ²⁰⁷Pb/²⁰⁴Pb_i = 15.689–15.742, ²⁰⁸Pb/²⁰⁴Pb_i = 38.589–38.986), suggesting that they were probably derived by partial melting of ancient granulitic crustal materials.The sulfide minerals exhibit a wide range of δ³⁴S_V-CDT values from −22.6 to 24.2‰, with ²⁰⁶Pb/²⁰⁴Pb of 17.669–19.708, ²⁰⁷Pb/²⁰⁴Pb of 15.492–15.714, and ²⁰⁸Pb/²⁰⁴Pb of 37.880–39.789, indicating that sulfur, lead, and other associated metals were derived from a mixture of magmatic components and the Carboniferous wall rocks. Fluid inclusions in pyrrhotite, sphalerite, and marmatite samples have ³He/⁴He ratios of 0.12 to 1.53 Ra, with calculated mantle helium proportions of 1.3 to 18.9%, indicating a predominantly crustal origin for the ore fluids, with minor inputs from the mantle. The Huangshaping deposit is a typical example of the genetic relationship both spatially and temporally between Jurassic magmatism and polymetallic metallogeny in the Nanling Range.     

锡钨锂矿化与外围脉状铅锌银铜矿化的内在成因关系和形成机制——以内蒙古维拉斯托锡钨锂多金属矿床为例

大兴安岭南段维拉斯托锡钨锂多金属矿是近年来新发现的大型矿床,具有"上脉下体"的垂向矿化分带特征,矿集区范围内表现出以花岗岩体为中心的高温锡钨钼矿化、中温铜锌矿化、外围低温铅锌银矿化的水平分带。目前,对锡钨锂多金属矿化与外围脉状铅锌银铜矿化的内在成因关系和形成机制及深部地质背景还缺乏足够的认识。Ar-Ar年代学研究结果表明,维拉斯托锡钨锂矿区石英脉型矿石中白云母的Ar-Ar坪年龄为(131.7±1.4)Ma,显示其与外围维拉斯托铜锌矿床和拜仁达坝银铅锌矿床的成矿时代基本一致,属同一构造-岩浆活动产物。石英斑岩中铁锂云母的Ar-Ar坪年龄为(121.9±1.3)Ma,可能代表了最晚期的岩浆活动时限,暗示维拉斯托矿区存在多期次岩浆-热液活动。本次研究还获得了维拉斯托矿床东南侧磨盘山岩体边部黑云母二长花岗岩锆石U-Pb年龄为(141.6±1.5)Ma(MSWD=0.75),该年龄不仅与含矿岩体石英斑岩体的年龄一致,也与北大山高分异杂岩体的形成年龄相近,揭示了维拉斯托外围高分异花岗杂岩体深边部及其与地层接触带部位还有寻找锡多金属矿的巨大潜力。综合本次工作和大量前人工作的基础上,笔者认为大兴安岭南段稀有金属矿床都形成于大陆边缘弧后伸展和软流圈上涌的构造背景,维拉斯托锡钨锂矿化与外围脉状铅锌银铜矿化属同一岩浆-热液成矿系统,不同金属元素在不同的矿化空间内的选择性沉淀是造成元素分带性的直接原因,其成矿特征上可类比南美玻利维亚锡银成矿带。值得提出的是,维拉斯托矿区岩石组合与松潘-甘孜造山带与锂矿化有关的片麻岩穹窿群类似,锡林郭勒杂岩可能为成矿提供了部分物质来源,对于岩浆-变形-变质-深熔作用过程及对稀有金属成矿的制约还需要进一步研究。     

The Chalukou deposit in the North Great Xing’an Range of China: A protracted porphyry Mo ore-forming system in a long-lived magmatic evolution cycle

