U–Pb and Re–Os Isotopic Systematics and Zircon Ce4+/Ce3+ Ratios in the Shiyaogou Mo Deposit in Eastern Qinling, Central Chin

Ore Geology Reviews 55 (2013) 29–47

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Ore Geology Reviews

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U–Pb and Re–Os isotopic systematics and zircon Ce4+/Ce3+ ratios in the Shiyaogou Mo deposit in eastern Qinling, central China: Insights into the oxidation state of granitoids and Mo (Au) mineralization

Yigui Han a,b,⁎, Shihong Zhang a, Franco Pirajno c, Xuewu Zhou d, Guochun Zhao b, Wenjun Qü e, Shihua Liu f, Jiangming Zhang f, Haibin Liang f, Ke Yang a,f a State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing 100083, China b Department of Earth Sciences, The University of Hong Kong, Pokfulam Road, Hong Kong c Centre for Exploration Targeting, School of Earth and Environment, University of Western Australia, 35 Stirling Highway, Crawley WA 6009, Australia d Faculty of Resources, China University of Geosciences, Wuhan 430074, China e National Research Center of Geoanalysis, Chinese Academy of Geological Sciences, Beijing 100037, China f The Sixth Gold Exploration Branch of Armed Police, Sanmenxia 472000, China article info abstract

Article history: The newly-discovered Shiyaogou molybdenum deposit is located in the eastern Qinling metallogenic belt in Received 5 November 2012 central China. The deposit contains at least 152,000 t of Mo metal and bears typical porphyry-type features in Received in revised form 23 April 2013 terms of its concentric alteration zonation, quartz vein-hosted Mo mineralization, veining sequence and the Accepted 23 April 2013 spatial association with concealed granite porphyries. Re–Os isotope analyses of molybdenite from the de- Available online 29 April 2013 posit yield an ore-forming age of 132.3 ± 2.8 Ma. LA-ICP-MS U–Pb zircon dating of ore-related porphyries yields crystallization ages from 135 Ma to 132 Ma, indicating a temporal link between granitic magmatism Keywords: Eastern Qinling and Mo mineralization. A population of captured magmatic zircons indicates another pulse of magmatism Shiyaogou at ~143 Ma. A barren granite intrusion near the deposit gives a zircon U–Pb age of 148.1 ± 1.1 Ma. These Porphyry molybdenum deposit magmatic activities were concurrent with the emplacement of the nearby Heyu granitic batholith, a largely U–Pb dating ore-barren intrusive complex formed from ~148 Ma to ~127 Ma. Zircon Ce4+/Ce3+ ratios of ore-related por- Re–Os dating phyries are obviously higher than those of contemporaneous barren granitoids, implying an afﬁnity between Ce anomaly Mo mineralization and highly oxidized magmas. Moreover, zircons from these granitoids overall have decreasing Ce4+/Ce3+ ratios from 148 Ma to 132 Ma, reﬂecting decreasing oxygen fugacities during magma evolution. Available geological, radiometric and stable isotopic evidence suggests that the decrease of magma oxygen fugacity was probably associated with an increase of mantle contribution to granitic magmatism and metallogenesis, which probably gave rise to successive mineralization of Mo and Au in the eastern Qinling. The intense magmatic–metallogenic events in the eastern Qinling during Late Jurassic to Early Cretaceous times are interpreted as a response to the large-scale lithosphere thinning and subsequent asthenosphere upwelling beneath the eastern part of the North China Craton. © 2013 Elsevier B.V. All rights reserved.

1. Introduction (2011b), along the Mianlue suture in the Jurassic. The region of eastern Qinling, referred to here, comprises the southern margin of the NCC The ~2000 km long Qinling–Dabie orogenic belt, extending east– and northeastern part of the Qinling belt (Fig. 1) since both units have westward in central China, was assembled by the collision between the been involved into an intracontinental tectonism since the Late Mesozoic North China craton (NCC) and the Yangtze craton (YZC) (Fig. 1). The (Dong et al., 2011b; Meng and Zhang, 1999; Zhang et al., 2001). This re- ﬁnal stage of the collision probably took place along the Shangdan suture gion has been recognized as a world-class molybdenum (Mo) ore district intheLateTriassic(Ames et al., 1993; Hacker et al., 1998; Kröner et al., and one of the most important gold (Au) and polymetallic ore districts in 1993; Mattauer et al., 1985; Meng and Zhang, 2000; Ratschbacher et China (Mao et al., 2011b). These ore deposits were dominantly formed in al., 2003; Zhang et al., 2001) or, as recently documented by Dong et al. an interval from ~235 Ma to ~110 Ma and have been received much in- vestigation in the last decade (Chen and Wang, 2011; Chen et al., 2008a, 2009a; Fan et al., 2011; Han et al., 2007a; C.Y. Li et al., 2011; N. Li et al., 2011; J.W. Li et al., 2012b; N. Li et al., 2012c; Mao et al., 2002, 2008, ⁎ Corresponding author at: Department of Earth Sciences, The University of Hong Kong, Pokfulam Road, Hong Kong. Tel.: +852 28578913. 2011b; Stein et al., 1997; Xu et al., 2010; Zhang et al., 2007, 2011; Zhu E-mail address: [email protected] (Y. Han). et al., 2009).

Fig. 1. Generalized geological map of the eastern Qinling area (modiﬁed after HBGMR, 1989; Mao et al., 2008), also showing the sampling site of 08LC57-1. Mo deposits: 1—Quanjiayu, 2—Shiyaogou, 3—Shangfanggou, 4—Sandaozhuang, 5—Nannihu, 6—Shapoling, 7—Leimengou, 8—Nangou, 9—Shimengou, 10—Banchang; Au deposits: 11—Hongtuling, 12—Dongchuang, 13—Liushugou, 14—Kangshan, 15—Qiyugou, 16—Qianhe; Granite batholiths: WY—Wenyu, NNS—Niangniangshan, ML—Mangling, HSI—Huashani, WZS—Wuzhangshan, Heyu—Heyu, TSM—Taishanmiao, LJS—Laojunshan, ELP—Erlangping.

