Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China

GR-01420; No of Pages 12 Gondwana Research xxx (2015) xxx–xxx

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Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China Xiao-Hua Deng a,b, Yan-Jing Chen b,⁎, M. Santosh c, Jun-Ming Yao d, Ya-Li Sun d a

Beijing Institute of Geology for Mineral Resources, Beijing 100012, China Key Laboratory of Orogen and Crust Evolution, Peking University, Beijing 100871, China School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China d Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China b c

a r t i c l e

i n f o

Article history: Received 31 October 2014 Received in revised form 13 February 2015 Accepted 23 February 2015 Available online xxxx Keywords: Re–Os geochronology Pb–Sr–Nd isotope systematics Ore-forming fluid Zhifang Mo deposit Qinling Orogen

a b s t r a c t The Zhifang Mo deposit is located in the northeastern Qinling Orogen along the southern margin of the North China Craton. The deposit represents a quartz-vein system hosted in the Mesoproterozoic Xiong'er Group volcanic rocks. We identify three hydrothermal stages (early, middle and late), characterized by veinlets of quartz–pyrite, quartz–molybdenite–pyrite–chalcopyrite–galena–sphalerite, and quartz–carbonate assemblages, respectively. Five molybdenite samples from the Zhifang deposit yield Re–Os ages ranging from 241.2 ± 1.6 Ma to 247.4 ± 2.5 Ma, with an isochron age of 246.0 ± 5.2 Ma (2σ, MSWD = 7.4), and a weighted mean age of 243.8 ± 2.8 Ma (2σ, MSWD = 5.5). The Re–Os age shows that the Mo mineralization occurred during the Indosinian Orogeny, and suggests that the mineralization is unrelated to the Yanshanian magmatism or the Paleo-Mesoproterozoic volcanic–hydrothermal event. This study also reports a new Sr–Nd–Pb isotope dataset from ore sulfides in an attempt to constrain the source of the ore-forming fluids. Ten sulfide samples from middle stage of the Zhifang Mo deposit yield ISr(t) ratios of 0.710286–0.711943, with an average of 0.711004; εNd(t) values between −19.5 and −14.8, with an average of − 16.7; and (206Pb/204Pb)i, (207Pb/204Pb)i and (208Pb/204Pb)i ratios of 17.126–17.535, 15.374–15.466 and 37.485–37.848, with averages of 17.380, 15.410 and 37.631, respectively. One pyrite from the early stage yield ISr(t) of 0.722711–0.722855, with an average of 0.722783, which is higher than those of the middle stage sulfides and suggests equilibration with wallrocks. The εNd(t) values are in the range of −17.3 to −16.6 with a mean at −17.0; and (206Pb/204Pb)i, (207Pb/204Pb)i and (208Pb/204Pb)i ratios are 17.386, 15.405 and 37.622, respectively. The ore sulfides show higher Pb-isotope ratios, higher εNd(t) and lower ISr(t) values than the host rocks. The results suggest that the ore-forming fluids had lower ISr(t), and higher εNd(t) values than the ore sulfides, and were possibly sourced from the Dengfeng Complex. The southward subduction of the North China Craton beneath the Huaxiong Block during the Triassic was possibly responsible for the formation of the Waifangshan orogenic Mo system. © 2015 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

1. Introduction The Qinling Orogen, located between the southern margin of the North China Craton (NCC) and the northern margin of the Yangtze Craton (Fig. 1), defines a potential metallogenic belt in China hosting one of the world's most important Mo district (Fig. 1c), with estimated reserves of N 6 Mt Mo metal, as well as Au, Ag, Pb–Zn, Hg and Sb deposits (Chen et al., 2000; Li et al., 2007; Chen et al., 2009; Mao et al., 2011; Yang et al., 2012). The majority of the Mo deposits in the East Qinling Molybdenum Belt (EQMB, Fig. 1c) are associated with Yanshanian (Jurassic– Cretaceous) porphyry/skarn systems and have been the targets of

⁎ Corresponding author. Tel.: +86 10 6275 7390. E-mail addresses: [email protected], [email protected] (Y.-J. Chen).

previous exploration (Hu, 1988; Stein et al., 1997; Zhang et al., 2011; Yang et al., 2012). However, the distribution of most of the Mo deposits in the EQMB along the southern margin of the NCC (Fig. 1c), in association with the Yanshanian granitoids in the Huaxiong Block, has remained enigmatic (Chen et al., 2009). Recently, several new Mo deposits were discovered in the carbonate-, quartz- and fluorite-dominated veins in the Huaxiong Block, such as the Huanglongpu (Xu et al., 2010) carbonatite vein system, Longmendian (Li et al., 2014), Zhaiwa (Deng et al., 2013a,b), Dahu (Li et al., 2011a; Ni et al., 2012, 2014) and Zhifang (Deng et al., 2014b) quartz vein system, and the Tumen (Deng et al., 2013c, 2014a) fluorite vein system. The available molybdenite Re–Os ages show that these veins were formed during different mineralization pulses (Fig. 1c), including the Paleoproterozoic (ca. 1.85 Ga, Li et al., 2011b; ca. 1.76 Ga, Deng et al., 2013a), Neoproterozoic (ca. 0.85 Ga, Deng et al., 2013c), Caledonian (ca. 0.43 Ga, Li et al., 2009), Indosinian

http://dx.doi.org/10.1016/j.gr.2015.02.020 1342-937X/© 2015 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