The Chalukou deposit is located in the North Great Xing’an Range of the Xing’an-Mongolia Orogen bordering and to the northeast of the North China Craton. The deposit is a high-F-type porphyry Mo deposit hosted by the Chalukou composite igneous body containing small intrusive bodies genetically related to Mo mineralization. The composite igneous body includes pre-mineralization dolerite, monzogranite and syenogranite, syn-mineralization rhyolitic porphyry, granitic porphyry and fine-grained monzogranite, and post-mineralization rhyolitic porphyry, quartz porphyry, dioritic porphyry and andesitic porphyry. Detailed laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb zircon dating of the igneous components of the composite igneous body was carried out to determine the temporal framework for magmatism in the Chalukou region. The new LA-ICP-MS U-Pb ages constraint documented here, together with the published ages, indicate that there was a protracted porphyry Mo ore-forming event of approximately 7 million years between ca. 152 when the ore related rhyolitic porphyry was emplaced and ca.145 Ma when molybdenite ceased being deposited. The dating reveals that the mineralization is a part of relatively long-lived magmatic cycle involving the emplacement of small doleritic stocks at ca. 165 Ma that progressively evolved into extensive granitic intrusions at ca. 164 Ma, and then diminished with the emplacement of mineralization-related porphyries to ca. 152 Ma. The emplacement of barren Early Cretaceous magmatism, represented by volcanic units in the ca. 136 Ma Guanghua Formation and porphyries, followed the mineralized magmatism.The syn-mineralization porphyry units associated with Mo contain zircons assaying ∼15 times higher in U and Th than the pre-mineralization magmatic phases. This indicates that there was a significant enrichment of Mo, U and Th in the magma, and directly associated with ore fluid exsolution. The return to their normal levels in the three elements in the post-mineralization magmatic phases indicates that they were exhausted from the magma chamber in the later phases. A genetic model is proposed for the enormous introduction of ore metals and enrichment at the Chalukou deposit. The protracted and multiphase igneous activity during the long-lived magmatism reflects a multistage enrichment of metal, and may play a crucial role in the formation of a volatile-enriched, fertile and large-volume magma chamber beneath the Chalukou deposit. Such a chamber is envisaged to be required for the formation of porphyry Mo deposits in general.     

The Jiguanshan porphyry Mo deposit in the Xilamulun metallogenic belt,northern margin of the North China Craton,U–Pb geochronology,isotope systematics,geochemistry and fluid inclusion studies: Implications for a genetic model

The Jiguanshan porphyry Mo deposit is located in the southern part of Xilamulun metallogenic belt at the northern margin of the North China Craton (NCC). In the Jiguanshan mining district, two stages of granitoids intrusions have been recognized: a pre-ore granite porphyry with stockworks and veins of Mo mineralization, and a granite porphyry with disseminated Mo mineralization. Zircon U–Pb data and Hf isotope analyses show that the dissemination-mineralized granite porphyry yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 156.0 ± 1.3 Ma, with a crustal ε_Hf(t) values from − 5.6 to + 0.2, and that the main group of magmatic zircons from the pre-ore granite porphyry have a weighted mean ²⁰⁶Pb/²³⁸U age of 167.7 ± 1.7 Ma with ε_Hf(t) values from − 3.2 to + 1.0. Combined with groundmass Ar–Ar age data of the granite porphyry and molybdenite Re–Os age, it is suggested that the Mo mineralization of Jiguanshan deposit was formed in the late Jurassic (153 ~ 155 Ma) during tectonic and magmatic events that affected northeast China. The Mo mineralization was a little bit later than the host granite porphyry. Besides disseminated in the host granite porphyry, Mo mineralization also presents in middle Jurassic pre-ore granite porphyry, Jurassic fine-grained diabase, Triassic quartz porphyry, and in rhyolitic volcanic rocks as well as syenite of Devonian age.The Jiguanshan mining district was affected by the tectonic events associated with the Paleo-Asian Ocean closure, and later by far-field tectonism, related to subduction of the Paleo-Pacific plate (Izanagi) in the Jurassic-Cretaceous. The tectonic and thermal events linked with the latter are commonly referred to as Yanshanian tectono-thermal event, and consists of a series of geodynamic, magmatic and ore-forming processes, which in the mining district area included the intrusion of the pre-ore granite porphyry, the host granite porphyry, Mo mineralization, and fine-grained diabase. Major and trace element analyses show that the host granite porphyry is characterized by high silica abundances (SiO₂ = 77.16 to 77.51%), high Rb/Sr ratios (13.57 to 14.83), high oxidation (Fe₂O₃/FeO = 34.25 to 62.00) and high alkalies (Na₂O + K₂O = 8.21 to 8.38%). Petrographic and microthermometry studies of the fluid inclusions from Mo mineralized veins, characterized by plenty of daughter mineral-bearing inclusions, showed that the predominant homogenization temperatures range from 250 to 440 °C. Combined with Laser Raman analysis of the fluid inclusions, it is indicated that Mo mineralization is related to a high-temperature, hypersaline and high-oxygen fugacity H₂O–NaCl fluid system, with high F contents.Based on geology, geochronology, isotope systematics, geochemistry and fluid inclusion studies as well as regional geology, we propose, for the first time, a genetic model for the Jiguanshan porphyry Mo deposit. During the Jurassic geodynamic evolution of northeast China, high silicic, high oxidized and alkaline-rich granitic magma probably derived from partial melting of the lower crust, episodically intruded along faults into the country rocks. This fluid system, fractionating from the highly differentiated granitic magma and bearing Mo with minor Cu metals, migrated upwards and interacted with the older wall rocks and associated fractures, in which the ore minerals precipitated, resulting in the development of what we refer to as the “Jiguanshan-type” porphyry Mo deposit.     