Molybdenum ore deposits in the eastern Qinling occur primarily as this deposit exceed 152,000 t (Zhang, 2010). The deposit is suggested porphyry and porphyry-skarn types and are spatially and genetically to be porphyry-type and formed at ~133 Ma (Y.L. Gao et al., 2010), associated with small granitic porphyry intrusions (Chen and Wang, which coincides with the nearest granite batholith (Heyu batholith, 2011; N. Li et al., 2012c; Mao et al., 2008; Zhu et al., 2009). By contrast, Fig. 1) that has been well documented recently (X.Y. Gao et al., large volumes of Late Mesozoic granitic plutons/batholiths distributed 2010; Guo et al., 2009; Han et al., 2007b; N. Li et al., 2012b; Mao et in the eastern Qinling are usually barren, such as Wuzhangshan, Heyu, al., 2010). Ore-bearing granitic porphyries have been discovered at Huashani, Laojunshan, Taishanmiao in the Xiong'er–Waifang Moun- depth beneath the deposit, which enables us to study the variation tains, and Huashan, Niangniangshan and Wenyu in the Xiaoqinling of oxidation states of ore-related/barren granitoids by an index of zir- (or lesser Qinling) Mountains (X.Y. Gao et al., 2010; Guo et al., 2009; con Ce4+/Ce3+ ratios (Ballard et al., 2002). In combination with geol- Han et al., 2007b; Mao et al., 2010; N. Li et al., 2012b). The genetic rela- ogy, U–Pb and Re–Os systematics, we discuss the genetic links tionships between the small porphyries and large plutons are still de- between magmatism and metallogenesis in the region and their tec- bated: the ore-related porphyries were evolved from deep-seated tonic implications in the eastern Qinling metallogenic belt. granite plutons (Mao et al., 2008, 2010; N. Li et al., 2012b), or they are essentially the same in origin except that they may represent different 2. Geological background intrusive depths (Chen et al., 2000). This controversy has led to different metallogenic models proposed for the formation of granitoids and Mo– 2.1. Regional geology Au deposits in the eastern Qinling belt (Chen et al., 2009a; J.W. Li et al., 2012a; Mao et al., 2008; Zhu et al., 2009). However, the oxidation states The general geology of the southern margin of the NCC and the of these granitoids and their significance to metallogenesis have not northeastern part of the Qinling belt, which constitute the eastern been fully investigated. Since the oxidation state of melts and fluids is Qinling region, is described separately (Fig. 1). The southern margin of a very important variable that can influence the behavior of Mo, Cu the NCC is generally named the region bounded by the Sanmenxia– andAu(Bali et al., 2012; Ballard et al., 2002; Blevin and Chappell, Lushan fault to the north and Luanchuan fault to the south. The region 1992; Candela and Bouton, 1990; Czamanske and Wones, 1973), in shares the same basement-cover sequence to the NCC, namely an Ar- this study we investigate the oxidation states of ore-bearing and barren chean to Paleoproterozoic basement, covered by Mesoproterozoic to granitoids and their relations to Mo (Au) mineralization by considering Phanerozoic sedimentary rocks. The crystalline basement of the NCC the case of the newly-discovered Shiyaogou Mo deposit in the eastern was affected by two Paleoproterozoic tectonic events: a 1.95–1.92 Ga Qinling. collision between the Yinshan Block and the Ordos Block to form the The Shiyaogou molybdenum deposit is located in the southern Western Block, and a ~1.85 Ga collision between the Western and the Xiong'er Mountains on the southern margin of the NCC (Fig. 1). It Eastern Blocks along the Trans-North China Orogen (Zhao, 2001; Zhao was discovered in recent years by the Sixth Gold Exploration Branch et al., 2005, 2011; G.C. Zhao et al., 2010). Afterwards, the craton proper of Armed Police Army of China. Measured molybdenum resources in maintained a steady state until the Late Mesozoic, when intensive and Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 31 large-scale magmatic, metallogenic and structural events (commonly basin setting in the Neoproterozoic (Diwu et al., 2010b). The meta- referred to as Yanshanian) occurred bordering the eastern part of the clastic rocks probably formed in the Early Paleozoic and may represent craton, likely due to lithospheric thinning and upwelling of astheno- a passive margin of the NCC or an accretionary wedge (Ratschbacher et spheric mantle (Chen et al., 2009b; Liu et al., 2008; Mao et al., 2011a; al., 2003). Pirajno, 2013; Sun et al., 2012; Wu et al., 2008; Yang et al., 2008; Zhu Voluminous magmatic rocks, dominated by granitic plutons and et al., 2011). felsic porphyries with minor volcanic rocks and dykes, were emplaced The basement of the southern margin of the NCC is represented by during the Mesozoic in the eastern Qinling. They can be divided into the Neoarchean to Paleoproterozoic Taihua Group (Fig. 1), which is two main stages according to their isotopic ages: 240–190 Ma and composed of graphite schist, marble, quartzite, banded iron-formation, 160–110 Ma (Guo et al., 2009; Han et al., 2007b; Lu et al., 1999; gneiss, amphibolite that underwent amphibolite and locally granulite Mao et al., 2010; Sun et al., 2000). Contemporaneous Mo, Au and facies metamorphism (Diwu et al., 2010a; Kröner et al., 1988; Wan et polymetallic mineralization took place and correlated well with al., 2006; Zhang et al., 2001). The Taihua Group is unconformably over- these two stages (Mao et al., 2010; Stein et al., 1997; Wang et al., lain by Paleo-Mesoproterozoic volcanic-dominated rocks of the Xiong'er 2002), indicating a close association between metallogenesis and Group, which is divided into four formations namely, from bottom to magmatism. top, Dagushi, Xushan, Jidanping and Majiahe (He et al., 2008, 2010a, 2010b; Zhao et al., 2002, 2009). The Dagushi Formation has sparse out- 2.2. Ore geology in Shiyaogou area crops locally and consists mainly of conglomerate, sandstone and mudstone. The Xushan Formation consists of porphyritic basaltic andesite The Shiyaogou area is underlain by Paleo-Mesoproterozoic volcanic and andesite with minor dacite and rhyolite. The Jidanping Formation rocks of the Xiong'er Group, of which only the upper three formations consists mainly of dacite and rhyolite with minor andesite. The Majiahe crop out, namely the Xushan, Jidanping and Majiahe formations Formation is composed primarily of basaltic andesite and andesite with (Fig. 2). The Xushan Formation is characterized by dark-greenish por- increasing interlayers of purple shale and mudstone. Zircon U–Pb dat- phyritic andesite and basaltic andesite. The Jidanping Formation con- ing results indicate the Xiong'er Group erupted at ~1.78 Ga, with sists mainly of reddish-gray rhyolitic dacite and minor andesite. The minor younger intrusions in the Jidanping Formation (He et al., 2009; Majiahe Formation is mainly composed of andesite, basaltic andesite Zhao et al., 2009 and references therein). Meso- to Neoproterozoic and trachyte with minor rhyolite and rhyolitic porphyry on its top. terrigenous clastic and neritic carbonate rocks unconformably overlie The intermediate-mafic rocks of this volcanic succession show low- the Xiong'er Group, named the Ruyang Group and the Guandaokou grade greenschist facies metamorphism. Group, which in turn are overlain by Neoproterozoic clastic and car- The Shiyaogou Mo deposit is surrounded by three gold deposits bonate successions. Pelaomagnetic investigations suggested that within 2–3 km, namely the Hongzhuang, Nanping and Yuanling gold these Precambrian strata were mainly formed in low paleolatitudinal deposits (Fig. 2). These Mo and Au deposits are controlled by three brit- regions (Zhang et al., 2000, 2012; S.H. Zhang et al., 2006). Similar to tle splays of the Machaoying fault zone: from north to south, these are the typical rock sequences on the NCC proper, carbonate and clastic Kangshan–Nanping, Tieling–Baitu–Xiayankan, Machaoying–Shizimiao– strata formed in the area during the Cambrian and Early Ordovician, Hongzhuang faults (Fig. 2)(Liu et al., 1998; Shi et al., 2004). These and a depositional hiatus developed in the period from the Middle brittle faults exhibit both sinistral strike–slip and tensional charac- Ordovician to the Early Carboniferous. Sedimentary rocks deposited teristics and were probably activated during Late Jurassic to Early from Middle Carboniferous to Triassic times comprise mainly terrig- Cretaceous times (Han et al., 2009; Zhang et al., 2001). enous mudstone, clastic rock and carbonate interbedded with coal seams. Strata of Jurassic to Cenozoic ages are relatively rare and con- 2.2.1. Concealed granitic porphyries fined to intra-continental basins. The Machaoying fault zone is an No igneous intrusions outcrop in the Shiyaogou area within a radi- important structure extending ~200 km west-eastward on the us of 5 km. However, recent drilling exploration has revealed southern margin of the NCC. Previous studies suggested that the deep-seated granitic porphyries in a few drillholes (Fig. 2). All discov- fault was a northward A-type subduction zone subjected to multi- ered porphyries are confined beneath the surface of the Shiyaogou stage deformation (Chen and Fu, 1992; Chen et al., 2008b; Liu et al., Mo deposit (Fig. 2); by contrast, no porphyry has been found at 1998). Recent 40Ar–39Ar dating of syn-tectonic biotite from the depths of surrounding Au deposits. The porphyries are encountered fault yields a plateau age of 524.9 ± 1.9 Ma, indicating a southward at a depth usually greater than 400 m, with core intersections ranging thrusting in the Early Paleozoic (Han et al., 2009). Multistage activa- from 0.7 m to 40 m. Drillhole ZK519 has the longest porphyry inter- tion of the fault zone probably has contributed significantly to the section of 129 m at the bottom and is still open at depth (Fig. 3), formation of mineral deposits in this area (Chen et al., 2008a, probably representing the top of a concealed porphyry intrusion. 2008b). The possible shapes of these intrusions inferred from drilling inter- The northeastern part of the Qinling belt is bound by the Luanchuan sections are shown in Fig. 3. fault to the north and the Shangdan suture to the south (Fig. 1). Rock According to their petrological characteristics, these porphyries successions in this area are, from south to north, Qinling, Erlangping can be classified into three types. Type 1 is a gray medium- to fine- and Kuanping groups, which are separated by regional faults. The grained biotite monzogranite with biotite, plagioclase, K-feldspar, Qinling Group consists mainly of Paleoproterozoic amphibole facies quartz (size b3 mm) and minor K-feldspar phenocrysts (b10 vol.%) metamorphic rocks and Early Paleozoic intrusions (Chen et al., 1991; (Fig. 4a-right). Type 2 is a pink coarse-grained porphyritic monzogranite Lu et al., 2006; You et al., 1993), which were regarded as an island-arc with ~25 vol.% phenocrysts, which include nearly equal K-feldspar terrane above a subduction zone in the Early Paleozoic (Dong et al., (0.5–1.5 cm in size, euhedral) and quartz (~7 mm in size) (Fig. 4b). 2011a). The Early Paleozoic Erlangping Group consists of low-grade The matrix consists of K-feldspar, plagioclase, quartz and sparse biotite. metamorphosed volcanic–sedimentary sequences and has been recog- Cooling margin adjacent to their contact revealed by drill cores indicates nized as ophiolite assemblages (Zhang et al., 2001). Pillow basalts in that the porphyry of type 1 was intruded by that of type 2 (Fig. 4c). Type the Erlangping Group possess calc-alkaline geochemical signatures, 3 is represented by pink fine-grained K-feldspar granitic veins with suggesting a back-arc setting (Lu et al., 2003). The Late Neoproterozoic equigranular texture and is composed of K-feldspar, plagioclase and to Early Paleozoic Kuanping Group comprises greenschist to amphibolite quartz, without maficminerals(Fig. 4a-left). These veins were probably facies mafic volcanic rocks and meta-clastic rocks including marble and differentiated from the aforementioned monzogranites during the two-mica quartz schists (Lu et al., 2003). The N-MORB geochemical late-stage of magmatic evolution. These three types of porphyries prob- signatures of meta-basalts of the Kuanping Group suggest a back-arc ably underwent similar alteration processes, as manifested by their 32 Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47

Fig. 2. Geological map in Shiyaogou area showing Shiyaogou Mo deposit and surrounding Au deposits. KNF—Kangshan–Nanping fault, TBXF—Tieling–Baitu–Xiayankan fault, MSHF— Machaoying–Shizimiao–Hongzhuang fault. intensive potassic and sericitic alterations and various degree of molyb- 2.2.2. Mo mineralization, hydrothermal alteration and veining sequences denum mineralization. Potassic and sericitic alterations are represented Molybdenite-bearing ore bodies of the Shiyaogou deposit are by growth of secondary K-feldspar matrix and replacement of plagio- within or adjacent to the Tieling–Baitu–Xiayankan fault (Fig. 2). clase by sericite (Fig. 4a, b, d). The margins of pre-existing K-feldspar The fault dips 50–80° north and extends ~800 m with a width of crystals were sometimes replaced by secondary muscovite and quartz 80–300 m. Intense Mo mineralization occurs at depths greater than (Fig. 4d), suggesting leaching of K+ and Na+ due to hydrothermal H+ 100 m with increasing density of ore-bearing veinlets towards the metasomatism. porphyries (Fig. 3). Abundant stockworks of quartz-molybdenite veins characterize the deposit. The ore-bearing veins are commonly 1–2cmthick(Fig. 4e, f). They are generally banded and symmetric with alternate quartz and molybdenite interlayers (Fig. 4e), indicating pulses of fracture opening and ingress of hydrothermal fluids, which were probably caused by multistage hydrofracturing due to vol- atile exsolution and phase separation at depth. Quartz-molybdenite veinlets are common at a shallower depth and mainly hosted in altered volcanic rocks. Disseminated fine-grained molybdenite is distributed in volcanic rocks and porphyries. Molybdenite in veins usually occurs as curved flakes between quartz grains. Ore minerals of the deposit consist of molybdenite, pyrite, magnetite, chalcopyrite with minor pyrrhotite, galena, bornite and hematite. Main gangue minerals are quartz, K-feldspar, calcite, sericite and chlorite. Although wall-rock alteration of the Shiyaogou Mo deposit is compli- cated due to widespread fracturing, alteration zones can be established approximately. Outward from the porphyries they are potassic, silicic, phyllic, argillic and propylitic zones (Fig. 3). Molybdenum mineralization is spatially related to potassic and phyllic alteration and silicification. Potassic and phyllic alteration zones are commonly near the top of the intrusion and extend ~600 m above it (Fig. 3). Potassic alteration is represented by occurrence of secondary K-feldspar or greenish biotite-bearing veins and becomes more intense toward the intrusion. Phyllic alteration assemblage comprises sericite, quartz, chlorite, pyrite and chalcopyrite. Silicification is very common and accompanies potassic and phyllic alteration. It is characterized by the formation of new quartz or opal in quartz-bearing veins and wall rocks. Argillic alteration occurs mainly in the upper part of the deposit and is characterized by the presence of montmorillonite and kaolinite. Propylitic alteration occurs in the outer part and is represented by albite, epidote, chlorite, and carbonate that replace plagioclase and maficminerals. Fig. 3. Cross section of exploration line A–B of the Shiyaogou deposit, showing sam- A veining sequence has been established on the basis of crosscut- pling sites, inferred granite porphyries at depth and wall-rock alteration zones. ting relationships of veins, from early to late, as follows: quartz-K- Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 33

Fig. 4. Sample- and micro-scale features of concealed porphyries and ores from the Shiyaogou deposit. Photos (a) and (b) show three types of porphyries: (a) left — K-feldspar granite (Type 3), (a) right — biotite monzogranite (Type 1), (b) — porphyritic monzogranite (Type 2). (c) — contact between porphyries of Type 1 and Type 2 revealed in drill core. (d) — microphotograph showing alteration characteristics of porphyry (crossed nicols). (e) — typical ores with banded quartz + molybdenite veins. (f) — quartz + molybdenite vein crosscuts quartz + K-feldspar vein. (g) — quartz + pyrite vein crosscuts quartz + molybdenite vein. (h) — clean quartz vein cuts through quartz + pyrite vein and secondary K-feldspars. Abbreviations: Bi — biotite, Qz — quartz, Ser(Pl) — pre-existing plagioclase replaced by sericite, sec-Kﬂ — secondary K-feldspar, pre-Kﬂ — pre-existing K-feldspar, Mus — muscovite, Mo — molybdenite, Py — pyrite.

