Genesis of the Bianjiadayuan Pb–Zn polymetallic deposit, Inner Mongolia, China: Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite

Geoscience Frontiers xxx (xxxx) xxx

H O S T E D BY

Contents lists available at ScienceDirect China University of Geosciences (Beijing)

Geoscience Frontiers journal homepage: www.elsevier.com/locate/gsf

Research Paper

Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite Kai-Rui Song a, Li Tang a, *, Shou-Ting Zhang a, M. Santosh a, b, Christopher J. Spencer c, Yu Zhao a, Hao-Xing Li a, Liang Wang a, An-Li Zhang d, Yin-Qiang Sun e a

School of the Earth Sciences and Resources, China University of Geosciences (Beijing), Beijing, 100083, China Centre for Tectonics, Exploration and Research, University of Adelaide, Adelaide, SA, 5005, Australia c School of Earth and Planetary Sciences, The Institute of Geoscience Research, Curtin University, Perth, WA, 6845, Australia d Lituo Mining Company, Chifeng, 024000, China e 243 Team, China Nuclear Geology, Chifeng, 024000, China b

a r t i c l e i n f o

a b s t r a c t

Article history: Received 6 September 2018 Received in revised form 10 November 2018 Accepted 18 February 2019 Available online xxx Handling Editor: Sohini Ganguly

The Southern Great Xing’an Range (SGXR) which forms part of the eastern segment of the Central Asian Orogenic Belt (CAOB) is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China, hosting a number of porphyry Mo (Cu), skarn Fe (Sn), epithermal Au-Ag, and hydrothermal veintype Ag-Pb-Zn ore deposits. Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR. Porphyry Sn
Cu
Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field. We identify a five-stage mineralization process based on field and petrologic studies including (i) the early porphyry mineralization stage, (ii) main porphyry mineralization stage, (iii) transition mineralization stage, (iv) vein-type mineralization stage and (v) late mineralization stage. Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage, and we identify corresponding four types of pyrites: Py1 is medium-grained subhedral to euhedral occurring in the early barren quartz vein; Py2 is medium- to fine-grained euhedral pyrite mainly coexisting with molybdenite, chalcopyrite, minor sphalerite and galena; Py3 is fine-grained, subhedral to irregular pyrite and displays cataclastic textures with micro-fractures; Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena. LA-ICP-MS trace element analyses of pyrite show that Cu, Pb, Zn, Ag, Sn, Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions, whereas Co, Ni, As and Se enter the lattice via isomorphism in all types of pyrite. The Cu, Zn, Ag, Cd concentrations gradually increase from Py1 to Py4, which we correlate with cooling and mixing of ore-forming fluid with meteoric water. Py2 contains the highest contents of Co, Ni, Se, Te and Bi, suggesting high temperature conditions for the porphyry mineralization stage. Ratios of Co/Ni (0.03e10.79, average 2.13) and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites. The d34SCDT values of Py1 (0.42&e1.61&, average 1.16&), Py2 (e1.23& to 0.82&, average 0.35&), Py3 (e0.36& to 2.47&, average 0.97&), Py4 (2.51& e3.72&, average 3.06&), and other sulfides are consistent with those of typical porphyry deposit (e5& to 5&), indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian (JurassiceCretaceous) magmatic-hydrothermal events. Variations of d34S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid. We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type PbeZn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region. Ó 2019, 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/).

Keywords: Trace elements In-situ sulfur isotope Pyrite Bianjiadayuan deposit Southern Great Xing’an range

* Corresponding author. E-mail addresses: [email protected], [email protected] (L. Tang). Peer-review under responsibility of China University of Geosciences (Beijing). https://doi.org/10.1016/j.gsf.2019.02.004 1674-9871/Ó 2019, 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-NCND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

2

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

1. Introduction Pyrite is one of the main constituents in many hydrothermal ore systems, and incorporate a wide array of trace elements (i.e., Co, Ni, Se, Te, Hg, Tl, Au, Ag, Cu, Pb, Zn, Bi). These trace elements occur in solid solution, as invisible sulfide nanoparticles, visible micron-sized sulfide inclusion, or as visible micron-sized silicate or oxide mineral inclusions (Cook and Chryssoulis, 1990; Large et al., 2009; Koglin et al., 2010; Thomas et al., 2011; Ulrich et al., 2011; Ciobanu et al., 2012; Ingham et al., 2014; Reich et al., 2016). Trace element geochemistry of pyrite plays a key role to evaluate metal scavenger and to monitor the changes in hydrothermal fluid composition (Deditius et al., 2011; Zhang et al., 2014a,b). Previous studies on trace elements of pyrite were mainly focused on orogenic gold deposits and Carlin-type gold deposits where pyrite is the major Au-bearing mineral (Zhao et al., 2011; Agangi et al., 2014; Zhang et al., 2014a,b; Belousov et al., 2016; Zhang et al., 2016; Feng et al., 2017; Ward et al., 2017; Chen et al., 2018; Yuan et al., 2018), volcanicassociated massive sulfide deposits (Maslennikov et al., 2009, 2017; Keith et al., 2016; Basril et al., 2018), SEDEX type Zn-Pb deposits (Mukherjee and Large, 2017), and porphyry Cu(-Au) and porphyry-epithermal Cu-Au deposits (Maydagán et al.,  et al., 2014; Deditius et al., 2013; Reich et al., 2013; Cioaca 2014; Zwahlen et al., 2014; Franchini et al., 2015; Zhang et al., 2016), whereas investigations on the trace element features of pyrite from composite porphyry and polymetallic vein mineralization are rare. The Southern Great Xing’an Range (SGXR) is one of the important polymetallic belts in northeast China, wherein more than fifty different types of deposits have been discovered since 1970s, including porphyry-, skarn- and vein-type deposits (Ouyang et al., 2014, 2015; Mei et al., 2015; Zhang et al., 2017; Liu et al., 2018; Wang et al., 2018; Zhou et al., 2018). Furthermore, three sub-polymetallic belts were recognized from west to east: the Xilinhot-Xilinguole Ag-Pb-Zn sub-belt, the HuanggangGanzhuermiao Fe-Sn-Zn-Pb sub-belt, and the Linxi-LindongTianshan-Tuquan Cu-Mo sub-belt (Fig. 1c). The Bianjiadayuan is a typical hydrothermal vein-type Ag-Pb-Zn ore deposit which belongs to the Huanggang-Ganzhuermiao Fe-Sn-Zn-Pb sub-belt in the southern part of the SGXR. On global scale, polymetallic vein mineralization genetically associated with porphyry mineralization systems have been widely reported (Lawley et al., 2010; Mao et al., 2011; Cao et al., 2015; Catchpole et al., 2015a,b). Based on field observations, geochronological constraints (zircon U-Pb, molybdenite Re-Os, and sericite 40Ar/39Ar dating), stable isotope, fluid inclusions and petrological geochemistry (Wang et al., 2013, 2014a,b,c; Ruan et al., 2015; Gu et al., 2017; Zhai et al., 2017, 2018a,b), the Ag-Pb-Zn veins are considered to have genetic relationship with the porphyry Sn
Cu
Mo mineralization associated with the Early Cretaceous porphyry intrusion in the Bianjiadayuan deposit. However, the metallogenic process and evolution between the diverse porphyry-type Sn
Cu
Mo mineralization and vein-type Ag-Pb-Zn mineralization remain an enigma. Recently, the techniques of secondary ion mass spectrometry (SIMS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have been widely used to determine the in situ S isotope and trace elements in pyrite, which provide clues for the source of sulfur and ore-forming fluid linked to ore genesis, metallogenic process and geodynamic framework (Lin et al., 2016; Dehnavi et al., 2018; Fielding et al., 2018; Morishita et al., 2018). Pyrite is a ubiquitous sulfide mineral that exists in all stages through the porphyry-type and vein-type ores, which makes it possible to elucidate the ore genesis,

