Timing of Formation of the Hongdonggou Pb-Zn Polymetallic Ore Deposit, Henan Province, China: Evidence from Rb-Sr Isotopic Dating of Sphalerites

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Research paper Timing of formation of the Hongdonggou Pb-Zn polymetallic ore deposit, Henan Province, China: Evidence from Rb-Sr isotopic dating of sphalerites

Fan Yang a, Gongwen Wang a,*, Huawen Cao b, Ruixi Li a, Li Tang a, Yufeng Huang a, Hao Zhang a,FeiXuea, Wenjuan Jia a, Nana Guo c a School of Earth Sciences and Resources, China University of Geosciences Beijing, 29 Xueyuan Road, Beijing 100083, China b Chengdu Center, China Geological Survey, Chengdu 610081, China c Luanchuan Bureau of Geology and Resources, Luoyang 417500, China article info abstract

Article history: The Hongdonggou Pb-Zn polymetallic ore deposit, located in the southwestern part of the Luanchuan Received 13 May 2016 Mo-W-Pb-Zn-Ag polymetallic ore mineralization in Henan Province, China, is an important part of the Received in revised form East Qinling metallogenic belt. The orebodies in the deposit, which are vein, bedded and lenticular, are 1 June 2016 mainly hosted in the syenite porphyry, and formed within the carbonate and clastic rocks of the Yuku Accepted 3 June 2016 and Qiumugou formations partially. The genesis of the deposit has previously been argued to be of Available online xxx hydrothermal-vein type or of skarn-hydrothermal type. In this study, we report the results of Rb-Sr isotopic dating based on sphalerites from the main orebody of the Hongdonggou Pb-Zn polymetallic Keywords: Sphalerite Rb-Sr geochronology ore deposit, which yield an isochron age of 135.7 3.2 Ma, constraining the timing of mineralization as Metallogeny early Cretaceous. The age is close to those reported for the Pb-Zn deposits in the Luanchuan ore belt. The 87 86 Pb-Zn deposit ( Sr/ Sr)i values of the sphalerites (0.71127 0.00010) are lower than that of terrigenous silicates Crust-mantle interaction (0.720) and higher than the mantle (0.707), suggesting that the metallogenic components were mainly Luanchuan ore belt derived through crust-mantle mixing. Combining the results from this study with those from previous work, we propose that the Hongdonggou Pb-Zn polymetallic ore deposit is a hydrothermal-vein deposit associated with the early Cretaceous tectonothermal event, and the mineralization is controlled by NW- and near EW-trending faults in the Luanchuan Mo-W-Pb-Zn-Ag polymetallic ore concentration belt. Ó 2016, China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/ licenses/by-nc-nd/4.0/).

1. Introduction including the Lengshuibeigou, Luotuoshan, Yindonggou, Xigou, Zhongyuku, Bailugou, Sandaogou, and Hongdougou deposits (Qi The Luanchuan Mo-W-Pb-Zn-Ag polymetallic ore concentration et al., 2007; Wang et al., 2007b; Yan et al., 2008, 2009; Qi et al., belt (abbreviated as “LOCB”) is located at the southern margin of 2009; Zhang et al., 2009; Duan et al., 2010a,b, 2011; Li et al., the North China Craton and forms part of the East Qinling metal- 2013; Cao et al., 2014, 2015; Wang et al., 2015). Among these, the logenic belt (Fig. 1a) in central China (Fig. 1b) (Lü et al., 2002; Li Hongdonggou Pb-Zn polymetallic ore deposit (abbreviated as et al., 2004; Yan et al., 2008, 2009; Wang et al., 2011a, 2012a,b, “HDG”) has been recognized as one of the typical Pb-Zn poly- 2015; Cao et al., 2014, 2015; Zhang et al., 2014; Tang et al., metallic ore deposits (Duan et al., 2010a; Tang et al., 2014b; Cao 2014a,b, 2015; Cao et al., 2015; Li et al., 2015; Li et al., 2016). et al., 2015). The HDG has been investigated by several workers Recent years witnessed major advance in exploration for Pb-Zn in focusing on the geological, aeromagnetic, and geochemical aspects the southern margin of the North China Craton, resulting in the including the team under the Party 3 of Henan Province Pro- discovery of a large number of medium-large scale Pb-Zn deposits specting Bureau of Geology and Mineral Resources (abbreviated as “HPGM”) and the Surveying and Mapping Team of Henan Province Regional Geological (abbreviated as “SMHP”). These teams also * Corresponding author. delineated the aeromagnetic anomaly, geochemical anomaly and E-mail addresses: [email protected] (F. Yang), [email protected] (G. Wang). Peer-review under responsibility of China University of Geosciences (Beijing). metallogenic belt carrying Mo, Pb, Zn, and Ag in this region. They http://dx.doi.org/10.1016/j.gsf.2016.06.001 1674-9871/Ó 2016, China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC- ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Figure 1. Geology and mineral resource of the LOCB (modiﬁed after Duan et al., 2010a,b). SF1, Shangdan Suture Zone; SF2, Mianlue Suture Zone; F1, Sanbao Fault; F2, Luanchuan Fault; HDG, Hongdonggou Pb-Zn polymetallic deposit.

also estimated more than 77.1 Mt of Pb-Zn ore reserve (Huang et al., 2013a,b; Huang et al., 2014; Cao et al., 2015; Hu et al., 2015; Yang 2008). However, the HDG in the LOCB remains poorly studied et al., 2015). In this study, based on the geological features of the (Huang et al., 2008), particularly related to isotopic age data on the HDG, we collected representative samples from the main metal- timing of mineralization. logenic stage (quartz-polymetallic sulﬁde stage) conduct Rb-Sr The precise dating of the timing of mineralization is of vital isotopic dating of sphalerites and obtain the isochron age. signiﬁcance in formulating guidelines for prospecting and exploration (Zhao and Jiang, 2004; Mao et al., 2005; Zhai et al., 2008; 2. Geological setting Zhang et al., 2008; Chugaev et al., 2010), and also to understand the genesis of ore deposit and the ore-controlling factors. One of The Qinling orogenic belt is bound to the north by the North the potential methods of dating of hydrothermal deposits is China Craton and to the south by the Yangtze Craton (Fig. 1a) (Tang through isotopic analysis of the ore minerals (Zhai et al., 2008; et al., 2014b, 2015; Dong and Santosh, 2016), and is composed of the Chugaev et al., 2010), and has been widely applied in the case of northern suture zone (Shangdan suture), the southern suture zone many Pb-Zn deposits (Peti and Dianmond, 1996; Li et al., 2002; Mao (Mianlue suture) and the major tectonic units: the southern margin et al., 2004; Paradis et al., 2007; Nebel et al., 2011; Hu et al., 2015). of the North China Craton, the North Qinling and the South Qinling The Rb-Sr isotopic dating of sphalerite is one of the commonly used belts (Fig. 1a). The Shangdan suture separates the North China methods in this context (Nakai et al., 1990, 1993; Christensen et al., Craton from the South Qinling belt, and the Mianlue suture sepa- 1995a,b; Liu et al., 1998; Schneider et al., 2002, 2007; Zhao and rates the South Qinling belt from the Yangtze Craton (Cao et al., Jiang, 2004; Venkatasubramanian and Narayanaswamy, 2013; 2015; Hu et al., 2015). The East Qinling orogenic belt is bound to Bolea-Fernandez et al., 2016a,b; Niu et al., 2016) and has been the south by the Shangdan suture (SF2) and to the north by the applied to obtain information on the timing of formation of several Sanbao fault (F1) (Fig. 1a). The HDG, situated in the south of the metallic deposits (Brannon et al., 1992a,b; Peti and Dianmond, Sanbao Fault and near the Luanchuan Fault, is an important part of 1996; Huang et al., 2004; Li et al., 2007a; Zhang et al., 2008; Tian the East Qinling orogenic belt (Duan et al., 2010a,b, 2011; Deng et al., 2009; Yin et al., 2009; Lin et al., 2010; Wang et al., 2011b; et al., 2013; Chen and Santosh, 2014; Cao et al., 2015)(Fig. 1a). Zhu et al., 2011; Hu et al., 2012; Xu et al., 2013; Zhou et al., The East Qinling orogenic belt is composed of a series of nappe

