Genesis of the Shangjinshan W–Mo polymetallic deposit in the Eastern Jiangnan tungsten belt: Evidences from geochemistry, geochronology and zircon Hf isotope analyses

Journal Pre-proofs Genesis of the Shangjinshan W–Mo polymetallic deposit in the Eastern Jiangnan tungsten belt: Evidences from geochemistry, geochronology and zircon Hf isotope analyses Cheng Tang, Xiaoyong Yang, Jingya Cao PII: DOI: Reference:

S0169-1368(18)31002-3 https://doi.org/10.1016/j.oregeorev.2019.103172 OREGEO 103172

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Ore Geology Reviews

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4 December 2018 28 August 2019 9 October 2019

Please cite this article as: C. Tang, X. Yang, J. Cao, Genesis of the Shangjinshan W–Mo polymetallic deposit in the Eastern Jiangnan tungsten belt: Evidences from geochemistry, geochronology and zircon Hf isotope analyses, Ore Geology Reviews (2019), doi: https://doi.org/10.1016/j.oregeorev.2019.103172

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Genesis of the Shangjinshan W–Mo polymetallic deposit in the Eastern Jiangnan tungsten belt: Evidences from geochemistry, geochronology and zircon Hf isotope analyses Cheng Tang1,2, Xiaoyong Yang1, 2*, Jingya Cao3 *

1. CAS Key laboratory of Crust–Mantle Materials and Environments, University of Science and Technology of China, Hefei 230026, China 2. CAS Center for Excellence in Comparative Planetology, University of Science and Technology of China, Hefei 230026, China 3. Geological Survey of Anhui Province, Hefei 230001 China Email addresses of corresponding authors: [email protected] (X.Y., Yang); [email protected] (J.Y., Cao)

Abstract The newly discovered Shangjinshan W‒Mo polymetallic deposit, located at the southern Anhui, southeast China, is a large-scale skarn-type tungsten polymetallic deposit. According to mineral assemblages, ore textures/structures and superposition relationships of the mineralization, three ore types have been recognized: veinletdisseminated skarn (the primary type), quartz vein type and porphyry type. The mineralized event of this deposit could be divided into four stages: (I) the prograde skarn stage, (II) retrograde skarn stage, (III) quartz-sulfide vein stage, and (IV) quartzcalcite vein stage. The intrusion in the tungsten-rich district of the Shangjinshan is mainly composed of the granodiorite with zircon U–Pb ages of 138.4 ± 1.2 Ma to 136.7 ± 1.3 Ma. Meanwhile, Re‒Os isotopic dating of five molybdenite samples yields an isochron age of 141.9 ± 3.1 Ma and a weighted average age of 139.3 ± 1.7 Ma,

respectively. The ore-forming ages are consistent with the rock-forming ages within errors, indicating that the W-Mo mineralization is genetically related to the Shangjinshan granodiorite. The granodiorite is I-type granites, characterized by metaluminous to slightly peraluminous and high-K cal-alkaline compositions. They are also enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depleted in high field strength elements (HFSEs) and heavy rare earth element (HREEs), with obviously negative Eu anomalies (Eu/Eu* = 0.50–0.84). The zircon εHf (t) values and two-stage Hf model ages (TDM2) fall into the range ‒6.18 to ‒2.04 and 1.3‒1.5 Ga, respectively. The relatively low rhenium contents in molybdenite and high radioactive Pb isotopes of the pyrites from stage II indicate that the oreforming material was derived from Shangjinshan granitic magmatism. Together with previously published data, we propose that the W-related granitoids in the JNB were likely generated by partial melting of the Shangxi Group with some additional mantle materials. The granitic magmatism was caused by the asthenosphere upwelling, triggered by the roll-back of subduced Paleo-Pacific plate during Late Jurassic to Early Cretaceous. These granitic stocks predominately contributed to the production of skarn alteration and mineralization, resulting in the giant tungsten polymetallic district in the Jiangnan tungsten belt.

Keywords: Zircon U‒Pb dating; Molybdenite Re‒Os dating; Hf isotope; granodiorite; Shangjinshan W‒Mo deposit; Jiangnan tungsten belt；South China

1.

Introduction Tungsten (W), one of the important rare metal, is widely used in modern

industrialization. As the main W-bearing minerals, scheelite and wolframite commonly occur in these tungsten deposits, including the skarn-, quartz vein-, and porphyry-type deposits (Allen and Folinsbee 1944; Xu 1957; Noble et al. 1984; Liu and Ma 1987; Zhang et al. 1990; Uspensky et al. 1998; Peng, et al. 2003; Wang et al. 2008). As one type of the most important tungsten deposits, skarn-type scheelite deposits supply over 70% of the global tungsten resources with high grades and large tonnages, and they are genetically related to the felsic granitic rocks (Blusson, 1968; Einaudi et al., 1981; Atkinson, 1984; Bowman et al., 1985; Bi, 1987; Meinert, 1992; Newberry, 1998; Rasmussen et al., 2011; Mao et al., 2015a; Jiang et al., 2016; Guo et al., 2016). These W-related granitic rocks can form either by partial melting of meta-igneous and metasedimentary supracrustal materials or by the fractional crystallization of mafic parent magma (Annen et al., 2006), and could be any types, such as I-type (Mao et al., 2017), S-type (Mao et al., 2015; Yokart et al., 2003), A-type (Breiter, 2012) and I-S transformation type (Guo et al., 2012). Some authors argued that the granitic melts sourced from the W-enriched rocks are one of the key factors leading to the W mineralization (Kwak, 1987; Heinrich, 1990). Source accumulation is necessary requirements for the formation of W mineralization, which was proposed by Romer and Kroner (2016). Although some early interpretations stressed role of the subducted slab or mantle, it became increasingly obvious that tungsten mineralization related igneous rocks is derived from the melting of crustal rocks (e.g., Štemprok, 1995; Sato, 2012; Mao et al., 2013a, Romer and Kroner, 2015). Consequently, the role of types, sources and petrogenesis of granitic rocks, as well as their relationship with scheelite

mineralization are the key factors in studying the W-related deposits. South China, well-known for the most abundant tungsten deposits in the world, hosts around 45% of the world’s known resources (Wang et al., 2011a; Chen et al., 2012; Mao et al., 2013b, 2015; Xiang et al., 2013, 2015; Tang et al., 2014a; Tang et al., 2014b; Chen et al., 2015a; Chen et al., 2015b; Mao et al., 2017; Su et al., 2018). The tungsten deposits in the South China constitute two world-class tungsten belts: the Nanling tungsten belt (Hu and Zhou, 2012; Mao et al., 2013a; Yuan et al., 2015b; Cheng et al., 2016) and the Jiangnan porphyry-skarn tungsten belt (JNB) (Mao et al., 2013a; Mao et al., 2017; Su et al., 2018). The Jiangnan porphyry-skarn tungsten belt can be divided into two sub-regions including south of the Anhui province and northeast of the Jiangxi province. More than eight giant to large tungsten polymetallic ore deposits are found in the belt, e.g., the giant Zhuxi W‒Cu‒Mo deposit, Dahutang W‒Mo deposit and Yangchuling W‒Mo (Table 1 and Fig. 1). The credible tungsten resource of this belt is estimated to ca. 4 million tons of WO3 (Chen et al., 2012, 2015b; Mao et al., 2013b, 2015; Xiang et al., 2013; Huang and Jiang, 2014; Wang et al., 2013b; Chen et al., 2015a; Mao et al., 2017; Su et al., 2018). The discovery of these deposits with large reserves has greatly increased the W reserves in China. Although a lot of studies have been carried out on the porphyry-skarn scheelite deposits in northeast of the Jiangxi province (e.g., Pan et al., 2017; Song et al., 2018; Mao et al., 2013b; Huang and Jiang, 2014; Mao et al., 2017), little attention has been paid to these deposits in the south of the Anhui province. The Shangjinshan tungsten-polymetallic deposit, located in the south of the Anhui province, was discovered by the Geophysical Survey Team of East China Metallurgical Bureau of Geological Exploration in 2014, and the estimated resource was reported to be 54,000 tons of WO3 (average grade of 0.284%), 9,000 tons of

molybdenum and 30 tons of silver (GSTMBGE, 2014) (Fig. 1). As a newly discovered large-scale tungsten deposit, the basic geological characteristics have not been well studied. Furthermore, the age, magma source of the Shangjinshan granodiorite are still unclear. Moreover, the mineralization age and its relation to the granodiorite are poorly understood. Therefore, we report precise zircon U‒Pb ages and Hf isotopes, whole-rock geochemical compositions, molybdenite Re‒Os isotopic compositions and sulfide Pb isotopic compositions, aiming to constrain: (1) the rock- and ore-forming ages; (2) the petrogenesis and sources of the ore-related granodiorite; (3) the relationship between the granodiorite and tungsten mineralization; (4) the probably tectonic setting of magmatism and W–Mo mineralization.

2. Geological setting 2.1 Regional geological background The Jiangnan Tungsten belt (JNB), on the southeastern margin of the Yangtze Block, mainly includes the Jiangnan Massif and its eastward extension region (Mao et al., 2017). The northern boundary of the JNB is composed of a series of NE faults dominated by the Yangxing-Changzhou fault zones (Mao et al., 2017), which separates it from the Middle-Lower Yangtze River Valley porphyry-skarn Cu‒Au‒Mo‒Fe belt (YRB) to the north, whereas the southern boundary of the belt is dominated by the NE trending Jiangshao ductile shear zone (Hu, 2001), which is also the boundary between the Yangtze Block in the northwest and the Cathaysia Block in the southeast. The eastern region of the Jiangnan Massif and its adjacent area are mainly underlain by the basement rocks of Neoproterozoic Shuangqiaoshan Group (Jixiannian) in the northeastern Jiangxi Province, Xikou Group (Jixiannian), Likou Group

(Qingbaikouan) and Xiuning (Nanhua) to Nantuo (Sinian) Formations in the southern Anhui province (Huang et al., 2003; Xue et al., 2010a; Ding, 2012; Fan et al., 2016). The Shuangqiaoshan Group is equivalent to the Xikou Group and composed of phyllites, slates and metasandstones intercalated with minor meta-volcanoclastic rocks (BGMRJX, 1984; Wang et al., 2007a; Wang et al., 2007b; Fan et al., 2016). Previous studies indicated that the Shangxi Group (Shuagnqiaoshan Group and Xikou Group) was likely formed at 830–880 Ma and underwent low-grade metamorphism with high concentrations of tungsten, tin, silver, and zinc (Gao et al., 2008; Wang et al., 2008; Zhao et al., 2011; Ding, 2012). The Likou Group which unconformably overlies the Xikou Group and mainly includes metamorphic rocks (Xue et al., 2010b), and the latest Neoproterterozoic Xiuning to Nantuo Formations unconformably overlie the Likou Group with the sandstone siltstone, grained sandstone, siltstone, calcareous sandstone and manganese bearing sandstone. The overlying Phanerozoic sequence in the eastern JNB including Silurian to Middle Triassic marine clastic rock, mudstone, carbonate rocks, and siliceous rock, and Later Triassic to Early Jurassic paralic clastic rocks. Middle or Late Jurassic to Cretaceous terrestrial sedimentary and volcanic rocks, which unconformably overlie the Early Jurassic paralic clastic rocks (Ding, 2012; Xue et al., 2010b) (Fig. 1). The tectonic framework is characterized by a group of EW- and NE-trending structures, which were mostly formed during the Indosinian and Yanshanian orogeny during the early to middle Triassic and the Late Triassic to late Cretaceous, respectively (Zhou et al., 2015; Jiang et al., 2016). These structures caused by the orogeny had controlled the emplacement of Mesozoic granites and the related deposits (Mao et al., 2017; Song et al., 2012; Su et al., 2018). The foundational faults are widespread in this region, e.g., the Gaotan fault, Jiangnan fault, Ningguo-Jixi fault, Zhouwang fault, and