Magmatic evolution of the Tuwu–Yandong porphyry Cu belt,NW China: Constraints from geochronology,geochemistry and Sr–Nd–Hf isotopes

The Tuwu–Yandong porphyry Cu belt is located in the Eastern Tianshan mountains in the eastern Central Asian Orogenic Belt. Petrochemical and geochronological data for intrusive and volcanic rocks from the Tuwu and Yandong deposits are combined with previous studies to provide constraints on their petrogenesis and tectonic affinity. New LA–ICP–MS zircon U–Pb ages of 348.3 ± 6.0 Ma, 339.3 ± 2.2 Ma, 323.6 ± 2.5 Ma and 324.1 ± 2.3 Ma have been attained from intrusive units associated with the deposits, including diorite, plagiogranite porphyry, quartz albite porphyry and quartz porphyry, respectively. The basalt and andesite, which host part of the Cu mineralization, are tholeiitic with high Al₂O₃, Cr, Ni and low TiO₂ contents, enriched LREEs and negative HFSE (Nb, Ta, Zr, Ti) anomalies consistent with arc magmas. Diorites are characterized by low SiO₂ content but high MgO, Cr and Ni contents, similar to those of high-Mg andesites. The parental magma of the basalt, andesite and diorite is interpreted to have been derived from partial melting of mantle-wedge peridotite that was previously metasomatized by slab melts. The ore-bearing plagiogranite porphyry is characterized by high Na₂O, Sr, Cr and Ni contents, low Y and Yb contents, low Na₂O/K₂O ratios and high Sr/Y ratios and high Mg#, suggesting an adakitic affinity. The high ε_Nd(t) (5.02–9.16), low I_Sr (0.703219–0.704281) and high ε_Hf(t) (8.55–12.99) of the plagiogranite porphyry suggest they were derived by a partial melting of the subducted oceanic crust followed by adakitic melt-mantle peridotite interaction. The quartz albite porphyry and quartz porphyry are characterized by similar Sr–Nd–Hf isotope but lower Mg# and whole-rock (La/Yb)_N ratios to the plagiogranite porphyry, suggesting they were derived from juvenile lower crust, and negative Eu anomalies suggest fractionation of plagioclase. We propose that a flat subduction that started ca. 340 Ma and resulted in formation of the adakitic plagiogranite porphyry after a period of “steady” subduction, and experienced slab rollback at around 323 Ma.     

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.     