Please cite this article in press as: Yang, F., et al., Timing of formation of the Hongdonggou Pb-Zn polymetallic ore deposit, Henan Province, China: Evidence from Rb-Sr isotopic dating of sphalerites, Geoscience Frontiers (2016), http://dx.doi.org/10.1016/j.gsf.2016.06.001 F. Yang et al. / Geoscience Frontiers xxx (2016) 1e12 3 thrust sheets between the Sanbao Fault and Luanchuan Fault from Extensive Neoproterozoic and Mesozoic magmatic events north to south (Duan et al., 2010a,b, 2011; Cao et al., 2014, 2015; occurred in the LOCB and include the Neoproterozoic meta-syenite Wang et al., 2015). porphyry, meta-gabbro (Wang et al., 2011b) and Mesozoic quartz The strata exposed in the LOCB are mainly of the lower Paleozoic monzonite (Mao et al., 2010). The meta-gabbros occur as banded Taowan Group, Neoproterozoic Luanchuan Group and Mesoproter- and lenticular bodies in the Guandaokou and Luanchuan groups ozoic Guandaokou Group from south to north (Duan et al., 2010a,b; showing NWWeNW trend. However, the meta-gabbros do not Cao et al., 2014; Tang et al., 2014b)(Fig. 1c). The lithologies include show any obvious relationship with Pb-Zn deposits (Yan et al., Proterozoic and Paleozoic rocks. The lower Paleozoic Taowan Group 2004). The Mesozoic magmatism in the LOCB generated granite is composed of Qiumugou, Fengmaimiao and Sanchakou formations batholith and granite porphyries. The granite porphyries (e.g., from top to bottom, and contains early Paleozoic carbonate and Nannihu, Yuku) are mostly composite bodies, which show close clastic rocks (Fig. 2), which unconformably overlie the Luanchuan relationship with the mineralization and are mainly distributed in Group and includes metamorphic siltstone, quartzite, phyllite, the tectonic intersection area with an NWeNNE trend (Tang et al., conglomerate and argillaceous marble (Cao et al., 2014, 2015). The 2014b). Yuku, Dahongkou, Meiyaogou, Nannihu and Sanchuan formations from top to bottom constitute the Luanchuan Group and carry me- 3. Ore geology dium- to low-grade metamorphic neritic clastic and carbonate rocks, siliceous and carbonaceous slate, feldspar-quartz sandstone, The HDG, located in the northern part of Taowan town and quartzite, marble, and dolomitic marble (Fig. 2). From top to bottom, about 22 km from Luanchuan County (Fig. 1a), is one of the most the Mesoproterozoic Guandaokou Group consists of the Baishugou, important Pb-Zn deposits in the LOCB, covering an area of 3.56 km2. Fengjiawan, Duguan, Xunjiansi, Longjiayuan and Gaoshanhe for- The strata in the HDG are composed of the Yuku Formation which mations, and includes terrigenous clastic rocks and sedimentary includes dark gray, white banded siliceous dolomite marble, dark carbonate formations. The Guandaokou Group, which is uncon- gray biotite schist and quartzite and the Qiumugou Formation formably overlain by Neoproterozoic sequence of the Luanchuan which contains muscovite quartz marble showing banded struc- Group, is one of the most important ore-bearing rocks. Among these, ture, banded tremolite marble, calcite quartzite, and micaceous as the Luanchuan and Guandaokou groups constitute the most well as calcic schist (Fig. 2). Three sets of faults are well developed important ore-bearing strata in the HDG and with Mo, Pb, Zn and in the HDG, represented by the NEE-trending, NWW-trending and other mineral resources (Tang et al., 2014b). NE-trending systems (Fig. 3a). The region of intersection of the The major faults in the LOCB show multi-stage brittle- and NEE- and NWW-trending faults in the southwest of the ore district ductile-deformation associated with the Triassic continental colli- hosts the No. I orebody. The syenite porphyry which is the main sion between the North China Craton and the Yangtze Craton, intrusive rock and formed during late Proterozoic intruded along which are also the branches of the Luanchuan Fault (Cao et al., NWeSE. The syenite porphyry exposed to the northeast of the ore 2015)(Fig. 1a). The regional structures are deﬁned by WNW- district covers about 0.4 km2 (Fig. 3a), and shows dark gray, gray striking thrust faults, with subordinate NE-striking strike-slip white, light red colors with porphyritic structure and massive faults and WNW-trending interlayer fractures which are developed texture. The mineral assemblage is composed of K-feldspar in the Luanchuan and Guandaokou groups (Shi et al., 1996). The (microcline), albite, arfvedsonite, aegirine-pyroxene, nepheline, interlayer tectonic systems are the main ore-controlling structures biotite and garnet. in the Pb-Zn polymetallic deposits (Duan et al., 2010a,b; Cao et al., The orebodies in the deposit are mainly hosted in the syenite 2015; Li et al., 2015). porphyry which shows NWW, and appear in the carbonate and

Figure 2. Stratigraphic column of the LOCB (modiﬁed after Huang et al., 2008).

Figure 3. Geological map of the HDG and geological section 107 of the No. I orebody (modiﬁed after Huang et al., 2008).

clastic rocks of the Yuku and Qiumugou formations partially and pyritization; (2) quartz-polymetallic sulfide stage (the main (Fig. 3a). The orebodies show vein, bedded and lenticular metallogenic stage), generating sphalerite and galena; and (3) structure (section 107) (Fig. 3b). Three main orebodies have been carbonatization stage, which is characterized by the appearance of identified along the NEE- and NE-trending of faults in the HDG abundant calcite (Tang et al., 2014b). (I, IV, and VI orebodies) (Fig. 3a). The metallic minerals in these are mainly composed of galena and sphalerite which show 4. Sampling and analytical techniques, and results subhedraleautomorphic granular texture. The gangue minerals include quartz, sericite, chlorite and epidote. The types of alteration Ten sphalerite samples (Table 1) were selected for Rb-Sr isotopic in the HDG include silicification, sericitization, chloritization, epi- dating from the main orebody (the No. I orebody) (Fig. 3a) which is dotization and carbonatization. However, when the orebodies are cut by later quartz veins (Fig. 4aed). These samples represent the closer to the syenite porphyry, the degree of alteration of wall rock main ore mineral of the deposit (Table 1), and were collected from becomes stronger, and therefore the wall rock alteration is usually fresh surface of tunnel from the No. I orebody and contain regarded as an important index for prospecting. sphalerite-rich massive ore (Fig. 4aec). The galena-rich massive Based on detailed field observations in the HDG, we divide the ores are hosted in marble (Fig. 4e and f). The samples of quartz- hydrothermal activity in this deposit into three metallogenic stages polymetallic sulfide stage are mainly composed of sphalerite, py- as follows: (1) quartz-pyrite stage, which includes the early quartz rite and galena.