character of pyrite and metallogenic process of the Bianjiadayuan deposit. In this contribution, we present results from integrated in situ analyses of trace elements and sulfur isotopes of pyrite from the Bianjiadayuan porphyry-type Sn-Cu-Mo ores and polymetallic (AgPb-Zn) veins by using LA-ICP-MS and SIMS techniques. Integrated with detailed field investigation and mineralogical studies, we attempt to constrain the genesis of the Sn-Cu-Mo-Pb-Zn-Ag mineralization. 2. Regional and ore deposit geology 2.1. Regional geology The Great Xing’an Range (GXAR) lies in the eastern segment of the Central Asian Orogenic Belt (CAOB). The CAOB is bound to the west by the East European Craton, to the north by the Siberian Craton and to the south by the Tarim, North China and Karakum Cratons (Fig. 1a). The CAOB is considered as one of the largest Phanerozoic accretionary orogens on Earth and is a collage of oceanic plateaus, island arcs, oceanic islands and micro-continents (Xiao et al., 2010; Kröner et al., 2014; Klemd et al., 2015; Safonova, 2017; Cai et al., 2018; Li et al., 2018; Yuan et al., 2018). The eastern part of the CAOB is termed as the Xing’aneMongolia orogenic belt (XMOB) that extends across Inner Mongolia and Northeast China (Xu et al., 2015). The SGXR is a wedge-shape zone partitioned by the Xar Moron fault in the south with North China Craton, Erlianhot-Hegenshan fault in the northwest with Erguna-Xing’an block, and Nenjiang fault in the northeast with Songliao basin (Fig. 1b; Liu et al., 2017). The Xilinhot massif known as the oldest formation in this region is a Paleozoic metamorphic complex exposes biotite-plagioclase gneiss, plagioclase-amphibole gneiss, plagioclase-amphibole schist and leptynite. Remnants of Ordovician, Silurian, Devonian, and Carboniferous detrital metasedimentary units and volcanic formations are locally distributed in this area. Permian volcano-sedimentary formations are extensively distributed, extending further the northeast, and constituting the host rocks for most of the ore deposits (Qin et al., 2001; Shu et al., 2013; Zhai et al., 2014). The domain rock types are carbonaceous clastic rocks, carbonate rocks, and mafic to intermediate volcanic rocks. Phanerozoic magmatic intrusions occur along a NE-trending belt throughout the SGXR. The Mesozoic granitic plutons, especially in the Yanshanian, consist of granodiorite, monzogranite, and syenogranite with ages range from 150 Ma to 131 Ma (Ouyang et al., 2015; Pei et al., 2018). Late Paleozoic granitoids including diorite, tonalite and granodiorite mainly expose on the western slope of the SGXR, with ages in the range of 321 Ma to 237 Ma (Wu et al., 2011). NE- and EW-trending faults dominate this area and control the distributions of JurassiceCretaceous intrusions and polymetallic deposits (Fig. 1c). Most of the polymetallic vein-, porphyry-, and skarn-type deposits are dominantly hosted by Permian volcanicesedimentary rocks, Mesozoic strata and plutons (Fig. 1c). Previous geochronological data show that these deposits mainly formed during Early Cretaceous (120e155 Ma; Ouyang et al., 2015; Wang et al., 2017) and are coeval with the granitic magmatism (Chen et al., 2016). 2.2. Ore deposit geology The exposed strata in the Bianjiadayuan PbeZn polymetallic deposit (N43 3100100 eN43 320 01, E118 020 5700 eE118 040 2700 ) (Fig. 1c) are dominantly represented by the Middle Permian Zhesi Formation consisting of argillaceous slate, silty slate and

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

3

Figure 1. (a) Schematic map of the Central Asian Orogenic Belt (modified after Ouyang et al., 2015), showing the location of northeastern China. (b) Simplified tectonic division of northeastern China, showing the location of the Southern Great Xing’an Range (modified after Wu et al., 2011). (c) Geologic map of the Southern Great Xing’an Range, showing the distribution of different types of ore deposits in Late Mesozoic (after Pei et al., 2017).

metamorphic sandstone (Fig. 2a). The NW-trending faults dominate the ore district, among which F1 cuts through the gabbro pluton, Permian slate and quartz porphyry dikes, serving as the major ore-controlling structure with a length over 1000 m and width of 0.4e1.8 m (Fig. 2a). The intrusive rocks in the Zhesi Formation include quartz porphyry, gabbro, and various types of dikes. Two major magmatic episodes are identified: 141e140 Ma and 133e130 Ma (Wang et al., 2013, 2014b; Zhai et al., 2017). Wang et al. (2014b) obtained emplacement age of 140
1.2 Ma from a quartz porphyry which is characterized by high K calcalkalic and strongly peraluminous features with A-type affinity, and can be correlated to extension after the subduction of the

Paleo-Pacific Plate. Zhai et al. (2017) reported LA-ICP-MS zircon UePb ages of quartz porphyry as 140.8
0.9 Ma and 140.2
0.6 Ma. Wang et al. (2013) reported Uranium-lead ages on zircons from gabbro and diorite as 133
0.86 Ma, 130
0.75 Ma, respectively. The molybdenite ReeOs age of 140.0
1.7 Ma from the porphyry-type mineralized veins and veinlet ore is comparable with the emplacement age of quartz porphyry, as constrained from sericite 40Ar/39Ar age of 138.7
1.0 Ma from the vein-type Pb-Zn-Ag mineralization. Although this age is slightly younger, it is broadly consistent with the timing of emplacement of the porphyry and related Sn-CuMo mineralization (Zhai et al., 2017).

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

4

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

Figure 2. (a) Simplified geological map of the Bianjiadayuan deposit (after Zhai et al., 2018a). (b) and (c) Representative cross-sections of the Bianjiadayuan deposit.

The vein-type Ag-Pb-Zn mineralization (91,669 tonnes @ 1.98% Pb, 92,061 tonnes @ 1.98% Zn, 66.35 tonnes @ 157.4 g/t Ag) occurs several hundred meters to the east of the porphyry Sn
Cu
Mo mineralized zones, and is mainly hosted by the Permian sandy slates. The buried Ag-Pb-Zn ore bodies are 0.82e28.75 m thick and occurs 44e467 m below the surface (Fig. 2c). Ore minerals include

galena, sphalerite, pyrite, chalcopyrite, pyrrhotite and arsenopyrite (Figs. 3 and 4), and Ag-bearing minerals are mainly antimonite, freibergite and pyrargyrite (Wang et al., 2014c). Hydrothermal alterations are characterized by sericitization, chloritization, epidotization, kaolinization and carbonatation. Porphyry-type Sn
Cu
Mo mineralization (8936 tonnes @ 0.35% Sn, 724

Figure 3. Mineral paragenetic sequence of the Bianjiadayuan deposit.

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

5

Figure 4. Hand specimen photographs of representative samples from the Bianjiadayuan deposit. (a) Stage I: Quartz-pyrite vein, pyrite occurs as oriented linear clusters among quartz vein. (b) Stage I: Pyrite veinlets developed within altered quartz porphyry. (c) Stage II: Cassiterite occurs as black, stout prismatic aggregation. (d) Stage II: Quartzmolybdenite-pyrite vein cuts through quartz veins of stage I. (e) Stage II: Quartz-chalcopyrite-arsenopyrite-pyrite vein. (f) Stage III: Quartz-chalcopyrite-arsenopyrite-sphaleritepyrite vein. (g) Stage IV: Sphalerite-galena vein occurs within slate of the Zhesi Formation. (h) Stage IV: Quartz-sphalerite-galena-pyrrhotite-pyrite vein. (i) Stage V: Quartzcalcite-fluorite veins. Mineral abbreviations: Py, pyrite; Qz, quartz; Ccp, chalcopyrite; Cst, cassiterite; Mo, molybdenite; Apy, arsenopyrite; Sp, sphalerite; Gn, galena; Po, pyrrhotite; Cal, calcite; Fl, fluorite.

tonnes @ 1.187% Cu, 551 tonnes @ 0.109% Mo, 505 tonnes @ 1.98% Pb, 805 tonnes @ 1.48% Zn) occurs within the quartz porphyry massif (Fig. 2b). The sulfide minerals are mainly cassiterite and stannite, with lesser amounts of pyrite, molybdenite, chalcopyrite, arsenopyrite, galena, and sphalerite (Fig. 4cef). The Sn
Cu
Mo orebodies mainly occur as veins, stockworks and veinlets cutting the quartz porphyry (Fig. 2b). Breccia-type Ag-Pb-Zn mineralization is also discovered above the porphyry pluton and the breccias mainly consist of fragments of slate and quartz porphyry, which are cemented by fine-grained rock fragments and sulfides. Sulfide minerals are dominantly pyrite, sphalerite, galena and minor chalcopyrite (Fig. 5f). The porphyry-type mineralization is characterized by phyllic, potassic, propylitic and argillic alterations, among which phyllic alteration is the most widespread and comprises quartz, sericite and pyrite. Sericite partially replaces plagioclase, and fine-grained sericite and quartz occur in the groundmass (Fig. 5a). Based on mineral paragenetic sequence and cross-cutting relationships (Figs. 3 and 4), five stages of mineralization can be distinguished from early to late: (i) the early stage (stage I) is characterized by milky barren quartz and weak mineralization, which is characterized by pyrite developed on the inner margin of quartz veins or occurring as veinlet extending along strike within

cracks or disseminations in the altered rock (Figs. 4a,b and 5b); (ii) porphyry mineralization stage (stage II) is defined by the quartzpolymetallic sulfide veins which predominantly include cassiterite, molybdenite, chalcopyrite, arsenopyrite and minor galena, sphalerite and pyrite, which are hosted in quartz-sericiteealtered quartz porphyry in the western part of ore deposit. The cassiterite occurs as irregular granular aggregate (Fig. 4c), and flaky molybdenite coexists with pyrite cutting through quartz veins of stage I (Fig. 4d). Arsenopyrite growing around pyrite and chalcopyrite indicates that pyrite and chalcopyrite is earlier than arsenopyrite, and the chalcopyrite is overprinted by minor sphalerite (Figs. 4e and 5c); (iii) transition mineralization stage (stage III) is dominated by chalcopyrite, sphalerite, galena, and pyrite, chalcopyrite commonly develops in sphalerite as exsolution lamellae (Fig. 4f); (iv) vein-type Ag-Pb-Zn stage (stage IV) is characterized by the occurrence of abundant base-metal sulfides (sphalerite, galena, pyrrhotite, and silver-bearing sulfosalts like freibergite, pyrargyrite, and boulangerite), few chalcopyrite and pyrite which mainly occur as veins within slate in the eastern part of ore deposit (Fig. 4g,h). Most sulfide-bearing veins contain intergrowths of galena, sphalerite, chalcopyrite, and pyrrhotite, silver-bearing sulfosalts which commonly coexist with galena. The silver-rich ores have Ag grades up to 3000 g/t; and (v) the late stage (stage V) is characterized by

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

6

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

Figure 5. Photomicrographs of mineralization features in the Bianjiadayuan deposit. (a) Pyrite-sericite-quartz alteration in quartz porphyry, sericite partially replaces plagioclase, and fine-grained sericite and quartz occur in the groundmass. (b) Pyrite disseminated within quartz porphyry is medium-grained with euhedral shape (stage I). (c) Abundant chalcopyrite and arsenopyrite coexist with less pyrite and sphalerite (stage II). (d) Pyrite occur as fine grain with subhedral or irregular shape, chalcopyrite shows directional exsolution texture in sphalerite (stage III). (e) Sphalerite intergrowths with chalcopyrite, pyrrhotite, arsenopyrite and pyrite (stage IV). (f) Mineralization of pyrite, sphalerite, galena, and minor chalcopyrite in the groundmass of breccia-type ores.

the assemblage of barren quartz, calcite and fluorite which form veins and veinlets; the quartz and calcite are generally subhedral to anhedral (Fig. 4i).

