Multiple dating and tectonic setting of the Early Cretaceous Xianglushan W deposit, Jiangxi Province, South China

Ore Geology Reviews 95 (2018) 1161–1178

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Multiple dating and tectonic setting of the Early Cretaceous Xianglushan W deposit, Jiangxi Province, South China

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Pan Daia, Jingwen Maoa, Shenghua Wua,b, , Guiqing Xiea, Xiaohong Luoc a

MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China Center of Deep Seep Research, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 2666071, China c Northwestern Geological Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration and Development, Jiujiang 332000, China b

A R T I C L E I N F O

A B S T R A C T

Keywords: Zircon U–Pb Molybdenite Re–Os Muscovite 40Ar/39Ar Hf isotopes Xianglushan W deposit Jiangnan porphyry–skarn W belt

The Xianglushan W deposit in northwestern Jiangxi Province, South China, is one of numerous large-size W deposits along the northern margin of the Jiangnan Massif. The deposit comprises lenticular and stratiform-like orebodies, mainly along the contact between argillaceous limestone of the Cambrian Yangliugang Formation and a biotite granite pluton. The mineralization is zoned from proximal W greisen within the cupolas of the biotite granite, through W skarn and sulfide-scheelite bands near the pluton, to distal quartz-sulfide ± scheelite veins. The granitic pluton and an aplitic dyke in the mining area contain zircon grains with U–Pb ages of 123.8 ± 0.8 Ma and 117.3 ± 1.7 Ma, respectively. Six molybdenite samples collected from skarn ores yielded a Re–Os weighted mean age of 125.5 ± 0.7 Ma, and muscovite separates from greisen ores yielded a 40Ar/39Ar plateau age of 122.8 ± 0.78 Ma. The molybdenite Re–Os and muscovite Ar–Ar ages are consistent with the zircon U–Pb age of the hosting granite. The Xianglushan deposit is formed by an Early Cretaceous W–dominated polymetallic ore-forming event in the Jiangnan porphyry–skarn W belt. Zircon from biotite granites in the Xianglushan deposit has negative εHf(t) values, generally from − 5.7 to − 3.1, with corresponding two-stage Hf model ages of 1363–1218 Ma, reflecting derivation of magmas from a crustal source. Molybdenite has Re contents from 12.12 to 22.77 ppm, indicative of a mixed crustal-mantle source, but with a dominantly crustal component. A compilation of precise ages for magmatism and mineralization in the Jiangnan porphyry–skarn W belt shows that there are two stages of mineralization at 150–135 Ma and 130–120 Ma, respectively. Integrated with published data, our results suggest that the Xianglushan W deposit formed in an extensional tectonic setting during the Early Cretaceous.

1. Introduction South China is the world’s most W-rich region, and many researchers have paid much attention to the large-scale metallogeny of the Nanling region, central part of South China (Mao et al., 2007; Hu and Zhou, 2012; Zhao et al., 2013, 2017b; Wu et al., 2017). In recent years, a new Yanshanian porphyry and skarn W belt, namely the Jiangnan porphyry–skarn W belt (JNB), has been recognized along the northern margin of the Jiangnan Massif. This new belt is to the south of the Middle-Lower Yangtze River porphyry–skarn Cu–Au–Mo–Fe ore belt and is hereinafter referred to as the YRB (Fig. 1a and b). The JNB extends from northern Jiangxi Province to southern Anhui Province, and hosts the Zhuxi W–Cu deposit (the world’s largest W deposit; Pan et al., 2017), Dahutang W deposit (Mao et al., 2013b, 2015), Xianglushan W deposit (Wu et al., 2012), and Yangchuling W–Mo deposit (Mao et al., 2017) in northern Jiangxi Province; and the Dongyuan

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W–Mo deposit (Zhou et al., 2011), Xiaoyao W–Ag–Zn–Pb–Cu–Mo deposit (Tang et al., 2014), Baizhangyan W–Mo deposit (Li et al., 2015), and Zhuxiling W–Mo deposit (Chen et al., 2013) in southern Anhui Province (Fig. 1b). The importance of the belt promotes the necessary of the study of mineralization, magmatism, geological setting, and metallogenic systems of the belt. Although these deposits in the JNB have been recently investigated (Song et al., 2012a,b; Mao et al., 2013a,b, 2015), the ages and tectonic setting of mineralization are still not well-known, especially for those deposits comprising stratiform-like orebodies. The Xianglushan skarn W deposit was discovered by the Geological Survey Team of the Jiangxi Bureau of Geology in 1958. Further work was done by the 706 Team of the Geophysical Exploration Brigade of the Jiangxi Bureau of Geology, and later by the No. 916 Geological Team during the period from 1977 to 1984. The deposit has been mined since 1993, and has measured reserves of ∼220,000 tons of WO3 with

Corresponding author at: Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China. E-mail address: [email protected] (S. Wu).

https://doi.org/10.1016/j.oregeorev.2017.11.017 Received 8 September 2017; Received in revised form 19 November 2017; Accepted 19 November 2017 Available online 21 November 2017 0169-1368/ © 2017 Published by Elsevier B.V.

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Fig. 1. Map showing the distribution of mineral deposits along the Middle-Lower Yangtze River porphyry–skarn Cu–Au–Mo–Fe ore belt (YRB) and Jiangnan porphyry–skarn W belt, modified after Mao et al. (2017).

during Neoproterozoic time (Zhao et al., 2011; Luo et al., 2017; Faure et al., 2017). The YRB is located along the Middle-Lower Yangtze River Valley at the northern margin of the Yangtze Block (Fig. 1). The Xiangfan–Guangji and Tancheng–Lujiang faults mark the northern margins of the belt, separating it from the Qinling–Dabieshan orogenic belt and North China Craton, respectively. The southern margin of YRB is defined by the Yangxing–Changzhou fault. The Jiangnan Massif, south of the YRB and the Yangxing–Changzhou fault, is the southeastern part of the Yangtze Block. The massif is ENE trending and ∼120 km wide by ∼1500 km long (Faure et al., 2017; Wang et al., 2007). There are two sedimentary successions separated by an unconformity in the region of Jiangnan Massif. The sedimentary successions below the unconformity comprise the Shuangqiaoshan Group in northern Jiangxi Province, and the coeval Shangxi Group in southern Anhui Province (Wang and Li, 2003). The Shuangqiaoshan Group is mainly a thick pile of flysch composed of pelite and sandstone, with volcaniclastic rock (Wang et al., 2008). Recent studies suggest that this Group is Neoproterozoic in age (Wang et al., 2008). The Neoproterozoic sedimentary strata above the unconformity, the Dengshan Group, in northeastern Jiangxi Province, are mainly composed of sandstone, slate, conglomerate, and pelite, and lesser carbonate, spilite, and volcaniclastic rock (Wang and Li, 2003; Wang et al., 2007). The sedimentary cover above the Neoproterozoic sedimentary strata in the area

an average grade of 0.641%. Although the deposit has been mined for a long time, very little research work has been done (Tian and Yuan, 2008; Zhang et al., 2008; Wu et al., 2014) and no precise ages for mineralization have been reported. Zhang et al. (2008) obtained Rb–Sr isochron ages of 128 ± 3 Ma and 126.2 ± 2.6 Ma for quartz and whole-rock biotite granite, respectively, and a Sm–Nd isochron age of 121 ± 11 Ma for scheelite. They suggested that the mineralization at Xianglushan formed at 130–120 Ma. However, the Rb–Sr isotopic system is easily disturbed by later thermal events, so it is still necessary to obtain precise ages for magmatism and mineralization. In this study, we describe the basic geology and mineralization of the deposit, and present LA–ICP–MS U–Pb ages and Hf isotopic compositions of zircon from felsic intrusions, and molybdenite Re–Os ages and muscovite 40 Ar/39Ar ages from W ores. Our objectives are to constrain the ages of magmatism and mineralization, and the genesis of the deposit, and to discuss the geodynamic setting of the mineralization.