Table 1 (0.710340 260). The Rb-Sr isotopic ages are calculated by using Locations and characteristics of samples from the HDG. Isoplot/Ex Version 3.75 software, and with l ¼ 1.42 10 11 a 1, 87 86 87 86 Sample Location Mineral Sample description using 1% errors for Rb/ Sr ratios and 0.005% errors for Sr/ Sr no. ratios at a confidence level of 95% (Ludwig, 2012). Eventually, the H012-1 No. I orebody Sphalerite Massive ore medium-fine grained geochemical data plotting is conducted by using the CGDK soft- sphalerite, distributed in the ware (Qiu et al., 2013). dolomitization marble The analytical data of the ten samples are listed in Table 2.The H012-2 No. I orebody Sphalerite Massive ore, dark brown medium-fine grained sphalerite Rb contents of the samples range from 0.1843 to 0.6374 ppm, and H012-3 No. I orebody Sphalerite, Massive ore rich in sphalerite, medium- the Sr contents range from 0.3846 to 6.248 ppm. The values of galena fine grained automorphic galena 87Rb/86Sr range from 0.1027 to 4.892, and the values of 87Sr/86Sr and pyrite containing less fine grained range from 0.711442 to 0.720706. The regression line for ten hypidiomorphic quartz points (Fig. 6a), yields a Rb-Sr isochron age of 133 18 Ma with H012-4 No. I orebody Sphalerite Massive ore medium-fine grained 87 86 sphalerite, distributed in the siliceous an initial Sr/ Sr ratio of 0.71149 0.00057 and MSWD value of marble 97 for the sphalerites. The three samples (H012-3, H012-8 and H012-5 No. I orebody Sphalerite, Massive ore rich in sphalerite, dark H012-10) taken from the contact zone of wall rock define a galena brown medium-fine grained sphalerite, fi discrete group (Fig. 6a). Excluding these three discrete points, the and pyrite with less ne grained pyrite H012-6 No. I orebody Sphalerite, Massive dark brown sphalerite analytical data yield an isochron age of 135.7 3.2 Ma with an 87 86 galena containing dense disseminated galena, initial Sr/ Sr ratio of 0.71127 0.00010 and MSWD value of H012-7 No. I orebody Sphalerite black middle-coarse grained 2.2 for the sphalerites (Fig. 6b). disseminated sphalerite, distributed in the quartz vein 5. Discussion H012-8 No. I orebody Sphalerite, Massive ore, dark brown fine grained galena sphalerite coexist with medium-fine grained galena 5.1. Timing of ore formation H012-9 No. I orebody Sphalerite Black middle-coarse grained vein sphalerite, distributed in the quartz The Rb-Sr isotopic dating has been widely used as a classical vein H012-10 No. I orebody Sphalerite Massive black middle-coarse grained dating method for magmatic rocks although there has been sphalerite some controversy regarding its application to the hydrothermal deposits (Bradley and Leach, 2003; Yang et al., 2009; Wang et al., 2011b). With advent of high precision mass spectrometers with low detection limit, it has become possible to date hydrothermal minerals (Cao et al., 2015; Hu et al., 2015), especially pyrite (Yang Polished blocks and thin sections of fresh samples from the No. I and Zhou, 2000), and sphalerite (Nakai et al., 1993; Zhang et al., orebody were prepared for ore microscopy and petrography. The 2008; Hu et al., 2012, 2015; Cao et al., 2015). Also, fluid in- sphalerites, which are red brown and fawn under microscope, clusions in sphalerite are widely used for dating Pb-Zn deposit display medium-coarse subhedral-xenomorphic structure (Fig. 5a, age (Nakai et al., 1990; Peti and Dianmond, 1996). Several pre- b, e). Many sphalerite grains are cut by quartz vein (Fig. 5a and e), vious studies have successfully applied Rb-Sr isotopic dating on and the samples cover the main metallogenic stage. The types of sphalerite from Pb-Zn deposits (e.g., Nakai et al., 1990, 1993; mineral association as follows: quartz þ galena (Fig. 5d), Zhang et al., 2008; Zheng et al., 2013; Hu et al., 2015,among sphalerite þ galena (Fig. 5c), galena þ pyrite þ sphalerite (Fig. 5a), others). quartz þ pyrite þ galena þ sphalerite (Fig. 5e). The basic prerequisites for Rb-Sr isotopic dating of hydro- Mineral separates were handpicked after crushing the sam- thermal mineral demand that the minerals have been deposited ples to a grain size of approximately 40e60 mesh by using pre- simultaneously, and that system remained close to Rb and Sr cleaned agate mortar and pestle. The purity of the minerals diffusion after the minerals formed, in order that the (87Sr/86Sr) grains is of more than 99% as examined under a binocular mi- i ratio should be consistent, with varying (87Rb/86Sr) ratios (Li croscope. The samples were rinsed several times by using i et al., 2002; Nebel et al., 2011; Hu et al., 2015). The metal- distilled water, and then individual minerals grains are crushed logenic epoch in a hydrothermal deposit can range up to few to <200 mesh by using an agate ball mill, and then washed in an million years, whereas the sphalerite of the hydrothermal stage ultrasonic bath and dried. For Rb-Sr isotopic analysis, 0.2e0.3 g of in the main metallogenic stage formed during several hundred or the sample powder was dissolved in Teflon beakers with a thousands of years. Therefore, for RbeSr isotopic dating, the mixture of HF and HNO . By adopting resin of AG50W8and 3 hydrothermal minerals can be regarded as having formed different eluent reagents, Rb and Sr were separated for isotopic simultaneously (Liu et al., 1998; Hu et al., 2015). Using the analysis. The REEs were separated from Rb-Sr by using conven- advanced solid thermal ionization mass spectrometer (IsoProbe- tional cation-exchange chromatography with eluent of HCl. Rb T), with an ultra-low background, Rb-Sr isotopic dating of single and Sr were separated through cation ion exchange column. The crystals of mica (Li et al., 2006) or pyrite (Han et al., 2007)has concentrations and isotopic ratios were measured following yielded highly precise results. For medium-low temperature Pb- standard procedures outlined in previous studies (Fang et al., Zn deposits, the homogenization temperature of the secondary 2002; Wang et al., 2007a; Tian et al., 2009; Yin et al., 2009; Hu inclusions and primary inclusions in minerals show considerable et al., 2012, 2015). difference, posing difficulties in separating the inclusions (Zhang The Rb-Sr isotopic analysis was performed at the Center of et al., 2008). In this study, the sulfide mineral grains were Modern Analysis, Nanjing University, Jiangsu Province, China. crushed to <200 mesh and cleaned by ultrasonic means to To correct for instrumental fractionation, the 87Sr/86Sr is normal- largely eliminate the interference between primary and second- ized to 86Sr/88Sr ¼ 0.1194. In this study, measurements for the ary inclusions (Liu et al., 1998). The analyzed samples for Rb-Sr American Standard Reference Material NBS987 Sr standard give isotopic dating were taken from the main metallogenic stage 87Sr/86Sr ¼ 0.710236 0.000007 (2s). The relative deviation is among massive ores which have no fissures and are mainly less than 0.015% compared with the certified value sphalerite-rich. The 87Sr/86Sr versus 1/Sr and 1/Rb versus

Figure 4. Ore types of the HDG (a) underground exposure at the Hongdonggou adit, illustrating cloddy Pb-Zn ore (above) and ore (bottom left) in contact with marble, and hosted in the marble (H012-10); (b) underground exposure at the Hongdonggou adit, illustrating cloddy Pb-Zn ore (below) and quartz (above) in contact with marble, hosted in the marble; (c) underground exposure at the Hongdonggou adit, illustrating massive Pb-Zn ore (below) hosted in the marble; (d) massive ore of sphalerite and galena with fine-grained pyrite (pale yellow) (H012-8); (e) compact massive ore with quartz vein, consisting of vein quartz, host rock (gray white layers) and sulfides (brown and black, mostly sphalerite, secondly galena) (H012-5); (f) disseminated sulfides (fine-grained sphalerite galena and pyrite) hosted in marble, containing thin layer molybdenum (H012-3). Abbreviations: Spesphalerite; Pyepyrite; Gnegalena; Qtzequartz; Moemolybdenum; Mbemarble.

87 86 87 86 Rb/ Sr plots are usually used to judge whether the ( Sr/ Sr)i suggesting that the isotopic system in the mineral is relatively remained unchanged during the growth of the sulﬁdes (Li et al., homogeneous and closed (Peti and Dianmond., 1996; Li et al., 2002). The 1/Sr and 1/Rb values of the samples do not show any 2002; Nebel et al., 2011), and the isochrons constructed are covariation with either 87Sr/86Sr or 87Rb/86Sr (Fig. 7a and b), meaningful (Fig. 6aandb).

Figure 5. (aef) Photomicrographs of the samples H012-3, H012-5, H012-8 and H012-10 under parallel nicols. (b, e, d and a) respectively represent the samples from fresh surface of tunnel, hand specimens and view under the microscope of the samplesH012-3, H012-5, H012-8 and H012-10. The samplesinclude massive ore richin sphalerite hosting in themarble (H012-10), the massive ore rich in pyrite occurring in the marble (H012-3), the massive ore in the marble, containing quartz (H012-5). Abbreviations: Spesphalerite; Pyepyrite; Gnegalena; Qtzequartz.

Table 2 Analytical data based on 10 points of Rb-Sr isotope ratios and Rb-Sr contents of the sphalerite samples from the HDG.