Distal Pb-Zn-Ag veins associated with the world-class Donggou porphyry Mo deposit,southern North China craton

The southern North China craton hosts numerous world-class porphyry Mo and Pb-Zn-Ag vein deposits. Whether or not the Pb-Zn-Ag veins are genetically associated with the porphyry Mo system remains contentious. Here we focus on the genetic relationships between the Sanyuangou Pb-Zn-Ag vein deposit and the world-class Donggou porphyry Mo deposit, and discuss the potential implications from the spatial and temporal relationships between porphyry and vein systems in the southern North China craton.At Sanyuangou, vein-hosted sulfide mineralization mainly comprises pyrite, sphalerite, and galena, with minor chalcopyrite, pyrrhotite, bornite, tetrahedrite, covellite, polybasite and argentite. The mineralization is hosted by a quartz diorite stock, which has a zircon U-Pb age of 1756 ± 9 Ma. However, sericite from alteration selvages of Pb-Zn-Ag sulfide mineralization yields a well-defined ⁴⁰Ar/³⁹Ar plateau age of 115.9 ± 0.9 Ma. Although nominally younger, the sericite ⁴⁰Ar/³⁹Ar age is similar to the age of the nearby Donggou porphyry Mo deposit (zircon U-Pb age of 117.8 ± 0.9; molybdenite Re-Os ages of 117.5 ± 0.8 Ma and 116.4 ± 0.6 Ma). Pyrite from Donggou has elevated contents of Mo and Bi, whereas pyrite from Sanyuangou is enriched in Cu, Zn, Pb, Ag, Au, and As. This trace element pattern is consistent with metal zonation typically observed in porphyry related metallogenic systems. Pyrite grains from Sanyuangou have lead isotopes overlapping those from Donggou (17.273–17.495 vs. 17.328–17.517 for ²⁰⁶Pb/²⁰⁴Pb, 15.431–15.566 vs. 15.408–15.551 for ²⁰⁷Pb/²⁰⁴Pb, and 37.991–38.337 vs. 38.080–38.436 for ²⁰⁸Pb/²⁰⁴Pb). Collectively, the geological, geochronological, and geochemical data support a magmatic-hydrothermal origin for the Sanyuangou Pb-Zn-Ag deposit and confirm that the Pb-Zn-Ag veins and the Donggou Mo deposit form a porphyry-related magmatic-hydrothermal system.Given the widespread Pb-Zn-Ag veins and Mo mineralized porphyries in many districts of the southern North China craton, the model derived from this study has broad implications for further exploration of Mo and Pb-Zn-Ag resources in the area.     

Zircon U–Pb and molybdenite Re–Os dating of the Chalukou porphyry Mo deposit in the northern Great Xing’an Range,China and its geological significance

The newly discovered Chalukou giant porphyry Mo deposit, located in the northern Great Xing’an Range, is the biggest Mo deposit in northeast China. The Chalukou Mo deposit occurs in an intermediate-acid complex and Jurassic volcano-sedimentary rocks, of which granite porphyry, quartz porphyry, and fine-grained granite are closely associated with Mo mineralization. However, the ages of the igneous rocks and Mo mineralization are poorly constrained. In this paper, we report precise in situ LA-ICP-MS zircon U–Pb dates for the monzogranite, granite porphyry, quartz porphyry, fine grained granite, rhyolite porphyry, diorite porphyry, and andesite porphyry in the Chalukou deposit, corresponding with ages of 162 ± 2 Ma, 149 ± 5 Ma, 148 ± 2 Ma, 148 ± 1 Ma, 137 ± 3 Ma, 133 ± 2 Ma, and 132 ± 2 Ma, respectively. Analyses of six molybdenite samples yielded a Re–Os isochron age of 148 ± 1 Ma. These data indicate that the sequence of the magmatic activity in the Chalukou deposit ranges from Jurassic volcano-sedimentary rocks and monzogranite, through late Jurassic granite porphyry, quartz porphyry, and fine-grained granite, to early Cretaceous rhyolite porphyry, diorite porphyry, and andesite porphyry. The Chalukou porphyry Mo deposit was formed in the late Jurassic, and occurred in a transitional tectonic setting from compression to extension caused by subduction of the Paleo-Pacific oceanic plate.     