2. Geological background 2.1. Regional geology The South China Block consists of the Yangtze Block in the northwest and the Cathaysia Block in the southeast (Fig. 1a), which were welded together along the Jiangnan Fold Belt, or the Jiangnan Massif, 1162

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stocks and aplitic dykes (Figs. 2 and 3). The biotite granite, which is located in the core of the Xianglushan anticline, intruded Sinian–Cambrian strata. It is exposed over 1.6 km2, northeast of the mine area. The biotite granite is fine grained at the top and edges, and downward gradually becomes medium to coarse grained. Biotite granite is light-gray to white, and comprises quartz (55%–60%), Kfeldspar (∼20%), plagioclase (10%–15%), and biotite (5%–10%) (Fig. 4a and b), with accessory minerals including ilmenite, apatite, zircon, and titanite. Aplitic dykes were emplaced along NNE- to NEtrending faults south of the Xianglushan anticline. The dykes cut the strata, the granite intrusion, and some of the orebodies (Fig. 3). Aplitic dykes are white and fine-grained, and comprise quartz (65%–70%), plagioclase (10%–15%), K-feldspar (5%–10%), and biotite (5%–10%) (Fig. 4c and d), with accessory minerals including zircon and small amounts of apatite.

consists mainly of marine sedimentary rocks deposited during the Sinian to Early Triassic. The Sinian to Permian strata comprise mainly neritic clastic and carbonate rocks, including early Sinian sandstone, shale and carbonate, Cambrian limestone and siliciclastic rocks, Ordovician marine siliciclastic and carbonate rocks, Silurian and Devonian clastic rocks, Carboniferous carbonate rocks, and Permian marine carbonate and coal. Neoproterozoic and Mesozoic granitic rocks are abundant in the Jiangnan Massif. The representative Neoproterozoic intrusion is the Jiuling granodioritic pluton (828 ± 8 Ma, Zhong et al., 2005), which intruded the Shuangqiaoshan Group mainly in northern Jiangxi province. Widespread Yanshanian granitic rocks form small stocks intruded into Neoproterozoic granodiorite batholiths, Precambrian strata, and some Phanerozoic sequences. The Yanshanian granitoids in JNB mainly include granite, biotite granite, two-mica granite, monzonitic granite, porphyritic granite, granodiorite, and porphyritic granodiorite (BGMRJX, 1984; Hou, 2005).

3. Deposit geology 2.2. Local Geology 3.1. Ore-controlling structure The Xianglushan skarn W deposit is located about 15 km northwest of Xiushui County, Jiangxi Province. The hosting strata in the Xianglushan ore district consist of the upper Sinian Doushantuo and Dengying formations, the lower Cambrian Wangyinpu and Guanyintang formations, the middle Cambrian Yangliugang Formation, and the upper Cambrian Huayansi Formation. The direct hosting strata are the 300 m thick Yangliugang Formation argillaceous limestone, some of which is siliceous and carbonaceous. The sedimentary successions in the Xianglushan region form an anticline with the core of the Sinian strata and limbs of Cambrian strata. Intrusive rocks in the Xianglushan mine area mainly consist of granitic

The Xianglushan anticline is the major structure in the mine area, and was important for the emplacement of intrusive rocks and the distribution of orebodies (Fig. 2). The anticline is > 8 km long, 3–4 km wide, and extends eastward to the Taiyang Mountain (Fig. 2). The anticline plunges at 10°–25°, and the dip angle of both limbs is 10°–35°. The hinge of the anticline is curved but overall strikes in a NE direction. Sinian strata, which can be observed in some drill holes, occupy the core of the anticline, and biotite granite intruded the core. In addition, there are NNW-, NNE-, and NE-trending faults developed in the mine area.

Fig. 2. Geological map of the Xianglushan W deposit.

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Fig. 3. Geological cross-section along the No. 12 exploration line through the Xianglushan W deposit.

Fig. 4. Photographs and photomicrographs of the biotite granite and an aplitic dyke from the Xianglushan W deposit: (a) biotite granite; (b) photomicrograph of biotite granite under cross-polarized light; (c) aplitic dyke; (d) photomicrograph of aplitic dyke under cross-polarized light. Abbreviations: Bt (biotite); Qtz (quartz); Kfs (K-feldspar); Pl (plagioclase).

3.2. Alteration and mineralization zones

Xianglushan skarn W deposit, and the ore types are skarn, greisen, and sulfide W ores. The ores are massive, veinlet-disseminated, and veinlet. The ‘1W’ orebody at the contact zone is a major skarn orebody. It is a stratiform-like orebody 1250 m long with an average thickness of 12.69 m, with WO3 reserves of ∼200,000 tons. Disseminated and veinlet-disseminated ores are the predominant styles, and most have

The major orebodies are at the contact between impure limestone of the middle Cambrian Yangliugang Formation and the late Yanshanian biotite granite. The orebodies are mainly stratiform-like and lenticular (Fig. 3). There are about 50 scheelite orebodies making up the 1164

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Fig. 5. Representative examples of alteration and mineralization (skarn and greisen) within the Xianglushan deposit: (a) field photograph of greisen veins in biotite granite; (b) field photograph of greisen vein in (a) under ultraviolet light; (c) photomicrograph of greisen under plane-polarized light; (d, e) field photographs of massive skarn; (f) field photograph of stockwork skarn; (g, h) field photographs of banded skarn; (i) hand specimen of skarn with alternating garnet and pyroxene layers; (j) hand specimen of skarn; (k) photograph of the same hand specimen in (j) under ultraviolet light showing scheelite in the skarn; (l) field photograph of skarn with sulfide vein cutting skarn. Abbreviations: Grt (garnet); Px (pyroxene); Sch (scheelite); Qtz (quartz); Ms (muscovite).

cupolas of the biotite granite, through W skarn and sulfide-scheelite bands near the pluton, to distal quartz-sulfide ± scheelite veins. Greisen stockworks and veins (Fig. 5a), up to 30 cm wide and tens of meters long, occur at the top of the biotite granite. Intense greisen veins are usually accompanied by high-grade scheelite mineralization. Greisen is mainly composed of quartz, muscovite, scheelite, and pyrrhotite (Fig. 5b and c). Scheelite in greisen occurs as disseminations and aggregates of anhedral grains (Fig. 5b and c). In proximity to the pluton

xenomorphic-hypidiomorphic granular textures. The ore mineral is scheelite. Alteration types in the deposit include calc-silicate (skarn), greisen, potassic metasomatism, silicification, chloritization, fluoritization, sericitization, actinolitization, and carbonate alteration. Calcsilicate (skarn) and greisen are the major alteration types. The main mineralization styles are skarn, greisen, sulfide bands, and quartz-sulfide-scheelite veins. The mineralization is zoned with the proximal W greisen within the 1165

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(caption on next page)

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Fig. 6. Representative examples of alteration and mineralization (retrograde alteration, banded sulfide, quartz-sulfide-scheelite vein, quartz-scheelite vein, calcite vein, fluorite vein) within the Xianglushan deposit: (a) photograph of retrograde alteration; (b) photograph of retrograde alteration under ultraviolet light showing the distribution of scheelite; (c) field photograph of banded sulfide; (d) photograph of sulfide in hand specimen; (e) photomicrograph of sulfide; (f) field photograph of quartz-sulfide-scheelite vein; (g) photograph of quartzsulfide-scheelite vein in hand specimen; (h) photograph of quartz-sulfide-scheelite in hand specimen under ultraviolet light highlighting the presence of scheelite; (i) photomicrograph of a quartz-sulfide-scheelite vein under plane-polarized light; (j) photomicrograph of a quartz-sulfide-scheelite vein under reflected light; (k) field photograph of a quartz-scheelite vein; (l) photograph of a hand specimen of a quartz-scheelite vein; (m) photograph of a quartz-scheelite vein under ultraviolet light highlighting the presence of scheelite; (n) photomicrograph of a quartz-scheelite vein under plane-polarized light; (o) field photograph showing late-stage calcite veins cut by a fluorite vein. Abbreviations: Ccp (chalcopyrite); Po (pyrrhotite); Sch (scheelite); Sp (sphalerite); Qtz (quartz); Cal (calcite).