Samples were collected from both underground mine workings and drill cores in the Bianjiadayuan ore district. Twenty samples were chosen for transmitted and reflected microscopy, among which four representative samples from the different stages were selected for trace element analysis and sulfur isotopic analysis. Other sulphide samples for sulfur isotopic analysis were collected from the pyriteemolybdeniteequartz veins and chalcopyriteearsenopyriteesphaleriteegalenaequartz veins of porphyry mineralization stage.

of Western Australia (UWA), following the procedures defined by LaFlamme et al. (2016). A gold coat of w30 nm thickness was applied on the sample surface and a normal-incidence electron gun was used for charge compensation. A primary 133Cs þ ion beam with an intensity of 2.5 nA in Gaussian mode and a total impact energy of 10 kV was focused to approximately 25 mm in diameter at the surface of the sample. The mass resolving power was set at w2500 to avoid isobaric interference. 32S, 33S and 34S were collected simultaneously by the multicollection system. The total analysis time for one spot was about 4 min. The pyrite standard (Sierra) is analyzed once every five to eight analyses, which is mounted as 0.5 mm wide fragments of pyrite from the 2 cm3 cube for SIMS analysis. The internal precision achieved under these conditions was better than 0.05& for 33S/32S and 0.03& for 34S/32S (1s). External precision of 33S/32S and 34S/32S determined from the Sierra standard for the analytical sessions were better than 0.09& and 0.14& (1s; n ¼ 24 and 31 for two sessions), respectively. The data define a significant regression with a gradient very close to the theoretical gradient of 0.515 (Fig. 6b), supporting a massdependent behavior (Hulston and Thode, 1965). Chalcopyrite, arsenopyrite, sphalerite and molybdenite were separated from the porphyry ores and handpicked to achieve a purity of >99% under the binocular microscope, followed by cleaning in doubly distilled water. Sulfur isotopic analysis was obtained on a Delta V Plus stable mass spectrometer at the Analytical Laboratory of the Beijing Research Institute of Uranium Geology. Each sample was mixed with Cu2O in definite proportions, and reacted at a temperature of 980  C under vacuum condition. SO2 was collected by freezing method for sulfur isotope analysis after purification. The results are reported with respect to the standard of Vienna Canon Diablo Troilite (V-CDT) and analytical precision is
0.2&.

4.2. Sulfur isotopic analyses

4.3. In-situ LA-ICP-MS trace element analyses

In situ sulfur isotopic analyses were conducted with a CAMECA IMS1280 large-geometry ion microprobe (SIMS) at the Centre for Microscopy, Characterisation and Analysis (CMCA), The University

Laser based analyses were carried out at GeoHistory Facility, John de Laeter Centre, Curtin University in Western Australia. The methodology followed those described in detail by Wang et al.

3. Pyrite types and textures In the Bianjiadayuan polymetallic deposit, four types of pyrite are distinguished from stage I to stage IV. (i) Py1 from the early stage I is medium-grained pyrite (100e800 mm) with euhedral to subhedral morphology and occurs as isolated or granular aggregates (Fig. 5b); (ii) Py2 from the porphyry mineralization stage II is mainly as medium- to fine-grained (40e200 mm) and intergrown with chalcopyrite, arsenopyrite and minor sphalerite (Fig. 5c); (iii) Py3 from the transition stage III is fine-grained, subhedral to irregular and displays cataclastic textures with micro-fractures; (iv) Py4 from the vein-type Ag-Pb-Zn mineralization stage IV forms irregularly shaped aggregates with cataclastic texture and marginal corrosion texture (Fig. 5e), ranging in size of 40e200 mm. 4. Sampling and analytical techniques 4.1. Samples

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

7

Figure 6. (a) Diagram showing the sulfur isotope (d34S and D33S) as determined by in situ analysis with an ion microprobe in different types of pyrite. (b) Plot of d34S versus d33S for the Bianjiadayuan deposit.

(2017). The analyses utilize a resonetics S-155-LR 193 nm excimer laser ablation system coupled to an Agilent 7700x quadrupole ICPMS. Analytical time for each sample consists of 30 s of background analysis and 45 s period of isotopic analysis. The laser instrument operated with 50e75 mm beam, 16e2.5 J/cm2 laser fluence and 7 Hz laser repetition rate. International glass standard GSD-1G was used as the primary reference material for the calculation of elemental concentrations, using stoichiometric 57Fe as the internal standard element, and to correct for instrument drift. Standard blocks were run every 10 unknowns. The analyzed

elements include Ga, Ge, Ag, As, Se, Au, Cd, Gd, Bi, Co, Cr, Cu, Mn, Mo, Ni, Pb, Te, Sn, Sb, In, Ti, V, W, Zn. 5. Results 5.1. Trace element characteristics of pyrite A total of 34 LA-ICP-MS trace element analyses were performed on the four pyrite types (Py1ePy4) from the Bianjiadayuan deposit and the results are shown in Table 1.

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

8

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

Table 1 Sulfur isotopic data (&) for pyrite from the Bianjiadayuan deposit. Spot No. Py1 BJDY-23@1 BJDY-23@2 BJDY-23@3 BJDY-23@4 BJDY-23@5 BJDY-23@6 BJDY-23@7 BJDY-23@8 Py2 BJDY-17@1 BJDY-17@2 BJDY-17@3 BJDY-17@4 BJDY-17@5 BJDY-17@6 BJDY-17@7 BJDY-17@8 BJDY-17@9 BJDY-17@10 BJDY-17@11 Py3 BJDY-18@1 BJDY-18@2 BJDY-18@3 BJDY-18@4 BJDY-18@5 BJDY-18@6 BJDY-18@7 BJDY-18@8 BJDY-18@9 BJDY18@10 BJDY18@11 BJDY18@12 BJDY18@13 Py4 BJDY-5@1 BJDY-5@2 BJDY-5@3 BJDY-5@4 BJDY-5@5 BJDY-5@6 BJDY-5@7 BJDY-5@8 BJDY-5@9 BJDY-5@10 BJDY-5@11 BJDY-5@12 BJDY-5@13 BJDY-5@14 BJDY-5@15

d33S

2s

d34S

2s

D33S

2s

0.78 0.54 0.62 0.50 0.64 0.80 0.54 0.25

0.11 0.14 0.11 0.11 0.11 0.12 0.15 0.14

1.47 1.16 1.22 1.06 1.40 1.61 0.96 0.42

0.14 0.14 0.14 0.14 0.14 0.14 0.24 0.24

0.02 0.06 0.00 0.05 0.07 0.03 0.05 0.07

0.12 0.14 0.12 0.12 0.12 0.13 0.13 0.12

0.39 0.02 0.60 0.19 0.43 0.47 0.24 0.29 0.44 0.18 0.28

0.11 0.11 0.12 0.11 0.11 0.11 0.15 0.15 0.14 0.14 0.15

0.71 0.08 1.23 0.40 0.77 0.82 0.61 0.58 0.81 0.27 0.69

0.14 0.14 0.14 0.14 0.15 0.15 0.24 0.24 0.24 0.24 0.24

0.02 0.06 0.03 0.01 0.03 0.05 0.07 0.00 0.02 0.04 0.08

0.12 0.12 0.13 0.13 0.12 0.12 0.12 0.13 0.12 0.12 0.13

1.47 1.23 0.58 0.53 0.48 0.41 0.12 0.19 0.55 0.19 0.47 0.18 0.08

0.14 0.17 0.12 0.11 0.11 0.11 0.11 0.11 0.16 0.15 0.16 0.15 0.15

2.74 2.41 1.26 1.14 1.07 0.85 0.38 0.50 1.20 0.32 0.91 0.36 0.22

0.23 0.23 0.15 0.14 0.14 0.15 0.14 0.14 0.25 0.25 0.25 0.24 0.24

0.06 0.01 0.06 0.06 0.07 0.03 0.08 0.06 0.07 0.02 0.00 0.00 0.03

0.15 0.18 0.13 0.12 0.12 0.13 0.12 0.12 0.15 0.13 0.24 0.23 0.23

1.31 1.57 1.70 1.49 1.54 1.58 1.62 1.70 1.68 1.48 1.92 1.84 1.52 1.84 1.55

0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.14 0.15 0.15 0.14 0.14 0.15 0.15 0.15

2.51 2.85 3.08 2.88 2.92 2.86 3.11 3.19 3.11 2.85 3.72 3.40 2.82 3.47 3.07

0.24 0.24 0.24 0.24 0.24 0.24 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.24