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Fig. 1. Maps showing (a) the major tectonic subdivisions of China, with the location of Qinling Orogen; (b) tectonic framework of the Qinling Orogen; and (c) distribution of Mo deposits in the East Qinling Mo Belt, with the location of the Waifangshan Mo ore district (modified from Chen et al., 2009, and references therein; Deng et al., 2014b). Names of numbered deposits: 1 — Balipo; 2 — Jinduicheng; 3 — Shijiawan; 4 — Huanglongpu; 5 — Mulonggou; 6 — Majiawa; 7 — Dahu; 8 — Yechangping; 9 — Yinjiagou; 10 — Zhaiwa; 11 — Longmendian; 12 — Shangfanggou; 13 — Nannihu; 14 — Sandaozhuang; 15 — Majuan; 16 — Zhuyuangou; 17 — Shiyaogou; 18 — Shapoling; 19 — Huangshui'an; 20 — Leimengou; 21 — Waifangshan Mo ore district; 22 — Yuchiling; 23 — Donggou; 24 — Tumen; 25 — Saozhoupo; 26 — Shimengou; 27 — Yindonggou; 28 — Qiushuwan. Abbreviation: CCO, Central China Orogen (includes the Kunlun, Qilian, Qinling, and Dabie orogenic belts).

(ca. 0.24 Ga, Gao et al., 2010) and Early Cretaceous (Chen et al., 2009). Thus, the origin of the EQMB, and the timing and mechanisms of formation of the pre-Yanshanian Mo-deposits remain as important aspects to be investigated. More than ten quartz vein-type Mo deposits have been discovered through geochemical survey by the No. 5 Party of Henan Bureau of Geological Exploration for Non-ferrous Metals in the Waifangshan area of the EQMB. These are the Zhifang, Fantaigou, Qianfanling, Xiangchungou, Kangjiagou, Badaogou, Shitishang, Dazhuanggou, Maogou and Daxigou deposits (Fig. 2). These veins yield an estimated reserve of more than 0.1 Mt Mo metal and expected resources up to 0.5 Mt, constituting the Waifangshan quartz vein-type Mo ore district (Bai and Xiao, 2009). These deposits have attracted several investigations (Chen, 2006, 2010; Gao et al., 2010; Lu et al., 2011; Mao et al., 2011; Deng et al., 2014b). Among these, the Zhifang Mo deposit has been considered as the representative, and geologically most studied. However, controversy surrounds the ore genesis based on geological characteristics such as: (1) the stratiform deposit associated with late Yanshanian magmatic hydrothermal system (Wen et al., 2008); (2) the stratabound deposit related to Paleo-Mesoproterozoic volcanic hydrothermal system (Bai and Xiao, 2009); and (3) the orogenic-type deposit (Chen, 2006; Deng et al., 2014b). Moreover, the source of the ore-forming fluids and metals, as well as genetic mechanism remains unclear.

Molybdenite Re–Os dating offers a useful technique to determine the timing of mineralization (Stein et al., 2001a; Conliffe et al., 2010). The isotopic data from the ore minerals and genetically associated sulfides can be used to evaluate the nature and source of the oreforming fluids (Jiang et al., 1999; Voicu et al., 2000; Kempe et al., 2001; Yang and Zhou, 2001; Chen et al., 2004; Barker et al., 2009; Pirajno, 2009; Zhang et al., 2009; Ni et al., 2012, 2014). In this contribution, we report new Re–Os geochronology and Sr–Nd–Pb isotope data from a comprehensive study of the Zhifang Mo deposit, and discuss the genetic type of the ores and the sources of ore-forming fluids. 2. Regional geology The Qinling Orogen is the central portion of the E–W-trending Central China Orogen Belt (CCOB) that evolved from the northernmost Paleo-Tethys Ocean and was finally built up by the Mesozoic collision between the NCC and Yangtze Craton (Fig. 1; Zhang et al., 2001; Chen et al., 2009; Dong et al., 2011a,b; Wu and Zheng, 2013; Zheng et al., 2013; Chen et al., 2014; Diwu et al., 2014; Li et al., 2015). The Qinling Orogen is composed of four tectonic units from north to south: the Huaxiong Block representing the reactivated southern margin of the NCC, the northern Qinling accretion belt, southern Qinling fold belt, and a foreland fold–thrust belt (e.g., Songpan fold belt) along the

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

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Fig. 2. Geology and distribution of Mo deposits in the Waifangshan area (after Deng et al., 2014b).

northern margin of the Yangtze Craton, with the San–Bao, Luanchuan, Shang–Dan, Mian–Lue and Longmenshan faults as their boundaries (Fig. 1b; Chen and Santosh, 2014). The Huaxiong Block is the reactivated southernmost margin of the North China Craton, which is bound to the south by the Luanchuan fault and to the north by the San–Bao fault (Fig. 1c). This region consists of crystalline basement of the Late Neoarchean–Paleoproterozoic Taihua Supergroup, the lowest cover of the Mesoproterozoic Xiong'er Group, and the Meso-Neoproterozoic Guandaokou and Luachuan Groups (Fig. 1c; Chen and Fu, 1992). The Taihua Supergroup includes the 3.0–2.55 Ga Beizi, 2.5–2.3 Ga Dangzehe, and 2.3–2.1 Ga Shuidigou Groups (Chen and Zhao, 1997; Xu et al., 2009), and was metamorphosed at amphibolite to granulite facies during 1.95–1.82 Ga coinciding with the global assembly of the Columbia supercontinent (Rogers and Santosh, 2002; Zhao et al., 2004; Wan et al., 2006; Santosh et al., 2007a,b; Rogers and Santosh, 2009; Zhao et al., 2009; Santosh, 2010; Zhai and Santosh, 2011; Rogers, 2012; Zhai and Santosh, 2013; Nance et al., 2014). The Xiong'er Group, unconformably overlying the Taihua