Qimeng-Qiankou fault. The folds in this area are mainly composed of large anticlinorium (Qidu-Hengbailing and Ningguo-Jixi) and synclinorium (Guichi and Taiping). A significant number of granitic plutons outcrop in this region and occupy an area of approximately 6000 km2 during the Jinningian and Yanshanian periods (Fig.1; Xie et al., 2016). The Jinningian intrusions (850–785 Ma), including Xucun, Xiuning, Shexian Lingshan, Lianhuashan and Shiershan, are mostly composed of granodiorite, granite porphyry and moyite (Appendix Table A4; Xue et al., 2010b; Wang et al., 2014; Jiang et al., 2016). Based on the rock compositions and precise ages, these Yanshanian granitic rocks in the JNB can be sub-divided into two groups: 155–135 Ma (group I) and 135–124 Ma (group II) (Fig. 1; Xue et al., 2009a; Wu et al., 2012; Su et al., 2013). Group I is mainly composed of hornblende-bearing I-type granodiorite and monzogranite peraluminous-metaluminous and high-K calc-alkaline granite (Huang and Jiang, 2012, 2013; Mao et al., 2015; Qin et al., 2010a; Qin et al., 2010b; Song et al., 2012; Wang et al., 2015), whereas group II mainly consists of peraluminous A- and S-type monzonitic granites and syenites (Wu et al., 2002; Zhou et al., 2008). These granites of Group I are genetically associated with porphyry and porphyry-skarn W– Cu–Mo deposits, forming the Jiangnan porphyry-skarn W metallogenic belt, such as Dahutang, Zhuxi, Yangchuling, Xiaoyao, and Zhuxiling (Mao et al., 2017). However, granites of Group II are associated with the formation of Mo–Pb–Zn deposits, such as Guilinzheng and Jianfengpo (Xu et al., 2015; Chen, 2016). 2.2 Geology of the ore deposit The Shangjinshan W–Mo deposit is one of the large-scale tungsten polymetallic deposits that was discovered in south Anhui province recently. The stratigraphic sequence outcropped in this deposit mainly comprise the Early Neoproterozoic Xiuning

and Nantuo Formations (Fig. 2a). The Xiuning Formation consists of feldspathic– quartz–sandstone siltstone, fine-grained sandstone, siltstone, calcareous sandstone and manganese bearing sandstones. The pebbly sandstone, gravel-bearing siltstone and conglomeratic tuffaceous sandstone of the Nantuo Formation occur as an unconformable contact with the Xiuning Formation. In addition, the most important structures are the Shangjinshan syncline and NE-trending fault (F2), which control the shape and location of orebodies (Fig. 2b). The fault (F2) is the post-metallogenic structure which destroyed the ore-bodies in the northern boundary. The Shangjinshan syncline core is the Nantuo Formation and both limbs are the Xiuning Formation in the central position of the deposit, which is the main the ore-hosting structure, and most of the ore bodies occur in the NW-wing of the Shangjinshan syncline (Fig. 2b and 2c). The granitic intrusion in the Shangjinshan deposit is exposed in the northwest and southwest parts of the mining area (Fig. 2a), and buries at the core of the Shangjinshan syncline (Fig. 2b). This granitic rock is composed of plagioclase (50–55%), K-feldspar (10–15%), quartz (20–25%), biotite and hornblende (5–10%) with medium to finegrained typical granitic texture and massive structure (Fig. 3a–3c). The accessory minerals are apatite, zircon, rutile, and titanite. This rock is generally characterized by potassic (K-feldspar and biotite) alteration, sericitization, and silicification (Fig. 3a–3c). Three types of ore bodies have been identified in the deposit, based on styles of mineralization, which are skarn- (Fig. 3d and 3f), quartz vein- (Fig. 3h, 3i, 3k, and 3l), and porphyry-type (Fig. 3e). However, the skarn-type ore bodies are dominated which account for more than 90% of the total tungsten resource. These ore bodies are mostly bed-like or lenticular in shape, occurring in the calcareous sandstone of the Xiuning Formation in the external contact zone of the buried granodiorite (Fig. 2a–2c). The ore bodies exhibit a generally NNE-trending and NW-dipping, with tens of meters in

thickness and 450 to 1000 meters in length. Furthermore, some Mo-bearing ore bodies occur in the fissures of the Nantuo formation. The main economic ore mineral is scheelite (Fig. 3d–3l, 4b–4d). The scheelite generally occurs as grains disseminated in the skarn (Fig. 3d and 3f), quartz vein (Fig. 3j, 3k, 3l), and granodiorite (Fig. 3e), and the grain size of the scheelite is generally 0.1–0.5 mm (Fig. 3e–3g). The associated minerals of scheelite are mainly molybdenite, chalcopyrite, pyrite, sphalerite, galena, epidote, diopside, tremolite, actinolite, chlorite, quartz and calcite (Fig. 3d–3l, 4a–4d and 4g–4j). These macro- and micro-textures show that skarn formation at Shangjinshan was similar to other tungsten skarns in the word (Einaudi, 1981; Newberry, 1982, 1998; Meinert, 1992, Singoyi and Zaw, 2001). Based on the mineral assemblages, ore textures/structures and superposition relationships of the mineralization, four main stages of skarn formation and ore deposition have been identified: (I) the prograde skarn stage, (II) retrograde skarn stage, (III) quartz-sulfide vein stage, and (IV) quartz-calcite vein stage. The paragenetic association of minerals of the four stages is comprehensively described as follows, and their paragenetic sequence is shown in Fig. 5. (I) The prograde skarn stage is characterized by the precipitation of large amounts of anhydrous minerals, e.g., garnet and diopside, which occur mainly in the banded skarn (Fig.3d, 4a, and 4c). In this stage, weak tungsten mineralization was developed with the skarn. The garnets are generally fine to coarse-grained and euhedral to hypidiomorphic (Fig. 4a and 4c), and commonly intergrowth with diopsides (Fig. 4b and 4c). The diopsides are generally pale blue to dark blue in color and occur as finegrained (0.1–0.2 mm) euhedral to hypidiomorphic minerals (Fig. 4b and 4c). They are always overprinted along the rims by chlorite and epidote (Fig. 4b and 4c). The scheelite in this stage generally occurs as dissemination in the garnet skarn (Fig, 3a and

3j). (II) The retrograde skarn stage mainly consists of hydrous minerals, such as epidote, chlorite, quartz, and scheelite, rarely tremolite and actinolite (Fig.4c–4f). The minerals of this stage pervasively or diffusively replaced the earlier prograde skarn minerals including diopside, garnet and the calcareous minerals in the sandstone. The epidote occurs as euhedral to hypidiomorphic grains with variable lengths from 0.05 to 2 mm (Fig. 4c and 4d). The scheelite generally is hypidiomorphic to anhedral crystals with the grain sizes generally 0.2–0.5 mm, and commonly occurs as disseminated, massive aggregates, along with fractures or veins with epidote and chlorite (Fig.4c and 4d). In addition, subordinately metallic minerals are produced at this stage, such as molybdenite, pyrite, chalcopyrite and pyrrhotine (Fig.3g, 4h–4l). (III) The mineral assemblage of the quartz-sulfide stage mainly consists of scheelite-molybdenite-pyrrhotite-chalcopyrite-calcite-quartz

(Fig.3h–3k).

Typical

features are the scheelite and sulfide-rich veins were intruded into the earlier scheelitebearing skarn ores (Fig. 3h–3k). In this stage, the size of the scheelite grains is large (0.5–1.5 mm), with the allotriomorphic granular texture (Fig. 4g). The metallic minerals appear as disseminated granules and are intergrowth with scheelite in the veins, such as molybdenite, pyrrhotite, and chalcopyrite (Fig.3h–3k). (IV) The quartz-calcite vein stage is mainly represented by calcite ± quartz veins crosscut the earlier scheelite skarn and quartz–scheelite vein (Fig. 3l). These veins can fill in the skarn, wall rock, and granites. The above four stages generally represent the evolution process of alteration and mineralization in this deposit. Because of the complexity of hydrothermal fluids, the stages are not completely isolated and are likely to overlap in timing.

3. Sampling and analytical methods 3.1 Sampling Based on the detailed field investigation, a series of granodiorite were collected from the drill cores, with the aim of conducting major and trace element analyses, zircon geochronology, and zircon Hf isotopic measurement. Five molybdenite samples were also separated from the ores for Re–Os isotopic dating. In addition, pyrite of stage II was also chosen for the in–situ Pb isotopic analyses. All the samples are fresh and the sampling positions, mineralogical and petrographic features of samples are also summarized in Table 2.

3.2 Whole-rock major and trace element analyses Whole-rock major and trace elements were analyzed at the ALS Global Analytical Company, Guangzhou, China. Fresh samples were crushed to B200 mesh using an agate. Major elements were determined using X-ray fluorescence (XRF) spectrometry (Norrish and Chappell, 1977). Ratios of ferric and ferrous iron were determined by wet chemical methods. Trace elements, including rare earth elements (REE), were determined by inductively coupled plasma mass spectrometry (ICP–MS) with a Finnegan MAT Element II mass spectrometer. Details of the analytical method used are described by Dulski (1994). Dissolved samples then were diluted to 80 g with 2% HNO3 prior to the analysis. The analytical precision was generally better than 5% (2σ).

3.3 Zircon U–Pb geochronology Zircon grains were separated from granodiorite samples and then identified by handpicking under a binocular microscope, mounted in epoxy resin and polished to expose the interior surface. The transmitted and reflected light images of the zircon

grains were photographed, and cathodoluminescence (CL) images of the zircons were taken using micro-probe JEOL JXA–8100 electron microanalyses to select the U–Pb dating points at CAS Key Laboratory of Crust-Mantle Materials and Environments in University of Science and Technology of China, Hefei. The U–Pb isotopic composition of zircons were analyzed by an Agilent 7500a ICP–MS coupled with a Resonetic Resolution 50-M ArF-Excimer laser source (λ = 193 nm) at CAS Key Laboratory of Crust-Mantle Materials and Environments in University of Science and Technology of China. Detailed operating conditions for the laser ablation system and the ICP–MS instrument and data reduction were outlined by Tu et al. (2011). Laser ablation was accomplished at constant energy of 70 mJ, with a repetition rate of 10 Hz and a spot diameter of 32 μm. During the analyses, the standard silicate glass NIST (610, 612 and 614) was used to optimize the system. 91500 zircons and NIST SRM 610 glass were used as external calibration standards for U–Pb dating and trace element analysis, respectively, and

29Si

are used as the internal standard. The standard operating

procedures have been described in detail by Li et al. (2015c). Off-line selection and integration of background and analytical signals, and time-drift correction and quantitative calibration for trace element analyses and U–Pb dating were performed by ICPMSDataCal 9.6 (Liu et al., 2008, 2010). The uncertainties for individual analyses are quoted at the 1σ level, whereas the errors in the Concordia and weighted mean ages are quoted at the 2σ level. The data quality was monitored by the 91500 standard (Wiedenbeck et al., 1995: ca. 1062.5 Ma). The weighted mean U–Pb ages (with 95% confidence) and concordant plots were processed using the ISOPLOT program (Ludwig, 2003). Common Pb was corrected according to the method proposed by Anderson (2002).

3.4 Zircon Hf isotope In-situ zircon Lu–Hf isotopic analyses were performed at the Key Laboratory for the study of focused Magmatism and Giant ore Deposits, MLR, in Xi'an Center of Geological Survey, China Geological Survey. Used a Nu-plasma multi-collector ICP– MS (MC–ICP–MS) coupled with a GeoLas 2005 193 nm ArF excimer laser. Sample sites for Lu–Hf isotope analyses were selected to use the same mounts as those used for U–Pb dating and data were collected over the U–Pb spots in most cases but, where this was not possible, the adjacent sites within the same CL domain were analyzed. The stationary laser ablation spot with a beam diameter and laser pulse frequency were 30 μm and 10 Hz, respectively. Details of the instrumental conditions and data acquisition procedures are similar to those described by Meng et al., (2014) and Hou et al. (2007). The isobaric superposition of 176Lu on 176Hf was corrected for by measuring the intensity of 175Lu and using the natural 176Lu on 175Hf ratio (1/40.02669; DeBievre and Taylor, 1993). 176Yb/172Yb was determined via analysis of a solution of the JMC475 Hf isotope standard sample, spiked with Yb (176Yb/172Yb = 0.58669) (Chu et al., 2002). The error for

176Hf/177Hf

measurements is estimated as ± 0.00002 (2σ), which is

equivalent to ± 0.7εHf. The reproducibility and accuracy of the analytical method have been discussed previously (Griffin et al., 2000, 2006, 2007). The mean measured 176Hf/177Hf

value of the standard was 0.282527 ± 28 (n = 10), which is within the

recommended 2σ interval of 0.282522 ± 42 (Griffin et al., 2007). Analysis of another international standard sample, Zircon GJ-1, yielded a

176Hf/177Hf

value of

0.282304 ± 42 (2σ), which is also within the recommended 2σ interval (Griffin et al., 2006, Griffin et al., 2007).

3.5 Molybdenite Re–Os dating

The samples for Re–Os dating were crushed in an agate mortar and then were handpicked under a binocular microscope to remove the impurities (purity >99%). All of the molybdenite crystals were fresh and not contaminated. The Re–Os isotope analysis was performed using an inductively coupled plasma-mass spectrometer (ICPMS) in the State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, China. The

185Re

spike, natural Os

standard solutions, and molybdenite samples were weighed and digested with the concentrated HNO3 for 24 h at 240 °C in sealed Carius tubes (Shirey and Walker, 1995). Os distilled as OsO4 from the supernatant was trapped using pure water and thus could be directly analyzed by ICP–MS (Sun et al. 2001, 2010). Re was determined by ICP– MS after separation and purification using anion exchange resin (AG1X8) (Sun et al. 2001, 2010). The correction of Re isotopic ratios in the sample-spike mixtures was based on the factors calculated from the average ratios on the bracketed standards relative to the International Union of Pure and Applied Chemistry (IUPAC) ratios (Rosman and Taylor 1998). Mass bias correction for Os was ascertained on-line in each operational procedure. The mass bias factor for normalization to

192Os/188Os

192Os/187Os

was obtained by

= 3.08271. A range of 2% for the correction factors has

been observed based on the results from the initial to final standard runs. Model ages were calculated using the equation: t = [ln (1+187Os/187Re)]/λ, where λ is the decay constant of

187Re

of 1.666×10−11 per year (Smoliar et al., 1996), and Re–Os isochron

age was calculated using ISOPLOT 3.0 (Ludwig 2003). Absolute uncertainties are given at the 2σ level (standard deviation). The molybdenite reference material of GBW04436 was repeatedly measured along with the samples. The Re–Os age of this reference material was 140.4 ± 2.3 Ma (2 s, n = 4). The result is consistent with certified values and the values previously reported by Du et al. (2004).