0.01 0.10 0.12 0.01 0.04 0.11 0.02 0.06 0.08 0.01 0.01 0.10 0.07 0.05 0.03

0.17 0.17 0.16 0.16 0.16 0.16 0.16 0.15 0.16 0.16 0.15 0.16 0.16 0.16 0.17

the positive correlation can also be observed between Ag and Sb, Cd and Zn, Co and Ni (Fig. 8). Concentrations of In (0.0023e19.2 ppm), Sn (0.33e6690 ppm), Sb (14e1900 ppm) in Py4 are higher than those in other three pyrite types. Py2 has the highest contents of Co (3.2e204 ppm), Ni (1.2e184 ppm), As (7.46e6360 ppm), Au (0.41e14 ppm) and Bi (16.1e322 ppm) among all pyrite types (Table 1). The Co/Ni ratios decrease from Py1 to Py4, with values of 1.327e10.798 (average 4.690), 1.159e3.288 (average 2.291), 0.111e1.849 (average 0.723), 0.031e0.866 (average 0.354), respectively. Concentrations of Ti, Ge and Cr are near constant in all pyrite types with an average of 12.71 ppm, 0.20 ppm, 6.29 ppm, respectively. Contents of Mn, Mo, Te, Gd and W in most pyrite samples are below detection limits, although some individual elements have concentrations as high as hundreds of ppm (Table 1). 5.2. Sulfur isotope results In situ sulfur isotopes were measured on 47 spots from the four pyrite types from the Bianjiadayuan deposit and the results are presented in Table 2. The d33S values display a narrow range from e0.60& to 1.92& with corresponding d34S values between e1.23& and 3.72&. The d33S values for Py1 from the early stage range from 0.25& to 0.80& (mean 0.58&) with corresponding d34S values between 0.42& and 1.61& (mean 1.16&). Py2 has d33S values ranging from e0.60& to 0.47& (mean 0.18&) and d34S values between e1.23& and 0.82& (mean 0.35&). The d33S values for Py3 range from e1.23& to 0.82& (mean 0.47&) with corresponding d34S values between e0.36& and 2.47& (mean 0.97&). Py4 from the vein-type Ag-Pb-Zn mineralization stage shows d33S ranging from e0.46& to 1.92& and d34S values between e0.86& and 3.73& (Table 2, Fig. 10). The observation of d34S coupled with tiny variation of slightly negative D33S, together with the observed isotopic gradient from Py1 to Py4 indicate a probable influence of changes in pH, H2S:SO4, or sulfur disproportionation during the evolution of ore-forming fluid (Fig. 6a; Ohmoto, 1986). Sulfur isotopic data on seven arsenopyrite, molybdenite, sphalerite, chalcopyrite samples from the porphyry mineralization stage (stage II) are listed in Supplementary Table 1. The sulfide minerals have d34SCDT values ranging from e0.4& to 4.8&, with a mean of 2.07& (Supplementary Table 1). The d34S values obtained from arsenopyrite and molybdenite range from 1.7& to 4.8& (mean 3.33&) and e0.4& to e0.1& (mean e0.25&), respectively. The chalcopyrite and sphalerite have d34S values of 1.5& and 4.4&, respectively (Supplementary Table 1). 6. Discussion

Representative time-resolved depth profiles for pyrites are illustrated in Fig. 7. The time resolved depth profiles for Co, Ni and As are similar to that of Fe. Measured values for Pb vary from different samples, of which the time-resolved depth profile for sample Py1 (Fig. 7a) and Py2 (Fig. 7b) is relatively smooth, nevertheless, obvious spikes of Pb occur in Py3 (Fig. 7c) and Py4 (Fig. 7d). All pyrites contain measurable quantities of Ag, and the trend for Ag is parallel to Pb and Sb in Py4. Spikes of Cu and Zn occur in the timeresolved depth profiles (Fig. 7). Arsenic is the most abundant trace element with concentrations ranging from 0.3 ppm to 6360 ppm, spanning four orders of magnitude, and shows positive correlation with Se (Fig. 8a). From Py1, Py2, Py3 to Py4, the Cu, Zn, Ag, Cd contents increase gradually (Fig. 9), and among these, the concentrations in Py4 are one order of magnitude higher than those in the other three pyrite types with contents up to 1470 ppm, 790 ppm, 1120 ppm, 5.8 ppm, respectively. Cu shows good correlation with Ag, Pb and Zn, furthermore,

6.1. Trace elements in pyrite It is generally recognized that siderophile and chalcophile elements comprising Co, Ni, Se, Te and As enter the lattice of pyrite via isomorphism (Tribovillard et al., 2006; Zhang et al., 2014a,b). Nickel and Co are readily incorporated into the pyrite lattice via isomorphous replacement of Fe, and is not released during recrystallization of hydrothermal pyrite, whereas Se and Te enter the lattice of pyrite by replacing S (Large et al., 2009; Koglin et al., 2010). Lead can hardly enter the lattice of pyrite crystal because of the large ionic size, and Pb-bearing sulfide has a faster precipitation rate than pyrite which leads to the formation of galena inclusions in pyrite (Morse and Luther, 1999). The dominant metallogenetic elements in the Bianjiadayuan deposit are Pb, Ag, Zn, Cu and Sn. The time resolved depth profiles of different pyrite types show consistent distributions of Co, Ni, As, Se and Fe, suggesting that these elements entered the lattice of pyrite via isomorphism, which is reflected by their concentrations

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

9

Figure 7. Representative time-resolved depth profiles for pyrite analyzed in this study, showing the occurrences of major metal elements. Fe exhibits a relatively flat distribution which is the typical feature of homogeneous pyrite. The elements Pb, Zn, Cu, Ag and Sn show spikes in the profiles.

and relationship (Fig. 8g,h). The Cu and Pb also show positive correlation (Fig. 8d), and the signal of Cu and Pb in time-resolved depth profiles of Py1 and Py2 is relatively smooth with a spiky signal in Py3 and Py4, indicating that Pb and Cu incorporate pyrite mainly as solid solution in Py1 and Py2, whereas they occur as inclusions of galena and chalcopyrite in Py3 and Py4 (Fig. 7c,d). The positive correlations between Ag and Cu, Ag and Sb (Fig. 8a,b) indicate that most Ag occurs as solid solution or inclusion of Sb-compounds (e.g. argyrythrose, matildite) in galena, in addition to native Ag, which is consistent with petrographic observations and electron microprobe analysis (Wang et al., 2014c). The weak positive correlation between Cu and Zn (Fig. 8c) and consistent time resolved depth profiles suggest that they are distribute as invisible or visible chalcopyrite or sphalerite inclusions especially in Py3 and Py4. Sn can enter the lattice or occurs as oxide inclusion in pyrite, in combination of positive correlation between Sn and In, indicating similar occurrence of Sn and In. 6.2. Origin of pyrite Trace element chemistry (especially Co/Ni ratio) and sulfur isotopic composition of pyrite are widely used to characterize the origin of pyrite and elucidate the genesis of hydrothermal ore deposits (Bajwah et al., 1987; Li et al., 2014; Reich et al., 2016). The Co/ Ni ratio of lower than 1 (average 0.63) is generally recognized to characterize syn-sedimentary pyrite (Price, 1972; Clark et al., 2004). In contrast, Co/Ni ratio of higher than one indicates that the pyrite is of hydrothermal origin, especially when the values are between 1 and 5. Nevertheless, geological evidence should also be considered such as mineralogical characteristics and genetic type of ore deposit when evaluating the origin of pyrite by Co/Ni ratios, as

hydrothermal pyrites also have low Co/Ni ratios of lower than 1 (Bralia et al., 1979). The Co/Ni ratios of Py1 and Py2 in our study range in 1.33e10.80 (average 4.70) and 1.16e3.29 (average 2.29), suggesting typical hydrothermal affinity. The maximum value of Co/Ni ratios in Py3 is 1.85 which is also attributed to hydrothermal origin. Although four spots of Py3 (Co/Ni ¼ 0.111e0.915, average 0.441) and eleven spots of Py4 (Co/Ni ¼ 0.031e0.866, average 0.354) show values below 1, the d34S values of Py3 and Py4 display a narrow range from e0.36& to 3.72& with an average of 2.09&, indicating the possibility of magmatic hydrothermal activity and later modification by fluidrock reaction. The Ni content of pyrite can provide useful information regarding the pyrite-precipitating fluid, and is mainly determined by the primary composition and modified via wall rock/fluid interaction (Zhao et al., 2011). Ultramafic and mafic rocks are strongly enriched in Ni (2200
500 ppm, Palme and Jones, 2003), whereas felsic rocks usually contain low Ni concentrations (19e60 ppm, Rudnick and Gao, 2003). In the Bianjiadayuan deposit, the highest Ni concentrations of pyrite is 184 ppm in Py2 and those in the other three pyrite types show an average of 3.73 ppm which is consistent with those of quartz porphyry (Ni ¼ 1.96e2.08 ppm, Wang et al., 2014b), indicating a felsic provenance of the pyrite. Moreover, the good correlations between Cu and Ag, Pb, Zn, in combination with the porphyry Sn
Cu
Mo mineralization in the Bianjiadayuan deposit, suggest that the Py3 and Py4 associated with the PbeZn mineralization have common magmatic origin  et al., 2014). The d34S values of pyrite with the Py1 and Py2 (Cioaca from the Bianjiadayuan deposit display a narrow range (e1.23& to 3.72&), indicating a homogeneous sulfur source, most likely magmatic (0
5&; Ohmoto, 1972; Rye and Ohmoto, 1974). In conclusion, the pyrites from the Bianjiadayuan deposit are mainly

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

10

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

Figure 8. Binary plots of (a) Cu vs. Ag, (b) Sb vs. Ag, (c) Cu vs. Zn, (d) Pb vs. Cu, (e) Cd vs. Zn, (f) Sn vs. In, (f) Se vs. As and (g) Co vs. Ni in different pyrite types. The trace element concentrations are from Table 1, and all measurements below minimum detection limit are discarded.