feldspar → quartz-molybdenite → quartz-pyrite → clean quartz → reflecting a hydrothermal environment evolved from high to low carbonate. Quartz and K-feldspar veins developed prior to quartz- temperature (Pirajno, 2009). molybdenite veins (Fig. 4f), which were normally crosscut by quartz-pyrite veins (Fig. 4g). Late-stage barren and clean quartz 3. U–Pb and Re–Os isotopic dating veins commonly cut quartz-pyrite and quartz-molybdenite veins (Fig. 4h) and was subsequently crosscut by latest-stage carbonate 3.1. Sampling veins. As the “fossil” expression of fluid discharging along fractures or channels, hydrothermal veins can reflect evolution of hydrother- Four samples of granitic rocks were selected for LA-ICP-MS U–Pb zir- mal fluids (Pirajno, 2009). The veining sequence of the Shiyaogou de- con dating and trace element analysis. Three of them are ore-bearing posit is comparable to typical veinlet sequence of Cu–Mo porphyry porphyries from the Shiyaogou deposit and one from a barren intrusion deposits (Sillitoe, 2010). The above-described veining sequence nearby (Fig. 3). Sample ZK51811-1 is a medium-grained biotite and alteration zoning indicate a succession of wall-rock alteration monzogranite (Type 1) collected from drillhole ZK518 (Location: 34°1′ types: potassic alteration → phyllic alteration → propylitic alteration, 48″N, 111°34′6″E, Fig. 3) at a depth of 422.5 m. Sample ZK518-14, a 34 Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 porphyritic monzogranite (Type 2), was also collected from the drillhole 3.2.2. Molybdenite Re–Os dating ZK518 at a depth of 507 m. Sample 08SYG01-4, a porphyritic coarse- Molybdenites Re–Os isotopic dating was conducted at the Re–Os grained monzogranite (Type 2), was collected from the bottom (800 m Laboratory, National Research Center of Geoanalysis, at the Chinese deep) of the drillhole ZK519, which is about 100 m to the north of the Academy of Geological Sciences in Beijing. Analytical procedures for drillhole ZK518. One barren medium-grained biotite monzogranite sam- chemical decomposition of sample, distillation and separation of Re ple 08LC57-1 (Location: 33°59′39″N, 111°25′2″E) was collected from a and Os are here omitted because they have been described in detail small granite intrusion in the Mazhuanggou valley ~15 km west to the in published literature (Du et al., 1994, 2004; Mao et al., 2006; Qu Shiyaogou deposit (Fig. 1). In order to calculate zircon Ce4+/Ce3+ ratios, and Du, 2003; Stein et al., 2001). Re and Os isotope ratios were deter- the sample 08SYG01-4 and 08LC57-1 were chosen for whole-rock trace mined by a TJA X-series type ICP-MS. Measured masses for Re were element analysis as they are relatively fresh. Five molybdenite-rich ores 185 and 187; mass 190 was used to monitor Os. Measured masses were collected from the No. 2 adit of the Shiyaogou deposit for Re–Os dat- for Os were 186, 187, 188, 189, 190 and 192; mass 185 was used to ing. The adit is located underneath the surface in between the drillhole monitor Re. Average blanks for the total procedure were ~40 pg for ZK518 and ZK519 (Fig. 2). Re, ~0.1 pg for Os and ~0.2 pg for 187Os. The reference material GBW04436 (JDC) was used to test analytical reliability. The resulted model ages of twice analyses were 139.2 ± 2.1 Ma and 139.2 ± 3.2. Analytical methods 1.9 Ma, respectively, which are consistent with the certified value of 139.6 ± 3.8 Ma (Du et al., 2004). Re–Os isochron was calculated 3.2.1. Zircon LA-ICP-MS U–Pb dating using the Isoplot program (Ludwig, 2003). Samples were crushed (b200 μm) and elutriated by water and then separated by a magnetic method to concentrate heavy minerals. Zircon 3.2.3. Whole-rock trace element analysis grains were hand-picked under a binocular microscope and then Whole-rock trace elements analyses were performed at the Geo- were mounted in epoxy resin and polished to expose grain interiors. logical Laboratory Center of the China University of Geosciences in Cathodoluminescence (CL) images were taken on a scanning electron Beijing. Analytical procedure for sample dissolution and treatment microscope (type Quanta 200F) plus a CL spectroscope (type Mono has been described in Han et al. (2007b). Trace elements of the solu- CL3+) at the Peking University. tions were determined using an ICP-MS (type Agilent 7500a) with an Zircon U–Pb dating was carried out at the LA-ICP-MS laboratory of analytical precision less than 10%. Rhodium solution was used as the China University of Geosciences in Beijing. The LA-ICP-MS consists online internal standard during analysis to correct mass discrimina- of a commercial 193 nm laser ablation system (type UP193SS) and a tion and diminish matrix effect. Reference materials analyzed for reli- quadruple ICP-MS (type Agilent 7500a). We have referred to Yuan et ability testing include one USGS andesite standard AGV-2 and one al. (2004) and Liu et al. (2007) for analytical designs in this study. Chinese standard GBW07103 (GSR-1, granite). Analytical results of Both the sample mount and a standard zircon mount were set up in a these standards indicate that all concentrations of trace elements SuperCellTM chamber. Helium was used as the carrier gas to transport presented here are within errors of certified values. ablated aerosol from the sample chamber. The aerosol was transferred through a one-meter-long PVC tube and then mixed with argon via a 3.3. Results Y-shaped joint before entering into the ICP-MS. The flow velocities of helium and argon were set at 0.9 L/min and 0.94 L/min, respectively. 3.3.1. Zircon U–Pb isotopic results Laser spot diameter was 36 μm with a frequency of 10 Hz. The energy Zircon U–Pb isotopes and trace elements from three ore-related density on the sample surface was about 8.5 J/cm2. The ICP-MS was op- and one barren granite samples are presented in Table 1. Spot analy- erated in a time-resolved analysis and peak-hopping mode. The dwell ses yielding fluctuant U–Pb isotopic ratios on their signal spectra times for isotopes were set at 6 ms for mass 29, 20 ms for masses 204, were discarded, including spots 8 and 13 of sample 08SYG01-4, and 206, 207, 208, 232 and 238, and 10 ms for other masses. The back- spots 16 and 19 of sample ZK51811-1. Analyses yielding discordant ground of each analysis was acquired for 40 s prior to the start of laser ages (the difference between 206Pb/238U and 207Pb/235U ages is larger ablation. Signal was acquired for 40 s. Standard silicate glass NIST 610 than 10%) were excluded from weighted average age calculation, and standard zircon 91500 and TEMORA 1 (TEM) were analyzed once including spot 5 of sample ZK518-14 and 1, 15, 18, 23 of sample every ten spot analyses. 08LC57-1 (Table 1). Data reduction was conducted using Glitter 4.4 software (Macquarie Sixteen concordant analyses for sample ZK51811-1 give an average University). Integrated signal intervals for U–Pb age calculation were 206Pb/238U age of 134.3 ± 1.1 Ma (MSWD = 1.4) (Fig. 5a). These data selected at the same range (~30 s) on their time-resolved signal spec- are obtained from euhedral zircons with oscillatory zoning (Fig. 6a) and tra. For elemental calculation, however, only the signal intervals with- Th/U = 0.4–1.0 (Table 1), indicating a magmatic origin (Belousova et out anomalously high counts of La and Pr were selected, because high al., 2002). We therefore interpret the age of 134.3 ± 1.1 Ma as the em- contents of La and Pr in zircon during in-situ microprobe analysis are placement time of the porphyry. Spot 21 placed on an inherited core usually caused by accidental analysis of inclusions in a size of a few mi- yields an apparent 206Pb/238U age of 151 ± 2 Ma. The core is euhedral crons (Hoskin and Schaltegger, 2003). and exhibits oscillatory zoning (Fig. 6a) with Th/U = 1.6, indicating a Zircon 91500 was used as external standard for isotopic ratio correc- magmatic origin. tions. The ComPbCorr program (ver. 3.16e) (Andersen, 2002) was used Twenty-four analyses for sample ZK518-14 give concordant Me- to evaluate common Pb of the data output from the Glitter, assuming sozoic ages and can be separated into two populations (Fig. 5b). recent lead-loss and a common-lead composition of 0.13 Ga given by The older population consists of eighteen analyses with a weighted Stacey and Kramers (1975). Elemental concentrations of zircons were average 206Pb/238U age of 142.8 ± 0.9 Ma (MSWD = 1.0), and the calculated by using NIST 610 as an external standard and 29Si as an younger one has six analyses with an average age of 134.0 ± 1.5 Ma internal standard. Weighted average ages, errors and concordia dia- (MSWD = 1.1). Zircons of the two populations are indistinguishable grams were generated using Isoplot v.3.23 program (Ludwig, 2003). in morphology and CL images (Fig. 6b). They also exhibit similar Twelve analyses of the zircon standard TEM yield a weighted average magmatic features, such as euhedral, oscillatory zoning and Th/U 206Pb/238U age of 416.6 ± 3.3 Ma (2 σ, MSWD = 0.4), which is in ratios (0.4–1.7, Table 1). We interpret that the younger age of agreement with the referred ages (Black et al., 2003). The measured 134.0 ± 1.5 Ma represents the emplacement time of the porphyry, elemental concentrations of 91500 are consistent with the values whereas the older zircons were captured from an earlier intrusion given by Yuan et al. (2004). (142.8 ± 0.9 Ma) during magma ascending. Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 35