Supergroup, is dominated by basaltic andesite, andesite, dacite and rhyolites with minor intermediate to silicic tuff and mafic to felsic sub-volcanic rocks (He et al., 2009, 2010). The volcanic rocks erupted intermittently from 1.84 Ga, through 1.78–1.75 Ga and 1.65 Ga, to 1.45 Ga (Zhao et al., 2009; Cui et al., 2011), and are considered to have formed in a continental rift (Sun et al., 1985; T.P. Zhao et al., 2002), a mantle plume (Peng et al., 2008), or an Andean-type continental arc (Chen and Fu, 1992; G.C. Zhao et al., 2002, 2004, 2009; He et al., 2009, 2010; Deng et al., 2013a,b). The Xiong'er Group is overlain by the Meso-Neoproterozoic Luanchuan and Guandaokou Groups that were composed mainly of carbonaceous carbonate–shale–chert and developed along the southern margin of the Huaxiong Block (Fig. 1c; Hu, 1988; Chen et al., 2004). The lithostratigraphic units discussed above are intruded by Mesozoic (Jurassic to Cretaceous) granitoids, such as the Huashan Complex and a number of mineralized porphyries, diatremes and breccia pipes (Fan et al., 2011; Li et al., 2012). The Songji Block is bound by the San–Bao fault to the south and by the Zhongtiaoshan fault to the west (Chen et al., 1991), and is

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

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Fig. 3. (a) Geology of the Zhifang Mo deposit in the Qinling Orogen showing the location of drill holes and samples collected for this study (modified after Wen et al., 2008). (b) Geological cross-section of exploration line 510 of the Zhifang Mo deposit (modified after Wen et al., 2008). (c) Stratigraphic column of the Waifangshan area (modified after T.P. Zhao et al., 2002).

characterized by the development of the Early Precambrian Dengfeng Complex. The Dengfeng Complex has been subdivided, from bottom to top, into the Mesoarchean Shipaihe TTG Suite (trondhjemite–tonalite– granodiorite–diorite), the Neoarchean Junzhao Group greenstone belt and the Lower Paleoproterozoic Angou Group volcanic–sedimentary sequence (Zhang et al., 1985; Chen et al., 1989; Chen and Zhao, 1997). The Shipaihe TTG Suite contains ultramafic enclaves; the protoliths of which are interpreted to represent a primary greenstone sequence. The Junzhao Group mainly consists of tholeiitic lavas, andesites and dacites. The Angou Group includes a variety of turbidite rocks intercalated with felsic rocks. LA–ICPMS magmatic zircon U–Pb age data show that the Junzhao Group was formed during 2547–2504 Ma (Diwu et al., 2011). 3. Deposit geology The Zhifang Mo deposit is located in the Waifangshan area of the Huaxiong Block (Fig. 2), and hosted by the Jidanping Formation of the Xiong'er Group that consists of dacites and rhyolites interlayered with basaltic andesites and andesites (Wen et al., 2008). The molybdenum

mineralization is associated with a series of quartz veins controlled by NW-, NE-, and minor NS- and EW-trending faults that are interpreted as a subsidiary fault system of the regional Machaoying fault (Figs. 2 and 3; Wen et al., 2008). Minor intrusive dikes are also exposed, such as the Jingningian diorite, Hercynian syenitoids and Yanshanian granitoids (Fig. 3a). Six mineralized bodies have been explored at Zhifang, including K1, K2, K3, K4, K5 and K6 (Fig. 3a). The ore is structurally controlled and form vein and/or stratiform ore bodies (Fig. 3b). Individual ore bodies vary from 100 m to 2800 m in length and 0.97 m to 8.19 m in thickness. Along the dip direction, the explored ore bodies extend to over 550 m below the surface. The Mo grade of the deposit changes from 0.07 to 0.16%, with an average of 0.12%. The ore bodies are associated with silicification and potassic alteration, and are characterized by a complex mineral assemblage. The major ore minerals are molybdenite and pyrite, with minor galena, chalcopyrite and sphalerite. The gangue minerals are predominantly quartz and K-feldspar along with some minor calcite, fluorite, barite, rutile, apatite, sericite and chlorite. Molybdenite shows lumpy and banded structure filling the fractures of quartz, or as film filling the

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

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fractures of quartz crystal. Deng et al. (2014b) divided the mineralization into three stages based on crosscutting relationships and mineral association: (1) an early stage, characterized by fractured or deformed quartzveins with minor idiomorphic granular pyrite and allotriomorphic barite; (2) a middle stage, represented by the formation of quartz + molybdenite + pyrite + chalcopyrite + galena + sphalerite, associated with early stage fractures; and (3) a late stage, represented by quartz, carbonate and minor pyrite. These authors also proposed that the Zhifang Mo deposit is an orogenic-type system formed in a transition zone from the Andean-type arc to back-arc continent.

20). A factor of 1‰ per mass unit for instrumental mass fractionation was applied to the Pb analyses, using NBS 981 as reference material. Measurement of the common-lead standard NBS 981 gave average values of 208Pb/204Pb = 36.53072 ± 0.00763; 207Pb/204Pb = 15.44012 ± 0.00324; and 206Pb/204Pb = 16.90046 ± 0.00339, with uncertainties of b0.1% at the 95% confidence level.

4. Samples and analytical methods

The Re–Os isotope analytical results for five molybdenite separates from samples of the Zhifang Mo deposit are listed in Table 1. The Re concentration in molybdenite ranges from 3.984 to 29.85 ppm, and the 187Os concentrations vary from 10.21 to 77.47 ppb. The samples yield individual Re–Os isotope model ages from 241.2 ± 1.6 to 247.4 ± 2.5 Ma (2σ). The data show a weighted mean age of 243.8 ± 2.8 Ma, with MSWD = 5.5 at 2σ level (Fig. 4a). When processed using the ISOPLOT program (Model 3) (Ludwig, 1999), the data yield an isochron age of 246.0 ± 5.2 Ma (2σ), with MSWD = 7.4 and an initial 187Os of −0.18 ± 0.83 ppb (Fig. 4b). Such low initial 187Os value (near zero) confirms the reliability of the Re–Os ages as indicator of the crystallization time of molybdenite. We therefore conclude that the Zhifang deposit was formed at ~244 Ma.