of hydrothermal origin from a magmatic source, and the trace elements of Py3 and Py4 were slightly modified by reaction with wall rock during the migration of ore-forming fluid. 6.3. Implication for ore-forming process Geochemical behavior of trace elements in magmatic and hydrothermal systems is controlled by the physico-chemical properties of fluids (Maslennikov et al., 2009). Trace element composition of pyrite varies systematically in response to changes of

physicochemical parameters of the parental fluid (WohlgemuthUeberwasser et al., 2015). Trace element composition vary among different pyrite types influenced by fluid-rock interactions, or changes in temperature of the ore fluids (Deditius et al., 2014). The temperature-sensitive elements such as Co, Ni, Se, Te, and Bi are commonly enriched in sulfides that precipitate under high temperature conditions. In the Bianjiadayuan deposit, contents of Co, Ni, Se, Te, and Bi in Py2 are the highest among all pyrite types, indicating high temperature conditions for the porphyry mineralization, as is also supported by the occurrence of molybdenite and

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

11

Figure 9. Diagrams showing the mean concentrations of analyzed trace elements in different types of pyrite.

chalcopyrite (Fig. 9). However, these elements are depleted in Py3 and Py4, implying their formation from the residual fluid phase under relatively low temperatures. The contents of Cu, Zn, Ag and Cd increase from Py1 to Py4 and show similar distribution with other porphyry deposits (Franchini et al., 2015; Jin et al., 2015). Trace elements behave differently under different conditions; for example, Zn and Pb remain in dissolved state at lower temperatures than Mo when forming chloride complexes (Hemley, 1992). Substantial trace element dissolution occurs in fluids during the porphyry mineralization stage at medium to high temperature, with sharply reduced concentrations when the temperature decreases (Kostova et al., 2004), resulting in enrichment of trace elements such as Cu, Zn, Ag, and Cd with the precipitation of pyrite at relatively low temperature (Maslennikov et al., 2009). Moreover, mechanisms like watererock reaction, mixing with meteoric water and reduction of coordination agent concentration lead to metal activation, migration, and precipitation (Tagirov and Seward, 2010). Hence, the enrichment of certain trace elements (Cu, Zn, Ag, Cd) in pyrite from the vein-type mineralization stage is probably related to the cooling and mixing of oreforming fluid with meteoric water. Ruan et al. (2015) based on thermometric and H-O isotope investigations of fluid inclusions in quartz from the Bianjiadayuan deposit, proposed that the fluid was derived dominantly by magmatic hydrothermal activity, with addition of meteoric water in the late stage. The d34S values display a gradual increase from Py2 to Py4. We postulate that the fractionation of S isotopes between pyrite and paragenetic minerals reached equilibrium. Other factors may have controlled the S isotope signatures, such as changes in the physicochemical conditions (e.g. T, pH, fO2 and fS), or mixing of multiple S reservoirs (Ohmoto, 1972; Hoefs, 2004). Previous studies suggested that physical and chemical conditions can cause large variations in S isotopes (Hoefs, 2015). Sulfate and some evaporates in the

Permian rocks have higher d34S values (more than 10&, Wang et al., 2001). From porphyry mineralization to vein-type mineralization stages, the ore forming fluid experienced long-distance transportation which experienced wall rock interaction and incorporation of meteoric water in the late stage. Furthermore, SO2 is 4 detected in fluid inclusions in vein-type mineralization, which might reflect the increase of d34S values of pyrite (Ruan et al., 2015). The shift to more positive d34S values from Py2 to Py4 may reflect the changes of pH, temperature, sulfur fugacity and oxygen fugacity during chemical reactions between the magmatic fluid and the wall rock along the fracture, and/or progressive mixing with meteoric water (Ward et al., 2017). Thus, the fluid-rock interactions, changes in temperature and mixing with meteoric water of ore-forming fluid are inferred to have caused the variation of trace element compositions and d34S values of pyrite in different stages. 6.4. Implication for ore genesis Stable isotopes, such as sulfur, hydrogen, oxygen and carbon, have been successfully applied to trace the sources of sulfur and ore-forming fluid in porphyry related ore systems (Du et al., 2017; Chen et al., 2018; Liu et al., 2018). The narrow range of sulfur isotope compositions (e1.23& to 4.8&) of sulfides from the Bianjiadayuan deposit is comparable with typical porphyry deposits around the world (Ohmoto, 1979), implying a relatively homogeneous magmatic sulfur source. In addition, consistent d34S values in the sulfide minerals of both porphyry and vein type mineralization suggest similar sulfur source. Studies on carbon, hydrogen and oxygen isotopic compositions, and micro-thermometry of fluid inclusions from the vein-type Ag-Pb-Zn mineralization in the eastern part of Bianjiadayuan deposit have revealed that the oreforming fluid evolved with changes in the physico-chemical conditions with successive precipitation of Pb, Zn and Ag. The ore fluid

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

12

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

Table 2 Sulfur isotopic compositions of sulfides from the Bianjiadayuan deposit. Deposit

Minerals

d34S (&)

References

Porphyry mineralization

Ccp Apy Apy Sp Apy Mo Mo Apy Apy Sp Sp Sp Sp Sp Po Po Ccp Gn Gn Gn Gn Gn Gn Py Po Gn Po Gn Sp Po Gn Po Gn Sp Py Sp Sp Ccp Gn Po Sp Gn Gn Po Ccp Po Py Gn Mrc Ccp Gn Sp Sp Gn Gn Mrc Gn Sp Po Sp

1.5 2.6 4.8 4.4 1.7 0.4 0.1 4.3 2.4 3.2 1.6 2.3 2.6 4.4 2.2 1.7 1.9 1.1 1.6 1.5 1.2 0.7 0.6 1.7 1.6 0.6 1.9 0.9 2.4 2.0 0.7 2.0 0.7 2.5 2.2 2.5 2.6 2.7 0.6 2.1 2.5 0.9 0.7 1.2 0.9 1.0 1.9 0.7 2.2 1.7 1.2 2.4 0.1 0.9 0.8 2.1 1.3 2.6 2.3 2.7

This study

Vein-type mineralization

Vein-type mineralization

Vein-type mineralization

Wang et al. (2014a)

Figure 10. Sulfur isotopic composition of sulfide mineral in Bianjiadayuan deposit (other d34S value of sulfide are from Wang et al., 2014a; Zhai et al., 2018a).

Zhou et al. (2018)

Zhou et al. (2018)

Abbreviations: Ccpechalcopyrite, Gnegalena, Mrcemarcasite, Spesphalerite, Poepyrrhotite, Apyearsenopyrite, Moemolybdenite.

2017). Geochemical characteristics of quartz porphyry suggest a crustal source for the magma (Wang et al., 2014b), as also supplemented by investigations on the source of Sn and Mo (Zhai et al., 2017). The SePb isotope data of sulfide in vein-type Ag-Pb-Zn deposit also indicate the origin of ore forming fluids and metals from a felsic magma (Zhai et al., 2018a). In conclusion, we correlate the magmaticehydrothermal mineralization in the Bianjiadayuan deposit with the quartz porphyries, which also compare with the typical features of porphyry systems around the world (Calagari, 2003; Sillitoe, 2010). 6.5. Implication for exploration

Pyepyrite,

was dominantly magmatic hydrothermal, with involvement of meteoric water in the late stage (Ruan et al., 2015). Magmatic activity in the Bianjiadayuan deposit was episodic during the Early Cretaceous and occurred during periods: 141e140 Ma and 133e130 Ma (Wang et al., 2013, 2014b; Zhai et al., 2017). The emplacement ages of 140.8
0.9 Ma and 140.2
0.6 Ma from the older quartz porphyries are contemporary with the ReeOs ages of 140.0
1.7 Ma of molybdenum mineralization (Zhai et al.,

The SGXR is one of the most important Pb-Zn-Ag-Sn polymetallic areas in China. In recent years, tin ore prospecting has achieved significant progress in this area, as several new deposits were discovered such as the Weilasituo and Bianjiadayuan tinpolymetallic deposits, Yuanzilin and Huanggang Fe-Sn deposits (Wang et al., 2005). It is widely accepted that Sn and Pb-Zn-Ag mineralization have close temporal-spatial relationship, and belong to the same metallogenic system (Wang et al., 2016). The genesis of tin deposits in this region is correlated to the Yanshanian magmatic event (Ouyang et al., 2015). The tin deposits in the SGXR show Early Cretaceous ages, such as the Huanggang Fe-Sn deposit (134.9
5.2 Ma, Zhai et al., 2012), Anle tin-polymetallic deposit (133
3 Ma, Ishiyama et al., 2001), Weilasituo tin-polymetallic deposit (135
6 Ma and 138
6 Ma, Wang et al., 2017). Notably, molybdenites from the Bianjiadayuan deposit yield ReeOs age of 140.0
1.7 Ma (Zhai et al., 2017), which is coeval with other tin deposit in the SGXR. The vein-type Ag-Pb-Zn mineralization is dated as 138.7
1.0 Ma (Zhai et al., 2017), slightly younger than the porphyry-related tin mineralization, although consistent with the timing of regional tin mineralization (140e135 Ma) in the SGXR. The contents of Sn in Py4 (vein-type mineralization stage) from the Bianjiadayuan deposit range from 0.33 ppm to 6690 ppm, with an average of 1157.87 ppm, which is remarkably higher than those in other deposits around the world, such as Chang’an orogenic gold deposit in Yunnan Province, China (w775 ppm, most of data are under detection, Zhang et al., 2014a,b), Jiaodong gold deposits in China (0.1e13.7 ppm, Mills et al., 2015), El Indio high-sulfidation AueAgeCu deposit in Chile (0.1e4.0 ppm, Tanner et al., 2016), volcanic-hosted Kuh-Pang copper deposit in Iran (w1.02 ppm, Rajabpour et al., 2017), SEDEX type Zn-Pb deposits in Australia (below detection, Mukherjee and Large, 2017), distal vein related Pb-Zn-Ag deposit associated with the world-class Donggou