Eighteen analyses for sample 08SYG01-4 are concordant and yield a of the Heyu granitic batholith in the Waifang Mountains, ~22 km east weighted average 206Pb/238U age of 132.8 ± 1.1 Ma (MSWD = 1.5) to the Shiyaogou deposit. Ten samples collected from the Heyu batho- (Fig. 5c). Both oscillatory zoning on CL images (Fig. 6c) and Th/U ratios lith have been dated using the zircon U–Pb and biotite 40Ar–39Ar (0.4–1.7, Table 1) of these zircons indicate a magmatic origin. The age of methods, giving isotopic ages ranging from ~148.2 Ma to ~131.8 Ma 132.8 ± 1.1 Ma then represents the emplacement time of the porphyry. (X.Y. Gao et al., 2010; Guo et al., 2009; Han et al., 2007b; N. Li et al., Eighteen analyses for the barren granite sample 08LC57-1 from the 2012b) except one younger age of 127 ± 1 Ma (Mao et al., 2010). The Mazhuanggou valley are concordant and give an average 206Pb/238U Re–Os isotopic results in this study indicate that Mo mineralization in age of 148.1 ± 1.1 Ma (MSWD = 0.9) (Fig. 5d). These grains are mag- the Shiyaogou deposit occurred at 132.3 ± 2.8 Ma, which is coeval matic zircons due to their oscillatory zoning and Th/U ratios (mainly with the emplacement of the porphyries in ~135–~132 Ma. The 14–2.5, Table 1). The granite intrusion therefore was emplaced at Shiyaogou Mo deposit thus formed in a typical porphyry system, as ~148 Ma. also supported by the alteration zoning and the veining sequence de- Four analyses placed on the cores of zircon grains from the Shiyaogou scribed in the Section 2.2.2. deposit give 207Pb/206Pb ages spanning 2294–2150 Ma (Table 1). One Re concentration in molybdenite can be potentially indicative of analysis placed on rounded core of a grain from the sample 08LC57-1 the metal sources of a deposit. Deposits involved mantle contribu- gives a 207Pb/206Pb age of 1954 Ma. These ages are consistent with the tions usually have higher Re contents (Stein et al., 2001). Mao et al. dating results from the upper Taihua Group (Wan et al., 2006), resulting (1999) summarized the Re concentrations of molybdenites from in the formation ages between 2.26 and 2.14 Ga and metamorphic ages major Mo deposits in China and has suggested that the Re concentra- about 1.9–1.8 Ga. These cores are hence interpreted as inherited grains tions decrease gradually from mantle sources, to mantle–crust mix- derived from the Taihua Group. ture and then to crust. Together with the Re–Os analytical results of Y.L. Gao et al. (2010), Re contents of molybdenite from the Shiyaogou 3.3.2. Zircon trace elements, Ce4+/Ce3+ ratio and Ti-in-zircon thermom- deposit vary from 8 μg/g to 88 μg/g, implying a mixed origin between eter calculation crust and mantle components for the ore materials (Mao et al., 1999). Elemental concentrations of rare earth elements (REEs), Ti, Th, U This is in accord with stable isotope studies on ore-fluids from ore de- and Hf in zircons are presented in Table 2. Chondrite-nomalized REE posits in the eastern Qinling belt (Chen et al., 2009a; J.W. Li et al., patterns of zircons are shown in Fig. 7. As the concentrations of La and 2012a; Zhu et al., 2009), as discussed below. Pr in zircons of this study are very low and close to minimum detection 1/2 4+ 3+ limits, the Ce anomalies usually expressed by CeN/(LaN ×PrN) could 4.2. Zircon Ce /Ce and Eu/Eu* ratios and oxidation state of magma deviate significantly due to the analytical uncertainties of La and Pr. We therefore employ a Ce4+/Ce3+ calculation method proposed by 4.2.1. Zircon trace elements and Ce4+/Ce3+ ratios Ballard et al. (2002),bywhichCe4+/Ce3+ ratios of zircon are calculated The physical and chemical durability of zircon enables it to be an im- on the basis of a lattice-strain model for mineral-melt partitioning of Ce4+ portant mineral for radiometric and geochemical investigations (Finch and Ce3+ cations. For Ce4+/Ce3+ calculation, trace elements of whole- and Hanchar, 2003; Hoskin and Schaltegger, 2003). According to zircon ⁎ rock samples have also been determined and used as a proxy for melt. EuN/EuN ratios and Th, U contents, the ore-related porphyries in the The Ti-in-zircon thermometer (Ferry and Watson, 2007)isemployedto Shiyaogou deposit were probably crystallized from more evolved estimate zircon crystallization temperature by setting activity of SiO2 magmas relative to the nearby ore-barren granitic intrusions, i.e. the and TiO2 to 1 and 0.6, respectively. The results are presented in Table 2. Mazhuanggou intrusion and the Heyu batholith. Although all these granites show similar zircon REE patterns (Fig. 7), the ore-related por- ⁎ 3.3.3. Re–Os isotopic results phyries have lower zircon EuN/EuN ratios (0.4–0.6, Table 2) than Re–Os dating results are presented in Table 3.Althoughthe those of the Mazhuanggou granite (mostly 0.6–0.75) and the Heyu decoupling of Re and Os may exist for molybdenite Re–Os analyt- batholith (0.5–0.8) (Guo et al., 2009; N. Li et al., 2012b), implying zir- ical method (Selby and Creaser, 2004), this is unlikely in this cons of the Shiyaogou porphyries crystallized in more evolved melts study due to the fine grains (usually b1 mm) and relatively possibly due to fractionation of plagioclase (Claiborne et al., 2010; young ages of the analyzed molybdenites. Model ages of the five Hoskin and Schaltegger, 2003). The barren granite (sample 08LC57-1) analyses vary from 129 ± 2 Ma to 134 ± 2 Ma and give a weight- from the Mazhuanggou valley has lower U and Th contents in both ed mean age of 132.3 ± 2.8 Ma (MSWD = 5.5) (Fig. 8). These zircons (180–500 ppm and 200–1200 ppm) and the whole rock analyses yield an isochron age of 135.2 ± 2.9 Ma (MSWD = 4.2) (1.65 ppm and 13.08 ppm) than those of the porphyries. Zircon Th/ with initial 187Os = −0.71 ± 0.89 (Fig. 8). Considering the initial U ratios (mainly 1.4–2.5) of the Mazhuanggou granite are relatively 187Os slightly deviates from zero, we interpret the mean model high (Table 2). These characteristics suggest that this intrusion is age of 132.3 ± 2.8 Ma as the ore-forming time. These ages are less evolved, as revealed by Claiborne et al. (2010) by investigating consistent well with the previous dating results by Y.L. Gao et al. variations of zircon trace elements during magmatic evolution in (2010), who reported an average model age of 133.4 ± 1.0 Ma the Spirit Mountain batholith in southern Nevada. and an isochron age of 135.2 ± 1.8 Ma, implying that Mo mineral- Zircons are commonly characterized by positive Ce and negative Eu ization of the deposit took place in relatively short period of time. anomalies on chondrite-normalized patterns because REEs in zircon are mainly trivalent except for Ce4+ and Eu2+, which thus show differ- 4. Discussion ent behaviors relative to other elements. Ce4+ has an ionic radius (0.97 Å) closer to Zr4+ (0.84 Å) and Hf4+ (0.83 Å) comparing to its re- 4.1. Timing of magmatism and Mo mineralization and metal source duced state Ce3+ (1.143 Å) and neighboring La3+ (1.16 Å) and Pr3+ (1.126 Å) (Shannon, 1976), it is therefore preferred by zircon over La Zircon U–Pb dating of three samples from ore-related granite por- and Pr. In contrast to Ce4+,Eu2+ is unlikely to substitute into the zircon phyries in the Shiyaogou deposit indicates that they were emplaced lattice due to its divalent charge and larger cation size (1.25 Å) (Hoskin during the period from ~135 Ma to ~132 Ma. The existence of a popu- and Schaltegger, 2003). An increasing number of experimental and geo- lation of captured older zircon grains suggests a magmatic event oc- logical studies have indicated that the magnitude of Ce anomalies in curred at ~142.8 Ma. The barren granite sample 08LC57-1 collected zircon can be used as a proxy for oxygen fugacity in geological environ- from the Mazhuanggou valley gives an earlier age of 148.1 ±1.1 Ma. ments (Ballard et al., 2002; Bolhar et al., 2008; Burnham and Berry, Therefore, the granitic magmatism in the Shiyaogou area spans a time 2012; Liang et al., 2006; Pettke et al., 2005; Trail et al., 2012). In a from ~148 Ma to ~132 Ma, which is in good agreement with the ages pioneering work, Ballard et al. (2002) investigated barren and ore- 36 Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47

Table 1 LA-ICP-MS analytical results of zircon U–Pb isotopic ratios and ages.

Spot Th/U Measured isotope ratio Apparent age (Ma) Note

207Pb/206Pb 1σ 207Pb/235U1σ 206Pb/238U1σ 207Pb/206Pb 1σ 207Pb/235U1σ 206Pb/238U1σ

Sample ZK51811-1 (ore-related) 1 0.6 0.04984 0.00120 0.14811 0.00363 0.02155 0.00028 188 56 140 3 137 2 2 0.6 0.04806 0.00205 0.14215 0.00602 0.02144 0.00032 102 101 135 5 137 2 3 0.8 0.04820 0.00175 0.14196 0.00515 0.02136 0.00030 109 86 135 5 136 2 4 0.7 0.05232 0.00211 0.15058 0.00741 0.02088 0.00030 299 92 142 7 133 2 5 0.6 0.04888 0.00131 0.14256 0.00385 0.02115 0.00028 142 63 135 3 135 2 6 0.8 0.04916 0.00136 0.14610 0.00408 0.02155 0.00029 155 65 138 4 137 2 7 1.0 0.05071 0.00155 0.14633 0.00450 0.02092 0.00029 228 71 139 4 133 2 8 0.8 0.05207 0.00151 0.14938 0.00434 0.02080 0.00028 288 66 141 4 133 2 9 0.9 0.04745 0.00108 0.13374 0.00312 0.02044 0.00027 72 54 127 3 130 2 10 0.5 0.04907 0.00112 0.14041 0.00327 0.02075 0.00027 151 53 133 3 132 2 11 0.8 0.05229 0.00144 0.15347 0.00427 0.02128 0.00029 298 63 145 4 136 2 12 0.8 0.13671 0.00318 7.06834 0.16690 0.37487 0.00527 2186 40 2120 21 2052 25 Core 13 0.6 0.05154 0.00130 0.14861 0.00380 0.02090 0.00028 265 58 141 3 133 2 14 0.6 0.13394 0.00257 6.95461 0.13873 0.37646 0.00491 2150 34 2106 18 2060 23 Core 15 0.7 0.04961 0.00125 0.14400 0.00368 0.02105 0.00028 177 59 137 3 134 2 ⁎ 16 0.9 0.05279 0.00396 0.15875 0.01377 0.02181 0.00042 320 170 150 12 139 3 Discarded 17 0.7 0.04811 0.00124 0.13760 0.00360 0.02074 0.00028 105 61 131 3 132 2 18 1.0 0.04650 0.00141 0.13723 0.00420 0.02140 0.00029 24 73 131 4 136 2 ⁎ 19 0.5 0.05440 0.00147 0.15468 0.00422 0.02062 0.00028 388 61 146 4 132 2 Discarded 20 0.6 0.05127 0.00126 0.14731 0.00367 0.02083 0.00028 253 57 140 3 133 2 21 1.6 0.05072 0.00124 0.16567 0.00411 0.02368 0.00031 228 56 156 4 151 2 Core

Sample ZK518-14 (ore-related) 1 0.6 0.09759 0.00169 3.65006 0.06554 0.27120 0.00339 1579 32 1561 14 1547 17 Core 2 0.6 0.04884 0.00141 0.15103 0.00436 0.02242 0.00030 140 68 143 4 143 2 3 0.6 0.04972 0.00123 0.14384 0.00359 0.02098 0.00027 182 58 136 3 134 2 4 0.5 0.04919 0.00132 0.15445 0.00415 0.02277 0.00030 157 63 146 4 145 2 5 0.4 0.12056 0.00206 4.00625 0.07093 0.24094 0.00301 1965 30 1635 14 1392 16 Disconcordant 6 1.7 0.04870 0.00179 0.14280 0.00520 0.02126 0.00030 133 86 136 5 136 2 7 0.8 0.04885 0.00266 0.14427 0.00776 0.02142 0.00035 141 128 137 7 137 2 8 0.8 0.05110 0.00141 0.16144 0.00445 0.02291 0.00030 245 64 152 4 146 2 9 1.0 0.04887 0.00217 0.14918 0.00654 0.02214 0.00033 142 104 141 6 141 2 10 0.7 0.04815 0.00154 0.14907 0.00475 0.02245 0.00030 107 76 141 4 143 2 11 0.6 0.04837 0.00148 0.14959 0.00457 0.02242 0.00030 117 72 142 4 143 2 12 0.9 0.05013 0.00189 0.14164 0.00529 0.02049 0.00029 201 88 135 5 131 2 13 0.4 0.05034 0.00150 0.15982 0.00476 0.02302 0.00031 211 69 151 4 147 2 14 1.9 0.04812 0.00216 0.13900 0.00618 0.02095 0.00031 105 106 132 6 134 2 15 0.8 0.04765 0.00111 0.14597 0.00345 0.02221 0.00028 82 55 138 3 142 2 16 0.8 0.04734 0.00120 0.14518 0.00371 0.02224 0.00029 66 60 138 3 142 2 17 1.0 0.04816 0.00140 0.14850 0.00430 0.02236 0.00030 107 69 141 4 143 2 18 0.7 0.04700 0.00164 0.13670 0.00475 0.02109 0.00029 49 83 130 4 135 2 19 0.6 0.04990 0.00119 0.15069 0.00362 0.02190 0.00028 190 55 143 3 140 2 20 0.6 0.05071 0.00154 0.15708 0.00474 0.02246 0.00030 228 70 148 4 143 2 21 0.8 0.04692 0.00132 0.14550 0.00410 0.02248 0.00030 45 67 138 4 143 2 22 0.7 0.04969 0.00147 0.15294 0.00454 0.02232 0.00030 181 69 145 4 142 2 23 0.5 0.04834 0.00132 0.15121 0.00415 0.02268 0.00030 116 64 143 4 145 2 24 0.8 0.04843 0.00115 0.14751 0.00355 0.02209 0.00028 120 56 140 3 141 2 25 0.5 0.04872 0.00129 0.15155 0.00403 0.02255 0.00029 134 62 143 4 144 2 26 0.6 0.04895 0.00119 0.14875 0.00365 0.02204 0.00028 145 57 141 3 141 2