4.1. Molybdenite Re–Os dating Five molybdenite separates were selected for this study from the molybdenite-bearing quartz veins at the Zhifang deposit for Re–Os dating (Fig. 3a). Among these, three samples (ZF-08, ZF-10-1 and ZF-10-2) occur as lumpy or pellicular molybdenite. Samples ZF-14 and ZF-16 show molybdenite occurring as disseminated clusters. Gravitational and magnetic separations were applied for molybdenite separation with final careful handpicking under a binocular microscope (purity N 99%). Re–Os sample dissolution and preparation were performed at the Key Laboratory of Isotope Geochronology and Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences. Re and Os concentration and isotopic composition were measured using an X-7 inductively coupled plasma mass spectrometer (ICP-MS) at the Open Research Laboratory of Mineralization and Its Dynamics, Department of Geology and Mineral Resource, Chang'an University, following the analytical method described by Sun et al. (2010). 4.2. Sr, Nd and Pb isotopes Eleven representative samples of sulfides were assayed for isotopes of Sr, Nd and Pb, and the crosscutting relationships of the mineralized veins were used to identify the stages of the sulfides analyzed. Among these, three molybdenite (ZF08, ZF10 and ZF16), five pyrite (ZF02, ZF008, ZF16-1, ZF18 and ZF20-2) and two galena (ZF12-6 and ZF14) samples were separated from middle stage mineralized quartz veins, and one pyrite sample (ZF01) was from the early stage quartz vein. All samples were collected from K4 and K5 quartz veins of the Zhifang deposit. The early stage pyrite occurs as 1–5 cm disseminated clusters within coarse-grained quartz–pyrite vein. The middle stage sulfides within fine-grained quartz–molybdenite–pyrite–galena veinlet are present along the fractures of early stage, and usually display close association with “smoky” quartz. The sulfide grains with at least 99% purity were separated through conventional preparation techniques including crushing, oscillation, heavy liquid and magnetic separation, and handpicking under a microscope. Sr, Nd, and Pb isotopic analyses were performed at Analytical Laboratory of the Tianjin Institute of Geology and Mineral Resources, China, using the procedures described by Ni et al. (2012) and Deng et al.(2013a), and are briefly summarized below. Sample powders were dissolved in HF + HNO3 + HClO4 mixture. Digested samples were dried and redissolved in 6 N HCl, dried again and redissolved in 0.5 N HCl (for Sr and Nd separation) or 0.5 N HBr (for Pb separation). Sr and Nd fractions were separated following standard chromatographic techniques using AG50x8 and PTFE–HDEHP resins with HCl as eluent, while Pb fraction was separated using strong alkali anion exchange resin with HBr and HCl as eluents. All isotopic measurements were made by thermal ionization mass spectrometry using Triton mass spectrometer. 87Sr/86Sr isotope ratios were normalized to 86Sr/88Sr = 0.1194 and 143Nd/144Nd isotope ratios to 146Nd/144Nd = 0.7219. The Jndi Nd-Standard yielded 143Nd/144Nd ratio of 0.512117 ± 2 (reference value 0.512115 ± 7; Tanaka et al., 2000) and the NBS 987 Sr standard yielded 87Sr/86Sr ratio of 0.710275 ± 4 (reference value 0.710250 ±

5. Results 5.1. Molybdenite Re–Os age

5.2. Sr isotopic compositions Table 2 and Appendix A list the Sr isotopic values for sulfides from the Zhifang deposit obtained in this study and the published Sr isotopic data of related lithologies in the southern margin of the NCC, respectively. The 87Rb/86Sr ratios were calculated according to the contents of Rb and Sr, and the measured isotope values of the samples. To evaluate the source of the fluids and metals using the isotope tracers, the Sr isotope ratios of the samples at 244 Ma were calculated, and reported as ISr(t). The 87Sr/86Sr ratios of middle stage sulfides of the Zhifang deposit scatter between 0.710306 and 0.712268, with an average of 0.711248. In contrast, the early stage pyrite has more radiogenic Sr and show a range of 87Sr/86Sr ratios in 0.724534–0.724678. The ISr(t) values of middle stage sulfides range from 0.710286 to 0.711943, with an average of 0.711092, lower than that of early stage pyrite which has ISr(t) values of 0.722783. 5.3. Nd isotopic compositions The Nd isotope analyses for sulfides from the Zhifang deposit and previously published Nd isotopic data from the major lithologies in the southern margin of the NCC are shown in Table 3 and Appendix B. The εNd(t) at 244 Ma was calculated for all the Nd isotope data in order to evaluate the origin of the Zhifang deposit. In the calculation, the chondrite (CHUR)Nd parameters of 143Nd/144Nd = 0.512638 and 147 Sm/144Nd = 0.1967 (Jacobsen and Wasserburg, 1980) were adopted. The 147Sm/144Nd and 143Nd/144Nd ratios of middle stage sulfides from the Zhifang deposit range 0.0668–0.1628, and 0.511507–0.511787, respectively, and overlap with early stage pyrite (Table 3). The calculated initial 143Nd/144Nd ratios at an age of 244 Ma for the middle stage sulfides (0.511323–0.511569) is close to that of the early stage pyrite (0.511437–0.511472; Table 3). The calculated εNd (244 Ma) values of middle stage sulfides range from −19.5 to − 14.7, with an average of −16.7 (Table 3). 5.4. Pb isotopic compositions Table 4 and Appendix C list the Pb isotopic values for sulfides from the Zhifang deposit and the published Pb isotopic data of related geologic bodies, respectively. Some of the data with U, Th and Pb contents were used to estimate the Pb isotope ratios at 244 Ma, which are