techniques, and were subsequently handpicked under a binocular microscope to obtain muscovite grains with > 99% purity.

there is massive and stockwork skarn which gradually passes outward into skarn bands (Fig. 5d–l). The W skarn comprises scheelite, garnet, pyroxene, amphibole, quartz, and actinolite, with minor chalcopyrite, pyrrhotite, pyrite, and molybdenite. Scheelite in skarns is white to offwhite in color, and mainly forms subhedral or anhedral grains, either disseminated or as veinlets. Retrograde alteration of skarn mainly comprises epidote, fluorite, quartz, scheelite, pyrite, pyrrhotite, chalcopyrite, and calcite (Fig. 6a and b). Multilayered sulfide bands (Fig. 6c), usually 0.3 m to 1.5 m thick, are generally interbedded with skarn bands to form orebodies. Minerals in the sulfide bands are mainly pyrrhotite, pyrite, chalcopyrite, sphalerite, molybdenite, scheelite, quartz, and calcite (Fig. 6d and e). Scheelite in sulfide bands is anhedral or subhedral, and comprises disseminated grains and veinlet-disseminated styles. Quartz-sulfide-scheelite veins of the outer contact zone, ∼0.05–0.5 m wide, mainly consist of pyrite, pyrrhotite, chalcopyrite, sphalerite, scheelite, quartz, and calcite (Fig. 6f–j). In addition, there are some quartz-scheelite veins several to dozens of centimeters thick, comprising quartz, scheelite, and minor pyrite and pyrrhotite (Fig. 6k–n). Scheelite comprises disseminated grains and veinlet-disseminated styles. This late stage of mineralization was followed by barren carbonate and fluorite veins (Fig. 6o). Mineral assemblages and textural relationships show that mineralization and alteration in the Xianglushan skarn W deposit can be divided into five stages: a skarn stage, including the formation of skarn and sulfide bands; a retrograde stage; a greisen stage; a quartz-sulfidescheelite stage, including the formation of quartz-sulfide-scheelite veins and quartz-scheelite veins; and a carbonate and fluorite vein stage.

4.2. Analytical methods LA–MC–ICP–MS zircon dating was completed at the Institute of Mineral Resources, Chinese Academy of Geological Sciences, using a Finnigan Neptune-type MC–ICP–MS and an associated Newwave UP213 laser-ablation system. Ablated material was transported to the MC–ICP–MS instrument using He carrier gas, and analyses were undertaken with a 32 μm spot width and a 10 Hz repetition rate. An analytical approach was undertaken whereby 5–7 measurements of unknown zircons were conducted between 3 measurements of standard zircons GJ-1 (n = 2) and Plesovice (n = 1). Data were processed using ICP–MS Datacal (Liu et al., 2010), and zircon U–Pb ages and concordia diagrams were obtained using Isoplot 3.0 (Ludwig, 2003). Analytical procedures were similar to those described by Hou et al. (2009). Molybdenite Re–Os isotopic analysis was undertaken in the Re–Os Laboratory of the National Research Center of Geoanalysis, Chinese Academy of Geological Sciences, Beijing, using a Thermo Electron TJA X-series ICP–MS instrument and analytical procedures outlined in Shirey and Walker (1995), Mao et al. (1999), and Du et al. (2004). The Re–Os model ages were calculated using the equation t = [ln (1 + 187Os/187Re)]/λ, where λ is the decay constant of 187Re, 1.666 × 10−11 y−1 (Smoliar et al., 1996). Average blanks for the total Carius tube procedure were 0.0022 ± 0.0011 ng for Re, 0.00073 ± 0.00005 ng for common Os, and 0.00012 ± 0.00001 ng for 187Re. In order to check accuracy, duplicate analyses of standard sample GBW04435 (HLP) were performed, and provided a Re–Os model age of 222.1 ± 3.2 Ma, which is in good agreement with the recommended Re–Os model age of 221.4 ± 5.6 Ma (Du et al., 2004). Based on these reliable results, model ages and isochron ages of the six samples were estimated using Isoplot software (Ludwig, 2003). Muscovite grains with a purity of > 99% separated for Ar–Ar dating were cleaned in an ultrasonic bath. After cleaning, the sample was sealed in a quartz bottle for irradiation in a nuclear reactor (Swimming Pool Reactor, Chinese Institute of Atomic Energy, Beijing). Irradiation time was 1444 min, neutron flux was ∼2.65 × 1013 nx cm−2 s−1, and the integrated neutron flux was 2.30 × 1018 n cm−2. The monitor used in this work is the ZBH-25 biotite standard, with an age of 132.7 ± 1.2 Ma and a potassium content of 7.6%, which was also irradiated. The sample and monitor were heated in a graphite furnace, with a heating time for each stage of 10 min, with 20 min for purification. Mass analysis was carried out by multiple collector noble-gas mass spectrometry (Helix MC), and 20 sets of data were obtained for each spectral peak. Analyses were performed at the Isotope Laboratory of the Institute of Geology, Chinese Academy of Geological Sciences. Measured isotopic ratios were corrected for mass discrimination, atmospheric Ar component, blanks, and radiation-induced mass interference. Correction factors for interfering isotopes produced during irradiation were determined by analysis of irradiated pure K2SO4 and CaF2, yielding the following ratios: (36Ar/37Ar0)Ca = 0.0002389; (40Ar/39Ar)K = 0.004782; (39Ar/37Ar0)Ca = 0.000806. The decay constant used for 40K is λ = 5.543 × 10−10 y−1 (Steiger and Jäger, 1977). All 37Ar abundances were corrected for radioactive decay, and the ISOPLOT program was used to calculate plateau ages, and to plot isochron and inverse-isochron diagrams (Ludwig, 2003). Age uncertainties

4. Sampling and analytical methods 4.1. Sampling Biotite granite and aplite samples were collected from the No. five mining pit in the Xianglushan W deposit for zircon separation. Samples were crushed and elutriated by water, then separated using heavy-liquid and magnetic methods. Zircon crystals were handpicked under a binocular microscope, mounted in epoxy resin, and polished to expose the grain interiors. Transmitted- and reflected-light photomicrographs and cathodoluminescence (CL) images of zircons were obtained to identify internal microstructures and to target sites within zoned zircon crystals. Transmitted- and reflected-light images were taken under a binocular microscope connected to a computer. Six molybdenite separates for Re–Os dating were collected from skarn ores in the No. five mining pit in the Xianglushan W deposit. Molybdenite characteristically forms flakes in skarns (Fig. 7a). Molybdenite crystals are mostly 0.5–2 mm long and intergrown with ore minerals including scheelite, pyrrhotite, and chalcopyrite (Fig. 7b). Molybdenite concentrates for Re–Os isotopic analysis were prepared using conventional methods: samples were crushed, then underwent gravity and magnetic separation, and molybdenite grains were handpicked under a binocular microscope to obtain molybdenite with > 99% purity. Muscovite was collected from greisen veins at the top of the biotite granite pluton in Line 22 at the Xianglushan deposit. Muscovite intergrowths with scheelite can be clearly observed (Fig. 7c–f). Muscovite grains were separated using standard magnetic and heavy-liquid 1167

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Fig. 7. Photographs and photomicrographs of samples used for molybdenite Re–Os dating and muscovite Ar–Ar dating: (a) photograph of molybdenite in skarn; (b) photomicrograph of molybdenite in skarn under reflected light; (c) photograph of greisen vein containing scheelite under ultraviolet light; (d) photograph of greisen vein containing scheelite; (e) photomicrograph of greisen vein containing scheelite under plane-polarized light (mineral assemblage comprises quartz, muscovite, and scheelite); (f) photomicrograph of greisen vein containing scheelite under cross-polarized light. Abbreviations: Ccp (chalcopyrite); Sch (scheelite); Po (pyrrhotite); Mo (molybdenite); Qtz (quartz); Ms. (muscovite).