3.6 In-situ Pb isotope analyses In-situ lead isotopic analyses of different sulfides were conducted polished sections, using a Nu PlasmaTM multi-collector ICPMS with a femtosecond laser ablation system (Fla–MC–ICPMS) at the State Key Laboratory of Continental Dynamics, Northwest University, Xi’an, China. Argon and helium were used as the carrier gases for laser ablation. The Tl aerosol and the sample aerosol was mixed homogeneously in a glass container and then introduced into the ICP for atomization and ionization. During the analysis, the Faraday collector L4, L3, L2, L1, AX, H1, H2 were used to collect the ion beam 202Hg, 203Tl, 204Hg + 204Pb, 205Tl, 206Pb, 207Pb, 208Pb, respectively. Thallium was used to monitor and correct for instrumental mass discrimination, and 202Hg was to correct for the isobaric overlap of 204Hg on 204Pb. The time-resolved analysis (TRA) mode with an integration time of 0.2 s was employed to obtain Pb isotopic ratios, and laser ablation was performed in the line scan ablation mode at a speed of 5 μm/s. Each line scan analysis consisted of background collection for 40 s followed by an additional 50 s of ablation for signal collection and 40 s of wash time to reduce memory effects and to allow the instrument to stabilize after each gas addition. To ensure the stability of

208Pb

signal obtained from different samples with

disparate Pb concentrations, samples were ablated with laser line scans approximately 120 μm in length and 30–65 μm in width with adjustable laser frequency. NIST 610 was used as a quality control sample and was analyzed once for every five sample points. Detailed description of the measuring procedures is available in Yuan et al. (2015a).

4. Results 4.1 Whole-rock major and trace element compositions The whole-rock chemical compositions of the Shangjinshan granodiorites are

shown in Appendix Table A1. The granodiorite samples have variable contents of SiO2 (67.18–74.02 wt. %), Al2O3 (13.24–15.58 wt. %), MgO (0.30–1.03 wt. %), CaO (1.45– 3.13wt. %), Na2O (2.5–3.3 wt. %), and K2O (3.37–5.13 wt. %). The DI (differentiation index) values of 76.76–89.42. The alkali content ranges from 6.67–8.24%, showing characteristics of the sub-alkaline series. All the samples are plotted in the field of the high-K calc-alkaline series on the SiO2 versus K2O diagram of Peccerillo and Taylor (1976) (Fig. 6a). A/CNK values [molar Al2O3/ (CaO + Na2O + K2O)] are range from 0.99 to 1.1, indicating that they belong to metaluminous to slightly peraluminous granites (Fig. 6b). P2O5, TiO2, Fe2O3T, MgO, CaO, Al2O3, Sr, Ba, Zr and ∑REE contents of the samples show negative correlations with SiO2, whereas Na2O and K2O exhibit invariable trends (Fig. 7). These samples show relatively low contents of rare earth elements (REEs), with ∑REE contents of 89–133 ppm. They are also enriched in light rare earth elements (LREEs) and depleted in heavy rare earth elements (HREEs), with (La/Yb) N ratios of 8.95–17.89 and negative Eu anomalies of Eu/Eu* = 0.50–0.84 (mean=0.62) (Fig. 8a). In primitive mantle-normalized variation diagrams (Fig. 8b), the samples are characterized by enrichment of large ion lithophile elements (LILEs), eg. Rb, Th, U, and K, and depletion in high strength field elements (HFSEs), eg. Ba, Nb, and Ti.

4.2 Zircon U–Pb geochronology and trace elements The U–Pb isotopic data of zircon grains from granodiorite samples (ZK45-1, ZKN01-2, and ZKN21-1) are listed in Appendix Table A2. The typical zircon crystals in these three samples are shown in cathodoluminescence (CL) images (Fig. 9b). The zircon crystals are colorless and translucent to transparent, and the size is 100–200 μm in length and 70–100 μm in width. Most of the zircon crystals are subhedral, equant to

elongate prismatic grains, and exhibit a dark-colored core and a narrow light-colored magmatic rim in cathodoluminescence (CL) images. These cores are mostly rounded and oblong in shape, showing well-defined concentric oscillatory zoning. These cores are mostly rounded and oblong in shape, showing well-defined concentric oscillatory zoning. The contents of U and Th in zircon grains of ZK45-1, ZKN01-2, and ZKN21-1 are 938–5547 ppm and 437–6613 ppm, 1245–5177 ppm and 583–5176 ppm, 1146– 5804 ppm and 341–5195 ppm, respectively. Their Th/U ratios range from 0.21 to 1.27, 0.18 to 1.69, and 0.15 to 1.55, respectively (Appendix Table A1). Based on the above the morphologic and chemical characteristics of zircon grains, which can be indicated as the type of magmatic zircons (Schaltegger et al., 1999; Belousova et al., 2002; Hoskin, 2000; Rubatto, 2002; Fernando et al., 2003). However, one phenomenon should not be ignored that these zircons have relatively higher uranium content of 1245–5178ppm (mean=3441ppm, ZKN01-2), 1145–5803ppm (mean=3050 ppm, ZK02-1) and 938–5547ppm (mean=3624 ppm, ZK45-1) than the uranium content of the zircon grains from the ore–related granites in the JNB, e.g. Xiaoyao granodiorite (mean=417ppm, Su et al., 2018), Zuxiling granodiorite (mean=556ppm, Huang, 2017), Baizhangyan granodiorite (mean=402ppm, Qin et al., 2010a) and Dongyuan granodiorite (mean=905ppm, Zhou et al., 2011). Previous studies have indicated that zircons with higher uranium content ([U]) might not the best choice for U/Pb dating because of their greater discordance of 235U-207Pb and

238U-206Pb

schemes than zircons with lower [U] (White and Ireland, 2012 and

references therein). Additionally, the apparent age of zircon was usually affected by [U] of zircon when the age of zircon is measured by ion microprobe analysis, and the dating result will change in apparent U-Pb age at 1–3% per 1000 μg/g change for the

zircon with higher [U] over 2500 ppm (Williams and Hergt, 2000) and with the full spectrum of [U] from several hundred μg/g to approximately 20 thousand μg/g (White and Ireland, 2000). As shown in Appendix Table A3, most of the zircons of the Shangjinshan granodiorite have [U] higher than 2500 ppm. However, there were no apparent positive relationships between the [U] vs. the apparent U-Pb ages (Appendix Fig. 2). It is indicated that the ages had no positive correlation with the uranium content and were not affected by the higher uranium at all. Therefore, these ages can represent the crystallization ages of the granodiorite samples, respectively. The analyses of twenty-three, twenty-one, and eighteen zircon grains from the ZK45-1 (center mining section), ZKN01-2 (west mining section), and ZKN21-1 (west mining section) are all plotting in a small region near the Concordia line (Fig. 9a), and yield weighted average 206Pb/238U ages of 136.7 ± 1.3 Ma (MSWD = 0.51), 138.4 ± 1.2 Ma (MSWD = 0.97), and 137.1 ± 1.5Ma (MSWD = 0.77), respectively.

4.3 Lu–Hf isotopes Sixty-two Lu–Hf isotope determinations were carried out on zircon grains from these samples, and results are listed in Appendix Table A3. Representative analytical spots with results are shown in Fig. 9b. The low

176Lu/177Hf

ratios (mean = 0.0012;

<0.002) indicate that radioactive Hf production was negligible; therefore, the measured 176Hf/177Hf

ratios are potentially close to the initial ratios of the samples.

Zircon176Hf/177Hf ratios are relatively homogeneous, with values between 0.282512 and 0.282629, (mean = 0.282567). Corresponding εHf (t) values are negative and range from −6.14 to −2.00 (mean = −4.22). The Hf-depleted mantle model ages (TDM1 (Hf)) are between 878 and 1054 Ma, while the two-stage model ages (TDM2 (Hf)) range from

1318 to 1579 Ma.

4.4 Molybdenite Re–Os ages Results of Re–Os isotopic analyses of five molybdenite samples from the Shangjinshan tungsten polymetallic skarn deposit are listed in Table 3. The total Re and 187Os

contents of molybdenite vary from 1.42 to 5.86 ppm and 2.08 to 8.69 ppb,

respectively. The Re–Os model ages of the five samples were in a relatively narrow range, varying from 138.1 ± 0.6 Ma to141.4 ± 0.8 Ma, yielding a weighted mean age of 139.3 ± 1.7 Ma and an isochronal age of 141.9 ± 3.1 Ma, respectively (Fig. 10). Both the model age and the isochron age are nearly identical, illustrating the reliability of these analytical results. Combining with the 187Os values (2.08 to 8.69 ppb), we confirm that almost all the

187Os

in the molybdenite are radiogenic and that the molybdenite

contains no measurable common Os. This indicates that the model age of the molybdenite samples is nearly identical in the error range, illustrating the reliability of these analytical results. Therefore, the age 139.3 ± 1.7 Ma is interpreted as the age of the molybdenite crystallization during the formation of the Shangjinshan tungsten skarn deposit.

4.5. Pb isotopic compositions In-situ Pb isotopic compositions of the samples of sulfide minerals from the Shangjinshan deposit are listed in Table 4. Five pyrite samples from three polished sections of stage II scheelite + pyrite ore from the Shangjinshan deposit yielded 206Pb/204Pb

values of 18.022–18.264 with an average of 18.221,

15.444–15.634 with an average of 15.607, and

208Pb/204Pb

207Pb/204Pb

values of

values of 38.097–38.492

with an average of 38.443. On a 206Pb/204Pb versus 207Pb/204Pb diagram and 206Pb/204Pb

versus

208Pb/204Pb

(Fig. 13), data for the samples of sulfide minerals define a narrow

range.

5. Discussion

5.1 Geochronological framework It was proposed that the granitic melts could contain the diverse zircon populations, including xenocrysts (inherited from older host rocks or melt source regions), antecrysts (recycled from earlier batches of magma), and autocrysts (grown in final melts) (e.g., Hildreth, 2004; Bacon and Lowenstern, 2005; Miller et al., 2007). The zircon populations in a single sample can be recognized by the high precision U/Pb zircon dating (e.g., Brown and Fletcher, 1999; Charlier et al., 2005; Bindeman et al., 2006; Claiborne et al., 2006; Matzel et al., 2006b; Miller et al., 2007; Walker et al., 2007). Generally, xenocrysts have much older U–Pb ages than any known ages in a singer sample. They are commonly identified texturally by their different CL images responses compared with magmatic crystals and by their partial resorption (Miles and Woodcock, 2018). In contrast to xenocrysts, antecrysts and autocrysts may exhibit similar compositional and petrographic characteristics, despite having grown in distinct parts of the magma reservoir (Miller et al., 2007). A zircon crystal (ZKN21-1-06) yields a U–Pb age of 807.27 ± 16.42 Ma (Appendix Table 2, in italics, Fig. 9b, in red), much older than the rest of the crystals ages in the same samples, indicating an xcenocryst origin. It is noteworthy that the U–Pb ages of these zircon grains from Shangjisnhan granodiorite range from 142.7 ± 3.1 Ma to 132.2 ± 2.5 Ma, however, these ages have a cluster of 135–140 Ma (Fig. 9c). All of the zircon analyses within each sample yield ages that overlap within error (± 1 sigma), forming a normal distribution. These zircon

crystals show a continuous age in range and no discernable variation. We may, therefore suggest the zircon crystals are likely to be autocrysts, indicating that these ages of the crystals are the most reliable estimate for final emplacement ages of the melts. Combined with the similar composition in mineralogy and geochemistry of the granodiorite, and yield the same isotope ages within analytical errors, it is suggested that the Shangjisnhan granodiorite are contemporary and formed at about ca. 137 Ma. In addition, five molybdenite samples, collected from the skarn ores, have a relatively narrow range of Re–Os model ages, varying from 138.1 to 141.4 Ma (Table 3). These samples yielded a well-constrained isochronal age of 141.9 ± 3.1 Ma (MSWD = 7.7), with a weighted mean age of 139.3 ± 1.7 Ma (MSWD = 12). The zircon U–Pb ages of granodiorite correspond fairly well to the molybdenite Re–Os ages within the analytical errors, which suggests that emplacement of Shangjinshan granodiorite was one of the significant factors in the formation of the Shangjinshan W polymetallic deposit. A series of medium to large-size tungsten polymetallic deposits were exploited in the eastern Jiangnan Massif tungsten belt ， for example, the Baizhangyan skarn tungsten deposit with rock-forming age of 134 ± 2.6 Ma and ore-forming age of 134.1 ± 2.2 Ma (Song et.al, 2012), the Jitoushan W–Mo skarn deposit with rock-forming age of ca.138 Ma and ore-forming age of 136.6 ± 1.5 Ma (Song et.al, 2012), the Dongyuan porphyry tungsten deposit with rock-forming age of 148.6 ± 1.8 Ma (Qin et al., 2010b) and ore-forming age of 146.4 ± 2.3 Ma (Zhou et al., 2011b), the Zuxiling skarn tungsten deposit with rock-forming age of 140.2 ± 1.7 Ma and ore-forming age of 142.7 ± 2.1Ma (Huang, 2017), the Xiaoyao skarn tungsten deposit with rock-forming age of 149.4 ± 1.1 Ma and ore-forming age of 148.7 ± 2.5Ma (Su et.al, 2018), and the Dahutang porphyry tungsten deposit with rock-forming age of ca. 145Ma (Mao et al., 2015) and ore-forming age of 139.2 ± 1.0 Ma (Mao et al., 2013b). These systematic and precise

geochronological studies indicate the W polymetallic mineralization event is associated to the widespread emplacement of the magmatic activity (155–135 Ma) in the Jiangnan Massif tungsten belt (Appendix Table A4; Appendix Fig. 3). The Shangjinshan deposit is one of the mostly important products which were formed by the large-scale tungsten mineralization in this period.