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

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Table 1 Re–Os isotopic data for molybdenite from the Zhifang Mo deposit. Sample

Weight (g)

Re (ppm)

Common Os (ppb)

187

ZF08 ZF10-1 ZF10-2 ZF14 ZF16

0.054 0.330 0.403 0.102 0.045

25.85 ± 0.12 3.984 ± 0.024 3.984 ± 0.026 29.85 ± 0.17 8.180 ± 0.022

1.356 ± 0.770 0.320 ± 0.063 0.294 ± 0.093 2.782 ± 1.247 2.583 ± 1.195

16.25 ± 0.07 2.504 ± 0.015 2.504 ± 0.017 18.76 ± 0.11 5.141 ± 0.014

Re (ppm)

187

Os (ppb)

66.15 ± 0.38 10.25 ± 0.04 10.21 ± 0.11 77.47 ± 0.63 20.70 ± 0.12

Age (Ma) 243.9 ± 1.8 245.2 ± 1.8 244.2 ± 3.2 247.4 ± 2.5 241.2 ± 1.6

Absolute uncertainties are reported at 2σ level. Decay constant (λ) used for 187Re is 1.666 × 10−11 year−1 (Smoliar et al., 1996). Age is calculated according to the equation: t = 1 / λ ln (1 + 187Os/187Re).

presented (208Pb/204Pb)i, (207Pb/204Pb)i and (206Pb/204Pb)i, respectively. The sulfides from the Zhifang deposit have 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values of 17.126–17.536, 15.374–15.466 and 37.485–37.848, with averages of 17.434, 15.413 and 37.633, respectively. Their calculated (206Pb/204Pb)i, (207Pb/204Pb)i and (208Pb/204Pb)i values are 17.126–17.535, 15.374–15.466 and 37.485–37.848, with averages of 17.380, 15.410 and 37.631, respectively (Table 4). The time-corrected Pb isotopic ratios of these sulfides are not significantly different from the measured values due to their very low U and Th contents. Therefore, the analytical data can be reliably used to trace the source of fluids or metals. 6. Discussion 6.1. Source of the ore-forming fluids 6.1.1. Re content The rhenium concentration in molybdenite from the ores at Zhifang provides clues for the source region and tectonic setting (Stein et al., 2001b). Mao et al. (1999) and Stein et al. (2001a) proposed that the Re content of molybdenite remarkably decreases from the mantle source and/or subducted oceanic slab to the crustal source. Ore deposits that involve significant mantle materials and/or subducted oceanic slab can be expected to show overall higher Re concentrations (generally N100 ppm) in the associated molybdenite. In contrast, ore deposits originating from continental crustal rocks or organic-poor sedimentary sequences generally have lower Re concentrations in the associated molybdenite (generally b 50 ppm) (Mao et al., 1999; Stein et al., 2001a; Mi et al., 2015; Ni et al., 2015). The Huanglongpu Mo deposit associated with carbonatite dykes which reflect the composition of their mantle source are characterized by high Re contents (278–289 ppm; Stein et al., 1997). Thus, the molybdenite from the Zhifang Mo deposit shows low rhenium contents (3.984 to 29.85 ppm) (Table 1), suggesting a crust-derived origin. The molybdenite from the Longmendian migmatitic–hydrothermal Mo deposit shows the highest Re content in EQMB of 504–1131 ppm (Li et al., 2011b), whereas the molybdenite from the Donggou porphyry deposit has the lowest Re content of 4.04–4.09 ppm (Li et al., 2007).

6.1.2. Strontium isotope The ISr(t) values of sulfides range from 0.710286 to 0.722855 (Table 2; Fig. 5), demonstrating a source of old continental crust. However, the early stage pyrite has higher ISr(t) values (0.722711–0.722783) than middle stage sulfides (0.710286–0.711943), which could be due to different fluid source or significant Sr exchange with wallrocks during the hydrothermal process (Voicu et al., 2000; Barker et al., 2009). The early and middle stage ores precipitated from the similar fluid source as inferred from the fluid inclusion study of the Zhifang Mo deposit (Deng et al., 2014b). Thus, the Sr isotopes progressively became rock-buffered along fluid flow pathways while externally-sourced fluids reacted with rocks (Barker et al., 2009). Considering that the ISr(t) ratios of wallrocks of the Xiong'er Group are between 0.711369 and 0.759769, with an average of 0.722277 (Appendix A), which are close to early stage pyrite. We thus suggest that the Sr isotopes of early stage fluid might have completely equilibrated with the wallrocks, which is also consistent with the conclusion from the S isotope data (Deng et al., 2014b). The middle stage ore sulfides show an average ISr(t) value (0.711092) which is lower than the minimum ISr(t) ratio (0.711369), and markedly lower than the average ISr(t) value (0.722277) of the ore-hosting Xiong'er Group suggesting a low ISr(t) fluid system. The ISr(t) values of the fluids that interacted with the wallrocks are no higher than 0.710286, which is the lowest ISr(t) ratio of sulfides. This excludes the possibility of Taihua Supergroup as the only source of the fluid that formed the Zhifang deposit (Appendix A; Fig. 5). The carbonate–shale–chert rocks of the Luanchuan and Guandaokou Groups from southward of the Maochaoying fault have ISr(t) values ranges 0.709030–0.785915 and 0.709030–0.812484 (Qi, 2006; Appendix A), with average values of 0.744176 and 0.753879, respectively, which are higher than the highest value of middle stage ore sulfides (Fig. 5). Thus, we eliminate these as the source of ore-forming fluids. The ISr(t) values of metavolcanic rocks in the Mian–Lue ophiolites that represent the remnants of the Mian–Lue oceanic crust range from 0.705328 to 0.709428, with an average of 0.707237 (Li et al., 1996; Xu et al., 2002). However, the high ISr(t) values (N 0.710) of the sulfides and the low Re content in the molybdenite from ores at Zhifang (Table 1) do not support a mantle origin. Considering the basement of the Songji Block is composed mainly of rocks of the Dengfeng Complex

Fig. 4. Weighted mean (a) and isochron (b) Re–Os ages for molybdenite from the Zhifang deposit.