Sample 08SYG01-4 (ore-related) 1 0.7 0.04948 0.00103 0.14124 0.00303 0.02070 0.00026 171 49 134 3 132 2 2 0.4 0.14352 0.00224 7.33606 0.12178 0.37069 0.00458 2270 27 2153 15 2033 22 Core 3 0.9 0.04882 0.00199 0.13942 0.00564 0.02071 0.00030 139 96 133 5 132 2 4 0.8 0.04903 0.00105 0.14011 0.00308 0.02072 0.00026 149 50 133 3 132 2 5 0.6 0.04996 0.00105 0.14087 0.00304 0.02045 0.00026 193 49 134 3 130 2 6 0.5 0.04838 0.00182 0.14341 0.00537 0.02150 0.00031 118 89 136 5 137 2 7 0.7 0.05131 0.00128 0.14325 0.00361 0.02025 0.00026 255 57 136 3 129 2 ⁎ 8 0.4 0.10774 0.00183 0.85376 0.01518 0.05746 0.00072 1762 31 627 8 360 4 Discarded 9 0.8 0.05031 0.00109 0.14236 0.00317 0.02052 0.00026 209 50 135 3 131 2 10 0.7 0.05058 0.00144 0.14885 0.00425 0.02134 0.00029 222 66 141 4 136 2 11 0.9 0.04932 0.00105 0.14138 0.00309 0.02079 0.00026 163 50 134 3 133 2 12 0.6 0.05089 0.00158 0.14788 0.00459 0.02107 0.00029 236 72 140 4 134 2 ⁎ 13 0.9 0.06461 0.00312 0.19634 0.00931 0.02203 0.00037 762 102 182 8 140 2 Discarded 14 0.6 0.05003 0.00135 0.14614 0.00397 0.02118 0.00028 196 63 138 4 135 2 15 0.5 0.04865 0.00110 0.13871 0.00321 0.02067 0.00027 131 53 132 3 132 2 16 1.7 0.05002 0.00154 0.14552 0.00449 0.02109 0.00029 196 72 138 4 135 2 17 0.5 0.04973 0.00119 0.14622 0.00357 0.02132 0.00028 182 56 139 3 136 2 18 0.9 0.14551 0.00245 8.55613 0.15169 0.42638 0.00537 2294 29 2292 16 2289 24 Core 19 0.7 0.04895 0.00119 0.14011 0.00345 0.02075 0.00027 145 57 133 3 132 2 20 0.8 0.04986 0.00111 0.14027 0.00319 0.02040 0.00026 188 52 133 3 130 2 21 0.5 0.04952 0.00101 0.14159 0.00297 0.02073 0.00026 173 48 134 3 132 2 22 0.4 0.04895 0.00169 0.14112 0.00485 0.02090 0.00029 145 81 134 4 133 2 Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 37

Table 1 (continued) Spot Th/U Measured isotope ratio Apparent age (Ma) Note

207Pb/206Pb 1σ 207Pb/235U1σ 206Pb/238U1σ 207Pb/206Pb 1σ 207Pb/235U1σ 206Pb/238U1σ

Sample 08LC57-1 (barren) 1 1.6 0.05555 0.00332 0.17476 0.01023 0.02281 0.00041 434 137 164 9 145 3 Disconcordant 2 1.9 0.04814 0.00218 0.15179 0.00678 0.02286 0.00035 106 102 143 6 146 2 3 1.6 0.04946 0.00341 0.15901 0.01076 0.02331 0.00043 170 157 150 9 149 3 4 2.1 0.04773 0.00201 0.15631 0.00650 0.02375 0.00035 86 94 147 6 151 2 5 2.5 0.05232 0.00301 0.16715 0.00943 0.02317 0.00040 299 134 157 8 148 3 6 1.5 0.04678 0.00514 0.14923 0.01613 0.02313 0.00057 38 226 141 14 147 4 7 2.0 0.04632 0.00309 0.14678 0.00962 0.02298 0.00042 14 147 139 9 146 3 8 2.1 0.04961 0.00299 0.16027 0.00949 0.02343 0.00041 177 138 151 8 149 3 9 1.5 0.04844 0.00313 0.15566 0.00988 0.02330 0.00042 121 145 147 9 148 3 10 1.7 0.04544 0.00346 0.14697 0.01102 0.02346 0.00046 −32 167 139 10 149 3 11 1.5 0.05123 0.00342 0.16449 0.01077 0.02328 0.00043 251 154 155 9 148 3 12 2.0 0.04658 0.00263 0.15079 0.00838 0.02348 0.00039 28 123 143 7 150 2 13 1.7 0.04732 0.00277 0.14834 0.00855 0.02273 0.00039 65 129 140 8 145 2 14 2.0 0.04961 0.00266 0.15787 0.00833 0.02308 0.00038 177 123 149 7 147 2 15 1.3 0.04117 0.00349 0.13757 0.01149 0.02423 0.00048 −223 158 131 10 154 3 Disconcordant 16 1.5 0.04950 0.00297 0.15338 0.00903 0.02247 0.00040 172 137 145 8 143 3 17 2.4 0.04829 0.00223 0.15403 0.00700 0.02313 0.00036 114 105 145 6 147 2 18 0.7 0.14455 0.00381 6.42920 0.16897 0.32253 0.00445 2282 46 2036 23 1802 22 Disconcordant 19 0.1 0.11988 0.00293 5.27345 0.12962 0.31898 0.00421 1954 45 1865 21 1785 21 Core 20 1.9 0.04957 0.00260 0.16048 0.00830 0.02347 0.00039 175 121 151 7 150 2 21 0.8 0.04667 0.00236 0.15397 0.00742 0.02393 0.00036 32 110 145 7 152 2 22 2.3 0.05288 0.00240 0.16788 0.00750 0.02302 0.00036 324 106 158 7 147 2 23 1.2 0.05702 0.00358 0.18274 0.01125 0.02324 0.00043 492 142 170 10 148 3 Disconcordant

⁎ Spots are discarded due to the ﬂuctuant U–Pb isotopic ratios on their signal spectra.

bearing felsic intrusions in the Chuquicamata–El Abra porphyry copper of ore-ﬂuids show an increasing trend of mantle contribution to Mo belt of northern Chile. Their results indicate that intrusions associat- mineralization (Zhuetal.,2009). The Sandaozhuang and Shijiawan ed directly with copper mineralization have Ce4+/Ce3+ >300 and Mo deposits (144–141 Ma, Mao et al., 2008)havelower3He/4He ra-

EuN/EuN* >0.4, indicative of a more oxidized signature for ore- tios (1.38–2.09 Ra), whereas the younger Jinduicheng and Donggou related magmatism. Recent study shows that, besides oxygen fugacity, Mo deposits (138 Ma and 114 Ma, Mao et al., 2008) exhibits higher 4+ 3+ 3 4 zircon Ce /Ce ratios could also be affected by the temperature at He/ He ratios (1.83–3.41 Ra and 2.42–3.64 Ra) approaching to man- which zircon crystallized (Trail et al., 2012). In this study, we have calcu- tle components (6–9Ra)(Zhu et al., 2009). This trend can also be ob- lated the crystallization temperatures of the porphyries and the Heyu served in Pb stable isotopic systematics (Zhu et al., 2009). Thirdly, the batholith according to the Ti-in-Zircon thermometer proposed by Ferry Heyu granite batholith has zircon εHf(t) values variant ranging from − and Watson (2007) (Table 2). The average results show that the porphy- 27.7 to −3.4 and Hf model ages from 1403 Ma to 2934 Ma (Guo et al., ries in the Shiyaogou area and the Heyu batholith crystallized at similar 2009; N. Li et al., 2012b), implying a magma source originated primarily temperature ranges of 709 ± 43 °C (1σ)and711±52°C(1σ), respec- from crustal materials. However, the much lower εHf(t) values (−62 to tively. This implies that the variations of zircon Ce4+/Ce3+ ratios in this −42) of the Taihua and Xiong'er groups at ~140 Ma require a mantle study are primarily controlled by oxygen fugacity, rather than the crystal- component to compensate the higher εHf(t) values of the Heyu granite lization temperature, of evolving magma melts. (Diwu et al., 2010a; N. Li et al., 2012b).Theevidencedescribedabove In this study, barren granitoids have average zircon Ce4+/Ce3+ ra- suggests that the mantle-derived mafic components contributed in- tios decreasing from ~148 Ma to ~130 Ma (Table 4, Fig. 9a), implying creasingly to the formation of the granites and ore deposits from progressively decreasing oxygen fugacities of evolved magma. This ~148 Ma to ~120 Ma in the eastern Qinling. This probably accounted trend differs from that of Ballard et al. (2002), who found that zircon for the decreasing trend of oxygen fugacity of these granitoids since Ce4+/Ce3+ ratios of igneous complexes in the Chuquicamata–El Abra mafic magma/material has the oxygen fugacity much lower than that porphyry copper belt increase from 43 Ma to 33 Ma, indicative of an of felsic one (Fudali, 1965). increase in magmatic oxidation state over time. They interpreted the It is noteworthy that the zircon Ce4+/Ce3+ ratios of the ore-related trend by association with an uninterrupted deep magma reservoir porphyries in the Shiyaogou area are systematically higher than those with an oxidized evolution. By contrast, the decreasing oxygen fugac- of barren granites, which means that the magma related to Mo mineral- ities of the barren intrusions observed in this study could be interpreted ization are more oxidized. In addition, the Ce4+/Ce3+ ratios of ore- by the increasing contribution of mafic components in magma evolving related porphyries also decrease and are parallel to the trend of barren and ascending in the eastern Qinling. This is supported by geological, granites, which coincide with our previous suggestion that the ore- geochronological, fluid helium-lead isotopic and zircon hafnium isoto- related porphyries are fractionated from the barren counterparts, pic evidence. Firstly, some dolerite and diorite dykes indicative of because oxygen fugacity of a magma increases during its differentiation mantle-derived components in the Xiaoqinling–Xiong'er–Waifang (Czamanske and Wones, 1973). The increasing oxygen fugacity during Mountains have been dated by using zircon U–Pb method and yielded magma differentiation facilitates the extraction of Mo, Cu and Au into 2− isotopic ages ranging from ~131 Ma to ~117 Ma (H.J. Zhao et al., the melts, owing to the much higher solubility of sulfate (SO4 ) 2010; Mao et al., 2010; Wang et al., 2008), slightly younger than granitic than that of sulfide (S2−) under oxidized conditions (Carroll and plutons in this region. Our field observations reveal that dioritic Rutherford, 1988). The exsolved hydrothermal fluids from this oxidized enclaves occur in granitic intrusions younger than ~130 Ma, and differentiated magma are likely to contain quite high Mo content e.g. Laojunshan granite (~120 Ma, unpublished), a phenomenon because the solubility of Mo in fluids is strongly dependent on the oxy- of mixing and mingling between felsic and maficmagmas(Barbarin, gen fugacity, as indicated by experimental evidence (Bali et al., 2012; 2005; Vernon, 1983). Secondly, helium and lead stable isotopic analyses Candela and Bouton, 1990)andverified by other studies on Cu and Mo 38 Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 (a) (b)