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

porphyry Mo deposit in Henan Province, China (0.09e6 ppm, Li et al., 2017), Marcona Fe-(Cu) deposit in Perú (w0.07 ppm, Li et al., 2017), Chah Zard epithermal AueAg deposit in Iran (w4 ppm, Kouhestani et al., 2017), and Chalukou porphyry Mo deposit and adjacent vein-type Pb-Zn deposit in Northern Great Xing’an Range (0.76e86.4 ppm, Jin et al., 2015). The remarkably high Sn contents in pyrite from the Bianjiadayuan deposit is attributed to the associated Sn mineralization. Thus, the high content of Sn in pyrite from the hydrothermal Ag-Pb-Zn vein can be used as a pathfinder to prospect for Sn mineralization in the SGXR. 7. Conclusions (1) A five-stage mineralization process is identified from field and petrologic studies including the early porphyry mineralization, main porphyry mineralization, transition mineralization, veintype mineralization and late mineralization stages. Four types of pyrites are identified from the four corresponding stages. (2) Trace element analysis of pyrite shows Cu, Pb, Zn, Ag, Sn, Cd, Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions, whereas Co, Ni, As, Se enter the lattice via isomorphism in all pyrite types. The Cu, Zn, Ag, Cd concentrations gradually increase from Py1 to Py4, probably due to the cooling and mixing of the ore-forming fluid with meteoric water. Contents of Co, Ni, Se, Te, and Bi are the highest in Py2, suggesting that the porphyry mineralization occurred under high temperature conditions. (3) The narrow range of sulfur isotope compositions of sulfides suggests a relatively homogeneous sulfur source. Variations of trace elements and d34S values are probably due to changes on physical and chemical properties of fluids, ore-forming temperatures, migration along the fractures, and mixture of with meteoric water. (4) The high Sn content of pyrite in hydrothermal Pb-Zn-Ag vein may be used as a pathfinder to prospect for potential Sn mineralization in the SGXR. Acknowledgments We thank Associate Editor Dr. Sohini Ganguly and two anonymous referees for helpful comments that improved this paper. This research was financially supported by National Key Research and Development Program of China (2016YFC0600504) and Fundamental Research Funds for the Central Universities (2652017218). We thank Junfeng Pan and Jianlong Guo at the Bureau of Land Resources of Linxi County, Chifeng, China for kind help during the fieldwork. Heejin Jeon, Brad McDonald are thanked for assistance with in situ SIMS S isotopic and in situ LA-ICP-MS trace element analysis. Xin-Kai Hu and Bo-Wei Sun are thanked for help during the sample preparation. Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.gsf.2019.02.004. References Agangi, A., Hofmann, A., Przyby1owicz, W., 2014. Trace element zoning of sulfides and quartz at Sheba and Fairview gold mines: clues to Mesoarchean mineralization in the Barberton Greenstone belt, South Africa. Ore Geology Reviews 56, 94e114. Bajwah, Z.U., Seccombe, P.K., Offler, R., 1987. Trace element distribution, Co: Ni ratios and genesis of the Big Cadia iron-copper deposit, New South Wales, Australia. Mineralium Deposita 22, 292e300.

13

Basril, M.B.I., Gilbert, S., Large, R.R., Zaw, K., 2018. Textures and trace element composition of pyrite from the Bukit Botol volcanic-hosted massive sulphide deposit, Peninsular Malaysia. Journal of Asian Earth Sciences 158, 173e185. Belousov, I., Large, R.R., Meffre, S., Danyushevsky, L.V., Steadman, J., Beardsmore, T., 2016. Pyrite compositions from VHMS and orogenic Au deposits in the Yilgarn Craton, Western Australia: implications for gold and copper exploration. Ore Geology Reviews 79, 474e499. Bralia, A., Sabatini, G., Troja, F., 1979. A revaluation of the Co/Ni ratio in pyrite as geochemical tool in ore genesis problems. Mineralium Deposita 14, 353e374. Cai, K.D., Long, X.P., Chen, H.Y., Sun, M., Xiao, W.J., 2018. Accretionary and collisional orogenesis in the south domain of the western Central Asian Orogenic Belt (CAOB). Journal of Asian Earth Sciences 153, 1e8. Calagari, A.A., 2003. Stable isotope (S, O, H and C) studies of the phyllic and potassicephyllic alteration zones of the porphyry copper deposit at sungun, east Azarbaidjan, Iran. Journal of Asian Earth Sciences 21, 767e780. Cao, H.W., Zhang, S.T., Santosh, M., Zheng, L., Tang, L., Li, D., Zhang, X.H., Zhang, Y.H., 2015. The Luanchuan Mo-W-Pb-Zn-Ag magmatic-hydrothermal system in the East Qinling metallogenic belt, China: constrains on metallogenesis from C-HO-S-Pb isotope compositions and Rb-Sr isochron ages. Journal of Asian Earth Sciences 111, 751e780. Catchpole, H., Kouzmanov, K., Bendezú, A., Ovtcharova, M., Spikings, R., Stein, H., Fontboté, L., 2015a. Timing of porphyry (Cu-Mo) and base metal (Zn-Pb-Ag-Cu) mineralisation in a magmatic-hydrothermal systemdMorococha district, Peru. Mineralium Deposita 50, 895e922. Catchpole, H., Kouzmanov, K., Putlitz, B., Hun Seo, J., Fontboté, L., 2015b. Zoned base metal mineralization in a porphyry system: origin and evolution of mineralizing fluids in the Morococha district, Peru. Economic Geology 110, 39e71. Chen, Y.J., Zhang, C., Wang, P., Pirajno, F., Li, N., 2016. The Mo deposits of northeast China: a powerful indicator of tectonic settings and associated evolutionary trends. Ore Geology Reviews 81, 602e640. Chen, F.C., Deng, J., Wang, Q.F., Li, G.J., Shu, Q.H., Yang, C.H., Liu, J.Y., Xu, R., 2018. The source and evolution of ore fluids in the Heiniuwa gold deposit, Baoshan block, Sanjiang region: constraints from sulfide trace element, fluid inclusion and stable isotope studies. Ore Geology Reviews 95, 725e745. , M.E., Munteanu, M., Qi, L., Costin, G., 2014. Trace element concentrations in Cioaca porphyry copper deposits from Metaliferi Mountains, Romania: a reconnaissance study. Ore Geology Reviews 63, 22e39. Ciobanu, C., Cook, N., Utsunomiya, S., Kogagwa, M., Green, L., Gilbert, S., Wade, B., 2012. Gold-telluride nanoparticles revealed in arsenic-free pyrite. American Mineralogist 97, 1515e1518. Clark, C., Grguric, B., Mumm, A.S., 2004. Genetic implications of pyrite chemistry from the Palaeoproterozoic olary domain and overlying Neoproterozoic Adelaidean sequences, northeastern south Australia. Ore Geology Reviews 25, 237e257. Cook, N.J., Chryssoulis, S.L., 1990. Concentrations of invisible gold in the common sulfides. The Canadian Mineralogist 28, 1e16. Deditius, A.P., Utsunomiya, S., Reich, M., Kesler, S.E., Ewing, R.C., Hough, R., Walshe, J., 2011. Trace metal nanoparticles in pyrite. Ore Geology Reviews 42, 32e46. Deditius, A.P., Reich, M., Kesler, S.E., Utsunomiya, S., Chryssoulis, S.L., Walshe, J., Ewing, R.C., 2014. The coupled geochemistry of Au and as in pyrite from hydrothermal ore deposits. Geochimica et Cosmochimica Acta 140, 644e670. Dehnavi, A.S., Mcfarlane, C.R.M., Lentz, D.R., Walker, J.A., 2018. Assessment of pyrite composition by LA-ICP-MS techniques from massive sulfide deposits of the Bathurst mining camp, Canada: from textural and chemical evolution to its application as a vectoring tool for the exploration of VMS deposits. Ore Geology Reviews 92, 656e671. Du, L.J., Li, B., Huang, Z.L., Zhou, J.X., Zou, G.F., Yan, Z.F., 2017. Carbon-oxygen isotopic geochemistry of the yangla cu skarn deposit, SW China: implications for the source and evolution of hydrothermal fluids. Ore Geology Reviews 88, 809e821. Feng, K., Fan, H.R., Hu, F.F., Yang, K.F., Liu, X., Shangguan, Y.N., Cai, Y.C., Jiang, P., 2017. Involvement of anomalously As-Au-rich fluids in the mineralization of the Heilan’gou gold deposit, Jiaodong, China: evidence from trace element mapping and in-situ sulfur isotope composition. Journal of Asian Earth Sciences 160, 304e321. Fielding, I.O.H., Johnson, S.P., Meffre, S., Zi, J.W., Sheppard, S., Large, R.R., Rasmussen, B., 2018. Linking gold mineralization to regional-scale drivers of mineral systems using in situ UePb geochronology and pyrite LA-ICP-MS. Geoscience Frontiers. https://doi.org/10.1016/j.gsf.2018.06.005. Franchini, M., McFarlane, C., Maydagán, L., Reich, M., Lentz, D.R., Meinert, L., Bouhier, V., 2015. Trace metals in pyrite and marcasite from the Agua Rica porphyry-high sulfidation epithermal deposit, Catamarca, Argentina: textural features and metal zoning at the porphyry to epithermal transition. Ore Geology Reviews 66, 366e387. Gu, Y.C., Chen, R.Y., Jia, B., Song, W.B., Yu, C.T., Ju, N., 2017. Zircon U-Pb dating and geochemistry of the syenogranite from the Bianjiadayuan Pb-Zn-Ag deposit of Inner Mongolia and its tectonic implications. Geology in China 44, 101e117 (in Chinese with English abstract). Hemley, J.J., 1992. Hydrothermal ore-forming processes in the light of studies in rock-buffered systems: I. Fe-Cu-Zn-Pb sulfide solubility relations. Economic Geology 87, 1e22. Hoefs, J., 2004. Variations of Stable Isotope Ratios in Nature[M]//Stable Isotope Geochemistry. Springer Berlin Heidelberg, pp. 93e227. Hoefs, J., 2015. Variations of Stable Isotope Ratios in Nature. Stable Isotope Geochemistry. J. Hoefs. Springer International Publishing, Cham, pp. 191e383.