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

X.-H. Deng et al. / Gondwana Research xxx (2015) xxx–xxx

7

Table 2 The Sr isotope ratios of sulfides from the Zhifang deposit. Sample no.

Mineral

Rb (ppm)

87

Sr (ppm)

Rb/86Sr

Early-stage ores of the Zhifang deposit ZF01a Pyrite ZF01b Pyrite Average N=2

1.32 1.32

7.28 7.28

0.5255 0.5255

Middle-stage ores of the Zhifang deposit ZF08a Molybdenite ZF08b Molybdenite ZF10 Molybdenite ZF16 Molybdenite ZF02 Pyrite ZF008a Pyrite ZF008b Pyrite ZF16-1 Pyrite ZF18 Pyrite ZF20-2 Pyrite ZF12-6a Galena ZF12-6b Galena ZF14a Galena ZF14b Galena Average N = 14

7.52 7.52 0.40 2.71 0.29 0.32 0.32 0.24 0.16 0.08 0.13 0.13 0.42 0.42

3646 3646 300 3974 14.4 9.86 9.86 18.7 10.5 26.6 4.01 4.01 28.0 28.0

0.0060 0.0060 0.0039 0.0020 0.0583 0.0939 0.0939 0.0371 0.0441 0.0087 0.0938 0.0938 0.0434 0.0434

(Zhang et al., 1985), the metabasalts and felsic volcanic rocks of Dengfeng Complex have ISr(t) values range from 0.6999 to 0.7020 (Guo, 1989), which are lower than the lowest ISr(t) value of middle stage sulfides (Fig. 5). Thus, the Sr-isotope system indicates that the basement of Songji Block could be one of the sources of the fluid that formed the ore deposit. 6.1.3. Neodymium isotope The (143Nd/144Nd)i ratios of ore sulfides range from 0.511323 to 0.511569, and an average of 0.511467, and the εNd(t) values are between −19.5 and −14.7, with an average of −16.7, demonstrating a source of old continental crust. Both of the (143Nd/144Nd)i ratios and the εNd(t) values of ore sulfides are higher than those of the wallrocks of the Xiong'er Group (0.510913–0.511258, − 27.5 to − 20.8, respectively; Appendix B). Thus, the fluids, which interacted with the Xiong'er Group to form the ore sulfides, must have (143Nd/144Nd)i and εNd(t) values not lower than 0.511323 and −14.7, respectively (Fig. 5). The Taihua Supergroup shows ( 143 Nd/ 144 Nd) i ratios of 0.510750–0.511313, and the εNd(t) values of −30.7 to −19.7 (Appendix B), excluding these as the only source of ore-forming fluid (Fig. 5). The metavolcanic rocks of the Mian–Lue ophiolite show the εNd(t) values of

87

Sr/86Sr

2σ

ISr (244 Ma)

0.724678 0.724534

0.000027 0.000003

0.722855 0.722711 0.722783

0.710398 0.710306 0.710952 0.710529 0.710518 0.711990 0.711990 0.711131 0.710535 0.711135 0.712122 0.712268 0.711771 0.711828

0.000017 0.000018 0.000004 0.000004 0.000006 0.000006 0.000007 0.000006 0.000008 0.000004 0.000024 0.000032 0.000011 0.000013

0.710377 0.710286 0.710938 0.710522 0.710316 0.711664 0.711664 0.711002 0.710382 0.711105 0.711796 0.711943 0.711620 0.711677 0.711092

3.2–12.5, with an average of 8.6 (Appendix B; Li et al., 1996; Xu and Han, 1996; Xu et al., 2002), which is higher than the values of the ore sulfides (Fig. 5). However, the remarkably negative εNd(t) values of the sulfides and the low Re content in the molybdenite from ores at Zhifang (Table 1) do not support a mantle origin. The metabasalts and felsic volcanic rocks of the Dengfeng Complex show εNd(t) values from −3.8 to 4.9, with an average of 2.1 (Appendix B; Li et al., 1987; Zhou et al., 2009), which is higher than the highest values of the ore sulfides (Fig. 5). Therefore, the high Nd isotopic ratios of the Dengfeng Complex suggest that the fluids were likely sourced from southward subduction of the basement of Songji Block. 6.1.4. Lead isotope The lead isotopic data of sulfide minerals from the middle stage ores and early stage ores at Zhifang show analogous ranges, with (206Pb/204Pb)i ratios of 17.126 to 17.535, (207Pb/204Pb)i ratios of 15.374 to 15.466, and (208Pb/204Pb)i ratios of 37.485 to 37.848 (Table 4). The wallrocks of the Xiong'er Group show larger variation in 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios with broad ranges of 16.125–17.577, 15.271–15.529 and 36.047–38.861, and averages of 16.682, 15.357 and 37.013, respectively (Appendix C). The rocks of the

Table 3 Nd isotope ratios of sulfides from the Zhifang deposit. Sample no.