Fig. 5. Representative CL images of zircons. deposits (Ballard et al., 2002; Liang et al., 2006; Luo et al., 2011). It has iron and hence reduce sulfate to sulﬁde in hydrothermal ﬂuids (Liang et been shown that magnetite crystallization is a crucial factor leading to al., 2009; Sun et al., 2004). In the case of the Shiyaogou deposit, magne- precipitation of Cu–Mo–Au deposits due to its ability to isolate trivalent tite is a common mineral phase in ores and probably played an

Fig. 6. Concordia diagram for zircon U–Pb analyses (only show analyses in Mesozoic age). Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 39 important role in reducing the oxidized ﬂuids and the precipitation of Mountains compare well with the emplacement of maﬁc-intermediate ore metals. dykes (Fig. 10), implying more mantle components contributing to Au mineralization. Similar patterns also exist in the Xiaoqinling region in

4.2.2. Zircon EuN/EuN* ratios the northwestern part of the eastern Qinling. Granitoids in this region The ore-related porphyries in the Shiyaogou area have lower zircon mainly intruded from ~158 Ma to ~124 Ma (Ding et al., 2010; Guo et Eu anomalies than the barren granites (Table 2, Fig. 9b). This seems to al., 2009; Jiao et al., 2009; J.W. Li et al., 2012b; Mao et al., 2010; Zhu et contradict to zircon/melt experiments showing that Eu anomalies are al., 2008), whereas mafic dykes were emplaced during 132–126 Ma normally correlated positively with Ce anomalies and can potentially (Mao et al., 2010; Wang et al., 2008; H.J. Zhao et al., 2010). Mo deposits be a proxy of oxygen fugacity of melt as well (Burnham and Berry, formed at a stage of 157–128 Ma (Jiao et al., 2009; J.W. Li et al., 2012a; 2012; Trail et al., 2012). Positive correlation between Ce and Eu anoma- Mao et al., 2008; Stein et al., 1997) and are followed by the main stage lies have also been observed in the Chuquicamata–El Abra porphyry of Au mineralization from 135 Ma to 120 Ma (J.W. Li et al., 2012a, copper belt by Ballard et al. (2002), who shows that ore-bearing intru- 2012b; Wang et al., 2002; Xu et al., 1998). Significant mantle-derived 4+ 3+ ⁎ sions have higher Ce /Ce and EuN/EuN ratios than barren intrusions. components that contribute to Au mineralization in the Xiaoqinling re- Although this could be true for an undisturbed and progressively ox- gion have been recently verified by systematic analyses of noble gas iso- idized parental magma reservoir (Ballard et al., 2002), in this study topes (He, Ne) of ore-fluids and ore-minerals (J.W. Li et al., 2012a, the lower zircon Eu anomalies of the Shiyaogou porphyries than bar- 2012b). Stable isotope studies (H, O, S) of ores and alteration minerals ren granites are probably resulted from fractionation of plagioclase also suggest a magmatic origin of ore-fluids, which has been interpreted during magma differentiation, as manifested by abundant large feld- as a mixing between granitic magmatism and mantle-derived magma spar phenocrysts in the Heyu batholith. Plagioclase incorporates (J.W. Li et al., 2012a, 2012b). Eu2+ preferentially and depletes the melt in Eu prior to zircon satu- In general, Mo mineralization formed, statistically, about a few ration, thereby causing lower Eu anomaly in zircon (Hoskin and million years earlier than Au in the region of the Xiong'er–Waifang– Schaltegger, 2003). From this study, we infer that the zircon Ce4+/ Xiaoqinling region. This is reasonable and consistent with the evolu- 3+ ⁎ Ce ratio, rather than EuN/EuN , is an effective indicator of oxygen tion history of a porphyry system according to Sillitoe (2010), who fugacity for fractionated intrusions. has synthesized that a transition from Mo to Au ore systems is usually associated with a hydrothermal system evolved from porphyry to 4.3. A genetic link between Mo and Au mineralization epithermal environment. Williams-Jones and Heinrich (2005) emphasize the importance of vapor transport of metals and also pointed Though lacking suitable minerals for isotopic dating so far, we pre- out that an intrusion-related magmatic system could evolve from fu- sume that the three gold deposits (Hongzhuang, Nanping and Yuanling, marole stage to porphyry stage and then to epithermal stage. The Fig. 2) surrounding the Shiyaogou porphyry molybdenum deposit lifespan for such a hydrothermal system can last from ~0.1 to several formed a few million years after the Mo mineralization. The transition million years (Sillitoe, 2010). from Mo to Au mineralization was probably related to the late-stage The above evidence implies that the successive mineralization of evolution of a deep-seated porphyry system. This is supported by stable porphyry-related Mo and Au deposits probably prevailed during the isotopic analyses of ore-fluids in quartz from the Yuanling gold deposit Late Jurassic to Early Cretaceous in the eastern Qinling. On the basis of by Liu et al. (2000), who obtained a mixed H–Oisotopesignaturebe- above discussions regarding zircon Ce4+/Ce3+ ratios in the Xiong'er tween magmatic fluids and meteoric water. The existence of gold-rich Mountains (Section 4.2.1), we suggest that the decreasing of oxygen fu- vuggy quartz bodies of the deposit (Liu et al., 2000)alsosuggestsa gacities for both ore-related porphyries and barren granitoids probably high-sulfidation epithermal environment, which is normally related accounted for the successive mineralization of Mo and Au. This is sup- to the late evolutionary stage of porphyry system (Hedenquist and ported by the studies in the Lachlan Fold Belt in Australia, where Lowenstern, 1994). Recent studies indicate that similar transitional Blevin and Chappell (1992, 1995) found that the Mo deposits have spe- processes from porphyry Mo to epithermal Au systems probably took cial affinity with more oxidized and fractionated granites, relative to Au place at nearby areas, e.g. the Qiyugou–Leimengou Mo–Au district and and Cu deposits, even though both of them are genetically related with the Qianhe deposit (Fig. 1). Granitic porphyries have recently been dis- oxidized I-type granites. covered in the Qiyugou deposit by drilling and dated by Yao et al. (2009), giving a zircon U–Pb age of 134.1 ± 2.3 Ma. Minor molybdenite 4.4. Tectonic implications in the deposit yields a coeval Re–Os age of 135.6 ± 5.6 Ma (Yao et al., 2009). 40Ar–39Ar and Rb–Sr dating of ore-related minerals indicates Recent geochronological results obtained in the eastern Qinling belt that Au mineralization of the deposit happened a few million years have indicated that intensive metallogenic-magmatic activities took afterwards at ~126 Ma (Han et al., 2007a; Wang et al., 2001). Geology, place in the area mainly in an interval of 150–115 Ma, for example stable and isotopic analyses of ore-fluids of the deposit revealed a poly-metallic mineralization (most importantly Mo and Au), granitic hydrothermal system evolved from magmatic to meteoric, corre- magmatism and emplacement of maficdykes(Chen et al., 2009a; X.Y. sponding to an environment developed from hypothermal through Gao et al., 2010; Guo et al., 2009; Han et al., 2007b; N. Li et al., 2012b; mesothermal to epithermal (Chen et al., 2009a; Fan et al., 2011; N. Mao et al., 2010). Several metallogenic models have been proposed to Li et al., 2012a; Zhang et al., 2007). Moreover, in the area of the interpret this enigma. Mao et al. (2008) proposed a three-stage model Qianhe deposit (Fig. 1), recent zircon U–Pb, molybdenite Re–Os on the basis of isotopic ages of Mo mineralization and characteristics of and sericite 40Ar–39Ar dating results reveal that the Au mineraliza- related granitoids in the East Qinling–Dabie belt. Apart from a distinct tion occurred at 127–124 Ma, a few million years younger than the early stage at 233–221 Ma, these authors suggested that the second Mo mineralization (135–134 Ma) and granitic dykes (~132 Ma) and third stages took place at 148–138 Ma and 131–112 Ma, respective- (Tang et al., 2013). ly, and accounted for the formation of most porphyry or porphyry-skarn In order to better constrain the timing of Mo and Au mineralization in type Mo deposits in the region. The second stage developed in a mag- the Xiong'er–Waifang Mountains, we have summarized 58 high-quality matic arc setting related to northwestward subduction of the paleo- isotopic ages in the region from recent literature, including granitic intru- Pacific Plate, whereas the third stage was caused by regional lithospheric sions, mafic-intermediate dykes and Mo/Au deposits (Fig. 10). The distri- delamination (Mao et al., 2008). This model hints at a metallogenic gap bution of these ages shows that Au mineralization mainly occurred in an from 138 Ma to 131 Ma that separated the last two stages. However, age span of 133–125 Ma, younger than the ore-forming interval of Mo this study and recently published isotopic dating results have revealed deposits (150–120 Ma). The ages of Au deposits in Xiong'er–Waifang new ore-forming ages of porphyry Mo deposits spanning this time 40 Table 2 4+ 3+ LA-ICP-MS analytical results of zircon trace elements (in ppm) and EuN/EuN*, Ce /Ce ratios.

4+ 3+ Spot La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th U Zr Hf Ti EuN/EuN*Ce/Ce TTi(°C) Apparent age (Ma) Sample ZK51811-1 (ore-related) 1 0.09 42.1 0.15 1.61 2.86 1.07 15.1 4.70 57.3 21.0 107 31.0 354 86.8 660 1076 9368 5.16 0.50 368 732 137 2 0.01 19.8 0.03 0.54 1.02 0.44 5.42 1.78 22.5 8.40 43.0 12.4 143 33.0 162 269 8935 3.54 0.57 481 698 137 3 0.01 49.9 0.11 2.16 4.45 1.62 20.5 6.48 80.9 28.1 131 33.6 358 83.9 317 380 8152 5.95 0.52 256 745 136 4 0.24 40.5 0.06 1.25 2.64 0.94 11.8 3.86 47.8 16.1 79.6 23.5 263 62.4 831 1278 9560 4.88 0.52 407 727 133 5 0.12 37.2 0.08 1.30 2.83 0.96 13.3 3.91 49.0 17.2 81.8 23.0 272 60.0 528 840 9255 4.03 0.48 300 710 135 6 0.05 40.9 0.10 1.35 3.20 1.05 13.9 4.09 52.8 18.0 84.6 23.0 271 62.2 617 771 8971 3.90 0.48 276 707 137 7 0.09 70.4 0.49 8.80 13.2 4.90 53.6 14.1 148 44.9 176 41.8 393 81.5 538 566 7936 6.47 0.56 64 753 133 8 0.08 36.0 0.15 2.12 3.92 1.42 18.9 5.68 70.3 24.3 113 31.6 342 76.3 636 777 8950 5.18 0.50 158 732 133 9 0.53 89.5 0.28 3.65 6.61 2.33 30.4 8.84 106 36.8 162 43.8 504 106 1522 1771 9014 6.50 0.50 202 753 130 10 0.18 49.5 0.12 1.60 2.89 1.26 19.0 5.69 76.1 27.4 137 39.3 478 112 860 1840 10390 4.01 0.52 355 709 132 11 0.04 88.3 0.71 10.7 17.3 4.29 60.2 16.9 174 51.0 201 47.2 434 92.3 531 633 8610 7.32 0.41 47 765 136 12 0.03 6.07 0.17 3.05 5.65 0.58 20.9 6.08 69.2 23.1 94.9 22.2 221 47.5 30.6 38.0 7480 2186 (core) 13 0.12 40.6 0.13 1.31 2.36 1.16 14.6 4.61 56.5 19.3 89.6 26.0 330 72.1 710 1181 9938 4.62 0.61 419 722 133 14 0.04 8.51 0.13 3.02 5.57 0.38 20.4 6.82 83.6 28.1 126 29.0 285 63.8 72.1 129 7438 2150 (core) 15 0.24 40.7 0.12 1.71 3.30 0.88 13.1 3.64 49.1 16.6 77.8 21.0 238 56.2 787 1191 9732 3.30 0.41 212 693 134 16 0.11 26.5 0.14 2.10 4.99 1.70 18.0 5.38 61.2 19.8 85.0 21.3 219 52.0 131 142 8055 Discarded 17 0.48 64.7 0.27 3.43 5.02 1.73 23.4 7.80 111 37.7 176 50.5 597 136 882 1327 9612 4.02 0.49 265 709 132 29 (2013) 55 Reviews Geology Ore / al. et Han Y. 18 0.40 90.8 0.68 9.90 17.4 5.36 70.3 17.9 200 59.2 238 55.4 563 111 701 676 8103 14.2 0.47 55 833 136 19 0.03 39.2 0.08 1.67 3.46 1.25 18.5 5.53 70.1 24.4 116 31.9 396 89.6 483 885 9650 Discarded 20 0.30 44.7 0.25 2.07 3.52 1.31 14.8 4.53 55.2 18.5 90.3 24.9 310 67.9 847 1327 9761 4.23 0.55 241 714 133 21 0.19 152 0.55 7.31 14.0 6.98 61.2 17.8 206 67.3 283 65.2 672 142 2137 1312 6987 151 (core)