87 86 87 86 87 86 Sample no. Mineral Rb (ppm) Sr (ppm) Rb/ Sr Sr/ Sr ( Sr/ Sr)i 1/Rb 1/Sr H012-1 Sphalerite 0.1843 2.294 0.2379 0.711832 9 0.71138 5.425935974 0.435919791 H012-2 Sphalerite 0.2637 2.482 0.3125 0.711871 8 0.71128 3.792188093 0.402900886 H012-3 Sphalerite 0.3279 1.059 0.9014 0.714018 7 0.71231 3.049710278 0.944287063 H012-4 Sphalerite 0.3053 1.905 0.4736 0.712059 9 0.71116 3.275466754 0.524934383 H012-5 Sphalerite 0.2164 6.248 0.1027 0.711442 8 0.71125 4.621072089 0.160051216 H012-6 Sphalerite 0.6374 0.3846 4.892 0.720706 9 0.71146 1.568873549 2.600104004 H012-7 Sphalerite 0.4812 0.4805 2.981 0.717007 7 0.71137 2.078137988 2.081165453 H012-8 Sphalerite 0.5209 0.4903 3.135 0.716695 6 0.71077 1.919754271 2.039567612 H012-9 Sphalerite 0.3503 0.7487 1.384 0.714008 8 0.71139 2.854695975 1.335648457 H012-10 Sphalerite 0.4587 0.5879 2.306 0.716732 9 0.71237 2.180074123 1.700969553

Figure 7. Plots (excluding H012-3, H012-8 and H012-10 points) (a) of 87Sr/86Sr versus 1/Sr and (b) of 1/Rb versus 87Rb/86Sr for HDG.

Figure 6. Rb-Sr isochron ages of sphalerites from the HDG (a) based on 10 points, and hydrothermal deposits have been discovered yet. However, the (b) 7 points (excluding spots H012-3, H012-8 and H012-10). hydrothermal-vein type Pb-Zn ore deposits in the LOCB, which was primarily controlled by the magmatic activities and the faults, are distributed within the Mesoproterozoic Guandaokou Group, the 5.2. Source of ore-forming material Neoproterozoic Luanchuan Group, and the early Paleozoic Taowan Group. The hydrothermal-vein type Pb-Zn deposits are considered The initial 87Sr/86Sr ratio is one of the important proxies for to be epigenetic (Cao et al., 2015). In combination with the present judging the material sources of magmatism and mineralization, study, we propose that the HDG is of hydrothermal-vein type. and is often used to indicate the source of ore forming components The HDG is one of the major Pb-Zn ore deposits of the LOCB, and from magmatic ﬂuid and crust-mantle interaction (Hou et al., other Pb-Zn deposits with same genetic type in the LOCB have 2006). Previous studies have showed that the initial 87Sr/86Sr ra- similar metallogenic age. The Mo-W deposits, ore-related granites tio from marine carbonate is 0.7081 0.0010, from modern and Pb-Zn deposits in the LOCB have similar mineralization ages seawater is 0.7093 0.0005 (Yi, 1988), and from the Paleozoic (Cao et al., 2015), as listed in Table 3. In this study, sphalerites from Marine source is 0.7093 0.0005 (Sun and He, 2001). In order to the main mineralization stage of the HDG yield a Rb-Sr isochron age avoid the effect of the 87Rb radioactive decay, the software of Geokit of 135.7 3.2 Ma, suggesting that the deposit formed during the (Lu, 2004) is used to calculate the initial isotopic value of sulﬁdes early Cretaceous. The HDG, Xigou, Sandaogou and Lengshuibeigou (Table 2). The results yield an isochron age of 135.7 3.2 Ma with deposits are located within the East Qinling metallogenic belt and an initial 87Sr/86Sr ratio of 0.71127 0.00010 and MSWD value of share similar genetic history (Table 3). By comparison with the 2.2 for sphalerites (Fig. 6b). The 87Sr/86Sr initial ratio is higher than schematic model of Luanchuan Mo-W-Pb-Zn-Ag metallogenic the Sr initial ratios of marine source. The 87Sr/86Sr initial ratio of the system (Fig. 8), these deposits have nearly consistent Rb-Sr HDG is between 0.711442 and 0.720706, with a mean value of isochron ages. The metallogenic ages of Pb-Zn deposits in the 0.711272. The 87Sr/86Sr initial ratio of the HGD is 0.711 which is LOCB are similar and slightly later than the ages of Mo-W deposits, lower than that of the continental crust mean value of 0.719 (Sun further attesting to the reliability of the ages from the HDG. The and He, 2001) and higher than that of the mantle initial ratio of ages of the ore-related granites and the Mo-W-Pb-Zn-Ag mineral- 0.707 (Faure, 1977). Therefore, the source materials for the metal- ization are almost identical (Cao et al., 2015). In addition, there is a logeny in the HDG may have been derived mainly from crust- close connection between granites and Pb-Zn deposits in the LOCB. mantle mixing. On the basis of these geological observations and the age data obtained in this study, the mineralization is considered to be the 5.3. Geological implications product of regional tectono-magmatic event in the East Qinling metallogenic belt, and has potential scope for prospecting the early Previous studies on the skarn-hydrothermal type of the HDG Cretaceous magmatic-hydrothermal Pb-Zn ore deposits in the remain controversial. No minerals related to typical skarn- LOCB.

Table 3 Isotopic ages recorded in granitic plutons, deposits of porphyry-skarn Mo-W deposit, hydrothermal-vein Pb-Zn deposit and deposits of skarn-hydrothermal Pb-Zn deposit in the LOCB (modiﬁed after Cao et al., 2015; Li et al., 2015).

Deposits/granites Sample types Mineral Methods Age (Ma) Reference Porphyry-skarn Mo-W deposit Nannihu Molybdenite ReeOs 146 1.1 Xiang et al. (2013) Molybdenite ReeOs 143.9 2.1 Xiang et al. (2012) Molybdenite ReeOs 144.4 2.2 Molybdenite ReeOs 145.8 2.3 Molybdenite ReeOs 145.8 2.2 Molybdenite ReeOs 143.4 2.0 Molybdenite ReeOs 139.3 2.3 Mao et al. (2008) Molybdenite ReeOs 144.8 2.1 Li et al. (2004) Molybdenite ReeOs 146 5 Huang et al. (1995) Molybdenite ReeOs 146.6 6 Molybdenite ReeOs 147 6 Molybdenite ReeOs 141.8 2.1 Li et al. (2003) Sandaozhuang Molybdenite ReeOs 145 2.2 Li et al. (2004) Molybdenite ReeOs 143.5 2.9 Mao et al. (2008) Molybdenite ReeOs 144.2 1.5 Molybdenite ReeOs 143.8 1.8 Molybdenite ReeOs 144.5 2.2 Li et al. (2003) Molybdenite ReeOs 145.4 2.0 Molybdenite ReeOs 145.0 2.2 Molybdenite ReeOs 144.6 2.5 Xiang et al. (2012) Molybdenite ReeOs 146.5 2.3 Molybdenite ReeOs 146.0 2.3 Molybdenite ReeOs 144.5 2.3 Molybdenite ReeOs 146.0 2.2 Shangfanggou Molybdenite ReeOs 144.8 2.1 Li et al. (2004) Molybdenite ReeOs 142.9 1.6 Mao et al. (2008) Molybdenite ReeOs 141.8 3.6 Molybdenite ReeOs 143.8 2.1 Li et al. (2003) Molybdenite ReeOs 145.8 2.1 Yuku Molybdenite ReeOs 146.9 2.1 Li et al. (2015) Molybdenite ReeOs 145.9 2.1 Molybdenite ReeOs 147.1 2.1 Molybdenite ReeOs 146.3 2.2 Molybdenite ReeOs 146.7 2.2 Molybdenite ReeOs 144.6 2.2 Majuan Molybdenite ReeOs 141.8 2.1 Hu et al. (1988) and Li et al. (2007b) Dongyuku Molybdenite ReeOs 146.6 0.9 Zhang (2014) Jiudinggou Molybdenite ReeOs 141 2.5 Dawanggou Molybdenite ReeOs 147.3 2.5 Mao et al. (2008) Molybdenite ReeOs 146.8 2.3 Molybdenite ReeOs 147.5 2.2 Molybdenite ReeOs 147.5 2.1 Molybdenite ReeOs 142.9 1.9 Molybdenite ReeOs 141.5 2.0 Skarn-hydrothermal type Pb-Zn deposits Luotuoshan Sphalerite Galena and Pyrite RbeSr 137.3 2.6 Yang et al. (2015) Hydrothermal-vein Pb-Zn-Ag deposit Lengshuibeigou Quartz AreAr 136.1 0.4 Wang et al. (2013) Sandaogou Sphalerite RbeSr 137.3 5.4 Cao et al. (2015) Xigou Sphalerite RbeSr 137.7 5.7 Hongdonggou Sphalerite RbeSr 135.7 3.2 This paper Ore-related granite Nannihu Granite porphyry Zircon LA-ICP-MS UePb 146.7 1.2 Xiang et al. (2012) Granite porphyry Zircon LA-ICP-MS UePb 145.2 1.5 Granite porphyry Zircon LA-ICP-MS UePb 176.3 1.7 Granite porphyry Zircon LA-ICP-MS UePb 158.2 1.2 Granite porphyry Zircon LA-ICP-MS UePb 145.7 1.2 Porphyritic granite Zircon LA-ICP-MS UePb 149.6 0.4 Bao et al. (2014) Granite porphyry Zircon SHRIMP UePb 157 3 Mao et al. (2010) Porphyritic granite Zircon SHRIMP UePb 158.2 3.1 Mao et al. (2005) Porphyritic granite Whole rock RbeSr 142 15 Hu et al. (1988) Porphyritic granite Whole rock KeAr 130.9 4.5 Porphyritic granite Whole rock KeAr 136.5 3.7 Granite porphyry Whole rock KeAr 162 Shangfanggou K-feldspar granite porphyry Zircon LA-ICP-MS UePb 135.4 0.3 Bao et al. (2014) Granite porphyry Zircon SHRIMP UePb 158 3 Mao et al. (2010) Alkali-feldspar granite Whole rock RbeSr 134 2 Hu et al. (1988) Granite porphyry Whole rock KeAr 145 Luo et al. (1991) Monzonite granite Biotite KeAr 145.5 4.5 Porphyritic granite Zircon SHRIMP UePb 157.6 2.7 Mao et al. (2005) Granite porphyry Zircon LA-ICP-MS UePb 135.4 0.3 Bao et al. (2009) Porphyritic granite Zircon LA-ICP-MS UePb 153.2 1.3 Li et al. (2015) (continued on next page)