5.2 Petrogenesis of the Shangjinshan granites 5.2.1 Geochemical affinities Previous studies have concluded that granitic rocks can be classified into I-, S-, M-, and A-types based on their respective geochemical signatures (Chappell and White, 1974; Collins et al., 1982; Pircher, 1983). The genetic type of magmatic rocks is critical for understanding magma source region, magmatic process, and tectonic setting (Barbarin, 1999). The Shangjinshan granodiorite has low Zr + Nb + Ce + Y contents and (K2O+Na2O)/CaO ratios, indicating that these granitoids are I- or S-types (Whalen et al., 1987; Fig. 6c). Furthermore, the appearance of hornblende and lacking muscovite and garnet indicate that the granodiorite is inconsistent with S-type granite (Chappell and White, 1974). On the contrary, the Shangjinshan granodiorite has high contents of CaO and Na2O, and low A/CNK ratios (mostly < 1.1, mean = 1.04, Fig. 6b), suggesting an I-type affinity (Chappell, 1999). In addition, the La (10.60–27.70 ppm) and Ce (22.00–61.80ppm) contents of the granodiorite are also consistent to those of the I-type granites (Chappell and White, 1992). This conclusion is further supported by the low P2O5 contents (0.05–0.17%) and the negative correlation between the SiO2 and P2O5 (Fig. 6d; Chappell and White, 1974; Chappell et al., 1998; Chappell and White, 2001). Therefore, we suggest that the granodiorite within the Shangjinshan deposit exhibit mainly I-type granites characteristics.

5.2.2 Fractional crystallization The differentiation index (DI) values of the granodiorite samples are within the range of 77–89, suggesting that they underwent a significant degree of fractional crystallization. The negative correlations of the SiO2 versus CaO and Al2O3 indicate that fractional crystallization of plagioclase and K-feldspar occurs during the magma evolution, which is supported by notable depletion in Sr and Ba, and Eu anomalies (Fig. 8). In addition, the negative correlations of Ba and Sr versus Eu are indicative of varying degrees of plagioclase and K-feldspar fractionation (Fig. 11a and 11b). Commonly, plagioclase fractionation will result in an increase in the Rb/Sr and Ba/Sr ratios, whereas the fractionation of K-feldspar will lead to a slight increase of Rb/Sr ratios and a decrease of Ba/Sr ratios (Bouseily and Sokkary, 1975). Therefore, the positive correlations between Rb/Sr and Ba/Sr show the trend of plagioclase fractionation (Fig. 11c). Bea et al., (1994) suggested the moderately negative correlation between Th and V may imply the fractional crystallization of the biotite which may result in the increase of the SiO2/Al2O3 ratios and the decrease of the V/Th ratios in residual melts. Therefore, the fractional crystallization of the biotite was confirmed by the negative correlations between V/Th and SiO2/Al2O3 ratios (Fig. 11d). Furthermore, the positive correlation between the Er and Dy may indicate the fractional crystallization of amphibole (Fig. 11e), which is proposed by the Drummond et al., (1996). The negative correlation between the total REE contents (∑REE) and SiO2 suggests the separation of accessory minerals with high partition coefficients of the REE (Fig. 7l), such as apatite, titanite, zircon, allanite, and monazite (Bea, 1996; Henderson, 1984). The positive relationship between (La/Yb)N and La may be caused by fractional crystallization of allanite and monazite (Fig. 11f; Mahood and Hildreth,1983; Yurimoto

et al., 1990). Therefore, fractional crystallization appears to play an important role in the formation of the Shangjinshan granodiorite.

5.2.3 Origin The genetic type of the granites associated with the W-bearing porphyry-skarn mineralization in the east Jiangnan Massif tungsten belt is mostly I-type (Fig. 6a). The origin of these granites are proposed to reflect the following: 1) partial melting of continental crust with additional mantle material (Zhou et al., 2004; Zhu et al., 2014; Xiang et al., 2015; Mao et al., 2017; Su et al., 2018); 2) partial melting of thickened region of Palaeoproterozoic to Mesoproterozoic lower crustal material (Su et al., 2013; Xie et al., 2017); 3) a crustal contamination in the fractional crystallization of basaltic magma (Song et al., 2012; Li et al., 2015a; Li et al., 2015b). As discussed above, the Shangjinshan granodiorite belongs to the high–K calc-alkaline series and has high SiO2 (ranging from 67.18 wt. % to 74.01 wt. %) and K2O (ranging from 3.37 wt. % to 5.13 wt. %), weakly peraluminous (A/CNK = 0.99–1.1, mostly ≤ 1.1), enrichment in some large-ion lithophile elements (LILEs), low Sr content (from 110 ppm to 282 ppm, mean = 191 ppm) and Sr/Y ratios (9.12 to 20.44, mean = 13.76), and depletion in high-fieldstrength elements (HFSEs), are consistent with the involvement of crustal components (Taylor and Mclennan, 1985, 1995). This suggestion is further proved by the Ce/Pb and Nb/Ta ratios, compared with the suggested Ce/Pb and Nb/Ta ratios of the depleted mantle (9, 17.5) and continental crust (4, 8–14) (Hofmann et al., 1986; Green, 1995; Stepanov and Hermann, 2013), the Ce/Pb and Nb/Ta ratios of the Shangjinshan granodiorites are within the range of 0.5–2.7 and 7–14, respectively, implying that they were likely originated from the crustal source. The Hf isotopic analyses in this study show that all of the sample zircons had low

Hf isotopic ratios and ancient Hf model ages, with εHf(t) values ranging from  −6.14 to −2.00 (mean = −4.22) and the corresponding Hf model ages of 1318–1579 Ma

(Appendix Table A3). In the εHf (t) versus T diagram (Fig. 12a), the three Shangjinshan granodiorites are primarily plotted along with the evolution array of the crust. In addition, the Hf isotopic compositions of the zircons from the Shangjinshan granodiorites were plotted in the evolution lines between the 1.8 Ga and 1.2 Ga. We simulate the evolution of εHf (t) values according to the Hf isotopic data of Neoproterozoic basement in JNB. The εHf (t) values of zircon grains from Neoproterozoic basement in JNB represent the whole rock εHf (t) values and evolve to 140 Ma at average crust

176Lu/177Hf

ratios (0.015). Finally, the εHf (t) values of

Neoproterozoic basement range from −11 to 3, consistent with granitoid in the JNB (Fig. 12a). Therefore, we suggest that the Neoproterozoic basement can be sources of granitoid in the JNB. The Shangxi Group is the widely dominant Neoproterozoic basement in the JNB, consisting mainly of tuffaceous sandstone, phyllite, tuff, slate, minor spilites and quartz-keratophyres (BGMRJX, 1984; Huang et al., 2003; Li and Li 2003; Wang et al., 2008). Previous studies showed that the Mesozoic granitic rocks were likely formed by directly melting of the metamorphic rocks of Shangxi Group (Chen et al., 1993; Huang and Jiang, 2014; Mao et al., 2017; Su et al., 2018; Pan et al., 2018). Subsequent studies emphasized that some component of mantle material were involved the generation of these granitic rocks (Xue et al., 2010b; Fan et al., 2016; Su et al., 2018). Moreover, the Nd isotopic compositions of granites associated with W- and Mo-mineralization in the JNB are within the range of Nd isotopic evolution envelop of the Shangxi Group rocks with εNd(t) values of –2.1 to –10.6 and the Nd model ages (TDM) of 1.1–1.9Ga (Ling et al., 1992; Ma and Xiang, 1993; Chen et al., 1993; Chen and Jahn, 1998; Li and

McCulloch, 1996; Zhang et al., 2000). The emergence of the Nd-isotopic TDM ages is consistent with the Hf model ages, indicating that the Shangxi Group rocks are a possible crustal source for those granitoid in the JNB. Furthermore, this conclusion is supported by the U–Pb zircon ages of abundant inherited zircons in these granitic rocks, which is consistent with the deposited age of the Shangxi Group (824Ma–880Ma; Wang et al., 2008; Gao et al., 2008). In addition, inherited zircons in the granodiorite record older magmatic event that occurred ca. 821–810Ma, e.g. Xiaoyao granite ( 810– 821Ma; Su et al., 2018), Zuxiling granite ( 810Ma; Chen et al., 2013), Dahutang granite (749–884; Huang and Jiang, 2014), Dongyuan granite (630–851; Zhou et al., 2015), Yangchuling granite (784–809; Mao et al., 2017) and Shangjinshan granite (807 Ma; Appendix Table A1). These ancient zircons from the early stage of granitic can be interpreted as xenocryst captured from the earlier stage of this magmatism and were derived from the basement rocks (Fig. 12a) (Mao et al., 2015). Therefore, it is suggested that the Neoproterozoic basement made a large contribution to the granitoid in the JNB. The Sr–Nd compositions of the granites can directly reflect their source features. Previous studies of the Nd isotopic composition, the higher εNd(t) and lower 87Sr/86Sr than the Sr–Nd isotopic compositions of the lower crust of the Neoproterozoic Shangxi Group can be found (Fig. 12b). This isotopic differences can be considered that the granites could not have been directly derived by partial melting of crustal material. Alternatively, the mantle material should be involved in the formation of the granites. Using the Nd isotopic composition, the proportion of the mantle component in the generation of the JNB granites can be estimated, and a simple two-component mixing model was adopted (Fig. 12b). EM was represented by the peridotite xenoliths hosted in Cenozoic Panshishan basalt (Chen et al., 1994). The Neoproterozoic basement was represented by the Shangxi low-grade metamorphic rocks and Neoproterozoic

magmatic rocks in the Yangtze Block with εNd(t) values of −8.75 (Chen et al., 2001). Most samples from the granites plot very close to the mixing lines of EM and Neoproterozoic basement. The modeling calculation results show that the crustal constituent (Neoproterozoic basement rocks) might account for more than 50%, (mostly between 80–90%), and additional mantle material is involved in the magma formation. This conclusion was supported by the occurrence of the mafic microgranular enclaves (MMEs) in the nearby Jingde granitic pluton (Zhang et al., 2012).

5.3 The relationship of the granitoid to tungsten mineralization The Shangjinshan deposit is a skarn W–Mo deposit dominated by scheelite and molybdenite. Several geological features as follows can genetically link Shangjinshan ore-forming materials to the granitic intrusion, and support that the ore-forming materials are mainly originated from a crustal source. Through the observation of drilling cores and petrological study, it is shown that the granodiorite intruding into calcareous strata mainly leads to the alteration and skarn-type mineralization, and the skarn assemblages include garnet diopside and garnet skarn (Fig. 2 and 4a – 4d). The skarn orebodies are distributed almost in the external contact zone of the granodiorite and the metasomatic calcareous sandstone, and the ore-rich resource site is controlled by the spatial shape of the granodiorite (Fig. 2). The degree of association between granodiorite and calcareous formations controls skarn and mineralization development (Fig. 2b). In addition, the Re–Os isochronal ages of molybdenite of 138.1 ± 0.6 Ma to 141.4 ± 0.8 Ma are consistent with the zircon 206Pb/238U age of the granodiorite. Thus, field observations and the ages of granodiorites and mineralized bodies clearly indicate that they are spatially and temporally associated with each other. Furthermore, the close relationship between the metallogenesis with magmatism is consistent with the

following geochemical characteristics. Firstly, In the

207Pb/204Pb

vs.

206Pb/204Pb

and 08Pb/204Pb vs.

206Pb/204Pb

diagrams

(Fig. 13a and 13b, Zartman and Doe, 1981), most of the lead isotopic ratios (206Pb/204Pb, 207Pb/204Pb,

and 208Pb/204Pb) of the pyrites are distributed in the area between the Upper

crust belt (or the Mantle belt) and the orogenic evolution line, and the presence of orogenic Pb is indicative of a short-lived environment, and is considered to result from mixing of crustal- and mantle-derived Pb. These observations suggest that the Pb in the sulfides was derived primarily from a crustal, and with some mantle contamination. In addition, these sulfides are characterized by moderate radiogenic Pb isotopes and medium μ values ranging from 9.37 to 9.55, thus further implying that the Pb has a mixing source involving both the crust (average μ at 9.58) and mantle (μ = 8–9; Doe and Zartman, 1979). Furthermore, the lead isotopic ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb)

are broadly consistent with those of the JNB granite and the sulfides

associated with granite in the JNB (Fig 13a and 13b). This similarity suggests that Pb in the granitoid and Pb in sulfide ores were derived from the same source in the JNB. Consequently, the granitoid magmatism was largely responsible for the skarn mineralization in the JNB. Secondly, the Re–Os isotopic system has been considered as a valid geochemical tracer to determine the age of mineralization and the source of the metal (Foster et al., 1996; Stein et al., 1997, 2006; Ruiz and Mathur, 1999; Wang et al., 2011b; Li et al., 2014). Compared with molybdenum-bearing deposits in the world, molybdenite from mantle sources, such as that in the Andes and the Cordillera area, have generally very high Re contents (>100 ppm, Selby and Creaser, 2001, 2005; Masterman et al., 2004; Barra et al., 2005; Chiaradia et al., 2009). In contrast, molybdenite derived solely from the continental crust, such as that in the Nanling region of China, has very low Re

contents (<10 ppm; Peng et al., 2006; Feng et al., 2011; Yao et al., 2007). The molybdenite related to crust with minor mixing with the mantle, such as that in the JNB has intermediate Re contents (Song et al., 2010; Mao et al., 2015; Li et al., 2015; Pan et al., 2017; Huang, 2017; Zhou et al., 2011b; Zhang, 2015). Thus, Mao et al., (1999) recognized that Re content molybdenite originated from different source, would have different Re content with a mantle source of n×10− 4g, a mixture of mantle and crust of n×10− 5g, and a crustal source of n×10− 6g, and this inference has been confirmed by numerous studies (McCandless et al., 1993; Suzuki et al., 1996; Zhang et al., 2004; Berzin et al., 2001, 2005; Selby and Creaser, 2005; Su et al., 2018). In this study, the lower Re contents in molybdenite from the Shangjinshan deposit range from 1.42×10− 6

to 5.86×10− 6 g, and point in the area of the JNB deposits (Table 3, Appendix Fig. 3),

implying the molybdenite is mainly originated from a crustal and mixing with the mantle source, which is consistent with the source of the Shangjinshan granodiorite. In summary, the mineralization of the Shangjinshan W–Mo deposit is closely associated with the Early Cretaceous granodiorite magmatism in a spatial, temporal, and genetically, and the Neoproterozoic basement (Shangxi Group) is the most likely source of the ore-forming metals and granodiorite.