Sample ZK518-14 (ore-related) 1 0.04 12.8 0.26 5.01 11.1 0.21 50.6 18.9 228 81.1 330 71.4 757 155 146 244 9212 1579 (core) 2 0.36 36.1 0.19 1.37 2.67 0.92 12.4 4.44 49.7 19.3 92.6 25.5 306 72.6 440 729 10649 1.74 0.49 349 641 143 3 0.02 29.9 0.08 1.09 2.50 0.79 10.4 3.24 37.2 14.2 65.6 19.8 255 56.0 752 1230 10084 1.79 0.47 268 644 134 4 0.06 23.7 0.11 1.43 2.03 0.81 8.53 2.75 30.7 11.7 56.3 16.5 211 50.4 485 915 11033 1.40 0.60 218 625 145 5 0.07 12.9 0.24 3.70 5.41 0.76 20.4 6.41 71.8 24.9 104 26.0 282 61.6 103 241 9327 Disconcordant 6 0.22 129 0.85 15.9 28.4 9.03 105 31.1 328 96.9 367 79.5 817 182 902 530 8904 4.63 0.51 57 722 136 7 0.02 37.1 0.07 1.57 3.08 1.41 15.3 5.57 66.7 24.5 108 27.9 304 68.1 166 215 8372 5.53 0.63 302 738 137 8 0.43 55.6 0.75 5.71 7.67 3.17 26.0 8.62 101 36.4 168 46.5 529 129 1522 1817 11454 4.93 0.69 105 728 146 9 0.06 47.0 0.11 1.99 3.89 1.45 17.8 5.83 62.4 21.3 88.4 22.2 239 57.6 292 306 8980 4.97 0.53 219 728 141 –

10 0.09 31.9 0.05 0.97 2.05 0.68 10.3 3.57 42.8 17.4 87.1 24.7 286 66.4 444 605 10097 3.17 0.46 456 689 143 47 11 b0.01 29.3 0.06 0.86 1.86 0.70 8.69 2.94 36.4 13.9 66.5 19.3 235 53.9 432 669 10632 2.51 0.53 379 670 143 12 0.02 42.3 0.08 1.27 2.65 1.07 13.9 4.53 55.8 20.8 93.6 25.5 265 67.5 432 472 9744 4.16 0.54 361 712 131 13 0.02 17.9 0.02 0.44 0.96 0.49 5.92 2.23 29.2 12.4 65.3 19.6 233 62.9 251 646 11628 1.51 0.63 775 631 147 14 0.18 154 1.45 27.2 44.9 14.4 152 43.4 415 122 435 92.2 988 218 675 350 7789 7.85 0.53 52 772 134 15 0.11 57.4 0.11 1.41 4.14 1.53 18.2 5.73 66.5 24.5 110 29.7 340 78.0 1107 1473 10725 3.06 0.54 357 686 142 16 0.05 52.0 0.10 1.62 3.28 1.20 16.1 5.51 60.8 21.3 96.5 27.5 319 70.0 954 1187 10997 2.72 0.50 332 676 142 17 0.17 63.9 0.14 2.29 4.45 1.56 21.6 7.19 79.1 27.5 121 31.5 348 82.6 800 770 10118 4.76 0.49 269 724 143 18 0.03 40.8 0.06 0.93 2.77 1.06 14.3 5.51 68.2 27.5 135 37.1 439 97.1 401 537 9929 4.03 0.52 563 710 135 19 0.03 37.5 0.04 1.11 2.23 0.93 11.3 4.10 47.9 18.4 90.6 25.7 325 76.6 798 1343 11455 1.91 0.57 574 648 140 20 0.05 27.5 0.02 0.74 1.46 0.69 8.73 3.10 41.5 16.8 85.1 24.8 313 76.1 376 665 11039 2.70 0.59 879 676 143 21 0.98 59.5 0.28 3.30 4.91 1.63 19.3 6.69 73.6 26.0 116 30.8 360 79.9 728 900 10814 3.82 0.51 140 705 143 22 0.05 34.5 0.10 1.33 2.60 0.97 10.2 3.87 48.7 18.8 94.8 27.3 335 80.7 510 745 11197 1.80 0.58 400 644 142 23 0.08 37.1 0.07 1.02 2.73 1.03 12.8 4.95 63.6 24.8 121 36.2 446 99.3 439 869 10634 2.62 0.53 458 673 145 24 2.51 62.1 0.74 3.85 4.88 1.18 16.5 5.57 66.8 24.9 118 33.0 393 90.1 1176 1487 11500 2.99 0.40 387 684 141 25 0.09 26.0 0.07 1.08 2.01 0.75 8.70 2.97 35.9 13.8 68.5 20.2 256 61.8 502 983 11818 2.34 0.55 282 664 144 26 0.31 46.0 0.44 3.72 4.93 2.57 20.5 7.34 82.4 30.1 142 38.7 463 112 786 1224 11373 3.07 0.78 154 686 141

Sample 08SYG01-4 (ore-related) 1 0.11 63.0 0.10 1.85 4.36 1.49 19.0 5.97 69.7 24.6 115 31.1 374 79.8 1027 1508 9184 4.64 0.50 367 722 132 2 0.17 16.8 0.09 1.69 4.12 0.08 23.1 8.67 115 42.4 197 47.8 460 96.2 257 664 9147 2270 (core) 3 b0.01 52.6 0.12 2.06 4.16 1.51 19.3 6.43 82.4 29.3 133 33.9 375 87.6 357 410 7979 8.58 0.52 275 780 132 Spot

4+ La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th U Zr Hf Ti EuN/ Ce / TTi(°C) Apparent age (Ma) 3+ EuN* Ce 4 0.19 59.4 0.13 1.91 3.95 1.42 19.3 5.86 70.2 25.4 116 30.9 367 80.0 1177 1536 9490 2.82 0.50 301 679 132 5 0.08 47.3 0.10 1.62 3.46 1.15 15.6 4.65 57.3 20.6 104 28.9 364 83.8 1057 1728 9926 3.37 0.48 321 694 130 6 b0.01 21.7 0.02 0.55 1.41 0.54 7.10 2.36 30.7 11.0 55.7 16.5 207 48.1 221 437 9484 3.06 0.53 675 686 137 7 0.20 42.0 0.19 2.13 3.70 1.33 14.5 4.85 57.2 18.8 86.1 24.7 289 62.2 861 1230 9627 3.42 0.56 153 696 129 8 0.08 29.5 0.08 0.86 2.09 0.71 9.46 3.25 41.5 15.7 80.0 24.0 296 68.6 544 1269 10966 Discarded 9 0.11 90.7 0.47 7.68 14.8 2.93 73.3 24.7 298 98.0 431 105 1120 247 1264 1620 7533 12.0 0.27 111 815 131 10 0.11 52.3 0.44 5.87 8.36 2.87 30.6 8.34 91.2 28.5 121 29.9 318 69.9 428 640 9161 4.32 0.55 56 716 136 11 4.42 129 1.35 9.38 10.2 3.25 45.4 12.8 149 48.6 207 52.7 543 116 1614 1729 8914 8.42 0.46 112 779 133 12 0.02 36.7 0.15 2.40 4.73 1.97 21.3 6.23 79.2 28.2 135 37.6 440 94.6 325 535 8742 4.40 0.60 157 717 134 13 0.34 37.5 0.61 7.03 12.3 4.69 47.9 13.2 149 48.1 203 49.5 491 106 290 313 8512 Discarded 14 0.04 37.4 0.09 1.52 3.17 1.14 13.9 4.50 57.0 20.0 97.6 27.4 296 69.8 461 800 9591 3.28 0.53 270 692 135 15 0.51 41.5 0.17 1.46 3.17 0.84 12.0 3.86 47.2 16.0 78.9 23.3 251 59.6 710 1346 9409 1.92 0.42 310 649 132 16 6.79 181 2.17 15.6 18.8 6.10 88.8 26.8 315 93.7 357 74.9 663 147 1200 716 8114 9.63 0.46 69 792 135 17 0.11 32.1 0.06 0.98 1.89 0.72 9.95 3.35 42.1 16.4 85.0 25.8 324 76.9 496 1084 10058 2.77 0.51 443 678 136 18 0.15 15.8 0.66 9.44 14.2 1.54 55.0 15.1 167 52.2 217 49.6 470 99.8 246 283 6534 2294 (core) 19 1.25 55.7 0.32 2.61 3.91 1.41 18.5 5.26 65.7 23.4 109 29.4 333 76.1 796 1135 9653 4.44 0.51 237 718 132 20 0.05 59.1 0.10 1.78 4.16 1.35 19.3 5.70 71.7 25.0 116 32.7 368 83.0 1187 1573 9848 3.10 0.46 359 687 130

21 0.11 49.4 0.12 1.35 3.39 1.03 15.6 4.72 60.1 21.7 110 32.1 378 92.8 1286 2419 10661 4.03 0.43 475 710 132 29 (2013) 55 Reviews Geology Ore / al. et Han Y. 22 0.19 25.8 0.21 1.77 3.15 1.00 13.5 4.76 61.0 20.6 96.6 28.5 328 76.0 343 785 9551 3.80 0.47 185 705 133 whole-rock 43.0 78.4 8.05 26.9 4.25 0.83 3.19 0.39 2.03 0.37 1.04 0.16 1.04 0.17 22.9 7.91 191 4.67