2012a). The energy density of laser ablation was 5.3 J cm−2. Helium was used as the carrier gas within the ablation cell and was merged with argon (make-up gas) after the ablation cell. As demonstrated by previous study, a consistent two-fold signal enhancement was achieved for the 193 nm laser in helium rather than argon (Hu et al., 2008a). A simple Y junction was used downstream of the sample cell to add small amounts of nitrogen (4 mL min−1) to the argon make-up gas (Hu et al., 2008b). Compared with the standard arrangement, the addition of nitrogen with the newly designed ‘X skimmer cone’ and ‘Jet sample cone’ in the Neptune Plus improved the signal intensity of Hf, Yb, and Lu by factors of 5.3, 4.0, and 2.4, respectively. All zircon data in this study

are reported at a 95% confidence level (2σ). Operational and dataprocessing procedures were similar to those described by Chen et al. (2006). LA–MC–ICP–MS zircon Hf isotope analyses were performed using a Neptune Plus MC–ICP–MS (Thermo Fisher Scientific, Germany) in combination with a Geolas 2005 excimer ArF laser-ablation system (Lambda Physik, Göttingen, Germany) hosted at the State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan. A “wire” signal-smoothing device is included in this laser ablation system, by which smooth signals are produced even at very low laser repetition rates of 1 Hz (Hu et al., 1168

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of 1.1:1–2.4:1. Oscillatory zoning is well developed in CL images (Fig. 8). Sixteen zircon crystals from biotite granite sample 15XLS-38 were analyzed (Table 1), with 238U and 232Th contents, respectively, of 243.7–2048.4 ppm and 188.6–3125.7 ppm. The derived Th/U ratios of 0.5–2.2 are indicative of magmatic origin (Corfu et al., 2003; Hoskin and Schaltegger, 2003). Analysis of these zircons yielded 206Pb/238U ages of 121.6 ± 1.7 Ma to 127.2 ± 1.4 Ma, with a weighted-mean age of 123.81 ± 0.77 Ma (MSWD = 0.94, Fig. 9a and b), which is interpreted as being the crystallization age of the biotite granite. Most zircons in the aplitic dyke are euhedral, colorless and transparent, except for some subhedral crystals. They are generally 50–140 μm long, with aspect ratios of approximately 1.1:1–3:1. Oscillatory zoning is well developed in some of the zircons in CL images (Fig. 8). Seven analyses were undertaken of zircon from aplitic dyke sample 15XLS-67 (Table 1), with 238U and 232Th contents, respectively, of 207–1376 ppm and 226–799 ppm, and Th/U ratios of 0.28–1.41. Analysis of these zircons yielded 206Pb/238U ages of 115.1 ± 2.8 Ma to 120.0 ± 1.8 Ma, with a weighted-mean age of 117.3 ± 1.7 Ma (MSWD = 0.96, Fig. 9c and d), which is interpreted as being the crystallization age of the aplitic dyke.

were acquired in a single-spot ablation mode, with a spot diameter of 44 μm. Each measurement consisted of 20 s of acquisition of background signal, followed by 50 s of ablation signal acquisition. Detailed operating conditions for the laser-ablation system, the MC–ICP–MS instrument, and the analytical method were as described by Hu et al. (2012b). The major accuracy limitation of zircon Hf isotope determinations by LA–MC–ICP–MS is the isobaric interference of 176Yb and, to a much lesser extent 176Lu, on 176Hf. It has been shown that the mass fractionation of Yb (βYb) is not constant over time and that βYb values obtained from the introduction of solutions is unsuitable for zircon measurements in situ (Woodhead et al., 2004). The under- or over-estimation of βYb undoubtedly affects the correction of 176Yb and the determined 176 Hf/177Hf ratio. We applied the directly obtained βYb value from the zircon sample itself in real-time in this study. The 179Hf/177Hf and 173 Yb/171Yb ratios were used to calculate the mass bias of Hf (βHf) and 179 Yb (βYb), normalized to Hf/177Hf = 0.7325 and 173 Yb/171Yb = 1.132685 (Fisher et al., 2014), using an exponential correction for mass bias. Interference of 176Yb on 176Hf was corrected by analysing the interference-free 173Yb isotope, and a ratio of 176 Yb/173Yb = 0.79639 (Fisher et al., 2014) to calculate 176Yb/177Hf. Similarly, the relatively minor interference of 176Lu on 176Hf was corrected by measuring the intensity of the interference-free 175Lu isotope, and using the recommended ratio 176Lu/175Lu = 0.02656 (Blichert-Toft et al., 1997) to calculate 176Lu/177Hf. The mass bias of Yb (βYb) was used to calculate the mass fractionation of Lu because of their similar physicochemical properties. Off-line selection and integration of analyte signals, and mass-bias calibrations were performed using ICPMSDataCal software (Liu et al., 2010).

5.2. Molybdenite Re–Os ages

5. Results

Analyses of molybdenite samples are reported in Table 2. Concentrations of 187Re and 187Os are, respectively, 7.62–14.31 ppm and 15.85–30.01 ppb. All six Re–Os model ages are consistent within error, and range from 124.9 ± 1.9 Ma to 126.1 ± 1.8 Ma, with a weightedmean age of 125.45 ± 0.73 Ma (Fig. 10a). An isochron age of 126.6 ± 2.5 Ma (MSWD = 0.59) was calculated using ISOPLOT (Fig. 10b; Ludwig, 2003). The consistency of the model and isochron ages for these six samples suggests that the results are reliable.

5.1. Zircon U–Pb ages

5.3. Muscovite Ar–Ar ages

Zircons separated from the biotite granite are euhedral, colorless, and transparent. They are generally 75–170 μm long, with aspect ratios

Muscovite 40Ar–39Ar age determinations were carried out on grains intergrown with scheelite from greisen veins. Analytical results are

Fig. 8. Cathodoluminescence images of zircon crystals from (a) biotite granite sample 15XLS-38; and (b) aplitic dyke sample 15XLS-67 from the Xianglushan deposit.

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Table 1 LA–ICP–MS zircon U–Pb data for samples of a biotite granite and an aplitic dyke from the Xianglushan deposit. spot

concentrations (ppm)

biotite granite (mean = 123.81 ± 0.77, MSWD = 0.96, n = 16) 15XLS-38-1 5 189 244 0.77 0.0544 15XLS-38-2 18 968 696 1.39 0.0525 15XLS-38-3 14 458 618 0.74 0.0504 15XLS-38-4 9 217 416 0.52 0.0532 15XLS-38-5 22 1205 845 1.43 0.0518 15XLS-38-6 12 658 430 1.53 0.051 15XLS-38-7 15 1026 477 2.15 0.0513 15XLS-38-8 21 1093 746 1.47 0.0513 15XLS-38-9 32 1118 1272 0.88 0.0522 15XLS-38-10 17 427 704 0.61 0.0509 15XLS-38-11 16 972 528 1.84 0.0514 15XLS-38-12 19 514 803 0.64 0.0497 15XLS-38-13 60 3126 2048 1.53 0.0534 15XLS-38-14 14 510 555 0.92 0.0533 15XLS-38-15 15 317 639 0.5 0.0523 15XLS-38-26 33 1144 1263 0.91 0.0513

0.0062 0.002 0.0029 0.0048 0.0065 0.0043 0.0019 0.002 0.0014 0.0019 0.0023 0.0026 0.0016 0.0023 0.0027 0.002

aplitic dyke (mean = 117.3 ± 1.7, MSWD = 0.96, n = 7) 15XLS-67-1 8 457 325 1.41 0.0514 15XLS-67-2 30 799 1376 0.58 0.051 15XLS-67-3 6 288 207 1.39 0.0554 15XLS-67-4 18 226 802 0.28 0.0515 15XLS-67-5 11 305 436 0.7 0.0494 15XLS-67-6 14 468 548 0.85 0.0513 15XLS-67-7 22 524 915 0.57 0.0499