Mineral

Early-stage ores of the Zhifang deposit ZF01a Pyrite ZF01b Pyrite Average N=2 Middle-stage ores of the Zhifang deposit ZF08a Molybdenite ZF08b Molybdenite ZF10a Molybdenite ZF10b Molybdenite ZF16a Molybdenite ZF16b Molybdenite ZF02a Pyrite ZF02b Pyrite ZF008 Pyrite ZF16-1 Pyrite ZF18 Pyrite ZF20-2 Pyrite ZF12-6a Galena ZF12-6b Galena ZF14 Galena Average N = 15

Sm (ppm)

Nd (ppm)

147

Sm/144Nd

143

Nd/144Nd

2σ

(143Nd/144Nd)i

εNd (244 Ma)

0.09 0.09

0.47 0.47

0.1158 0.1158

0.511657 0.511621

0.000041 0.000005

0.511472 0.511437 0.511454

−16.6 −17.3 −17.0

234.8 234.8 158.6 158.6 331.7 331.7 0.1 0.1 0.51 1.06 0.07 0.27 0.12 0.12 0.72

1038 1038 1437 1437 1743 1743 0.59 0.59 3.01 5.01 0.26 1.68 0.46 0.46 4.3

0.1368 0.1368 0.0667 0.0667 0.1150 0.1150 0.1025 0.1025 0.1024 0.1279 0.1628 0.0972 0.1577 0.1577 0.1012

0.511773 0.511787 0.511567 0.511558 0.511507 0.511714 0.511535 0.511557 0.511640 0.511687 0.511749 0.511686 0.511732 0.511704 0.511597

0.000008 0.000011 0.000005 0.000004 0.000065 0.000004 0.000006 0.000005 0.000006 0.000003 0.000005 0.000005 0.000013 0.000007 0.000003

0.511554 0.511569 0.511461 0.511452 0.511323 0.511530 0.511371 0.511394 0.511476 0.511483 0.511489 0.511531 0.511480 0.511452 0.511435 0.511467

−15.0 −14.7 −16.8 −17.0 −19.5 −15.5 −18.6 −18.2 −16.5 −16.4 −16.3 −15.5 −16.5 −17.0 −17.3 −16.7

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

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Table 4 Pb isotope values of sulfides from the Zhifang deposit. Sample no.

Mineral

208

Pb/204Pb

207

Pb/204Pb

206

Pb/204Pb

Pb (ppm)

Th (ppm)

U (ppm)

(208Pb/204Pb)ia

(207Pb/204Pb)ia

(206Pb/204Pb)ia

Early-stage ores of the Zhifang deposit ZF01 Pyrite 37.622

15.405

17.386

2040

0.09

0.12

37.622

15.405

17.386

Middle-stage ores of the Zhifang deposit ZF08 Molybdenite 37.676 ZF10a Molybdenite 37.580 ZF10b Molybdenite 37.734 ZF16a Molybdenite 37.675 ZF16b Molybdenite 37.600 ZF02 Pyrite 37.848 ZF008 Pyrite 37.618 ZF16-1 Pyrite 37.558 ZF18 Pyrite 37.604 ZF20-2 Pyrite 37.605 ZF1206 Galena 37.610 ZF14 Galena 37.485 Average N = 12 37.633

15.423 15.404 15.452 15.429 15.407 15.466 15.403 15.390 15.402 15.400 15.403 15.374 15.413

17.497 17.478 17.513 17.489 17.473 17.536 17.468 17.390 17.428 17.441 17.372 17.126 17.434

7649 6436 6436 10,289 10,289 1675 474 2332 1187 7494 470,699 435,999

9.34 55.0 55.0 47.9 47.9 0.05 0.10 0.13 0.02 0.04 0.06 0.13

135 387 387 652 652 0.62 0.63 8.98 0.06 0.10 0.07 0.30

37.675 37.574 37.727 37.672 37.597 37.848 37.618 37.558 37.604 37.605 37.610 37.485 37.631

15.420 15.397 15.444 15.422 15.399 15.466 15.403 15.390 15.402 15.400 15.403 15.374 15.410

17.455 17.334 17.369 17.338 17.322 17.535 17.464 17.381 17.428 17.441 17.372 17.126 17.380

a

Calculated at t = 244 Ma.

Taihua Supergroup also show larger variation in 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values with ranges of 15.406–17.609, 15.188–15.620 and 35.902–38.569, and averages of 17.036, 15.399 and 37.510, respectively (Appendix C), overlapping the domain of the Xiong'er Group and the sulfide samples from the Zhifang deposit (Fig. 6). The ore-forming fluids were mainly sourced from the metamorphic fluids (Deng et al., 2014b) which initially originated from the dehydration of the subducted slab. During the formation of the Zhifang deposit, the fluids leached the metals from metamorphic rocks of the Taihua Supergroup and volcanic rocks of the Xiong'er Group, and thereby inherited the Pb-isotope signatures of the wallrocks. During the hydrothermal processes or fluid–rock interactions, radiogenic Pb isotopes (208Pb, 207Pb and 206Pb) were preferentially leached out from the rocks and incorporated into the fluids, analogous to the commonlyobserved stepwise leaching effect in Pb isotope analysis (Frei et al., 1998; Peng et al., 2006). This would lead to generally higher Pb isotope ratios of the sulfides from the ores as compared to the majority of samples from the ore-forming rocks (Deng et al., 2013a; Ni et al., 2015). Thus, we conclude that the ore-forming fluids of the Zhifang deposit were likely sourced from the dehydration of the Taihua Supergroup and Xiong'er Group (Fig. 6).