Indium in cassiterite and ores of tin deposits

The results obtained with LA-ICP-MS by less abundant lighter ¹¹³In isotope and EPMA show that in cassiterite of cassiterite–quartz veins the indium contents do not exceed 160 ppm, while cassiterite from Sn–sulfide veins is characterized by higher indium contents from 40 to 485 ppm; sulfides of Sn–sulfide veins unlike sulfides of cassiterite–quartz veins also have the highest indium contents: Fe-sphalerite (100–25,000 ppm), chalcopyrite (up to 1000 ppm), and stannite (up to 60,000 ppm). Indium contents in the Sn–sulfide ore of the Tigrinoe and Pravourmiiskoe deposits obtained using SR-XRF, ICP-MS and atomic absorption methods range from 10 to 433 ppm with average values of 56–65 ppm. Indium-rich Sn–sulfide mineralization in five large Sn–Ag ore districts of the Far East Russia (Khingansky, Badzhalsky, Komsomolsky, Arminsky, Kavalerovsky) provides the impetus for further exploration of deposits with Sn–sulfide mineralization as the most promising indium resources in Russia. Empirical observations from geology and geochronology of cassiterite–quartz and Sn–sulfide mineralization show that the combined contribution from granite and alkaline–subalkaline mafic sources and multistage ore-forming processes doubled indium resources of deposits being the main factors in the formation of high grade indium mineralization.     

Petrogenesis of ore-bearing porphyry from the Tangjiaping porphyry Mo deposit,Dabie orogen: Zircon U-Pb geochronology,geochemistry and Sr-Nd-Hf isotopic constraints

Extensive Early Cretaceous post-collisional igneous rocks, especially the large volume of granitoids developed in the Dabie orogen. Some of these granitic rocks are spatially, temporally, and genetically associated with economically important molybdenum deposits. The Tangjiaping large-scale (> 0.1 million ton) porphyry Mo deposit is located in the northwest of the Northern Dabie Complex unit. The Mo mineralization is mainly hosted in molybdenite-bearing quartz veinlets and stockworks in the Tangjiaping granite porphyry, which intruded into Proterozoic biotite-plagioclase gneiss and amphibole-plagioclase gneiss. Two alteration zones from the porphyry centre outwards and downwards can be recognized: (1) K-silicate alteration-silicification zone; (2) silicification-phyllic alteration zone. The Tangjiaping ore-bearing granite porphyry occurs as an individual stock with an outcrop of 0.4 km². LA-ICP-MS zircon U-Pb dating of the Tangjiaping granite porphyry yields crystallization age of 115 ± 1 Ma, which is consistent with the molybdenite Re-Os age of the deposit given by previous studies. The Tangjiaping granitic rocks are metaluminous and belong to high-K calc-alkaline and shoshonitic series. They are relatively enriched in light rare earth elements and have moderately negative Eu anomalies. Geochemical and mineralogical characteristics indicate that the Tangjiaping granite is an A-type granite and was generated by partial melting of intermediate-felsic rocks at pressures of ca. 0.4–0.8 GPa. There are high initial ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.707367 to 0.709410 and negative ε_Nd(t) values varying from − 15.0 to − 14.2 for the Tangjiaping granite. In situ zircon Hf isotopic analyses show that the ε_Hf(t) values of zircons from the Tangjiaping granite porphyry vary from − 17.0 to − 6.0. The geochemical data and Sr-Nd-Hf isotopes, coupled with the Neoproterozoic inherited zircon age (652 ± 21 Ma), indicate that the Tangjiaping granite porphyry was most likely derived from partial melting of the Northern Dabie gneiss with some relatively enriched mantle materials involved. The Tangjiaping Mo ore-forming granite porphyry was formed in an extensional setting. The Early Cretaceous asthenospheric upwelling might have played an important role in the formation of the approximately coeval Mo-bearing magmas in the Dabie orogen.     

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.     

Geochronology and geochemistry of the Wunugetushan porphyry Cu–Mo deposit in NE china,and their geological significance