0.0028 0.0015 0.0058 0.0033 0.0044 0.0032 0.0025

U

207

Pb/206Pb

Age (Ma) 207

Th

238

isotope ratio 1σ

Pb

232

Th/U

Pb/235U

1σ

206

0.1415 0.1409 0.1337 0.1377 0.1401 0.1374 0.1331 0.138 0.1386 0.1389 0.1359 0.133 0.1414 0.14 0.1362 0.1353

0.0157 0.0053 0.0076 0.0114 0.0196 0.013 0.0049 0.0053 0.0035 0.0051 0.0059 0.0073 0.0041 0.0056 0.0072 0.0053

0.1323 0.128 0.1317 0.127 0.1212 0.128 0.1296

0.0079 0.0046 0.013 0.0076 0.0101 0.0073 0.0071

Pb/238U

1σ

207

Pb/206Pb

1σ

207

0.0193 0.0196 0.0194 0.0192 0.0192 0.0193 0.0192 0.0196 0.0194 0.0199 0.0196 0.0193 0.0192 0.0193 0.019 0.0192

0.0005 0.0002 0.0003 0.0004 0.0006 0.0006 0.0002 0.0003 0.0002 0.0002 0.0002 0.0002 0.0002 0.0002 0.0003 0.0002

387 309 217 339 280 239 254 254 295 239 257 183 346 343 302 254

262 89 137 206 263 203 85 89 68 85 106 122 67 96 120 88

0.0188 0.0182 0.0183 0.018 0.018 0.0183 0.0188

0.0004 0.0003 0.0011 0.0003 0.0004 0.0004 0.0003

257 243 428 261 165 257 191

131 67 240 150 200 144 114

Pb/235U

1σ

206

Pb/238U

1σ

134 134 127 131 133 131 127 131 132 132 129 127 134 133 130 129

14 5 7 10 18 12 4 5 3 5 5 7 4 5 6 5

123 125 124 122 123 123 122 125 124 127 125 123 123 123 122 123

3 1 2 3 4 4 1 2 1 1 2 1 1 1 2 1

126 122 126 121 116 122 124

7 4 12 7 9 7 6

120 116 117 115 115 117 120

2 2 7 2 3 3 2

Fig. 9. LA–ICP–MS U–Pb Concordia diagrams and weighted-mean age diagrams for samples of a biotite granite (15XLS-38) and an aplitic dyke (15XLS-67). Diagrams (a) and (b) refer to the biotite granite and diagrams (c) and (d) refer to the aplitic dyke.

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Table 2 Re–Os data for molybdenite from the Xianglushan deposit. Sample No.

15XLS-42 15XLS-43 15XLS-44 15XLS-45 15XLS-46 15XLS-47

Weight (g)

0.02348 0.01057 0.01050 0.01077 0.01007 0.01031

Re (ppb)

Common Os (ppb)

187

187

Re (ppb)

Os (ppb)

Model ages (Ma)

Measured

2σ

Measured

2σ

Measured

2σ

Measured

2σ

Measured

2σ

19.65 16.52 12.12 19.06 13.77 22.77

0.20 0.12 0.08 0.13 0.09 0.19

0.2302 0.2841 0.1566 0.2762 0.4041 1.0141

0.0063 0.0155 0.0096 0.0408 0.0372 0.0215

12.35 10.38 7.616 11.98 8.652 14.31

0.12 0.07 0.053 0.08 0.059 0.12

25.74 21.84 15.85 25.09 18.10 30.01

0.15 0.15 0.11 0.18 0.15 0.23

124.9 126.1 124.8 125.6 125.5 125.8

1.9 1.8 1.7 1.8 1.8 1.9

molybdenite, many studies indicate that a decoupling effect may exist in the Re–Os system of molybdenite (Stein et al., 2003). However, geologically younger, fine-grained (< 2 mm) molybdenite samples appear to show little Re and 187Os decoupling (Selby and Creaser, 2004). Molybdenite from the Xianglushan deposit is fine grained, so decoupling of Re and Os is unlikely and Re–Os age data obtained during this study are therefore considered reliable. The Re–Os isochron age of molybdenite separated from skarn ore is 126.6 ± 2.5 Ma and, because the molybdenite is intergrown with scheelite, this age also represents the time of mineralization of the skarn W ore. The molybdenite Re–Os age is consistent with the U–Pb zircon age of 123.81 ± 0.77 Ma for the biotite granite. The 40Ar–39Ar dating of muscovite intergrown with scheelite in greisen yielded indistinguishable plateau, isochron, and inverse-isochron ages, within analytical uncertainty. The plateau age (122.28 ± 0.78 Ma) is considered a better estimate of the crystallization age of the muscovite, and it is interpreted as being the age of the greisen ore. The 40Ar–39Ar plateau age is consistent with the zircon LA–ICP–MS U–Pb age of 123.81 ± 0.77 Ma for the biotite granite in the Xianglushan deposit. On the basis of the zircon LA–ICP–MS U–Pb, molybdenite Re–Os, and muscovite 40Ar–39Ar ages, together with the development of skarn at the contact with the biotite granite and the presence of greisen at the top of the biotite granite, we conclude that W mineralization at the Xianglushan deposit is genetically related to the granite. Magmatism and mineralization in the Xianglushan mining area occurred during the Early Cretaceous. We infer from the molybdenite Re–Os and muscovite Ar–Ar ages that mineralization in the Xianglushan deposit occurred during the period of ca 126 Ma to ca 122 Ma.

listed in Table 3 and illustrated in Fig. 11. Ten continuous steps at temperatures of 860 °C–1140 °C constitute a uniform and remarkably flat 40Ar/39Ar age spectrum with 91.3% of 39Ar released. These steps yield a well-defined plateau age of 122.28 ± 0.78 Ma (MSWD = 0.46), an isochron age of 122.1 ± 1.3 Ma (MSWD = 2.1) at an initial 40 Ar/36Ar ratio of 295.0 ± 7.5, and an inverse-isochron age of 122.0 ± 1.2 Ma (MSWD = 6.9) at an initial 40Ar/36Ar ratio of 297 ± 11 (Fig. 11). 5.4. Zircon Hf isotopic compositions The Lu–Hf isotopic compositions of zircons separated from the biotite granite are listed in Table 4. Previously measured 206Pb/238U ages were used in the calculation of the initial Hf ratios. Fifteen analyses were conducted on zircon crystals from the biotite granite (Sample 15XLS-38) yielding 176Hf/177Hf ratios of 0.28628–0.282409, but mostly between 0.282613 and 0.282537. Calculated εHf(t) values are −2.5 to −10.2, with most in the range −3.1 and −5.7. The corresponding TDM2 ages are 1611–1185 Ma, with most being in the range 1363–1218 Ma (Table 4). 6. Discussion 6.1. Timing of magmatism and associated W mineralization Our LA–ICP–MS zircon U–Pb dating indicates that the biotite granite formed at 123.81 ± 0.77 Ma, whereas the aplitic dyke formed at 117.3 ± 1.7 Ma. The dyke is younger than the biotite granite. The molybdenite Re–Os geochronometer is remarkably robust, and is generally not disturbed by prolonged (e.g., 2–8 Myr) or high-temperature (400 °C–500 °C) hydrothermal activity (Selby and Creaser, 2001), or by later tectonothermal events (Stein et al., 1998). Although Re–Os geochronology can provide accurate and precise ages for

6.2. Timing of Yanshanian magmatism and mineralization of the JNB Previous studies have revealed that the extensive Mesozoic deposits

Fig. 10. A Re–Os mean-age diagram and a isochron for six samples of molybdenite from the Xianglushan W deposit. Diagram (a) refers to mean-age diagram, diagram (b) refers to Re–Os isochron diagram.