Sample 08LC57-1 (ore-barren) 1 0.02 58.9 0.12 2.10 4.43 1.92 20.4 7.44 94.7 37.5 177 43.9 446 102 369 224 9062 Disconcordant 2 0.02 92.9 0.14 2.89 7.14 3.43 36.0 13.7 171 67.2 307 77.0 770 170 789 426 9126 0.65 397 146 3 b0.01 42.0 0.10 1.88 3.25 1.59 15.8 5.63 74.2 29.1 142 36.3 378 86.9 291 183 8654 0.68 268 149 4 0.02 126 0.23 4.31 9.80 4.84 49.4 17.7 223 83.6 375 92.0 916 197 1056 512 8698 0.67 327 151 5 0.11 76.5 0.80 13.0 18.9 9.02 71.8 21.8 250 87.5 380 88.6 836 186 626 252 7728 0.75 43 148 6 0.22 33.4 0.18 3.34 5.20 2.53 21.6 7.23 88.4 33.3 155 39.8 402 90.3 182 122 8476 0.73 103 147 7 0.02 64.2 0.13 2.69 4.14 2.21 22.3 8.03 97.1 35.6 162 39.3 401 88.1 466 236 8467 0.70 274 146 8 0.01 54.5 0.13 2.15 3.87 1.94 17.8 6.55 79.1 29.5 133 32.7 331 71.5 558 268 8398 0.71 247 149 9 0.01 53.1 0.13 2.09 4.11 1.86 18.3 7.29 94.2 38.2 180 46.1 468 108 290 198 8525 0.66 293 148 10 0.05 55.3 0.27 4.79 7.74 3.23 33.6 11.7 144 53.1 239 57.8 570 124 363 212 7750 0.61 113 149 11 b0.01 48.1 0.09 1.67 3.13 1.66 15.8 5.76 71.3 26.9 124 31.7 326 71.0 289 189 8420 0.72 328 148

12 0.02 75.1 0.14 2.89 5.24 2.38 25.3 8.83 112 42.3 194 49.5 496 106 577 290 8478 0.63 299 150 – 47 13 b0.01 50.0 0.14 2.37 4.51 2.05 20.0 7.26 93.3 36.7 173 44.9 473 102 345 208 7783 0.66 234 145 14 0.02 73.4 0.15 2.79 4.83 2.53 25.0 8.77 106 39.7 180 44.5 448 95.5 612 302 8052 0.70 278 147 15 0.01 37.1 0.15 2.59 4.45 2.25 20.1 7.10 89.8 35.2 162 42.5 440 97.0 179 134 8041 Disconcordant 16 0.01 88.5 0.12 2.90 6.08 3.12 31.5 12.3 158 63.4 290 74.4 759 160 572 385 8336 0.69 437 143 17 0.02 87.1 0.15 3.04 5.61 2.79 28.2 9.70 118 43.7 198 48.2 480 106 886 376 8511 0.68 311 147 18 b0.01 30.5 0.08 2.00 3.37 0.91 18.9 7.25 97.3 37.0 170 40.7 380 80.3 279 376 9140 Disconcordant 19 0.07 7.85 0.05 0.53 1.13 0.18 7.34 3.44 51.6 23.0 128 37.3 427 110 190 3232 12803 1954 (core) 20 0.01 66.7 0.12 2.41 4.76 2.39 23.6 8.47 105 41.2 186 46.5 476 104 514 272 8645 0.69 326 150 21 1.40 56.2 0.61 4.93 7.31 2.98 46.7 22.2 327 141 665 170 1724 359 1388 1733 10462 0.49 211 152 22 0.01 83.1 0.17 2.67 5.40 2.66 26.5 9.40 113 41.5 190 46.4 462 98.8 899 395 8577 0.68 301 147 23 b0.01 41.1 0.10 1.54 3.31 1.60 15.8 6.30 84.0 34.6 167 43.1 456 104 180 156 7699 Disconcordant whole-rock 22.6 49.6 5.98 20.9 3.45 1.23 2.78 0.38 2.26 0.44 1.35 0.20 1.29 0.20 13.1 1.65 116 3.27

1/2 4+ 3+ Note: EuN/EuN*=EuN/(SmN*GdN) , where the subscript N means chondrite-normalized ratio. Ce /Ce ratios are calculated following the procedure of Ballard et al. (2002). Zircon crystallization temperatures (TTi(°C)) are calculated using the method of Ferry and Watson (2007) by setting activity of SiO2 and TiO2 to 1 and 0.6, respectively. 41 42 Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47

(a) (b)

Fig. 7. Chondrite-nomalized REE patterns of zircons (only show analyses in Mesozoic age). The pattern of the Heyu granite batholith is summarized from N. Li et al. (2012b) and Guo et al. (2009). Chondritite values are from Sun and McDonough (1989).

Table 3 Re–Os dating results of molybdenite from the Shiyaogou deposit.

Sample Run No. Weight (g) Total Re (μg/g) Common Os (ng/g) Re187 (μg/g) Os187 (ng/g) Model age (Ma)

Measured 2σ Measured 2σ Measured 2σ Measured 2σ age 2σ

SYG-1-1 090505-12 0.05009 37.95 0.42 0.0153 0.0211 23.85 0.27 53.37 0.46 134.1 2.2 SYG-1-2 090512-1 0.03048 38.00 0.29 0.0299 0.0310 23.88 0.18 53.20 0.42 133.6 1.8 SYG-2 090512-2 0.00402 16.45 0.14 0.1142 0.0724 10.34 0.09 22.23 0.19 128.9 1.9 SYG-3 090512-3 0.03035 87.22 0.85 0.0684 0.0349 54.82 0.53 122.6 1.0 134.1 2.0 SYG-4 090512-4 0.03028 12.07 0.10 0.0950 0.0321 7.588 0.063 16.62 0.14 131.3 1.9 interval, for example Shiyaogou (132.3 ± 2.8 Ma, this study), Qiyugou signature of ore-fluids related to crust and mantle interactions, which (135.6 ± 5.6 Ma, Yao et al., 2009), Yuchiling (131.2 ± 1.4 Ma, Zhou et they interpreted as a consequence of regional lithospheric extension al., 2009), Qianhe (134.6 ± 0.6 Ma, Tang et al., 2013), Baishuling in the Early Cretaceous subsequent to the Triassic collision of the (134.5–131.0 Ma, J.W. Li et al., 2012a) and Simuyu (131.3 ± 0.5 Ma, North China and Yangtze cratons. This model did not emphasize the J.W. Li et al., 2012a) deposits. We therefore consider the duration of temporal change of mantle contributions and genetic links between porphyry-related Mo mineralization in the 150–115 Ma time in the Mo and Au mineralization. eastern Qinling belt as a continuous process, rather than two distinct Alternatively, a NCC-destruction-related model has been proposed stages. A post-collision to extension model was proposed by Chen et by J.W. Li et al. (2012a), who carried out studies on Mo–Au deposits in al. (2009a) and Zhu et al. (2009) on the basis of H–O–C isotope analyses the Xiaoqinling region, including mica 40Ar/39Ar and molybdenite Re– of ore-fluids of the Qiyugou Au deposit and He–Ar isotopic studies of Os dating, He–Ne and S–O stable isotope analyses of fluid inclusions fluid inclusions from four Mo deposits in the eastern Qinling, respec- and ore-materials. The results indicate that the Au mineralization tively. Both H–O–CandHe–Ar systematics indicate a mixing isotopic stage (mainly 134–118 Ma) is obviously younger than the Mo stage (154–131 Ma) and mantle-derived components involved into the ore system. By comparison with the coeval metallogenic-magmatic events in the eastern NCC, J.W. Li et al. (2012a) ascribe these characteristics to a regional asthenosphere upwelling triggered by lithospheric destruction of the NCC. This model is favored by our study as it has linked the Mo and Au mineralization together in porphyry–related systems within a coherent tectonic regime. In this study, Re–Os and U–Pb geochronology and zircon Ce4+/Ce3+ ratios of the Shiyaogou deposit and related granitoids have strengthened the perspective that mantle- derived components contributed to both magmatism and ore systems. In addition, we propose that the differentiated magmas with elevated oxygen fugacity gave rise to long-lasting porphyry-related systems. (a) (b) Meanwhile, increasing mantle contributions around 132 Ma decreased the oxygen fugacity of evolving magmas and accounted for the successive mineralization of Mo and Au in the eastern Qinling belt. In many re- spects this model also coincides with recent studies on metamorphic Fig. 8. Diagram for molybdenite Re–Os dating. core complex (135–123 Ma, Zhang and Zheng, 1999), transpressional Y. Han et al. / Ore Geology Reviews 55 (2013) 29–47 43

Table 4 4+ 3+ ⁎ Average Ce /Ce and EuN/EuN ratios for granitoids in Shiyaogou area and Heyu batholith.

4+ 3+ Type Intrusion Sample Age (Ma) (Ce /Ce )avg (EuN/EuN*)avg Reference Ore-related Shiyaogou porphyry 08SYG01-4 132.8 271 0.49 This study ZK518-14 134.0 267 0.53 This study ZK518-14 142.8 374 0.55 This study ZK51811 134.3 257 0.51 This study Yuchiling porphyry YCL0722 133.6 310 0.63 N. Li et al., 2012b Barren Mazhuang granite 08LC57-1 148.1 266 0.67 This study Heyu granite batholith HY0702 138.4 212 0.56 N. Li et al., 2012b YCL0722 142.6 251 0.59 N. Li et al., 2012b HY0701 143.0 198 0.63 N. Li et al., 2012b HY02 134.5 184 0.63 Guo et al., 2009

(a) (b)

4+ 3+ ⁎ Fig. 9. Average zircon Ce /Ce (a) and EuN/EuN (b) ratios for ore–bearing porphyries from the Shiyaogou deposit and ore-barren granitoids from the Mazhuanggou granite and the Heyu batholith. Symbols 1–5 are from this study. Symbols 6–10 represent the Heyu batholith and are calculated using the data from N. Li et al. (2012b) and Guo et al. (2009). The whole-rock trace elements of the Heyu batholith for Ce4+/Ce3+ calculation are averaged from Han et al. (2007b) and Guo et al. (2009).

Fig. 10. Distribution of isotopic ages for granitoids, mafic dykes, Mo and Au deposits in the region of the Xiong'er–Waifang Mountains. These ages were obtained by zircon U–Pb, molybdenite Re–Os or monomineral 40Ar–39Ar methods (data from Dai et al., 2009; X.Y. Gao et al., 2010; Y.L. Gao et al., 2010; Guo et al., 2009; Han et al., 2007b; Huang et al., 2010; Li et al., 2009; N. Li et al., 2012b; Liu et al., 2011; Mao et al., 2008, 2010; Su et al., 2009; Tang et al., 2013; Wang et al., 2001, 2005; Xie et al., 2007; Yang et al., 2004, 2010; Yao et al., 2009; Z.Q. Zhang et al., 2006; Zhou et al., 2009; Zhu et al., 1999). to extensional structures (160–120 Ma, Han et al., 2009; Ratschbacher the interval of 150–120 Ma (Mao et al., 2011a; Sun et al., 2007; Wu et et al., 2003; Zhang et al., 2001; Y.H. Zhang et al., 2006) and I- to al., 2005; Yang et al., 2003; Zhu et al., 2011). Along with concurrent A-type transition of Late Jurassic–Early Cretaceous granitoids (Chen et compressional–extensional structures (Liu et al., 2008; Wang and Li, al., 2004, 2009a; Guo et al., 2009; Han et al., 2007b; N. Li et al., 2012b; 2008), they are suggested to be manifestations of a large-scale litho- Mao et al., 2010) in the eastern Qinling, which overall suggest a tectonic spheric thinning and subsequent “destruction” (or decratonization) of setting transitional from compression to extension during the Late the eastern part of the NCC (Fan and Menzies, 1992; Griffinetal., Mesozoic. 1998; Menzies et al., 1993; Pirajno, 2013; Wu et al., 2008; Yang et al., Coeval widespread magmatism and metallogenesis (especially for 2008; Zhu et al., 2011). More and more investigations have suggested Au and Mo) took place in eastern China during the Late Mesozoic, in that the event of lithospheric thinning of the NCC was related to the 44 Y. 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