The Wunugetushan porphyry Cu–Mo deposit is located in the Manzhouli district of NE China, on the southern margin of the Mesozoic Mongol–Okhotsk Orogenic Belt. Concentric rings of hydrothermal alteration and Cu–Mo mineralization surround an Early–Middle Jurassic monzogranitic porphyry. The Cu–Mo mineralization is clearly related to the quartz–potassic and quartz–sericite alteration. Molybdenite Re–Os and groundmass ⁴⁰Ar/³⁹Ar of the host porphyry dates indicate that the ore-formation and porphyry-emplacement occurred at 177.6 ± 4.5 Ma and 179.0 ± 1.9 Ma, respectively. Geochemically, the host porphyry of the deposit is characterized by strong LREE/HREE fractionation, enrichment in LILE, Ba, Rb, U, Th and Pb, and depletion of HFSE, Nb, Ta, Ti and HREE. The Sr–Nd–Pb isotopic compositions of the porphyry display an varied initial (⁸⁷Sr/⁸⁶Sr)_i ratio, a positive ε_Nd(t) values and high ²⁰⁶Pb/²⁰⁴Pb_t, ²⁰⁷Pb/²⁰⁴Pb_t and ²⁰⁸Pb/²⁰⁴Pb_t ratios. These data indicate that the magmatic source of the host porphyry comprised two end-members: lithospheric mantle metasomatized by fluids derived from the subducted slab; and continental crust. We infer that the primitive magma of the host porphyry was derived from crust–mantle transition zone. Based on regional geology and geochemistry of the host porphyry, the Wunugetushan deposit is suggested to form in a continental collision environment after closure of the Mongol–Okhotsk Ocean.     

Geology,geochronology and geochemistry of granitic intrusions and the related ores at the Hongshan Cu-polymetallic deposit: Insights into the Late Cretaceous post-collisional porphyry-related mineralization systems in the southern Yidun arc,SW China

The Hongshan Cu-polymetallic deposit is located in the southern Yidun arc in southwestern China, where both subduction-related (Late Triassic) and post-collisional (Late Cretaceous) porphyry–skarn–epithermal mineralization systems have been previously recognized. In this study, two distinct magmatic events, represented by diorite porphyry and quartz monzonite porphyry, have been revealed in the Hongshan deposit, with zircon SHRIMP U–Pb ages of 214 ± 2 Ma and 73.4 ± 0.7 Ma, respectively. The 73 Ma age is comparable to the Re–Os ages of 77 to 80 Ma of ore minerals from the Hongshan deposit, indicating that the mineralization is related to the Late Cretaceous quartz monzonite porphyries rather than Late Triassic diorite porphyries. The Late Triassic diorite porphyries belong to the high-K calc-alkaline series and show arc magmatic geochemical characteristics such as enrichment in Rb, Ba, Th and U and depletion in HFSEs, indicating that they were formed during the westward subduction of the Garzê–Litang Ocean. In contrast, the Late Cretaceous quartz monzonite porphyries show shoshonitic I-type geochemical characteristics, with high SiO₂, K₂O, LILE, low HREE, Y and Yb contents, and high LREE/HREE and La/Yb ratios. These geochemical characteristics, together with the Sr–Nd–Pb isotopic compositions (average (⁸⁷Sr/⁸⁶Sr)_i = 0.7085; ε_Nd(t) = − 6.0; ²⁰⁶Pb/²⁰⁴Pb = 19.064, ²⁰⁷Pb/²⁰⁴Pb = 15.738, ²⁰⁸Pb/²⁰⁴Pb = 39.733) suggest that the quartz monzonite porphyries originated from the partial melting of the ancient lower crust in response to underplating of mafic magma from subduction metasomatized mantle lithosphere, possibly triggered by regional extension in the post-collisional tectonic stage. The S isotopic compositions (δ³⁴S_V-CDT = 3.81‰ to 5.80‰) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.014 to 18.809, ²⁰⁷Pb/²⁰⁴Pb = 15.550 to 15.785, and ²⁰⁸Pb/²⁰⁴Pb = 38.057 to 39.468) of ore sulfides indicate that the sulfur and metals were derived from mixed mantle and crustal sources. It is proposed that although the Late Triassic magmatic event is not directly related to mineralization, it contributed to the Late Cretaceous mineralization system through the storage of large amounts of sulfur and metals as well as water in the cumulate zone in the mantle lithosphere through subduction metasomatism. Re-melting of the mantle lithosphere including the hydrous cumulate zone and ancient lower crust during the post-collisional stage produced fertile magmas, which ascended to shallow depths to form quartz monzonite porphyries. Hydrothermal fluids released from the intrusions resulted in porphyry-type Mo–Cu ores in and near the intrusions, skarn-type Cu–Mo ores in the country rocks above the intrusions, and hydrothermal Pb–Zn ores in the periphery.