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Table 3 40 Ar–39Ar data for muscovite from greisen vein ore in the Xianglushan deposit. T(°C)

(40Ar/39Ar)m

(36

Ar/39Ar)m

(37Ar/39Ar)m

15XLS-31, sample weight = 14.15 mg, J = 0.004629 800 42.7487 0.0978 0.0903 860 23.3583 0.0281 0.0069 890 19.6315 0.0151 0.0091 920 15.8974 0.0028 0.0144 950 15.5466 0.0015 0.0045 980 15.6074 0.0017 0.0082 1010 15.8892 0.0025 0.0000 1040 16.6187 0.0048 0.0064 1070 16.6817 0.0055 0.0453 1100 16.6612 0.0043 0.0000 1140 15.8566 0.0020 0.0000 1180 16.9173 0.0039 0.0308 1400 157.0826 0.4467 4.7727

(38Ar/39Ar)m

40

0.0327 0.0176 0.0155 0.0130 0.0128 0.0128 0.0128 0.0132 0.0137 0.0135 0.0128 0.0129 0.1186

32.37 64.38 77.25 94.86 97.05 96.71 95.33 91.38 90.31 92.42 96.26 93.21 16.18

40

Ar (%)

Ar*/39Ar

39

13.8371 15.0382 15.1658 15.0808 15.0873 15.0935 15.1471 15.1865 15.0660 15.3990 15.2631 15.7693 25.5102

Ar(×10−14mol)

0.61 1.45 2.75 4.91 6.72 5.62 4.42 1.90 1.55 1.90 3.50 2.69 0.01

39

Ar(Cum.) (%)

1.60 5.40 12.63 25.53 43.21 57.99 69.62 74.63 78.71 83.70 92.91 99.97 100.00

Apparent age ( ± 1σ)/Ma

112.0 ± 1.5 121.4 ± 1.3 122.4 ± 1.2 121.7 ± 1.2 121.8 ± 1.2 121.8 ± 1.2 122.3 ± 1.2 122.6 ± 1.2 121.6 ± 1.2 124.2 ± 1.3 123.2 ± 1.2 127.1 ± 1.3 201 ± 67

Fig. 11. Plateau, isochron, and inverse-isochron 40Ar–39Ar ages of muscovite from the greisen-type ore in the Xianglushan W deposit. Diagram (a) refers to Plateau age, diagram (b) refers to isochron age, and diagram (c) refers to inverse-isochron age.

area formed at 148–135 Ma, and most mineralization is of 150–140 Ma age (Feng et al., 2012; Mao et al., 2013b, 2015). Previous geochronological data for deposits in the JNB are listed in Table 5. These data, along with our new age data, demonstrate that Yanshanian magmatic events in the JNB mainly occurred at 155–135 Ma and 135–120 Ma corresponding to two stages of mineralization at 150–135 Ma and 130–120 Ma (Fig. 12, Table 5). Mao et al. (2011) recognized two episodes of magmatism and mineralization in the Middle-Lower Yangtze River Valley metallogenic belt, 156–137 Ma high-K calc-alkaline granitoids associated with 148–135 Ma porphyry–skarn-stratabound Cu–Au–Mo–Fe deposits; and 135–123 Ma shoshonitic series associated with 135–123 Ma magnetite-apatite deposits. Zhou et al. (2015) concluded that there are three stages of porphyry

of South China are products of multiple pulses of magmatism and mineralization. In the last several years, some precise age determinations for intrusive rocks and mineralization in the JNB have been obtained (Table 5). The majority of Yanshanian granite and associated porphyry–skarn W deposits in the JNB formed in the Late Jurassic (152–135 Ma), but there are also granites and granite-related W and Sn deposits that formed in the Early Cretaceous (135–122 Ma) (Mao et al., 2011; Hu et al., 2017a,b). These Early Cretaceous granites and deposits are represented by the Pengshan granite (129–128 Ma; Luo et al., 2010), Jianfengpo tin deposit (130–128 Ma; Xu et al., 2015), and Xianglushan tungsten deposit (this study). There are 134–130 Ma granites in the Dahutang porphyry–tungsten deposit (Huang and Jiang, 2014; Jiang et al., 2015), although most granites in the Dahutang mine

Table 4 Zircon Lu–Hf isotopic data for zircon from biotite granite in the Xianglushan deposit. Rock

Spot number

Age (Ma)

176

Yb/177Hf

176

Lu/177Hf

176

biotite granite

G132-XLS-38-2 G132-XLS-38-3 G132-XLS-38-4 G132-XLS-38-5 G132-XLS-38-6 G132-XLS-38-7 G132-XLS-38-8 G132-XLS-38-9 G132-XLS-38-11 G132-XLS-38-12 G132-XLS-38-13 G132-XLS-38-14 G132-XLS-38-15 G132-XLS-38-16 G132-XLS-38-17

123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81 123.81

0.030040 0.018110 0.060065 0.038449 0.038726 0.053415 0.043013 0.046474 0.024495 0.069008 0.027215 0.034350 0.039796 0.056520 0.040874

0.001191 0.000635 0.002254 0.001503 0.001507 0.002040 0.001647 0.001809 0.000961 0.002555 0.001027 0.001349 0.001546 0.001998 0.001550

0.282592 0.282409 0.282613 0.282562 0.282564 0.282562 0.282555 0.282588 0.282568 0.282571 0.282537 0.282628 0.282600 0.282608 0.282573

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Hf/177Hf

1σ

εHf(0)

εHf(t)

TDM1(Ma)

TDM2(Ma)

fLu/Hf

0.000019 0.000019 0.000018 0.000018 0.000021 0.000022 0.000022 0.000032 0.000017 0.000021 0.000020 0.000020 0.000021 0.000019 0.000020

-6.4 -12.8 -5.6 -7.4 -7.3 -7.4 -7.7 -6.5 -7.2 -7.1 -8.3 -5.1 -6.1 -5.8 -7.0

-3.7 -10.2 -3.1 -4.8 -4.7 -4.9 -5.1 -4.0 -4.6 -4.6 -5.7 -2.5 -3.5 -3.2 -4.4

939 1180 935 990 986 1004 1003 961 967 1005 1013 892 937 936 975

1255 1611 1218 1316 1310 1318 1329 1266 1301 1302 1363 1185 1242 1227 1293

-0.96 -0.98 -0.93 -0.95 -0.95 -0.94 -0.95 -0.95 -0.97 -0.92 -0.97 -0.96 -0.95 -0.94 -0.95

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Table 5 Compilation of ages for Yanshanian magmatism and mineralization along the Jiangnan porphyry–skarn W belt. Deposit

mineralization type

rock

analyzed mineral

method

age (Ma)

refference

Zhuxi

skarn W–Cu deposit

fine-grain muscovite granite

zircon

146.9 ± 0.97

granite porphyry

zircon

LA–ICP–MS U–Pb LA–ICP–MS U–Pb Ar–Ar Re–Os

Wang et al. (2015) Li et al. (2014)

muscovite molybdenite Dahutang

porphyry W deposit

Shimensi (Dahutang ore field) Dalingshang (Dahutang ore field) Yangchuling

porphyry W–Mo deposit

Xianglushan

skarn W deposit

Matou

porphyry Cu–Mo deposit

granite porphyry

zircon

granite porphyry

zircon

Porphyritic muscovite granite porphyritic-like two-mica granite middle- to fine-grained muscovite granite porphyritic two-mica granite

zircon zircon zircon zircon

fine-grained two-mica granite porphyritic biotite granite fine-grained granite granite porphyry

zircon zircon zircon

biotite granite porphyry

molybdenite zircon

monzonitic granite porphyry

zircon

granodiorite

zircon

zircon

Dongyuan

skarn–porphyry type W–Mo deposit

porphyry W–Mo deposit

150 146.7 ± 0.9

Pan et al. (2017)

146.01 ± 0.78

Xiang et al. (2015) Huang and Jiang (2013) Huang and Jiang (2012) Huang and Jiang (2014)

134.6 ± 1.2 144.2 ± 1.3 144.0 ± 0.6 133.7 ± 0.5 130.3 ± 1.1 130.7 ± 1.1 147.4 ± 0.58–148.3 ± 1.9 144.7 ± 0.47–146.1 ± 0.64 143.0 ± 0.76–143.1 ± 1.2

Mao et al. (2015)