5.4 Tectonic setting of magmatism and W–Mo mineralization The geochronological studies have documented the significant Mesozoic igneous rocks are widespread in the South China tectonic block (SCB), and economically significant multi-metal deposit, such as W, Mo, Sn, Cu, are genetically associated with these rocks (Mao et al., 2011a, 2013a; Sun et al., 2012; Zhou et al., 2008; Sun et al., 2010; Liu et al., 1982; Mao et al., 2011b) (Fig. 1). There are two periods of tectonicmagmatism are recognized in the Mesozoic, i.e., the Indosinian Period and the

Yanshanian Period. The former includes the Early (251–234 Ma) and Late (234–205 Ma) Indosinian sub-periods, and the latter includes the Early (180–150 Ma) and Late (150–67 Ma) sub-periods (Zhou et al., 2006). The magmatic inactive period lasted from 205 Ma to 180Ma. This period was considered as the influence of the tectonic regime change from the Indosinian orogeny to the Yanshanian orogeny, which was controlled by Tethyan tectonics and the Paleo-Pacific plate subduction beneath the eastern Asian margin (Zhou et al., 2006; Wang et al., 2013a). Therefore, this viewpoint of eastern China was an active continental margin in late Mesozoic, and closely associated with subduction of the Paleo-Pacific plate is accepted by most of researchers (Li and Li 2007; Jiang et al., 2008; Mao et al., 2011c, 2013a,; Sun et al., 2007, 2012; Gu et al., 2017; Deng et al., 2016; Yan et al., 2015, 2017). As a significant part of the SCB, the Late Mesozoic igneous rocks are widespread in the JNB. The Late Mesozoic magmatism experienced three stages (Zhou et al., 2006): (1) intraplate magmatism including initial rift-type magmatism at the Early Yanshanian stage (Middle to Late Jurassic period); (2) continental margin arc magmatism at the early Late Yanshanian stage (Early Cretaceous); and (3) tholeiitic basalt volcanism recorded in red beds of back-arc basins at the Late Yanshanian stage (Late Cretaceous). The high-precision zircon U–Pb ages have been accumulated and extensive field investigation indicated that the granites associated with the W-polymetal deposit are mostly formed at the early Late Yanshanian stage (Wang et al., 2011a; Chen et al., 2012; Mao et al., 2013b, 2017; Xiang et al., 2013,2015; Tang et al., 2014a; Tang et al., 2014b; Chen et al., 2015a; Chen et al., 2015b; Mao et al., 2015; Su et al., 2018), and are controlled by the subduction of the Paleo-Pacific plate (Zhou and Li 2000, Zhou et al., 2006, Li and Li, 2007, Sun et al., 2007a). The tectonic discrimination diagrams of Pearce et al., (1984) (Fig. 14) showing

that the date from the granodiorite in the JNB fall in the compositional space straddling from volcanic arc granite to syn-collisional granite, and most of them are plotted in the volcanic arc granite fields. These geochemical signatures suggest this magmatism which associated with the formation of the W-polymetal deposit occurred in an active continental margin, and formed as a result of roll-back of the subducted Palaeo-Pacific slab (Zhou et al., 2012; Zhou et al., 2013a; Xie et al., 2016). In addition, the granodiorite samples are high-K calc-alkaline granitoid suite (Fig. 6a) and have high Y/Nb ratios (generally >1.2), enriched in LREE, LILE, depleted in HFSE and heavy REE (Fig. 8); these major and trace element features showing a typical signature of subductionrelated magmas (Rollinson, 1993; Zhu et al., 2015; Xie et al., 2016). Based on the evidence provided in this study, a simplified geodynamic model involving slab subduction is described. Prior to ca. 155 Ma, the Palaeo-Pacific plate was being subducted beneath the continental lithosphere of the Yangtze Block at low angles (Zhou and Li, 2000; Li and Li; 2007). However, during 155 and 135 Ma, the dip angle of the subduction slab increased, possibly lead to the increasing density and rollback of the subducted slab (Zhou and Li, 2000). Meanwhile, this change might lead to the transformation of tectonism from a continental arc to an extensional setting and cause the upwelling of asthenosphere mantle (Xie et al., 2017). In addition, the upwelling of asthenosphere mantle could result in the partial melting of the lithospheric mantle, leading to the formation of the basaltic melt. Then the upwelling of the basaltic melt reached to the middle-upper Crust, resulting in the reworking of Neoproterozoic crust (Shangxi Group) and formation of the I-type intrusive rocks in JNB (Fig. 15a). Consequently, the ore-bearing granitoid was intruded into the surrounding carbonate rocks, leading to a series of reaction and alteration between the metal-enriched magmatic-hydrothermal fluids and these carbonate rocks and large-scale tungsten

polymetallic mineralization in the JNB (Fig. 15b).

6. Conclusions

(1)The Shangjinshan granodiorite was formed at 137.1 ±1.5 Ma to 139.1 ±2.1 Ma, which were consistent to the molybdenite Re–Os weighted mean age of 139.3 ± 1.7 Ma, indicating that the granodiorite is closely related to the tungsten mineralization. (2)Geochemical characteristics suggest that the granodiorite exhibits an Itype affinity and was mainly derived from the partial melting of the Neoproterozoic Shangxi basement, with additional mantle components involved. (3)The low Re content in molybdenite and high radioactive lead isotopes of the pyrite suggest that the ore-forming metals have an affinity with the granodiorite. (4)Formation of the granodiorite was related to an extensional setting, which was caused by the roll-back of the subducted Paleo-Pacific plate. Acknowledgments This study is supported by the National Key R&D Program of China (No. 2016YFC0600404), National Natural Science Foundation of China (No. 41673040) and Project of Science and Technology of Anhui Provincial Bureau of Natural Resources (2014-k-4). Special thanks are extended to two anonymous reviewers for their constructive comments and suggestions.

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Table captions Table 1 Characteristics of Tungsten polymetallic deposits in Anhui Province, in the Jiangnan Massif tungsten belt.

Table 2 Locality and lithology of the granodiorites from the Shangjinshan mining area. Table 3 Re-Os data of molybdenite from the Shangjinshan deposit. Appendix Table A1 Zircon LA-ICP-MS U-Pb analytical data and trace elements (ppm) in zircon from the Shangjinshan granitoids. Appendix Table A2 Major (wt. %) and trace element (ppm) analyses of the Shangjinshan granodiorites. Appendix Table A3 Zircon Hf isotope analyses for the Shangjinshan granodiorites. Appendix Table A4 Ages of the Late Mesozoic granitoids and mineralization in the Jiangnan Massiftungsten belt.

Figure captions Fig. 1 Distribution of the Middle-Lower Yangtze River Valley porphyry-skarn Cu-AuMo-Fe ore belt (YRB) in the north and the Jiangnan porphyry-skarn tungsten belt (JNB) in the south (after Mao et al., 2017). The stratigraphic columns in the eastern segment of the JNB. 1-Middle Jurassic to Cretaceous sedimentary and volcanic rocks; 2Cambrian to Early Triassic strata marine clastic and carbonate rocks and Middle Triassic to Early Jurassic paralic clastic rocks; 3-Jiangnan Massif: Neoproteroizoic epimetamorphic and sedimentary rocks; 4-Cretaceous granitoid; 5-Jurassic granitoid; 6-Neoproterozoic granite; 7-Neoproterozoic ophiolite; 8-River and lake; 9-W deposits; 10-Sn deposits; 11-Cu deposits; 12-Au deposits; 13-Pb-Zn deposits; 14-Research deposit. Fig. 2 Geological sketch map and the No. 4 prospecting section of the Shangjinshan tungsten polymetallic deposit (Geophysical Survey Team of East China Metallurgical Bureau of Geological Exploration, 2014). Fig. 3 Photographs (a) and photomicrographs (b, c) of the Shangjinshan granodiorite. (a) sample of the granodiorite; (b, c) granitic texture and primary minerals under crossed polarized light; Photos showing selected aspects of the ores and related rocks in the Shangjinshan deposit. (d) Garnet- chlorite skarn and garnet skarn

under the fluorescent lamp; (e) small grain scheelites characterized by blue luminescence in the granodiorite; (f) scheelite and molybdenite in the skarn and scheelite under the fluorescent lamp; (g) scheelite–sulfides in the skarn; (h) quartzmolybdenite-sulfides vein in the garnet skarn; (i) quartz-scheelite-molybdenite-sulfides vein cutting the garnet skarn and quartz-scheelite-molybdenite-sulfides vein under the fluorescent lamp; (j) quartz-scheelite-sulfides vein cutting the pyroxene skarn; (k) quartz-scheelite-sulfides cutting the garnet skarn with the scheelite; (l) calcitemolybdenite vein cutting the wall rock. Scheelites characterized by blue luminescence in the picture. Grt–garnet; Chl–chlorite; Px–pyroxene; Sch–scheelite; Mo–molybdenite; Ccp–chalcopyrite; Cal–calcite; Qz–quartz; Pl–plagioclase; Kfs–K-feldspar; Bt–biotite; Hbl–hornblende. Fig. 4 Photomicrographs showing ores and related rocks in the Shangjinshan deposit. (a) the prograde skarn stage garnet; (b–d) the retrograde alteration stage scheelite; (c– d) the retrograde stage epidote and clinopyroxene intergrowth with scheelite; (e) diopside intergrowth the garnet; (f) the retrograde stage tremolite replaced by chalcopyrite; (g) scheelite in the skarn; (h) pyrite intergrowth with scheelite; (i) molybdenite intergrowth with scheelite; (j) sphalerite intergrowth with pyrite and galena; (k) pyrrhotite intergrowth with pyrite; (l) chalcopyrite intergrowth with pyrite; Sch–scheelite; Ccp–chalcopyrite; Mo–molybdenite; Sp–sphalerite; Gn–galena; Po– pyrrhotite; Grt–garnet; Di- diopside; Chl–chlorite; Qz–quartz; Cal-calcite; Ep–epidote; Cpx–clinopyroxene. Fig. 5 Paragenesis of the main alteration and mineralization phases in the Shangjinshan W-Mo deposit. Fig. 6 Diagrams of the (a) K2O versus SiO2 (after Peccerillo and Taylor, 1976), (b) A/NK (Al2O3/ (Na2O + K2O)) molar ratio versus the A/CNK (Al2O3/ (CaO + Na2O + K2O)) molar ratio (after Maniar and Piccoli, 1989), (c) Plot of Zr + Nb + Ce + Y vs. (CaO + K2O)/CaO (after Whalen et al., 1987) and (d) SiO2 versus P2O5 (after Chappell, 1999) for the Shangjinshan granodiorites. The trend in the arrow direction represent I style granodiorites in the figure 6d. Granodiorites of Zuxiling from Chen et al. (2013) and Huang. (2017), granodiorites of Xiaoyao from Shi et al. (2017) and Su et al. (2018), granodiorites of Dongyuan from Zhou. (2013) and Wang et al. (2013b), granodiorites

of Yangchuling from Mao et al. (2017). Fig. 7 Harker diagram of SiO2 versus the major elements and trace/ rare element in the Shangjinshan granodiorites. The trend in the arrow direction represent the relationship between the SiO2 with the major elements and trace/ rare element. Fig. 8 Chondrite-normalized rare earth element patterns (a) and primitive mantlenormalized incompatible element patterns (b) for. Normalized values are from Sun and McDonough (1989). Granodiorites of Zuxiling from Chen et al. (2013) and Huang. (2017), granodiorites of Xiaoyao from Shi et al. (2017) and Su et al. (2018), granodiorites of Dongyuan from Zhou. (2013) and Wang et al. (2013b), granodiorites of Yangchuling from Mao et al. (2017). Fig. 9 Representative Cathodoluminescence (CL) images of zircon grains, zircon U– Pb Concordia diagrams and weighted average diagrams of the zircon U–Pb data of the granodiorite in the Shangjinshan deposit. (a): Concordia diagram and weighted average diagram of the zircon U–Pb data of the granodiorite. (b): Cathodoluminescence (CL) images of zircon grains (the scale bar is 32 μm). (c): Histograms for the ages of zircon crystals analyzed. Fig. 10 Molybdenite Re-Os isochron (a) and weighted mean age of Re-Os isotopes (b) from the molybdenite in the Shangjinshan deposit. Fig. 11 (a) Ba versus Eu, (b) Sr versus Eu, (c) Ba/Sr versus Rb/Sr, (d) V/Th versus SiO2/Al2O3, (e) Dy versus Er, and (f) La versus (La/Yb)N diagrams. La versus (La/Yb)N diagram, partition coefficients are from Fujimaki (1986) for apatite, Mahood and Hildreth (1983) for zircon and allanite, and Yurimoto et al. (1990) for monazite. Partition coefficients of Sr and Ba are from Philpotts and Schnetzler (1970), and Eu is from Arth (1976). Pl–plagioclase; Kf–K-feldspar; Bt–biotite; Aln–allanite; Mnz– monazite; Ap–apatite; Zrn–zircon. Fig. 12. (a) Hf isotope evolution diagram and (b) initial Sr-Nd isotopic compositions of I-type granites in the eastern of JNB. The Hf isotopic data of some I-type granites in the eastern JNB are from Huang et al., 2017; Mao et al., 2017; Huang and Jiang, 2013,