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

14

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx

Hulston, J.R., Thode, H.G., 1965. Variations in the 33S, 34S, and 36S contents of meteorites and their relation to chemical and nuclear effects. Journal of Geophysical Research 70, 3475e3484. Ingham, E.S., Cook, N.J., Cliff, J., Ciobanu, C., Huddleston, A.L., 2014. A combined chemical, isotopic and microstructural study of pyrite from roll-front uranium deposits, Lake Eyre Basin, South Australia. Geochimica et Cosmochimica Acta 125, 440e465. Ishiyama, D., Sato, R., Mizuta, T., Ishikawa, Y., Wang, J.B., 2001. Characteristic features of tineironecopper mineralization in the Anle-Huanggangliang mining area, Inner Mongolia, China. Resource Geology 51 (4), 377e392. Jin, L.Y., Qin, K.Z., Li, G.M., Li, Z.Z., Song, G.Y., Meng, Z.J., 2015. Trace element distribution in sulfides from the Chalukou porphyry Mo-vein-type Zn-Pb system, northern Great Xing’an Range, China: implications for metal source and ore exploration. Acta Petrologica Sinica 31, 2417e2434 (in Chinese with English abstract). Keith, M., Haase, K.M., Klemd, R., Krumm, S., Strauss, H., 2016. Systematic variations of trace element and sulfur isotope compositions in pyrite with stratigraphic depth in the Skouriotissa volcanic-hosted massive sulfide deposit, Troodos ophiolite, Cyprus. Chemical Geology 423, 7e18. Klemd, R., Gao, J., Li, J.L., Meyer, M., 2015. Metamorphic evolution of (ultra)-highpressure subduction-related transient crust in the south Tianshan orogen (central Asian orogenic belt): geodynamic implications. Gondwana Research 28 (1), 1e25. Koglin, N., Frimmel, H.E., Lawrie Minter, W.E., Brätz, H., 2010. Trace-element characteristics of different pyrite types in Mesoarchaean to Palaeoproterozoic placer deposits. Mineralium Deposita 45 (3), 259e280. Kostova, B., Pettke, T., Driesner, T., Petrov, P.A., Heinrich, C., 2004. LA ICP-MS study of fluid inclusions in quartz from the Yuzhna Petrovitsa deposit, Madan ore field, Bulgaria. Schweizerische Mineralogische und Petrographische Mitteilungen 84 (1), 25e36. Kouhestani, H., Ghaderi, M., Large, R.R., Zaw, K., 2017. Texture and chemistry of pyrite at Chah Zard epithermal goldesilver deposit, Iran. Ore Geology Reviews 84, 80e101. Kröner, A., Kovach, V., Belousova, E., Hegner, E., Armstrong, R., Dolgopolova, A., Seltmann, R., Alexeiev, D.V., Hoffmann, J.E., Wong, J., Sun, M., Cai, K., Wang, T., Tong, Y., Wilde, S.A., Degtyarev, K.E., Rytsk, E., 2014. Reassessment of continental growth during the accretionary history of the central Asian orogenic belt. Gondwana Research 25 (1), 103e125. LaFlamme, C., Martin, L., Jeon, H., Reddy, S.M., Selvaraja, V., Caruso, S., Bui, T.H., Roberts, M.P., Voute, F., Hagemann, S., Wacey, D., Littman, S., Wing, B., Fiorentini, M., Kilburn, M.R., 2016. In situ multiple sulfur isotope analysis by SIMS of pyrite, chalcopyrite, pyrrhotite, and pentlandite to refine magmatic ore genetic models. Chemical Geology 444, 1e15. Large, R., Danyushevsky, L., Hollit, C., Maslennikov, V., Meffre, S., Gilbert, S., Bull, S., Scott, R., Emsbo, P., Thomas, H., Singh, B., Foster, J., 2009. Gold and trace element Zonation in pyrite using a laser imaging technique: implications for the timing of gold in orogenic and Carlin-style sediment-hosted deposits. Economic Geology 104, 635e668. Lawley, C., Richards, J., Anderson, R.G., Creaser, R.A., Heaman, L., 2010. Geochronology and geochemistry of the MAX porphyry Mo deposit and its relationship to Pb-Zn-Ag mineralization, Kootenay arc, Southeastern British Columbia, Canada. Economic Geology 105, 1113e1142. Li, N., Deng, J., Yang, L.Q., Goldfarb, R.J., Zhang, C., Marsh, E., Lei, S.B., Koenig, A., Lowers, H., 2014. Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt, West Qinling, China. Mineralium Deposita 49 (4), 427e449. Li, P.F., Sun, M., Rosenbaum, G., Yuan, C., Safonova, I., Cai, K.D., Jiang, Y.D., Zhang, Y.Y., 2018. Geometry, kinematics and tectonic models of the Kazakhstan Orocline, central Asian orogenic belt. Journal of Asian Earth Sciences 153, 42e56. Li, R.C., Chen, H.Y., Xia, X.P., Yang, Q., Li, L., Xu, J., Huang, C., Danyushevsky, L.V., 2017a. Ore fluid evolution in the giant Marcona Fe-(Cu) deposit, Perú: evidence from in-situ sulfur isotope and trace element geochemistry of sulfides. Ore Geology Reviews 86, 624e638. Li, Z.K., Bi, S.J., Li, J.W., Zhang, W., Cooke, D.R., Selby, D., 2017b. Distal Pb-Zn-Ag veins associated with the world-class Donggou porphyry Mo deposit, southern North China Craton. Ore Geology Reviews 82, 232e251. Lin, Z.Y., Sun, X.M., Peckmann, J., Lu, Y., Xu, L., Strauss, H., Zhou, H.Y., Gong, J.L., Lu, H.F., Teichert, B.M.A., 2016. How sulfate-driven anaerobic oxidation of methane affects the sulfur isotopic composition of pyrite: a SIMS study from the south China sea. Chemical Geology 440, 26e41. Liu, Y., Jiang, S.H., Bagas, L., Han, N., Chen, C.L., Kang, H., 2017. Isotopic (CeOeS) geochemistry and ReeOs geochronology of the Haobugao ZneFe deposit in Inner Mongolia, NE China. Ore Geology Reviews 82, 130e147. Liu, L.J., Zhou, T.F., Zhang, D.Y., Yuan, F., Liu, G.X., Zhao, Z.C., Sun, J., White, N., 2018. S isotopic geochemistry, zircon and cassiterite UePb geochronology of the Haobugao Sn polymetallic deposit, southern Great Xing’an Range, NE China. Ore Geology Reviews 93, 168e180. Mao, J.W., Pirajno, F., Xiang, J.F., Gao, J.J., Ye, H.S., Li, Y.F., Guo, B.J., 2011. Mesozoic molybdenum deposits in the east QinlingeDabie orogenic belt: characteristics and tectonic settings. Ore Geology Reviews 43 (1), 264e293. Maslennikov, V.V., Maslennikova, S.P., Large, R.R., Danyushevsky, L.V., 2009. Study of trace element Zonation in vent Chimneys from the Silurian Yaman-Kasy volcanic-hosted massive sulfide deposit (southern Urals, Russia) using laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS). Economic Geology 104, 1111e1141.