The basement of the Songji Block is composed mainly of rocks belonging to the Dengfeng Complex (Zhang et al., 1985). The metabasalts and felsic volcanic rocks of Dengfeng Complex show limited variation in 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values with ranges of 16.126–17.267, 15.265–15.351 and 37.099–37.342, respectively, which are lower than those of the sulfides, suggesting that these rocks could be one of the fluid sources forming the ore deposit. However, the rocks of the Luanchuan Group, Guandaokou Group, and the Mian– Lue ophiolites which represent the northward subduction of the Mian–Lue oceanic crust have more radiogenic Pb-isotope ratios than sulfides (Fig. 6), which rules out the possibility of the Luanchuan Group, Guandaokou Group, and the Mian–Lue ophiolites as source of the ore lead. 6.2. Ore genesis models for the Zhifang deposit The Re–Os ages of the Zhifang Mo deposit shows that molybdenum mineralization occurred during the Indosinian Orogeny, and is not related to the Yanshanian magmatism (emplaced during 115–156 Ma, Chen et al., 2009), or the Paleo-Mesoproterozoic volcanic–hydrothermal event (most of the Xiong'er volcanic rocks formed at 1.78–1.75 Ga,

Fig. 5. The εNd(t) vs. ISr(t) plots of the Zhifang Mo deposit. Base map is from Depaolo and Wasserburg (1979). References for the ranges of other units are given in the text.

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

X.-H. Deng et al. / Gondwana Research xxx (2015) xxx–xxx

Fig. 6. The plumbotectonic model for the Zhifang Mo deposit. Base map is from Zartman and Doe (1981). References for the ranges of other units are given in the text.

with minor felsic volcanic rocks erupting at ~ 1.45 Ga, He et al., 2009). The geological and geochemical characteristics of the Zhifang molybdenum deposit are characterized by low salinity and high CO2 content (Deng et al., 2014b), and are similar to those of the orogenic-type deposits both in the Qinling Orogen, such as the Shanggong (Chen et al., 2008), Tieluping Ag deposit (Chen et al., 2004), Weishancheng Ag–Au belt (Zhang et al., 2013), Yindonggou Ag–polymetal deposit (Yue et al., 2014), Lengshuibeigou Pb–Zn deposit (Qi et al., 2007), Wangpingxigou Pb–Zn deposit (Yao et al., 2008), and Dahu Au–Mo deposit (Li et al., 2011a; Ni et al., 2012, 2014), as well as those in other parts of the world (Groves et al., 1998; Kerrich et al., 2000; Chen et al., 2005; Goldfarb et al., 2005; Larsen and Stein, 2007; Zhang et al., 2012;

9

Zheng et al., 2012; Zhong et al., 2012; Zhou et al., 2014a,b; Zheng et al., 2015; Zhou et al., 2015). Therefore, the Zhifang deposit has been classified as an orogenic-type molybdenum deposit (Deng et al., 2014b). However, the characteristics and abundance of such deposits in orogenic belts are not yet well established. The Zhifang Mo deposit occurs in a transitional zone between Andean-type arc and back-arc continent (Fig. 7), which is unique compared to the world's orogenictype hydrothermal deposits that generally occur either in fore-arc accretionary terranes or collisional orogens (Chen et al., 1998; Groves et al., 1998; Goldfarb et al., 2005; Pirajno, 2009; Chen, 2013; Pirajno, 2013; Chen et al., 2014; Goldfarb et al., 2014). The metallogenic history of Zhifang includes three stages, which from early to late, are characterized by the mineral assemblages of quartz–pyrite, quartz–molybdenite– pyrite–chalcopyrite–galena–sphalerite, and quartz–carbonates, respectively. The fluid inclusion study of this deposit supports the view that the ore-forming fluids evolved from an early stage deep-sourced metamorphic fluid, through a middle stage of mixed deep- and shallowsourced fluids, to a late stage of shallow-sourced meteoric fluids (Deng et al., 2014b). The Sr–Nd–Pb isotopic systematics shows that the ore-forming metals could not have been provided solely, or as mixtures of the Xiong'er Group, the Taihua Supergroup, the Luanchuan and Guandaokou Groups, or the lower crust and/or the mantle. Taken together, the isotopic data suggest that the ore-forming fluids are most likely generated from metamorphic devolatilization of the metabasalts and felsic volcanic rocks of Dengfeng Complex, exposed in the Songji Block, north of the San–Bao fault (Chen and Fu, 1992). The northward B-type subduction of the Mian–Lue oceanic plate, the transpression and southward underthrusting (or A-type subduction) and metamorphic devolatilization of the NCC beneath the Huaxiong Block may have been key factors for the metallogenesis of the orogenic molybdenum deposits in Waifangshan area (Fig. 7). 7. Conclusions (1) The molybdenite from the Zhifang Mo deposit yield a weighted mean Re–Os age of 243.8 ± 2.8 Ma (2σ), suggesting that the Zhifang deposit is an orogenic-type mineral system, and does not belong to the Yanshanian magmatic hydrothermal or the Paleo-Mesoproterozoic volcanic–hydrothermal systems. (2) The Sr–Nd–Pb isotope systems of the Zhifang deposit indicate that the possible ore-forming fluids should have low ISr(t) values and high εNd(t) values compared to those of ore sulfides, suggesting the initial ore-forming fluids were sourced from the basement of Songji Block.

Fig. 7. Triassic tectonic–magmatic–metallogenic scenario in Qinling Orogen. Modified after Chen and Santosh (2014) and Li et al. (2015).

Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020

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(3) The Zhifang deposit can be interpreted by a model involving the southward subduction of the North China Craton beneath the Huaxiong Block.

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Please cite this article as: Deng, X.-H., et al., Re–Os and Sr–Nd–Pb isotope constraints on source of fluids in the Zhifang Mo deposit, Qinling Orogen, China, Gondwana Research (2015), http://dx.doi.org/10.1016/j.gr.2015.02.020