2014; Pan et al., 2018; Song et al. 2012 and Wang et al., 2011a. Neoproterozoic inherited zircons are collected from the granitoid (Wu et al. 2012; Yang and Zhang, 2012). Data for the Neoproterozoic granites are from Zhang and Zheng (2013), Wang et al., (2013a, 2013c). The fields of EM and PM are from Hofmann (2003); Neoproterozoic basement (Shangxi low-grade metamorphic rocks and Neoproterozoic magmatic rocks in the eastern JNB are from Chen et al., (2001); The Sr-Nd data of Itype granites in the eastern JNB are from Huang et al., 2017; Mao et al., 2017; Huang and Jiang, 2013, 2014; Pan et al., 2018; Song et al. 2012 and Wang et al., 2011a. Fig. 13 Plot of Pb isotopic compositions of the Shangjinshan tungsten deposit (Zartman and Doe, 1981). Data sources: The Pb isotopic compositions of I-type granites in the eastern JNB are from Du et al., 2013 and Du et al., 2017; L, lower crust; O, orogen; M, mantle; U, upper crust. Fig. 14 Tectonic discrimination diagrams for the I-type granites in the eastern of JNB. (a) Nb versus Y, (b) Ta versus Yb, (c) Rb versus (Y + Nb), and (d) Rb versus (Yb + Ta) (after Pearce et al., 1984). Granodiorites of Zuxiling from Chen et al. (2013) and Huang. (2017), granodiorites of Xiaoyao from Shi et al. (2017) and Su et al. (2018), granodiorites of Dongyuan from Zhou. (2013) and Wang et al. (2013b), granodiorites of Yangchuling from Mao et al. (2017) and granodiorites of Zhuxi from Pan et al., 2018. VAG, volcanic arc granite; ORG, oceanic ridge granite; Syn-COLG, syn-collision granite; POG, post- collision granite; and WPG, intra-plate granite. Fig. 15 (a) Model of the formation of the Yanshsanian I-types granitoid (modified from Wang et al. (2015) and Zhao et al. (2015). (b) Model describing the formation of Shangjinshan W-Mo deposit. Appendix Fig. A1 Plots of U contents ([u]) versus zircon ages for Shangjinshan granodiorites. Appendix Fig. A2 Age histograms of the Late Mesozoic granitoid and mineralization in the Jiangnan Massiftungsten belt.

Appendix Fig. A3 Re versus 187Os diagram for various typical Mo-bearing deposits in the world (after Zhou et al., 2011a). The Re isotopic compositions: the Cordillera, Selby and Creaser, 2001, Barra et al., 2005, Valencia et al., 2005; the Andes, Masterman et al., 2004, Chiaradia et al., 2009, the Nanling region, Peng et al., 2006; Feng et al., 2011; Yao et al., 2007, the JNB :Song et al., 2010; Mao et al., 2015; Li et al., 2015; Pan et al., 2017; Huang, 2017; Zhou et al., 2011b; Zhang, 2015).

Highlights  The Shangjinshan deposit is a newly exploited skarn-type tungsten polymetallic deposit in the world-class Jiangnan Tungsten belt.  The

Shangjinshan

granodiorite

were

weakly

peraluminous

to

peraluminous I-type granites, formed at 139.1 Ma to 137.1 Ma, which were consistent with the molybdenite Re-Os isotopic age of 141.9 ± 3.1 Ma.  Partial melting of the Neoproterozoic crustal rocks of the Shangxi Group contributes to the formation of Shangjinshan magmas.

Table 1 Characteristics of Tungsten polymetallic deposits in the eastern Jiangnan Massif tungsten belt.

on

Name of deposit

f South Anhui

Resource(W Metal

O3)

Tectonic setting

Host rock/age

Eastern Jiangnan Massif of

Fine-sandstone, siltstone

Skarn W-

0.055/0.20.4%

Skarn WXiaoyao

vince

Associated intrusions/size

Grt,Px,Chl,Ep,

Granodiorite,

Tr,Kfs，

(1-2km2)

Scheelite, molybdenite,Ag Mo,Ag

f South Anhui

Alteration minerals

(Mt)/grade

Shangjinshan

vince

Major ore minerals

Yangtze Block

/Nh1,Nh2

Eastern Jiangnan Massif of

Arenaceous shale,mudstone,

Scheelite,

Grt,Px,Chl,Ep,

Granodiorite

Yangtze Block

/Nh2,Z1

molybdenite,Cu,Ag

Tr,Kfs,Cal,Fl

(1-2 km2)

0.05/0.2-0.9% Mo,Cu

the South

Zuxiling

Skarn W-Ag-

0.087/0.2-

Northeastern Jiangnan Massif

limestone, slate,

Scheelite,

Grt,Di,Tr,Kfs,

Granodiorite

vince

deposit

Mo

0.9%

of Yangtze Block

siltstone ,mudstone / Z1

molybdenite,magnetite,Ag

Chl,Ep,Ser

(1.5km2)

Dongyuan

Porphyry W-

0.096/0.1-

Centre part of Jiangnan Massif

granodiorite

Kfs,Ser,Chl,

Granodiorite,Granite

Ep,

orphyry,(1.3Km2);

art of the

Province

Scheelite, molybdenite, deposit

Mo

Baizhangyan

Skarn W-Mo

rt of the

Province

0.3%

of Yangtze Block

Granite porphyry

0.016/0.2-

Southern part of Jiangnan

Arenaceous shale, mudstone/

Scheelite, molybdenite,

Grt,Act,

Fine-grained granite,

0.3%

transition belt

Nh2,Z1

pyrite

Cal,Chl,Ep,Pl,

(0.24km2)

Skarn-

rt of the

0.062/0.2Gaojiabang

porphyry

Province

Carbonaceous shale,

Scheelite, molybdenite,

Fine-grained porphyritic, Ep,Chl, Kfs,Cal

0.4%

transition belt

marble ,limestone /Є1

magnetite, pyrite

Southern part of Jiangnan

Neoproterozoic biotite

Scheelite, wolframite,

Gr,Kfs,Ser,Chl,

granodiorite (790km2)

belt

granodiorite

Molybdenite, chalcopyrite

Ep

Porphyritic biotite

Southern part of Jiangnan

Granodiorite

Scheelite, Molybdenite,

Gr,Kfs,Ser,Chl,

belt

Granite porphyry

chalcopyrite

Ep

Southern part of Jiangnan

Cambrian metasandstone

Scheelite, magnetite, pyrite,

Mo,Au

rt of the

Porphyry Dahutang

ovince

2.0/0.152% W-Cu-Mo

rt of the

Porphyry Yangchuling

ovince

0.063/0.2% W-Mo

granodiorite (2.7km2)

Medium-to fine- grained

rt of the

ovince

Southern part of Jiangnan

W-

Zhuxi

Skarn W-Cu

2.86/0.491%

Si,Ch, Cal,Ser. belt

and slate

biotite ranite ,porphyritic

pyrrhotite, arsenopyrite biotite granite

Grt–garnet; Px–pyroxene; Chl–chlorite; Ep–epidote; Tr–tremolite; Kfs–K-feldspar; Cal–calcite; Fl–fluorite; Act– actinolite; Pl–plagioclase; Di–diopside;S er–sericite;

Sample

Locality

Drill

ZKN21–1

West mining section

ZKN21

ZKN21–2

West mining section

ZKNO1–1

Sampling depth

Lithology

Mineralogy

305

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

ZKN21

430

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

West mining section

ZKN01

320

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

ZKNO1–2

West mining section

ZKN01

468

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

ZKN01–3

West mining section

ZKN01

505

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

ZK45–1

Center mining section

ZK45

423

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

ZK45–2

Center mining section

ZK45

450

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

ZK45–3

Center mining section

ZK45

505

Granodiorite

Plagioclase, K–feldspar, quartz, biotite, hornblende

ZK64–1

Center mining section

ZK64

28

skarn

Pyroxene, garnet, molybdenite, scheelite

ZK64–2

Center mining section

ZK64

30

skarn

Pyroxene, garnet, molybdenite, scheelite

ZK45–6

Center mining section

ZK45

212

skarn

Pyroxene, garnet, molybdenite, scheelite

ZK42–1

Center mining section

ZK43

354

skarn

Pyroxene, garnet, molybdenite, scheelite

ZK43–2

Center mining section

ZK43

289

skarn

Pyroxene, garnet, molybdenite, scheelite

SJS–T1b

Center mining section

ZK45

215

skarn

Pyroxene, garnet, molybdenite, pytite, scheelite

SJS–T3

Center mining section

ZK45

275

skarn

Pyroxene, garnet, molybdenite, pytite, scheelite

SJS–T4

Center mining section

ZK43

289

skarn

Pyroxene, garnet, molybdenite, pytite, scheelite

(meter)

Table 2 Locality and lithology of the granodiorites from the Shangjinshan mining area

Table 3 Re-Os isotopic compositions of molybdenite from the Shangjinshan deposit Re (ppm)

No .

Sampl e

1

ZK64-1

1.4566

2

ZK64-2

3.2854

3

ZK45-6

5.8644

4

ZK42-1

1.4215

5

ZK43-2

2.9266

Measure d

2σ 0.006 5 0.015 1 0.029 2 0.010 4 0.016 6

187Re

(ppb)

Measure d 0.91551 2.065

2σ 0.0040 8 0.0094 8

187Os

Measure d 2.1093 4.7801

3.686

0.0183

8.692

0.89348

0.0065 2

2.0807

1.8394

0.0106

4.3037

(ppm) 2σ 0.002 4 0.005 3 0.021 0.009 5 0.030 1

Model age (Ma) Measure d

2σ

138.1

0.6

138.9

0.6

141.4

0.8

139.6

1.2

140.3

1.3

Table 4 In-situ Pb isotopic compositions of the sulfides from the Shangjisnhan deposit. 59

Sample no.

stages

Analyzed

208Pb/204Pb

±1σ

207Pb/204Pb

±1σ

206Pb/204Pb

±1σ

mineral

SJS-T3-1

II

Pyrite

38.425

0.057

15.615

0.023

18.218

0.024

SJS-T3-2

II

Pyrite

38.414

0.186

15.539

0.080

18.130

0.094

SJS-T3-3

II

Pyrite

38.491

0.013

15.631

0.005

18.223

0.005

SJS-T4-1

II

Pyrite

38.407

0.027

15.611

0.011

18.242

0.013

SJS-T4-2

II

Pyrite

38.431

0.059

15.613

0.025

18.247

0.028

SJS-T1b-1

II

Pyrite

38.492

0.014

15.634

0.006

18.264

0.006

60

61

Table A1. Major (wt. %) and trace element (ppm) analyses of the Shangjinshan granodiorites. Sample