Table 3 (continued )

Deposits/granites Sample types Mineral Methods Age (Ma) Reference Shibaogou Monzonite granite Zircon LA-ICP-MS UePb 156 1 Yang et al. (2013) Monzonite granite Zircon LA-ICP-MS UePb 157 1 Monzonite granite Zircon SHRIMP UePb 150.3 0.3 Liu et al. (2008) Monzonite granite Whole rock RbeSr 142.7 5 Yang et al. (1997) Monzonite granite Zircon SHRIMP UePb 147.2 1.7 Bao et al. (2014) Syenogranite porphyry Zircon SHRIMP UePb 145.3 1.4 Monzonite granite Zircon SHRIMP UePb 150.3 1.5 Liu (2007) Yuku Granite porphyry Zircon LA-ICP-MS UePb 150.5 0.8 Zhang (2014) Granite porphyry Zircon LA-ICP-MS UePb 154.1 1.8 Granite porphyry Zircon LA-ICP-MS UePb 148.3 1 Granite porphyry Zircon LA-ICP-MS UePb 154.1 1.8 Li et al. (2015) Granite porphyry Zircon LA-ICP-MS UePb 148.3 1.0 Daping Granite porphyry Zircon LA-ICP-MS UePb 141.2 0.5 Zhang (2014)

Figure 8. Schematic model of the Luanchuan Mo-W-Pb-Zn-Ag metallogenic system (modiﬁed after Cao et al., 2015). The names of the deposits are as follows: DYK, Dongyuku; HDG, Hongdonggou; LSBG, Lengshuibeigou; LTS, Luotuoshan; NNH, Nannihu; SDZ, Sandaozhuang; YDG, Yindonggou; YSA, Yangshuao; ZYK, Zhongyuku.

6. Conclusions thank Mr. Xuhuang Zhang (Luanchuan Bureau of Geology and Re- sources) and Dr. Jiangwei Han (Henan Institute of Geological Sur- (1) Rb-Sr isotopic dating of sphalerites from the main stage of vey) for their help during the ﬁeldwork. This research was mineralization of the Hongdonggou Pb-Zn polymetallic ore supported by the National Science and Technology Support Project deposit yield an isochron age of 135.7 3.2 Ma, suggesting that of the 12th “Five-Year Plan” (Grant No. 2011BAB04B06), the the deposit formed during the early Cretaceous; Fundamental Research Funds for the Central Universities of China 87 86 (2) The ( Sr/ Sr)i value of the sphalerite (0.71127 0.00010) University of Geosciences, Beijing (Grant No. 2-9-2012-143), and indicates that the metallogenic source involved materials from the National Natural Science Foundation of China (Grant No. crust-mantle mixing; 41572318). (3) By integrating the present results from previous studies in this region, we propose that the Hongdonggou Pb-Zn polymetallic ore deposit is a product of regional tectono-magmatic and References metallogenic processes during the early Cretaceous. Bao, Z.W., Zeng, Q.S., Zhao, T.P., Yuan, Z.L., 2009. Geochemistry and petrogenesis of the ore related Nannihu and Shangfanggou granite porphyries from East Qin- ling belt and their constrains on the molybdenum mineralization. Acta Petro- Acknowledgments logica Sinica 25, 2523e2536 (in Chinese with English abstract). Bao, Z.W., Wang, C.Y., Zhao, T.P., Li, C.J., Gao, X.Y., 2014. Petrogenesis of the Mesozoic We are grateful to Dr. Qiongyan Yang, an anonymous reviewer granites and Mo mineralization of the Luanchuan ore ﬁeld in the East Qinling Mo mineralization belt, central China. Ore Geology Reviews 57, 132e153. and Editor-in-Chief Prof. M. Santosh for their constructive com- Bolea-Fernandez, E., Van Malderen, S.J.M., Balcaen, L., Resano, M., Vanhaecke, F., ments which improved an earlier version of this paper. We also 2016a. Laser ablation-tandem ICP-mass spectrometry (LA-I CP-MS/MS) for