Re–Os LA–ICP–MS U–Pb

139.18 ± 0.97(isochron age) 130.4 ± 1.6

Mao et al. (2013b) Peng et al. (2015)

143.8 ± 0.5

Mao et al. (2017)

149.8 ± 0.6

molybdenite

LA–ICP–MS U–Pb LA–ICP–MS U–Pb Re–Os Rb–Sr isochron Sm–Nd isochorn Rb–Sr isochron

128 ± 3 M a 121 ± 11 M a 126.6 ± 2.6

Zhang et al. (2008)

biotite granite

quartz scheelite whole rock

granodiorite porphyry

zircon

LA–ICP–MS U–Pb Re–Os

146.7 ± 2.3

Wang (2012)

148 ± 1 (isochron age) 146 ± 1 (mean age) 147 ± 2

Liu et al. (2012)

148.6 ± 2.1 150.2 ± 2.7 139.5 ± 1.5

Yang et al. (2014a) Zhu et al. (2014)

136.3 ± 2.6 (isochron age) 130 ± 1.5 134.1 ± 2.2 (isochron age) 133.3 ± 1.3 129.0 ± 1.2

Qin et al. (2010b)

molybdenite

Baizhangyan

LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb

149.5 ± 1.9 and 151 ± 2

granodiorite porphyry

zircon

porphyry type ore sand-slate type ore granodiorite porphyry

molybdenite molybdenite zircon

disseminated molybdenite fine-grain granite fine-grain granite monzonitic granite

molybdenite zircon molybdenite zircon Zircon

fine-grained granite

Zircon

diorite dykes

Zircon

granodiorite porphyry granodiorite porphyry granite porphyry medium-fine grain granodiorite porphyry

LA–ICP–MS U–Pb Re–Os Re–Os LA–ICP–MS U–Pb

molybdenite

Re–Os SHRIMP U–Pb Re–Os SIMS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb Re–Os

molybdenite

Re–Os

zircon zircon zircon molybdenite zircon

SHRIMP SHRIMP SHRIMP Re–Os SHRIMP

U–Pb U–Pb U–Pb U–Pb

146.4 ± 1.0

Song et al. (2012b) Li et al. (2015b)

135.34 ± 0.92 145.3 ± 1.7 136.9 135.0 143.8 146.3

± ± ± ±

4.5 (isochron age) 1.2 (mean age) 2.1 2.0

149 ± 1 152 ± 1 148.6 ± 1.8 146.4 ± 2.3 46 ± 1

Wang et al. (2011) Qin et al. (2010a) Zhou et al. (2011) Zhou et al. (2011) (continued on next page)

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Table 5 (continued) Deposit

mineralization type

rock

analyzed mineral

method

age (Ma)

refference

Jitoushan

skarn W–Mo deposit

granodiorite

zircon

SIMS U–Pb

138.8 ± 1.0

Song et al. (2012a)

granite porphyry quartz porphyry

zircon molybdenite zircon

SIMS U–Pb Re–Os SIMS U–Pb

138.3 ± 1.2 136.6 ± 1.5 127.12 ± 0.92

granite

zircon

LA–ICP–MS U–Pb LA–ICP–MS U–Pb LA–ICP–MS U–Pb

140.5 ± 1.3

Zhuxiling

skarn W–Ag–Mopolymetallic deposit

zircon zircon Kaobeijian

Xiaoyao

skarnW–Cu–Mo deposit

Chen et al. (2013)

138.7 ± 1.6 142 ± 1.6

granodiorite porphyry

zircon zircon zircon

SHRIMP U–Pb

151.9 ± 1.1 147.7 ± 1.3 152.7 ± 1.7

Zhou et al. (2012)

granodiorite porphyry

biotite

Ar–Ar

141.46 ± 0.62

Hou (2005) Jiang et al. (2015)

Shiweidong| (Dahutang ore field)

muscovite porphyritic (or two-mica) granite

∼144

Shimensi (Dahutang ore field)

porphyritic biotite granite

∼144

Shiweidong Dahutang ore field)

medium-fine grain granite or granite porphyry

∼135–130

Dalingshang (Dahutang ore field)

medium-fine grain granite or granite porphyry

∼135–131

Dengjiawu Lanhualing

Mo deposit skarn W–Mo deposit

granite

molybdenite zircon

Re–Os LA–ICP–MS U–Pb

141. 8 ± 2. 2(isochron age) 148.17 ± 0.94

Li et al. (2012) Chen et al. (2015)

Dawujian

skarn W–Mo deposit

granodiorite porphyry

zircon

148.3 ± 2.2, 148.5 ± 2.1

Li et al. (2015a)

skarn W–Mo ore

molybdenite

LA–ICP–MS U–Pb Re–Os

granite

zircon

LA–ICP–MS U–Pb

128～129

Luo et al. (2010)

cassiterite

LA–ICP–MS U–Pb

128–130

Xu et al. (2015)

biotite granite

zircon

123.81 ± 0.77

This study

molybdenite in skarn ore

molybdenite

LA–ICP–MS U–Pb Re–Os

greisen vein

muscovite

Ar–Ar

Pengshan Jianfengpo

Skarn Sn deposit

Xianglushan

skarn W deposit

144.4 ± 1.5

126.6 ± 2.5 (isochron age) 125.45 ± 0.73(mean age) 122.8 ± 0.78

values mostly of −3.1 to −5.7, with corresponding two-stage Hf model ages of 1363–1218 Ma. These results indicate that the biotite granite at the Xianglushan deposit may have been derived mainly from partial melting of older crust (Fig. 13). The Re–Os isotopic system can not only constrain the timing of mineralization, but also provide information on metal sources. Based on comprehensive studies comparing the Re contents of molybdenite in the Mo-bearing deposits in China, Mao et al. (1999) suggested that Re contents in molybdenite decrease progressively from mantle, mixing of mantle and crust, to crustal sources. These differences have been confirmed and were emphasized in various genetic models (Stein et al., 2001; Guo et al., 2011; Xie et al., 2011a; Wu et al., 2015). The Re content of molybdenite is noticeably high (usually hundreds of ppm) when metallogenetic materials of ore deposits are derived mainly from the mantle, moderate (typically tens of ppm) with mixed mantle-crustal sources, and usually only several ppm with crustal sources. In the Xianglushan deposit, molybdenite Re contents are 12.12–22.77 ppm, which indicates that the ore-forming materials within the deposit have a mixed mantle-crustal source, but were derived predominantly from the crust.

magmatism and mineralization in the Middle-Lower Yangtze River Valley Metallogenic Belt: namely early (ca 149–135 Ma), middle (ca 133–125 Ma), and late (ca 123–105 Ma) stages. Both the early and late stages had porphyry–skarn mineralization, whereas the middle stage had porphyry-style mineralization. Therefore, we conclude that magmatism and mineralization in the JNB was almost contemporaneous with that in the YRB, and that both are younger than events in the Nanling W–Sn metallogenic area (165–150 Ma; Mao et al., 2007). 6.3. Origin of the hosting pluton and sources of ore metals Zircon is strongly resistant to weathering, has high Hf contents and low Lu/Hf ratios, and is a common accessory mineral in granitoids. These features, when combined with high closure temperatures of the Hf isotopic system, make zircon an ideal mineral for constraining the origin of magmas, elucidating processes involved in formation and evolution of crustal melts, and assessing mantle-crust interaction (Griffin et al., 2002). Zircon from the Cretaceous biotite granite within the Xianglushan deposit has negative εHf(t) values. These zircon crystals have 176 Hf/177Hf ratios mainly in the 0.282613–0.282537 range, and εHf(t) 1174