ZKN21

ZKN21

ZKNO1

ZKNO1

ZKNO1

ZK45

ZK45

ZK45

1

2

1

2

3

1

2

3

Rock

granodiorite

SiO2

74.02

72.56

68.33

67.93

67.18

71.41

70.92

71.56

TiO2

0.19

0.16

0.52

0.34

0.48

0.32

0.32

0.31

Al2O3

13.24

13.56

14.57

15.24

15.58

13.52

13.78

13.92

TFe2O3

1.73

1.58

3.85

2.70

3.11

2.63

2.74

2.49

MnO

0.04

0.06

0.09

0.06

0.08

0.07

0.07

0.06

MgO

0.31

0.30

1.03

0.62

0.91

0.60

0.59

0.57

CaO

1.45

1.51

3.13

2.27

2.75

1.92

1.96

1.97

Na2O

2.50

3.11

3.30

3.23

3.16

3.05

3.11

3.13

K2O

4.84

5.13

3.37

4.27

4.43

4.24

4.28

4.52

P2O5

0.05

0.07

0.17

0.11

0.15

0.12

0.12

0.12

LOI

1.11

0.37

1.01

1.82

0.92

0.48

0.62

1.14

Total

99.48

98.41

99.37

98.59

98.75

98.36

98.51

99.79

TFeO

1.56

1.42

3.47

2.43

2.80

2.37

2.47

2.24

A/NK

1.42

1.27

1.61

1.53

1.56

1.41

1.41

1.39

A/CNK

1.10

1.01

0.99

1.08

1.04

1.03

1.04

1.02

Mg#

0.24

0.25

0.32

0.29

0.34

0.29

0.28

0.29

DI

88.37

89.42

76.76

81.98

79.16

84.91

84.54

85.18

62

La

20.20

10.60

27.70

18.40

20.00

26.70

25.60

20.00

Ce

39.50

22.00

61.80

39.80

60.50

57.40

57.10

61.20

Pr

4.46

2.60

7.16

4.91

7.13

6.63

6.74

7.28

Nd

15.50

10.00

28.30

19.90

25.90

26.50

26.00

26.20

Sm

2.78

2.26

6.02

4.39

5.33

5.59

5.58

5.35

Eu

0.46

0.50

1.07

1.12

1.08

0.77

0.79

0.79

Gd

1.91

1.99

4.58

3.77

4.21

4.12

4.22

4.35

Tb

0.25

0.30

0.65

0.53

0.60

0.57

0.61

0.65

Dy

1.39

1.63

3.51

2.85

3.12

3.02

3.18

3.44

Ho

0.27

0.30

0.61

0.51

0.56

0.50

0.51

0.60

Er

0.75

0.83

1.59

1.36

1.41

1.23

1.34

1.48

Tm

0.11

0.12

0.21

0.18

0.19

0.17

0.19

0.21

Yb

0.81

0.85

1.33

1.10

1.28

1.06

1.15

1.41

Lu

0.13

0.14

0.19

0.17

0.18

0.15

0.16

0.20

Y

7.60

9.00

17.00

13.70

16.40

14.70

15.60

18.10

Sc

3.40

3.90

6.80

4.80

6.00

4.70

4.90

4.00

V

20.00

15.00

60.00

44.00

57.00

32.00

32.00

33.00

Cr

11.00

10.00

13.00

10.00

10.00

9.00

10.00

10.00

Ni

1.50

1.30

2.90

2.10

0.90

2.00

2.20

0.90

Cu

11.10

1.00

4.40

3.10

2.00

6.20

5.70

3.00

Zn

37.00

49.00

76.00

47.00

64.00

59.00

59.00

55.00

Sr

109.50

111.00

234.00

280.00

282.00

166.00

180.00

165.00

Co

2.10

1.80

6.90

4.30

6.00

4.10

4.10

4.00

Rb

264.00

257.00

150.00

148.50

199.50

249.00

250.00

267.00

Zr

40.40

40.30

33.90

18.60

43.00

58.80

60.00

55.00

Nb

9.10

10.80

12.30

8.80

11.00

15.70

15.70

15.00

Ba

210.00

180.00

330.00

380.00

450.00

300.00

310.00

346.00

Hf

1.60

1.70

1.30

0.70

1.20

2.10

2.20

2.40

Ta

0.72

0.84

1.00

0.81

0.80

1.98

2.16

1.70

Pb

35.20

48.20

22.30

36.00

31.00

36.70

37.80

43.00

Th

19.20

13.70

18.80

9.50

15.95

16.30

17.50

18.75

U

7.00

5.40

4.20

2.30

3.67

8.30

8.20

8.27

Ga

17.25

17.35

19.50

17.00

19.30

17.90

19.50

18.70

Bi

5.06

10.25

0.79

2.66

1.09

0.19

0.91

1.86

Mo

1.01

3.70

0.91

0.82

0.96

0.53

0.61

0.92

W

23.30

19.90

2.80

4.80

6.80

0.90

2.10

7.90

Cs

20.60

11.65

4.60

4.63

5.50

14.95

13.20

7.11

Rb/Sr

0.41

0.40

0.34

0.35

0.34

0.34

0.37

0.35

K/Rb

0.29

0.25

0.10

0.12

0.11

0.11

0.12

0.10

Sr/Y

14.41

12.33

13.76

20.44

17.20

11.29

11.54

9.12

/Na2O

1.94

1.65

1.02

1.29

1.40

1.39

1.38

1.44

Ce/Pb

1.12

0.46

2.77

1.11

1.95

1.56

1.51

1.42

Nb/Ta

12.64

12.86

12.30

10.86

13.75

7.93

7.27

8.82

K2O

63

Zr/Hf

25.25

23.71

26.08

26.57

35.83

28.00

27.27

22.92

REE

88.52

54.12

144.72

98.99

131.49

134.41

133.17

133.16

Eu/Eu*

0.61

0.72

0.62

0.84

0.70

0.49

0.50

0.50

(La/Yb)N

17.89

8.95

14.94

12.00

11.21

18.07

15.97

10.17

Table A2. Zircon LA-ICP-MS U-Pb analytical data and trace elements (ppm) in zircon from the Shangjinshan granitoids. Sample ZK45-105 ZK45-106 ZK45-107 ZK45-109 ZK45-110 ZK45-111 ZK45-112 ZK45-114 ZK45-115 ZK45-116 ZK45-117 ZK45-118 ZK45-119 ZK45-120

Th

U

(10-6)

(10-6)

3923.30

2789.37

1857.26

Pb/206Pb

Pb/235U

207

Th/U

Pb/238U

207

Pb/232Th

206

Pb

208

207

Ratios

1σ

Ratios

1σ

Ratios

1σ

Ratios

1σ

Age（Ma）

1.41

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

130.58

5547.60

0.33

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

129.01

1231.44

4143.03

0.30

0.04

0.00

0.13

0.01

0.02

0.00

0.01

0.00

124.87

1078.15

4015.03

0.27

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

145.37

1246.09

4138.27

0.30

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

146.41

2733.31

4133.15

0.66

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

145.01

2024.74

5362.26

0.38

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

150.19

1183.11

3875.05

0.31

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

146.89

437.21

1679.88

0.26

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

151.43

941.31

938.32

1.00

0.05

0.01

0.16

0.02

0.02

0.00

0.01

0.00

149.59

6613.04

4550.60

1.45

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

141.62

3832.70

2479.11

1.55

0.05

0.00

0.14

0.01

0.02

0.00

0.01

0.00

133.43

2937.71

2966.91

0.99

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

148.69

1515.31

3928.97

0.39

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

147.80

64

ZK45-123 ZK45-124 ZK45-125 ZK45-126 ZK45-128 ZK45-129 ZK45-130 ZK45-131 ZK45-132

ZKN012-01 ZKN012-02 ZKN012-03 ZKN012-04 ZKN012-05 ZKN012-06 ZKN012-07 ZKN012-10 ZKN012-11 ZKN012-12 ZKN012-13 ZKN012-15

1932.75

4863.57

0.40

0.05

0.00

0.14

0.01

0.02

0.00

0.01

0.00

136.62

1142.06

3885.18

0.29

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

147.88

947.30

3368.14

0.28

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

147.73

753.46

4918.14

0.15

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

143.99

724.19

3558.92

0.20

0.05

0.00

0.14

0.01

0.02

0.00

0.01

0.00

133.84

530.82

1657.30

0.32

0.05

0.01

0.15

0.02

0.02

0.00

0.01

0.00

143.45

683.72

3165.90

0.22

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

134.31

771.96

3189.97

0.24

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

131.94

1270.72

4185.93

0.30

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

131.80

832.33

3084.01

0.27

0.05

0.00

0.14

0.01

0.02

0.00

0.01

0.00

136.92

798.40

2556.29

0.31

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

150.46

1574.56

4381.46

0.36

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

143.77

1055.56

3232.12

0.33

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

129.03

1105.04

2788.87

0.40

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

148.68

5175.79

4064.03

1.27

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

137.72

1490.94

4238.21

0.35

0.05

0.00

0.14

0.01

0.02

0.00

0.01

0.00

131.64

806.75

3039.45

0.27

0.04

0.00

0.13

0.01

0.02

0.00

0.01

0.00

124.35

645.13

2173.87

0.30

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

152.61

1103.25

5177.56

0.21

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

142.74

2878.39

3125.30

0.92

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

141.63

1329.55

4050.66

0.33

0.04

0.00

0.13

0.01

0.02

0.00

0.01

0.00

124.84

65

ZKN012-16 ZKN012-17 ZKN012-19 ZKN012-20 ZKN012-21 ZKN012-22 ZKN012-25 ZKN012-29 ZKN012-32

ZKN211-01 ZKN211-02 ZKN211-03 ZKN211-04 ZKN211-05 ZKN21-106 ZKN211-10 ZKN211-11 ZKN211-14 ZKN211-17 ZKN211-19 ZKN211-21

1029.53

2665.27

0.39

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

143.03

2130.06

4235.82

0.50

0.05

0.00

0.14

0.01

0.02

0.00

0.01

0.00

137.04

1728.71

4214.89

0.41

0.04

0.00

0.13

0.01

0.02

0.00

0.01

0.00

126.40

4527.50

5002.13

0.91

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

139.80

2567.71

4407.15

0.58

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

146.31

696.17

2516.28

0.28

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

139.57

1237.32

3546.21

0.35

0.05

0.01

0.14

0.03

0.02

0.00

0.02

0.01

133.80

695.20

1245.29

0.56

0.04

0.01

0.13

0.03

0.02

0.00

0.01

0.00

122.64

583.23

2520.10

0.23

0.05

0.01

0.14

0.02

0.02

0.00

0.01

0.00

134.26

911.26

3189.18

0.29

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

129.56

1088.00

3209.67

0.34

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

142.80

720.72

3989.58

0.18

0.05

0.01

0.16

0.03

0.02

0.00

0.01

0.00

152.27

1132.13

1344.04

0.84

0.06

0.01

0.14

0.01

0.02

0.00

0.01

0.00

129.84

1484.05

2743.30

0.54

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

137.50

162.57

753.79

0.22

0.06

0.00

1.20

0.07

0.13

0.00

0.04

0.00

798.82

943.87

2788.35

0.34

0.05

0.00

0.16

0.01

0.02

0.00

0.01

0.00

153.72

1389.44

2810.55

0.49

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

146.07

772.39

2753.62

0.28

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

140.79

1183.05

2796.03

0.42

0.05

0.01

0.16

0.02

0.02

0.00

0.01

0.00

148.22

2507.85

5803.57

0.43

0.04

0.00

0.13

0.01

0.02

0.00

0.01

0.00

123.95

767.60

2462.07

0.31

0.05

0.00

0.13

0.01

0.02

0.00

0.01

0.00

126.31

66

ZKN211-23 ZKN211-25 ZKN211-26 ZKN211-28 ZKN211-29 ZKN211-30 ZKN211-32

5194.86

3067.84

1.69

0.04

0.01

0.13

0.02

0.02

0.00

0.01

0.00

127.76

927.83

2670.42

0.35

0.04

0.01

0.13

0.02

0.02

0.00

0.01

0.00

127.84

874.09

3770.46

0.23

0.04

0.01

0.13

0.02

0.02

0.00

0.01

0.00

128.13

1944.41

4628.44

0.42

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

143.45

1165.20

1829.45

0.64

0.05

0.00

0.15

0.01

0.02

0.00

0.01

0.00

144.79

340.93

1145.49

0.30

0.05

0.01

0.16

0.01

0.02

0.00

0.01

0.00

147.08

1325.99

3897.52

0.34

0.04

0.00

0.14

0.01

0.02

0.00

0.01

0.00

129.40

Table A3. Zircon Hf isotope analyses for the Shangjinshan granodiorites. Sample spot# ZKN01-21 ZKN01-22 ZKN01-23 ZKN01-24 ZKN01-25 ZKN01-26 ZKN01-27 ZKN01-210 ZKN01-211 ZKN01-212 ZKN01-213

176Yb/177Hf

2σ

176Lu/177Hf

2σ

176Hf/177Hf

2σ

(176Hf/177Hf)i

εHf(t)

139 Ma

0.016407

0.000259

0.000681

0.000009

0.282550

0.000015

0.282549

-4.85

0.037413

0.001579

0.001427

0.000059

0.282571

0.000016

0.282567

-4.18

0.018154

0.000217

0.000793

0.000009

0.282576

0.000014

0.282573

-3.97

0.007643

0.000080

0.000367

0.000004

0.282563

0.000013

0.282562

-4.37

0.054338

0.001880

0.001876

0.000059

0.282604

0.000015

0.282599

-3.08

0.035119

0.002292

0.001393

0.000089

0.282536

0.000015

0.282533

-5.41

0.034280

0.002334

0.001390

0.000087

0.282563

0.000017

0.282559

-4.47

0.018562

0.000136

0.000806

0.000005

0.282550

0.000014

0.282548

-4.88

0.016338

0.000235

0.000708

0.000008

0.282589

0.000014

0.282587

-3.50

0.024470

0.000337

0.000970

0.000010

0.282558

0.000014

0.282555

-4.61

0.024440

0.001129

0.000969

0.000035

0.282572

0.000014

0.282569

-4.12

67

ZKN01-215 ZKN01-216 ZKN01-217 ZKN01-219 ZKN01-220 ZKN01-221 ZKN01-222 ZKN01-225 ZKN01-229 ZKN01-232 Sample spot# ZKN21-11 ZKN21-12 ZKN21-13 ZKN21-14 ZKN21-15 ZKN21-110 ZKN21-111 ZKN21-114 ZKN21-117 ZKN21-119 ZKN21-121

0.024710

0.000296

0.001063

0.000014

0.282557

0.000013

0.282554

-4.65

0.015712

0.000268

0.000727

0.000009

0.282549

0.000013

0.282547

-4.89

0.025507

0.001154

0.001034

0.000039

0.282558

0.000014

0.282556

-4.61

0.022457

0.000507

0.000980

0.000022

0.282535

0.000014

0.282533

-5.41

0.052183

0.000660

0.001994

0.000021

0.282543

0.000016

0.282538

-5.22

0.019555

0.000516

0.000819

0.000019

0.282547

0.000014

0.282545

-4.97

0.014889

0.000269

0.000662

0.000009

0.282530

0.000014

0.282529

-5.56

0.020995

0.000505

0.000803

0.000017

0.282566

0.000016

0.282564

-4.31

0.047205

0.001786

0.001939

0.000072

0.282567

0.000018

0.282562

-4.39

0.014981

0.000273

0.000662

0.000008

0.282557

0.000016

0.282555

-4.63

176Yb/177Hf

2σ

176Lu/177Hf

2σ

176Hf/177Hf

2σ

(176Hf/177Hf)i

εHf(t)

139Ma

0.026050

0.000126

0.001101

0.000007

0.282549

0.000016

0.282546

-4.93

0.092047

0.005160

0.003620

0.000198

0.282560

0.000020

0.282550

-4.79

0.019520

0.000298

0.000845

0.000013

0.282597

0.000015

0.282595

-3.23

0.036646

0.000531

0.001402

0.000017

0.282551

0.000021

0.282548

-4.88

0.049926

0.001693

0.001834

0.000057

0.282587

0.000019

0.282583

-3.65

0.052835

0.001259

0.002116

0.000051

0.282568

0.000017

0.282562

-4.37

0.045414

0.000399

0.001733

0.000008

0.282580

0.000019

0.282575

-3.92

0.026742

0.001903

0.000927

0.000051

0.282632

0.000016

0.282629

-2.00

0.027166

0.000833

0.000959

0.000026

0.282572

0.000016

0.282569

-4.13

0.018165

0.000492

0.000696

0.000019

0.282539

0.000014

0.282537

-5.26

0.022104

0.000280

0.000883

0.000008

0.282558

0.000014

0.282556

-4.59

68

ZKN21-123 ZKN21-125 ZKN21-126 ZKN21-128 ZKN21-129 ZKN21-130 ZKN21-132 Sample spot#