direct Sr isotopic analysis of solid samples with high Rb/Sr ratios. Journal of Province Prospecting Bureau of Geology and Mineral Resources, pp. 1e63 (in Analytical Atomic Spectrometry 31, 464e472. Chinese). Bolea-Fernandez, E., Balcaen, L., Resano, M., Vanhaecke, F., 2016b. Tandem ICP-mass Huang, H., Zhang, C.Q., Zhou, Y.M., Xie, H.F., Liu, B., Xie, Y.F., Dong, Y.T., Yang, C.H., spectrometry for Sr isotopic analysis without prior Rb/Sr separation. Journal of Dong, W.W., 2014. Rb-Sr isochron age of Jingchanghe Fe-Cu-Pb-Zn polymetallic Analytical Atomic Spectrometry 31, 303e310. deposit in Yunnan Province and its geological significance. Mineral Deposits 33, Brannon, J.C., Podosek, F.A., McLimans, R.K., 1992a. A Permian Rb-Sr age for 123e136 (in Chinese with English abstract). sphalerite from the Upper Mississippi zinc-lead district, Wisconsin. Nature 356, Li, W.B., Huang, Z.L., Xu, D.R., Chen, J., Xu, C., Guan, T., 2002. The Rb-Sr dating 509e511. research review of Pb-Zn deposit. Geotectonica et Metallogenia 26, 436e441 (in Brannon, J.C., Frank, A., Podosek, F.A., McLimans, R.K., 1992b. A clue to the origin of Chinese). dark and light bands of the 270 Ma Upper Mis-sissippi Valley (UMV) zinc-lead Li, Y.F., Mao, J.W., Bai, F.J., Li, J.P., He, Z.J., 2003. Re-Os isotopic dating of molybdenites district, southwest Wisconsin. In: Abstracts with Programs-Geological Society in the Nannihu molybdenum (W) ore field in the eastern Qinling and its of America, vol. 24, p. 353. geological significance. Geological Review 49, 292e304 (in Chinese with En- Bradley, D.C., Leach, D.L., 2003. Tectonic controls of Mississippi Valley-type leadezinc glish abstract). mineralization in orogenic forelands. Mineralium Deposita 38, 652e667. Li, Y.F., Mao, J.W., Guo, B.J., Shao, Y.J., Fei, H.C., Hu, H.B., 2004. Re-Os Dating of Cao, H.W., Zhang, S.T., Zheng, L., Liu, R.P., Tian, H.H., Zhang, X.H., Li, J.J., 2014. Trace molybdenite from the Nannihu Mo (-W) orefield in the East Qinling and its element geochemical characteristics of sphalerite in the Zhongyuku (Pb)-Zn geodynamic significance. Acta Geologica Sinica (English Edition) 78, 463e470. deposit of the Luanchuan, Southwest of China. Journal of Mineralogy and Li, Q.L., Chen, F.K., Wang, X.L., Li, X.H., Li, C.F., 2006. The ultra-low background Petrology 34, 50e59 (in Chinese with English abstract). chemical processes and single particle mica Rb-Sr isochron dating. Chinese Cao, H.W., Zhang, S.T., Santosh, M., Zheng, L., Tang, L., Li, D., Zhang, X.H., Zhang, Y.H., Science Bulletin 51, 321e325 (in Chinese). 2015. The Luanchuan MoeWePbeZneAg magmaticehydrothermal system in Li, H.M., Chen, Y.C., Wang, D.H., Li, H.Q., 2007a. Geochemistry and mineralization the East Qinling metallogenic belt, China: constrains on metallogenesis from age of the mayuan zinc deposit, Nanzheng, southern Shanxi, China. Geological CeHeOeSePb isotope compositions and RbeSr isochron ages. Journal of Asian Bulletin of China 26, 546e552 (in Chinese with English abstract). Earth Sciences 111, 751e780. Li, N., Chen, Y.J., Zhang, H., 2007b. Molybdenum deposits in East Qinling. Earth Chen, Y.J., Santosh, M., 2014. Triassic tectonics and mineral systems in the Qinling Science Frontiers 14, 186e198 (in Chinese with English abstract). orogen, central China. Geological Journal 49, 338e358. Li, Z.K., Li, J.W., Zhao, X.F., Zhou, M.F., Selby, D., Bi, S.J., Sui, J.X., Zhao, Z.J., 2013. Christensen, J.N., Halliday, A.N., Leigh, K.E., Randell, R.N., Kesler, S.E., 1995a. Direct Crustal-extension Ag-Pb-Zn veins in the Xiong’ershan District, Southern North dating of sulfides by Rb-Sr: a critical test using the Polaris Mississippi Valley- China craton: constraints from the Shagou deposit. Economic Geology 108, type Zn-Pb deposit. Geochimica et Cosmochimica Acta 59, 5191e5197. 1703e1729. Christensen, J.N., Halliday, A.N., Vearncombe, J.R., Kesler, S.E., 1995b. Testing models Li, D., Han, J.W., Zhang, S.T., Yan, C.H., Cao, H.W., Song, Y.W., 2015. Temporal evo- of large-scale crustal fluid flow using direct dating of sulfides; Rb-Sr evidence lution of granitic magmas in the Luanchuan metallogenic belt, east Qinling for early dewatering and formation of Mississippi Valley-type deposits, Canning orogen, central China: implications for Mo metallogenesis. Journal of Asian Basin, Australia. Economic Geology 90, 877e884. Earth Sciences 111, 663e680. Chugaev, A.V., Chernyshov, I.V., Gamyanin, G.N., Bortnikov, N.S., Baranova, A.N., Li, R.X., Wang, G.W., Carranza, E.J.M., 2016. GeoCube: a 3D mineral resources 2010. Rb-Sr isotopic systematic of hydrothermal minerals, age, and matter quantitative prediction and assessment system. Computers & Geosciences 89, sources of the Nezhdaninskoe gold deposit (Yakutia). Doklady Earth Sciences 161e173. 434, 1337e1341. Lin, Z.Y., Wang, D.H., Zhang, C.Q., 2010. RbeSr isotopic age of sphalerite from the Deng, X.H., Chen, Y.J., Santosh, M., Yao, J.M., 2013. ReeOs geochronology, fluid in- Paoma leadezinc deposit in Sichuan Province and its implications. Geology in clusions and genesis of the 0.85 Ga Tumen molybdeniteefluorite deposit in China 37, 488e494 (in Chinese with English abstract). Eastern Qinling, China: implications for pre-Mesozoic Mo enrichment and Liu, J.M., Zhan, S.R., Shen, J., Jiang, N., Huo, W.G., 1998. Review on direct isotopic tectonic setting. Geological Journal 48, 484e497. dating of hydrothermal ore-forming processes. Progress in Geophysics 13, Dong, Y., Santosh, M., 2016. Tectonic architecture and multiple orogeny of the 46e55 (in Chinese with English abstract). Qinling orogenic belt, Central China. Gondwana Research 29, 1e40. Liu, G.Y., 2007. The PbeZneAg Metallogeny and Prospecting Target in the South Duan, S.G., Xue, C.J., Liu, G.Y., Yan, C.H., Feng, Q.W., Song, Y.W., Chu, J.J., 2010a. Ge- Marge