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and the JNB. The two belts are away from each other for several hundred kilometers and were formed during different time periods. The JNB is adjacent, and almost parallel to, the Middle-Lower Yangtze River porphyry–skarn Cu–Au–Mo–Fe belt to the south. Furthermore, magmatism and mineralization in these two nearby belts were almost contemporaneous. Considering that these belts have such close spatial and temporal relationships, we suggest that they could have formed in the same tectonic setting. A variety of tectonic models has been proposed to account for the Late Mesozoic large-scale magmatism and mineralization in South China, with most models invoking subduction of the paleo-Pacific plate (Mao et al., 2006, 2011, 2013a; Sun et al., 2012; Zhao et al., 2017a). However, the tectonic framework responsible for Late Mesozoic mineral systems and associated magmatism in South China remains controversial (Xie et al., 2012). Mao et al. (2011, 2013a) and Wu et al. (2015) suggested that at about 160 Ma, events in the Middle-Lower Yangtze River Valley area (and even southern China) were initially related to oblique subduction of the Izanagi plate beneath the Eurasian continent, and that after 135 Ma the subducting plate changed direction, with parallel subduction to the Eurasian continental margin, leading to large-scale continental extension. Zhao et al. (2017a) suggested that break-off along the subducted mid ocean ridge between the Pacific and Izanagi plates resulted in emplacement of highly fractionated granites in the Nanling region in the Middle Jurassic; later anticlockwise rotation of the paleo-Pacific plate created widespread Stype granitoids and associated Middle Jurassic to Early Cretaceous W mineralization in the interior of South China; since 136 Ma, rollback of the subducting Pacific plate resulted in weak W mineralization across South China; finally, a change of direction in the retreating plate from SE to ESE resulted in intensive mineralization of the southwestern part of South China. Yang et al. (2014b) suggested that Cu–Au-related adakitic rocks in eastern China and the Lower Yangtze River Belt are related to rollback of the paleo-Pacific slab, the appearance of A-type granites at ca 125 Ma indicates asthenospheric upwelling and an extensional crustal environment. Ling et al. (2009) proposed that a ridgesubduction model with an associated slab window could explain the distribution of different magmatic rocks and ore deposits in the Lower Yangtze river belt in the Early Cretaceous (140–125 Ma). Wu et al. (2012) divided magmatism in southern Anhui Province into two separate stages, of 150–136 Ma and 136–120 Ma, through precise zircon U–Pb dating. The first stage of granitic rocks is considered to have formed by slab tear during paleo-Pacific subduction, while the second is interpreted as being related to an extensional setting. Further studies have indicated that magmatism and mineralization in South China took place in an extensional tectonic setting during the Early Cretaceous (Mao et al., 2013b; Xie et al., 2008, 2011b; Li et al., 2010; Wu et al., 2012; Hu et al., 2017a,b). The occurrence of basins with Early Cretaceous volcanic rocks (Xue et al., 2015), and A-type granitic and volcanic rocks along the Middle-Lower Yangtze River Valley also indicate an extensional setting. Furthermore the distribution of 136–120 Ma A-type granite and syenite, their volcanic counterparts in southern Anhui Province, mainly around and within fault-controlled volcanic basins, indicate an extensional setting (Wu et al., 2012). The ore-related granitoids in JNB are derived from the partial melting of upper crust with some input of mantle materials at extensional setting, supported by: (1) granitoids of Yangchuling deposit having initial 87 Sr/86Sr and εNd(t) of 0.7104–0.7116 and −5.05 to −5.67 (Mao et al., 2017); (2) granitoids at Dahutang deposit have initial 87Sr/86Sr of 0.7153–0.7365 and εNd(t) of −5.06 to −7.99 (Mao et al., 2015); (3) granitoids of Yangchuling deposit having homogeneous εHf(t) values between −1.39 and -2.17 (Mao et al., 2017); (4) zircon εHf(t) values ranging from −8.44 to −2.13 for Dahutang granitoids (Huang and Jiang, 2014); and (5) Zhuxi granite porphyry has zircon εHf(t) values of −16.5–0.6 (Li et al., 2014). Besides, negative εHf(t) values (−3.1 to −5.7) of zircons from biotite granite and molybdenite Re content of 12.12–22.77 ppm form Xianglushan deposit, indicate the mixed of

Fig. 12. Histogram of ages for Yanshanian magmatism and mineralization along the Jiangnan porphyry–skarn W belt.

Fig. 13. Plot of εHf(t) vs t (Ma) for zircon crystals from biotite granite in the Xianglushan W deposit.

6.4. Tectonic setting of the W mineralization in the JNB South China is one of the world’s most important metallogenic provinces (Sun et al., 2012, 2015; Mao et al., 2013a). There are two W belts in southern China, including the Nanling W–Sn metallogenic belt

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small amount of mantle materials when forming, which may imply upwelling of mantle materials under an extensional setting. Thus, we infer that Early Cretaceous magmatism and mineralization in the JNB formed in an extensional tectonic setting, with this study also showing that magmatism and mineralization in the Xianglushan deposit took place during the same extensional event.

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7. Conclusions A Re–Os isochron age of 126.6 ± 2.5 Ma was obtained for molybdenite separated from skarn ore, and a plateau age of 122.8 ± 0.78 Ma was determined for muscovite from a greisen vein using the Ar–Ar method. These ages coincide well with a zircon U–Pb age of 123.81 ± 0.77 Ma for the biotite granite at the mine. These coincident ages, together with close spatial relationships, indicate that mineralization at the Xianglushan W deposit is related to the biotite granite. A zircon U–Pb age of 117.3 ± 1.7 Ma was obtained for an aplitic dyke in the Xianglushan ore district. Zircon separated from the biotite granite in the Xianglushan deposit has negative εHf(t) values of −3.1 to −5.7, with corresponding twostage Hf model ages of 1363–1218 Ma, which indicates ancient crust as a major source for the granite magma. Molybdenite from the Xianglushan deposit is characterized by Re contents of 12.12–22.77 ppm, implying a mixed mantle-crust source for oreforming materials, but with a dominantly crustal component. Previously published geochronological data combined with those obtained in this study indicate that there are two stages of Mesozoic magmatism in the JNB at 155–135 Ma and 135–120 Ma, corresponding to two stages of mineralization at 150–135 Ma and 130–120 Ma, respectively. The Early Cretaceous Xianglushan skarn W deposit is an important component of the JNB. Our results, in combination with published data suggest that the Xianglushan W deposit was related to an Early Cretaceous extensional event. Acknowledgments This research was jointly supported by the State Key Program of National Natural Science Foundation of China (No. 41430314) and National Nonprofit Institute Research Grant of Chinese Academy of Geological Sciences (No. K1617). We are grateful to Xianglushan Tungsten Ltd in Xiushui County, Jiangxi Province, for their help and support. We thank colleagues in Northwestern Geological Team, Jiangxi Bureau of Geology, and Tao Gao, Bingbing Cheng, Hong Ni, and Xin Zhang from Xianglushan Tungsten Ltd in Xiushui County for their help and constructive discussions during fieldwork. We thank Dr. Wei Jian for his help to improve the language. We thank the two anonymous reviewers who gave many constructive comments and useful suggestions. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.oregeorev.2017.11.017. References BGMRJX (Jiangxi Bureau of Geology And Mineral Resources), 1984. Regional Geology of Jiangxi Province. Geological Publishing House, Beijing (In Chinese). Blichert-Toft, J., Chauvel, C., Albarède, F., 1997. Separation of Hf and Lu for high-precision isotope analysis of rock samples by magnetic sector-multiple collector ICP–MS. Contrib. Miner. Petrol. 127, 248–260. Chen, W., Zhang, Y., Zhang, Y.Q., Jin, G.S., Wang, Q.L., 2006. Late Cenozoic episodic uplifting in southeastern part of the Tibetan plateau-evidence from Ar–Ar thermochronology. Acta Petrol. Sin. 22 (4), 867–872 (in Chinese with English abstract). Chen, X.F., Wang, Y.G., Sun, W.D., Yang, X.Y., 2013. Zircon U-Pb chronology, geochemistry and genesis of the Zhuxiling granite in Ningguo, southern Anhui. Acta Geol. Sin. 87 (11), 1662–1678 (in Chinese with English abstract). Chen, F., Wang, D.H., Du, J.G., Xu, W., Wang, K.Y., Yu, Y.L., Tang, J.L., 2015.

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