0.026004

0.000456

0.001143

0.000015

0.282562

0.000015

0.282559

-4.47

0.021636

0.000712

0.000864

0.000020

0.282585

0.000014

0.282582

-3.65

0.021953

0.000357

0.000958

0.000015

0.282552

0.000013

0.282550

-4.80

0.042665

0.000871

0.001638

0.000030

0.282541

0.000017

0.282537

-5.27

0.017429

0.000992

0.000600

0.000024

0.282514

0.000016

0.282512

-6.14

0.042278

0.002067

0.001765

0.000090

0.282627

0.000017

0.282622

-2.25

0.039823

0.000805

0.001441

0.000030

0.282608

0.000018

0.282604

-2.88

176Yb/177Hf

2σ

176Lu/177Hf

2σ

176Hf/177Hf

2σ

(176Hf/177Hf)i

εHf(t)

137Ma

ZK45-1-5

0.044531

0.001577

0.001746

0.000061

0.282598

0.000016

0.282593

-3.32

ZK45-1-6

0.025407

0.000497

0.001076

0.000011

0.282569

0.000014

0.282567

-4.26

ZK45-1-7

0.037380

0.000906

0.001389

0.000034

0.282627

0.000018

0.282624

-2.24

ZK45-1-9

0.025425

0.001565

0.000996

0.000058

0.282546

0.000014

0.282543

-5.08

0.018323

0.000223

0.000826

0.000011

0.282548

0.000014

0.282546

-5.00

0.049164

0.001469

0.001905

0.000057

0.282586

0.000015

0.282582

-3.73

0.030730

0.001430

0.001142

0.000049

0.282560

0.000016

0.282557

-4.60

0.037967

0.001311

0.001448

0.000048

0.282559

0.000015

0.282556

-4.65

0.013935

0.000377

0.000578

0.000011

0.282600

0.000015

0.282599

-3.12

0.080151

0.001894

0.003016

0.000082

0.282614

0.000023

0.282606

-2.86

0.032968

0.000766

0.001292

0.000029

0.282587

0.000015

0.282584

-3.64

0.045637

0.001717

0.001630

0.000053

0.282582

0.000017

0.282578

-3.86

0.016569

0.000476

0.000592

0.000016

0.282556

0.000017

0.282555

-4.67

0.016919

0.000311

0.000699

0.000010

0.282562

0.000015

0.282560

-4.50

0.020662

0.000420

0.000869

0.000011

0.282584

0.000013

0.282582

-3.72

0.022386

0.000257

0.000894

0.000011

0.282573

0.000014

0.282571

-4.10

ZK45-110 ZK45-111 ZK45-112 ZK45-114 ZK45-115 ZK45-116 ZK45-117 ZK45-118 ZK45-119 ZK45-120 ZK45-123 ZK45-124

69

ZK45-125 ZK45-126 ZK45-128 ZK45-129 ZK45-130 ZK45-131 ZK45-132

0.034326

0.001076

0.001314

0.000037

0.282533

0.000013

0.282530

-5.56

0.021882

0.001346

0.000955

0.000057

0.282574

0.000013

0.282572

-4.08

0.021348

0.000855

0.000884

0.000031

0.282566

0.000012

0.282564

-4.35

0.014689

0.000350

0.000561

0.000006

0.282594

0.000014

0.282593

-3.32

0.020510

0.000647

0.000904

0.000025

0.282586

0.000015

0.282584

-3.65

0.019738

0.000263

0.000789

0.000007

0.282600

0.000014

0.282598

-3.14

0.021004

0.000911

0.000804

0.000034

0.282603

0.000013

0.282601

-3.06

ε Hf(t)=[( 176Hf/177Hf )S-(176Lu/177Hf )S*(eλt-1)]/[( 176Hf/177Hf )]CHUR,0-(176Lu/177Hf ) CHUR,0×(eλt-1)] ×104; TDM1=1/λ×=ln {[((176Hf/177Hf )S-(176Hf/177Hf )DM]/[ (176Lu/177Hf )DM+1]};TDM2= TDM1-(TDM1-t) × (fCC-fS)/(fCC-fDM), Where fLu/Hf= ((176Lu/177Hf )S/(176Lu/177Hf) CHUR-1, (176Lu/177Hf) (Bouvier et al, 2008), (176Lu/177Hf )

(176Lu/177Hf )

CC=0.015

DM=0.0384

CHUR,0=0.0336

(Griffin et al., 2000),

and (176Hf/177Hf)

(176Hf/177Hf )

(Griffin et al., 2000), S=sample, λ=decay constant of

DM=0.28325

CHUR,0=0.282785

(Nowell et al., 1998),

176Lu(0.01867Ga-1).

Table A4. Ages of the Late Mesozoic granitoids and mineralization in the Jiangnan Massiftungsten belt. Location

Ore-forming age

Shangjinshan

Rock types

Rock-forming a

granodiorite

137.1 ± 1.5Ma（LA-ICP

granodiorite

139.1 ± 2.1Ma（LA-ICP

granodiorite

139.1 ± 1.2Ma（LA-ICP

granodiorite

139~142 Ma

monzonitic granite

132.8～133.2 M

granite

131～138 Ma

granite

140.7 ± 1.8（LA-ICPM

141.9 ± 3.1Ma（Re-Os molybdenite）

Qingyang

Jiuhuashan

monzonitic granite

130.8～137.6（LA-ICP

syenogranite

130.3～131.0（LA-ICP

moyite

127.5～131.7（LA-ICP

granite porphyry granodiorite Taiping

70

132.0 ± 2.0（LA-ICPM

139.0～143.6 M

monzonitic granite

145.1 ± 1.7（LA-ICPM

aplite

140.0 ± 2.1（LA-ICPM

alkali feldspar granite Huangshan

Jingde Maolin

monzonitic granite

125.2 ± 5.5(SHRIMP

granite

138 ± 1（LA-ICPMS

moyite

125.8～128.2（LA-ICP

granodiorite

139.7 ± 1.3（LA-ICPM

granodiorite

139.8 ± 1.1（SHIMP

granite porphyry

140.7 ± 2.3（LA-ICPM

syenogranite syenogranite AF granite Fuling

syenogranite AF granite K-feldspar granite K-feldspar granite

Liucun

123.7～134.9（LA-ICP

129.5 ± 1.5 Ma (LA zircon)

124 ± 0.7 Ma (LA-ICP

133.0 ± 1.2 Ma (LA zircon)

131.8 ± 1.1 Ma (SIM

130.6 ± 1.5 Ma (LA zircon)

129.9 ± 0.7 Ma (LA-ICP

133.9 ± 1.1 Ma (LA zircon)

granite

132.8 ± 0.6（LA-ICPM

monzonitic granite

127.7 ± 1.6（LA-ICPM

monzonitic granite

129.2～129.6（LA-ICP

Tangshe

monzonitic granite

131.4 ± 2.4（LA-ICPM

Xianxia

granodiorite

132.0 ± 1.7（LA-ICPM

granodiorite

151.9～152.7（SHIM

granodiorite

147.7 ± 1.3（SHIMP

Kaobeijian

monzonitic granite Cheng'an

131.2～132.4（LA-ICP

granodiorite

151.0 ± 2.8（LA-ICPM

syenogranite

129.4 ± 1.5（LA-ICPM

Changhai

granite

142.2 ± 1.7（LA-ICPM

Lanhualing

granodiorite

148.2 ± 0.9 Ma (LA zircon)

148.7 ± 2.5Ma（Re-Os molybdenite） granodiorite granite porphyry

Xiaoyao

Jitoushan

136.6 ± 1.5 Ma（Re-Os molybdenite） 71

149.4 ± 1.1 Ma (LA zircon)

133.2 ± 0.7 Ma (LA zircon)

granodiorite porphyry

151.9 ± 1.1Ma (SHRI

granodiorite porphyry

152.7 ± 1.1 Ma (SHRI

granodiorite porphyry

147.7 ± 1.3 Ma (SHRI

granodiorite-porphyry

138.8 ± 1.0 Ma（SIM

granite porphyry

138.3 ± 1.2 Ma（SIM

quartz porphyry

127.1 ± 0.9 Ma (SIM

granodiorite porphyry Matou

148 ± 3 Ma（Re-Os molybdenite）

granodiorite

139.5 ± 1.5 Ma（LA-ICP

144.6 ± 1.2（LA-ICPM

146.7 ± 3.9（Re-Os molybdenite） Dawujian

144.4 ± 1.5 Ma（Re-Os molybdenite）

Lidongkeng

144.9 ± 1.9（Re-Os molybdenite）

Dengjiawu

141.8 ± 2.2 Ma（Re-Os molybdenite）

granodiorite-porphyry

148.3 ± 2.2 Ma（LA-ICP

granodiorite-porphyry

148.5 ± 2.1 Ma（LA-ICP

granodiorite

153.01 ± 0.9（LA-ICPM

136.3 ± 2.6（Re-Os molybdenite）

granite

130 ± 1.5Ma(SHIMP

134.1 ± 2.2（Re-Os model ages molybdenite）

fine-grained granite

133.3 ± 1.3 Ma (SIM

136.9 ± 4.5 Ma (Re-Os molybdenite)

monzonitic granite

Baizhangyan

fine-grained granite diorite dike diorite dike 142.7 ± 2.1Ma（Re-Os model ages molybdenite）

Zuxiling

Guilinzheng

145.7 ± 1.7 Ma (LA zircon)

140.2 ± 1.7 Ma (LA-ICP

granodiorite

140.5 ± 1.3 Ma (LA zircon)

138.7 ± 1.6 Ma (LA zircon)

142 ± 1.6 Ma (LA-ICP

144.9 ± 1.2 Ma (LA zircon)

granodiorite porphyry

145 ± 2 Ma (LA-ICPM

granodiorite porphyry

149 ± 1 Ma (SHRIM

granite porphyry granodiorite

Jianfengpo

zircon)

granodiorite

granodiorite 127. 5 Ma (Re-Os molybdenite)

145.3 ± 1.7 Ma (LA

143.3 ± 1.9 Ma (LA-ICP

granite porphyry

Dongyuan

zircon)

granite porphyry

granite

146.4 ± 2.3 Ma (Re-Os molybdenite)

135.3 ± 0.9 Ma (LA

139.8 ± 2.0 Ma (LA-ICP

granite

Gaojiabang

zircon)

granodiorite

granite

146.1 ± 4.8 Ma (Re-Os molybdenite)

129.0 ± 1.2 Ma (LA

148.6 ± 1.8 Ma (LA zircon)

146.7 ± 1.5 Ma (LA zircon)

126.8 ± 1.4 Ma (LA zircon)

127.6 ± 1.5Ma (LA-ICP

129.7 Ma ± 2.5 Ma (U-Pb cassiterite) granite

Dahutang

72

129 ± 2 Ma (LA-ICPM

porphyritic biotite granite

147.4 ± 0.6 Ma（LA-ICP

fine-grained granite

146.1 ± 0.6 Ma（LA-ICP

granite porphyry

143.0 ± 0.8 Ma（LA-ICP

139.2 ± 1.0 Ma（Re-Os molybdenite） 143.7 ± 1.2 Ma（Re-Os molybdenite） 149.6 ± 1.4 Ma（Re-Os molybdenite） granite

138 Ma（LA-ICPMS

granite porphyry

135 Ma（LA-ICPMS

Porphyric-like two-mica granite

Shimensi

porphyric biotite monzogranite fine-grained monzogranite granite porphyry granite porphyry

144.0 ± 0.6 Ma（LA-ICP

150.0 ± 0.7 Ma（LA monazite)

149 ± 1 Ma（LA-ICPMS

148.2 ± 1.2 Ma（LA monazite)

146.1 ± 0.8 Ma（LA monazite)

142.4 ± 8.9 Ma（Sm-Nd scheelite) Shiweidong

140.9 ± 3.6 Ma（Re-Os molybdenite）

Dalingshang

muscovite granite

144.2 ± 1.3 Ma（LA-ICP

granite porphyry

134.6 ± 1.2 Ma（LA-ICP

porphyritic biotite granite

148.3 ± 1.9 Ma（LA-ICP

fine-grained granite

144.7 ± 0.5 Ma（LA-ICP

145.9 ± 2 Ma（Re-Os molybdenite）

Zhuxi

Yangchuling

146 ± 1.0 Ma（Re-Os molybdenite）

granite porphyry

153.4 ± 1（SHIMP

biotite granitic

153.5 ± 1（SHIMP

white grantic

152.9 ± 1.7（SHIMP

granite porphyry

150.6 ± 1.9 Ma（LA-ICP

granite porphyry

149.5 ± 1.9 Ma（LA-ICP

Fine-granite porphyry

146.9 ± 0.9 Ma（LA-ICP

granite

149.2 ± 1.5 Ma（LA-ICP

granite porphyry

148.4 ± 3.4 Ma（LA-ICP

monzogranitic porphyry

143.8 ± 0.5 Ma（LA-ICP

granodoitite

149.8 ± 0.6 Ma（LA-ICP

Xucun

granodoitite

850 ± 10 Ma（LA-ICPM

Xiuning

granodoitite

832 ± 8 Ma（LA-ICPM

Shexian

granodoitite

838 ± 11 Ma（LA-ICPM

Liangshan

k-feldspar granite porphyry

823 ± 18 Ma（LA-ICPM

Lianhuashan

k-feldspar granite porphyry

814 ± 26 Ma（LA-ICPM

Shiershan

granite porphyry

785 ± 11 Ma（LA-ICPM

73