of North China Craton. Ph. D thesis. China University of Geoscience ology and sulfur isotope geochemistry of lead-zinc deposits in Luanchuan (Beijing), Beijing, pp. 22e38 (in Chinese with English abstract). district, Henan Province, China. Earth Science Frontiers 17, 375e384. Liu, G.Y., Yan, C.H., Xue, C.J., Zhang, D.H., Di, Y.J., Duan, S.G., Song, Y.W., Zeng, X.Y., Duan, S.G., Xue, C.J., Liu, G.Y., Yan, C.H., Feng, Q.W., Song, Y.W., Gao, B.Y., 2010b. Wang, J.Z., Zhang, M.B., Lu, S.W., Yao, X.N., Lu, W.D., Zhao, R.J., Ding, H.Y., Geology, fluid inclusions and stable isotopic geochemistry of Bailugou PbeZn Wang, F.Y., Lu, Y.H., He, Y.L., Ye, P., 2008. The Study of Metallogenic Regularities deposit in Luanchuan area, Henan Province. Mineral Deposits 5, 006 (in Chinese and Prospecting Direction of the Pb-Zn-Ag-Mo Ore Concentration Area in with English abstract). Southwestern Henan Province. Henan Institute of Geological Survey, Zhengz- Duan, S.G., Xue, C.J., Chi, G.X., Liu, G.Y., Yan, C.H., Feng, Q.W., Song, Y.W., 2011. Ore hou, pp. 1e303 (in Chinese). geology, fluid inclusion, and S- and Pb- isotopic constraints on the genesis of Lu, Y.F., 2004. GeoKit: a geochemical toolkit for Microsoft Excel. Geochimica 33, the Chitudian Zn-Pb deposit, southern margin of the North China craton. 459e464 (in Chinese with English abstract). Resource Geology 61, 224e240. Lü, W.D., Sun, W.Z., Wang, X.H., Xiao, Z.J., Xu, W.C., Yang, G.Q., 2002. Metallogenic Fang, W.X., Hu, R.Z., Su, W.C., Xiao, J.F., Qi, L., Jiang, G.H., 2002. The emplacement age geological condition and prospects of Ag Pb and Zn deposits in Chitudian re- of lamproite in the Zhengyuan region, Guizhou province. Chinese Science gion, Luanchuan County, Henan Province. Progress In Precambrian Research 25, Bulletin 47, 307e312 (in Chinese with English abstract). 4 (in Chinese with English abstract). Faure, G., 1977. Principles of Isotope Geology. John Wiley & Sons Inc, New York, Ludwig, K.R., 2012. User’s Manual for Isoplot 3.75: a Geochronological Toolkit for pp. 1e120. Microsoft Excel. Berkeley Geochronology Center, Berkeley, pp. 1e70. Han, Y.G., Li, X.H., Zhang, S.H., Zhang, Y., Chen, F.K., 2007. Single grain Rb-Sr dating of Luo, M.J., Zhang, F.M., Dong, Q.Y., Xu, Y.R., Li, S.M., Li, K.H., 1991. Molybdenum De- euhedral and cataclastic pyrite from the Qiyugou gold deposit in western posits in China. Henan Science Technology Press, Zhengzhou, pp. 1e445 (in Henan, central China. Chinese Science Bulletin 52, 1820e1826 (in Chinese with Chinese). English abstract). Mao, J.W., Xie, G., Li, X.F., 2004. Mesozoic large-scale mineralization and multiple Hou, M.L., Jiang, S.Y., Jiang, Y.H., Ling, H.F., 2006. S-Pb isotope geochemistry and Rb- lithospheric extensions in South China. Acta Geologica Sinica (English Edition) Sr geochronology of the Penglai gold field in the eastern Shangdong province. 80, 420e431. Acta Petrologica Sinica 22, 2525e2533 (in Chinese with English abstract). Mao, J.W., Xie, G.Q., Zhang, Z.H., Li, X.F., Wang, Y.T., Zhang, C.Q., Li, Y.F., 2005. Hu, S.X., Lin, Q.L., Chen, Z.M., Li, S.M., 1988. The Geology and Metallogeny of the Mesozoic large-scale metallogenic pulses in North China and corresponding Amalgamation Zone between Ancient North China Plate and South China Plate geodynamic settings. Acta Petrologica Sinica 21, 169e188. (Taking Qinling-Tongbai as an Example). Press of Nanjing University, Nanjing, Mao, J.W., Xie, G.Q., Bierlein, F., Qü, W.J., Du, A.D., Ye, H.S., Pirajno, F., Li, H.M., pp. 1e145. Yang, Z.Q., 2008. Tectonic implications from ReeOs dating of Mesozoic mo- Hu, Q.Q., Wang, Y.T., Wang, R.T., Li, J.H., Dai, J.Z., Wang, S.Y., 2012. Ore-forming time lybdenum deposits in the East QinlingeDabie orogenic belt. Geochimica et of the Erlihe PbeZn deposit in the FengxianeTaibai ore concentration area, Cosmochimica Acta 72, 4607e4626. Shaanxi Province: evidence from the RbeSr isotopic dating of sphalerites. Acta Mao, J.W., Xie, G.Q., Pirajno, F., Ye, H.S., Wang, Y.B., Li, Y.F., Xiang, J.F., Zhao, H.J., 2010. Petrologica Sinica 28, 258e266 (in Chinese with English abstract). Late JurassiceEarly Cretaceous granitoid magmatism in Eastern Qinling, Hu, Q.Q., Wang, Y.T., Mao, J.W., Wei, R., Liu, S.Y., Ye, D.J., Yuan, Q.H., Dou, P., 2015. central-eastern China: SHRIMP zircon UePb ages and tectonic implications. Timing of the formation of the ChangbaeLijiagou PbeZn ore deposit, Gansu Australian Journal of Earth Sciences 57, 51e78. Province, China: evidence from RbeSr isotopic dating of sulfides. Journal of Nakai, S.I., Halliday, A.N., Kesler, S.E., 1990. Rb-Sr dating of sphalerites from Ten- Asian Earth Sciences 103, 350e359. nessee and the genesis of Mississippi Valley type. Nature 346. Huang, D., Wu, C., Du, A., He, H., 1995. Re-Os isotope ages of molybdenum deposits Nakai, S.I., Halliday, A.N., Kesler, S.E., Jones, H.D., Kyle, J.R., Lane, T.E., 1993. Rb-Sr in East Qinling and their significance. Chinese Journal of Geochemistry 14, dating of sphalerites from Mississippi Valley-type (MVT) ore deposits. Geo- 313e322. chimica et Cosmochimica Acta 57, 417e427. Huang, Z.L., Li, W.B., Zhang, Z.L., Han, R.S., Chen, J., 2004. Several problems in the Nebel, O., Scherer, E.E., Mezger, K., 2011. Evaluation of the 87 Rb decay constant by research of genesis of Huize super-lage Pb-Zn deposit in Yunnan province. Acta age comparison against the UePb system. Earth and Planetary Science Letters Mineralogica Sinica 24, 105e111 (in Chinese). 301, 1e8. Huang, F., Gu, T.B., Cheng, Q.S., Yang, Y.J., 2008. The Detailed Exploration Report of Niu, S.D., Li, S.R., Santosh, M., Zhang, D.H., Li, Z.D., Shan, M.J., Lan, X.Y., Gao, D.R., the Hongdonggou Pb-Zn Polymetallic Deposit, China. The Party 3 of Henan Zhao, W.B., 2016. Mineralogical and isotopic studies of base metal sulfides from

the Jiawula AgePbeZn deposit, Inner Mongolia, NE China. Journal of Asian Wang, G.W., Li, R.X., Carranza, E.J.M., Zhang, S.T., Yan, C.H., Zhu, Y.Y., Qu, J.N., Earth Sciences 115, 480e491. Hong, D.M., Song, Y.W., Han, J.W., Ma, Z.B., Zhang, H., Yang, F., 2015. 3D Paradis, S., Hannigan, P.E.T.E.R., Dewing, K.E.I.T.H., 2007. Mississippi Valley-type geological modeling for prediction of subsurface Mo targets in the Luanchuan Lead-Zinc Deposits. Mineral Deposits of Canada: a Synthesis of Major district, China. Ore Geology Reviews 71, 592e610. Deposit-types, District Metallogeny, the Evolution of Geological Provinces, and Xiang, J.F., Mao, J.W., Pei, R.F., Ye, H.S., Wang, C.Y., Tian, Z.H., Wang, H.L., 2012. New Exploration Methods. Geological Association of Canada, Mineral Deposits Di- geochronological data of granites and ores from the Nannihu-Sandaozhuang vision, Special Publication 5, pp. 185e203. Mo (W) deposit. Geology in China 39, 458e473 (in Chinese with English Peti, T., Dianmond, W., 1996. Rb-Sr dating of sphalerite based on fluid inclusion-host abstract). mineral isochrons: a clarification of why it works. Economic Geology 91, Xiang, J.F., Pei, R.F., Ye, H.S., Wang, C.Y., Tian, Z.H., 2013. Source and evolution of the 951e956. ore-forming fluid in the NannihueSandaozhuang Mo (W) deposit: constraints Qi, J.P., Chen, Y.J., Ni, P., Lai, Y., Ding, J.Y., Song, Y.W., Tang, G.J., 2007. Fluid inclusion from CeHeO stable isotope data. Geology in China 6, 022 (in Chinese with constraints on the origin of the Lengshuibeigou Pb-Zn-Ag deposit, Henan English abstract). Province. Acta Petrologica Sinica 23, 2119e2130 (in Chinese with English Xu, Y.G., Wu, Y.G., Wang, C.M., Zhang, D., Zhang, Y.Y., 2013. Rb-Sr isochron age of abstract). Lengshuikeng Ag-Pb-Zn polymetallic deposit on sphalerate in Jiangxi Province Qi, J.P., Song, Y.W., Li, S.Q., Chen, F.K., 2009. RbeSr isotope study of the Xigou and its geological significance. Acta Geology Sinica 87, 621e633 (in Chinese). PbeZneAg deposit, Luanchuan County, Henan Province. Acta Petrologica Sinica Yan, C.H., Song, Y.W., Liu, G.Y., Xing, K., 2004. The geological characteristics of MVT 25, 2843e2854 (in Chinese with English abstract). Pb-Zn ore belt of Luanchuan Yangshuao-Bailugou in Henan Province. Geological Qiu, J.T., Song, W.J., Jiang, C.X., Wu, H., Dong, R.M., 2013. CGDK: an extensible Cor- Survey and Research 27, 249e254 (in Chinese). elDRAW VBA program for geological drafting. Computers & Geosciences 51, Yan, C.H., Xu, Y.H., Peng, Y., Zhao, T.P., 2008. Geological-geochemical characteristics 34e48. and genesis of massive sulfide deposits in Er’langping Group of East Qinling. Schneider, J., Boni, M., Lapponi, F., Bechstädt, T., 2002. Carbonate-hosted zinc-lead Minetal Deposits 27, 14 (in Chinese with English abstract). deposits in the Lower Cambrian of Hunan, South China: a radiogenic (Pb, Sr) Yan, C.H., Liu, G.Y., Peng, Y., 2009. The Pb-Zn-Ag Metallogenetic Regularities in isotope study. Economic Geology 97, 1815e1827. Southwest Henan Province. Geological Press, Beijing, pp. 1e115 (in Chinese). Schneider, J., Melcher, F., Brauns, M., 2007. Concordant ages for the giant Kipushi Yang, R.Y., Xu, Z.W., Ren, Q.J., 1997. Ages and magma sources of Shibaogou and base metal deposit (DR Congo) from direct RbeSr and ReeOs dating of sulfides. Huoshenmiao complexes in east Qinling. Bulletin of Mineralogy, Petrology and Mineralium Deposita 42, 791e797. Geochemistry 16, 15e18 (in Chinese with English abstract). Shi, Q.Z., Tao, Z.Q., Pang, J.Q., Qu, M.X., 1996. The research of Luanchuan Group in the Yang, J.H., Zhou, X.H., 2000. RbeSr isochron ages of the ore and gold bearing southern margin of north China plate. North China Journal of Geology and minerals in Linglong gold deposit and it’s ore-forming ages, eastern of Jiaozhou Mineral Resources 11, 51e59 (in Chinese). Peninsula. Chinese Science Bulletin 45, 1547e1553 (in Chinese with English Sun, S.L., He, Z.L., 2001. Devonian Hydrocarbon Alkali Fluid Metallogenic Series abstract). Study in Xicheng Metallogenic Clusters, West Qinling. Chengdu University of Yang, X.R., Peng, J.T., Hu, R.Z., 2009. The discussion on sphalerite Rb-Sr isotope Technology, Chendu, pp. 1e143 (in Chinese with English abstract). isochron. Geological Review 3, 370e374 (in Chinese). Tang, L., Santosh, M., Dong, Y.P., Tsunogae, T., Zhang, S.T., Cao, H.W., 2014a. Early Yang, Y., Wang, X.X., Ke, C.H., Li, J.B., 2013. Zircon U-Pb age, geochemistry and Hf Paleozoic tectonic evolution of the North Qinling orogenic belt: evidence from isotopic compositions of Shibaogou granitoid pluton in the Nannihu ore district, geochemistry, phase equilibrium modeling and geochronology of meta- western Henan Province. Geology in China 39, 1525e1542 (in Chinese with morphosed mafic rocks from the Songshugou ophiolite. Gondwana Research English abstract). 30, 48e64. Yang,C.Y.,Ye,H.S.,Xiang,J.F.,Chen,X.D.,Xing,B.,Li,L.,Wang,S.,2015.Rb-Sr Tang, L., Zhang, S.T., Cao, H.W., Li, D., Zhang, X.H., Zhang, Y.H., Tian, H.H., Zhang, H., Isochron Age of Sulfide from Luotuoshan Polymetallic Deposit in West 2014b. The Mo-W-Pb-Zn-Ag polymetallic metallogenic system and evolution Henan Province and its Geological Significance. The 15th Annual Seminar characteristics in the Luanchuan ore concentration area, Henan Province. Abstract of Chinese Society for Mineralogy, Petrology and Geochemistry, 3 Journal of Chengdu University of Technology (Science & Technology Edition) 41, (in Chinese). 356e368 (in Chinese). Yi, G., 1988. Isotope Hydrogeochemistry. Chengdu University of Technology Press, Tang, L., Santosh, M., Dong, Y.P., 2015. Tectonic evolution of a complex orogenic Chengdu, pp. 1e290 (in Chinese). system: evidence from the northern Qinling belt, central China. Journal of Asian Yin, M., Li, W., Sun, X., 2009. Rb-Sr isotopic dating of sphalerite from the giant Huize Earth Sciences 113, 544e559. Zn-Pb ore field, Yunnan Province, Southwestern China. Chinese Journal of Tian, S.H., Yang, Z.S., Hou, Z.Q., Liu, Y.C., Gao, Y.G., Wang, Z.L., Su, A.N., 2009. RbeSr Geochemistry 28, 70e75. and SmeNd isochron ages of Dongmozhazhua and Mohailaheng PbeZn ore Zhai, Y.S., Wang, J.P., Deng, J., Peng, R.M., Liu, J.J., 2008. Temporal-spatial evolution of deposits in Yushu area, southern Qinghai and their geological implications. metallogenic systems and its significance to mineral exploration. Geoscience Mineral Deposits 28, 747e758 (in Chinese with English abstract). 22, 143e150 (in Chinese with English abstract). Venkatasubramanian, V.S., Narayanaswamy, R., 2013. Studies in Rb-Sr geochro- Zhang, C.Q., Li, X.H., Yu, J.J., Mao, J.W., Chen, F.K., Li, H.M., 2008. RbeSr dating of nology and trace element geochemistry in granitoids of Mysore craton, India. single sphalerites from the Daliangzi PbeZn deposit, Sichuan, and its geological Journal of the Indian Institute of Science 56, 19. significances. Geological Review 54, 532e538 (in Chinese with English Wang, Y.X., Yang, J.D., Chen, J., Zhang, K.J., Rao, W.B., 2007a. The Sr and Nd isotopic abstract). variations of the Chinese Loess Plateau during the past 7 Ma: implications for Zhang, J., Yang, Y., Hu, H.Z., Wang, Z.G., Li, G.P., Li, Z.L., 2009. CS-Pb isotope the East Asian winter monsoon and source areas of loess. Palaeogeography, geochemistry of the Yindonggou orogenic-type silver deposit in Henan Prov- Palaeoclimatology, Palaeoecology 249, 351e361. ince. Acta Petrologica Sinica 25, 2833e2842 (in Chinese with English abstract). Wang, C.M., Zhang, S.T., Deng, J., Sun, Y.X., Yan, C.H., Ye, H.S., 2007b. Geological- Zhang, J., Ye, H.S., Zhou, K., Meng, F., 2014. Processes of ore genesis at the world- geochemical features and genesis of Lengshuibeigou Pb-Zn deposit in Henan. class Yuchiling molybdenum deposit, Henan Province, China. Journal of Asian Mineral Deposits 26, 175e183 (in Chinese with English abstract). Earth Sciences 79, 666e681. Wang, G.W., Zhang, S.T., Yan, C.H., Song, Y.W., Sun, Y., Li, D., Xu, F.M., 2011a. Mineral Zhang, Y.H., 2014. Late-mesozoic Tectonic-magma Evolution and its Relationship- potential targeting and resource assessment based on 3D geological modeling with Mineralization in Luanchuan County. Master thesis. China University of in Luanchuan region, China. Computers & Geosciences 37, 1976e1988. Geosciences, Beijing, pp. 1e79 (in Chinese with English abstract). Wang, X.L., Jiang, S.Y., Dai, B.Z., Griffin, W.L., Dai, M.N., Yang, Y.H., 2011b. Age, Zhao, K.D., Jiang, S.Y., 2004. Direct isotope dating for metallic ore deposits. Earth geochemistry and tectonic setting of the Neoproterozoic (ca 830 Ma) gabbros Science Frontiers 11, 425e434 (in Chinese with English abstract). on the southern margin of the North China craton. Precambrian Research 190, Zheng, W., Chen, M.H., Xu, L.G., Zhao, H.J., Ling, S.B., Wu, Y., Hu, Y.G., Tian, Y., 35e47. Wu, X.D., 2013. Rb-Sr isochron age of Tiantang Cu-Pb-Zn polymetallic deposit in Wang, G.W., Zhang, S.T., Yan, C.H., Xu, G.Y., Ma, M., Li, K., Feng, Y., 2012a. Application Guangdong Province and its geological significance. Mineral Deposits 32, of the multifractal singular value decomposition for delineating geophysical 259e272 (in Chinese with English abstract). anomalies associated with molybdenum occurrences in the Luanchuan ore field Zhou, J., Huang, Z., Zhou, M., Li, X., Jin, Z., 2013a. Constraints of CeOeSePb isotope (China). Journal of Applied Geophysics 86, 109e119. compositions and RbeSr isotopic age on the origin of the Tianqiao carbonate- Wang, G.W., Zhu, Y.Y., Zhang, S.T., Yan, C.H., Song, Y.W., Ma, Z.B., Hong, D.M., hosted PbeZn deposit, SW China. Ore Geology Reviews 53, 77e92. Chen, T.Z., 2012b. 3D geological modeling based on gravitational and magnetic Zhou, J., Huang, Z., Bao, G., 2013b. Geological and sulfur-lead-strontium isotopic data inversion in the Luanchuan ore region, Henan Province, China. Journal of studies of the Shaojiwan Pb-Zn deposit, southwest China: implications for the Applied Geophysics 80, 1e11. origin of hydrothermal fluids. Journal of Geochemical Exploration 128, 51e61. Wang, C., He, X., Yan, C., Lü, W., Sun, W., 2013. Ore geology, and H, O, S, Pb, Ar Zhu, F.L., Tao, Y., Hu, R.Z., Liao, M.Y., Wang, Y.X., Li, Y.B., 2011. Formation age of the isotopic constraints on the genesis of the Lengshuibeigou Pb-Zn-Ag deposit, Luziyuan leadezinc deposit in Zhengkang, Yunnan. Bulletin of Mineralogy, China. Geosciences Journal 17, 197e210. Petrology and Geochemistry 30, 73e77 (in Chinese with English abstract).