Maslennikov, V.V., Maslennikova, S.P., Large, R.R., Danyushevsky, L.V., Herrington, R.J., Ayupova, N.R., Zaykov, V.V., Lein, A.Y., Tseluyko, A.S., Melekestseva, I.Y., Tessalina, S.G., 2017. Chimneys in Paleozoic massive sulfide mounds of the Urals VMS deposits: mineral and trace element comparison with modern black, grey, white and clear smokers. Ore Geology Reviews 85, 64e106. Maydagán, L., Franchini, M., Lentz, D., Pons, J., McFarlane, C., 2013. Sulfide composition and isotopic signature of the Altar Cu-Au deposit, Argentina: constraints on the evolution of the porphyry-epithermal system. The Canadian Mineralogist 51 (6), 813e840. Mei, W., Lv, X.B., Cao, X.F., Liu, Z., Zhao, Y., Ai, Z.Z., Tang, R.K., Abfaua, M.M., 2015. Ore genesis and hydrothermal evolution of the Huanggang skarn ironetin polymetallic deposit, southern Great Xing’an Range: evidence from fluid inclusions and isotope analyses. Ore Geology Reviews 64 (Suppl. C), 239e252. Mills, S.E., Tomkins, A.G., Weinberg, R.F., Fan, H.R., 2015. Implications of pyrite geochemistry for gold mineralization and remobilization in the Jiaodong gold district, northeast China. Ore Geology Reviews 71, 150e168. Morishita, Y., Shimada, N., Shimada, K., 2018. Invisible gold in arsenian pyrite from the high-grade Hishikari gold deposit, Japan: significance of variation and distribution of Au/As ratios in pyrite[J]. Ore Geology Reviews 95, 79e93. Morse, J.W., Luther, G.W., 1999. Chemical influences on trace metal-sulfide interactions in anoxic sediments. Geochimica et Cosmochimica Acta 63 (19), 3373e3378. Mukherjee, I., Large, R., 2017. Application of pyrite trace element chemistry to exploration for SEDEX style Zn-Pb deposits: McArthur Basin, Northern Territory, Australia. Ore Geology Reviews 81, 1249e1270. Part 4. Ohmoto, H., 1972. Systematics of sulfur and carbon isotopes in hydrothermal ore deposits. Economic Geology 67 (5), 551e578. Ohmoto, H., 1979. Isotope of sulfur and carbon. Geochemistry of Hydrothermal Ore Deposits 509e567. Ohmoto, H., 1986. Stable isotope geochemistry of ore deposits. Reviews in Mineralogy 16, 491e560. Ouyang, H.G., Mao, J.W., Santosh, M., Wu, Y., Hou, L., Wang, X.F., 2014. The Early Cretaceous Weilasituo ZneCueAg vein deposit in the southern Great Xing’an Range, northeast China: fluid inclusions, H, O, S, Pb isotope geochemistry and genetic implications. Ore Geology Reviews 56, 503e515. Ouyang, H.G., Mao, J.W., Zhou, Z.H., Su, H.M., 2015. Late Mesozoic metallogeny and intracontinental magmatism, southern Great Xing’an Range, northeastern China. Gondwana Research 27 (3), 1153e1172. Palme, H., Jones, A., 2003. 1.03 e solar system Abundances of the elements. Treatise on Geochemistry 37 (2), 41e61. Pei, Q.M., Zhang, S.T., Santosh, M., Cao, H.W., Zhang, W., Hu, X.K., Wang, L., 2017. Geochronology, geochemistry, fluid inclusion and C, O and Hf isotope compositions of the Shuitou fluorite deposit, Inner Mongolia, China. Ore Geology Reviews 83, 174e190. Pei, Q.M., Zhang, S.T., Hayashi, K.I., Cao, H.W., Li, D., Tang, L., Hu, X.K., Li, H.X., Fang, D.R., 2018. Permoetriassic granitoids of the Xing’aneMongolia segment of the central Asian orogenic belt, northeast China: age, composition, and tectonic implications. International Geology Review 60, 1172e1194. Price, B.J., 1972. Minor Elements in Pyrites from the Smithers Map Area, B. C. and Exploration Applications of Minor Element Studies Text. Thesis. University of British Columbia. Qin, G.J., Kawachi, Y., Zhao, L.Q., Wang, Y.Z., Ou, Q., 2001. The Upper Permian sedimentary Facies and its role in the Dajing Cu-Sn deposit, Linxi county, Inner Mongolia, China. Resource Geology 51, 293e305. Rajabpour, S., Behzadi, M., Jiang, S.Y., Rasa, I., Lehmann, B., Ma, Y., 2017. Sulfide chemistry and sulfur isotope characteristics of the Cenozoic volcanic-hosted Kuh-Pang copper deposit, Saveh county, northwestern central Iran. Ore Geology Reviews 86, 563e583. Reich, M., Deditius, A., Chryssoulis, S., Li, J.W., Ma, C.Q., Parada, M.A., Barra, F., Mittermayr, F., 2013. Pyrite as a record of hydrothermal fluid evolution in a porphyry copper system: a SIMS/EMPA trace element study. Geochimica et Cosmochimica Acta 104 (Suppl. C), 42e62. Reich, M., Simon, A., Deditius, A., Barra, F., Chrysoullis, S., Lagas, G., Tardani, D., Knipping, J., Bilenker, L., Sánchez, P., Roberts, M., Minizaga, R., 2016. Trace element signature of pyrite from the los colorados iron oxide-apatite (IOA) Deposit, Chile: a missing link between Andean Ioa and iron oxide copper-gold systems? Economic Geology 111, 743e761. Ruan, B.X., Lv, X.B., Yang, W., Liu, S.T., Yu, Y.M., Wu, C.M., Adam, M.M.A., 2015. Geology, geochemistry and fluid inclusions of the Bianjiadayuan PbeZneAg deposit, Inner Mongolia, NE China: implications for tectonic setting and metallogeny. Ore Geology Reviews 71, 121e137. Rudnick, R.L., Gao, S., 2003. Composition of the continental crust. Treatise on Geochemistry 3, 1e64. Rye, R., Ohmoto, H., 1974. Sulfur and carbon isotopes and ore genesis: a review. Economic Geology 69 (6), 826e842. Safonova, I., 2017. Juvenile versus recycled crust in the Central Asian Orogenic Belt: implications from ocean plate stratigraphy, blueschist belts and intra-oceanic arcs. Gondwana Research 47, 6e27. Shu, Q.H., Lai, Y., Sun, Y., Wang, C.M., Meng, S., 2013. Ore genesis and hydrothermal evolution of the Baiyinnuo’er zinc-lead skarn deposit, northeast China: evidence from isotopes (S, Pb) and fluid inclusions. Economic Geology 108, 835e860. Sillitoe, R.H., 2010. Porphyry copper systems. Economic Geology 105, 3e41.

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004

K.-R. Song et al. / Geoscience Frontiers xxx (xxxx) xxx Tagirov, B.R., Seward, T.M., 2010. Hydrosulfide/sulfide complexes of zinc to 250 C and the thermodynamic properties of sphalerite. Chemical Geology 269 (3), 301e311. Tanner, D., Henley, R.W., Mavrogenes, J.A., Holden, P., 2016. Sulfur isotope and trace element systematics of zoned pyrite crystals from the El Indio AueCueAg deposit, Chile. Contributions to Mineralogy and Petrology 171 (4), 1e17. Thomas, H., Large, R., Bull, S., Maslennikov, V., Berry, R., Fraser, R., Froud, S., Moye, R., 2011. Pyrite and pyrrhotite textures and composition in sediments, laminated quartz veins, and Reefs at Bendigo gold mine, Australia: insights for ore genesis. Economic Geology 106, 1e31. Tribovillard, N., Algeo, T.J., Lyons, T., Riboulleau, A., 2006. Trace metals as paleoredox and paleoproductivity proxies: an update. Chemical Geology 232, 12e32. Ulrich, T., Long, D., Kamber, B.J., Whitehouse, M., 2011. In situ trace element and sulfur isotope analysis of pyrite in a Paleoproterozoic gold placer deposit, Pardo and Clement Townships, Ontario, Canada. Economic Geology 106, 667e686. Wang, C.M., Yang, L.F., Bagas, L., Evans, N., Chen, J.Y., Du, B., 2017a. Mineralization processes at the giant Jinding ZnePb deposit, Lanping Basin, Sanjiang Tethys Orogen: evidence from in situ trace element analysis of pyrite and marcasite. Geological Journal. https://doi.org/10.1002/gj.2956. Wang, C.N., Wang, Q.M., Yu, X.F., Han, Z.Z., 2016. Metallognetic characteristics of tin and ore-search prospect in the southern part of Da Hinggan mountains. Geology and Prospecting 52, 220e227 (in Chinese with English abstract). Wang, F.X., Bagas, L., Jiang, S.H., Liu, Y.F., 2017b. Geological, geochemical, and geochronological characteristics of Weilasituo Sn-polymetal deposit, Inner Mongolia, China. Ore Geology Reviews 80 (Suppl. C), 1206e1229. Wang, J.B., Wang, Y.W., Wang, L.J., Uemoto, T., 2001. Tin-polymetallic mineralization in the southern part of the Da Hinggan mountains, China. Resource Geology 51, 283e291. Wang, J.B., Wang, Y.W., Wang, L.J., 2005. Tin-polymetallic metallogenic series in the southern part of Da Hinggan mountains, China. Geology and Prospecting 41, 15e20 (in Chinese with English abstract). Wang, X.D., Xu, D.M., Lv, X.B., Wei, W., Mei, W., Fan, X.J., Sun, B.K., 2018. Origin of the Haobugao skarn Fe-Zn polymetallic deposit, Southern Great Xing’an range, NE China: geochronological, geochemical, and Sr-Nd-Pb isotopic constraints. Ore Geology Reviews 94, 58e72. Wang, X.L., Liu, J.J., Zhai, D.G., Yang, Y.Q., Wang, J.P., Zhang, Q.B., Zhang, A.L., Wang, X.L., 2013. LA-ICP-MS zircon U-Pb dating, geochemistry of the intrusive rocks from the Bianjiadayuan Pb-Zn-Ag deposit, inner Mongolia, China and tectonic implications. Geotectonica et Metallogenia 37, 730e742 (in Chinese with English abstract). Wang, X.L., Liu, J.J., Zhai, D.G., Wang, J.P., Zhang, Q.B., Zhang, A.L., 2014a. A study of isotope geochemistry and sources of ore-forming materials of the Bianjiadayuan silver polymetallic deposit in Linxi, Inner Mongolia. Geology in China 41, 1288e1303 (in Chinese with English abstract). Wang, X.L., Liu, J.J., Zhai, D.G., Yang, Y.Q., Wang, J.P., Zhang, Q.B., Zhang, A.L., 2014b. U-Pb dating, geochemistry and tectonic implications of Bianjiadayuan quartz porphyry, Inner Mongolia, China. Bulletin of Mineralogy, Petrology and Geochemistry 33, 654e665 (in Chinese with English abstract). Wang, X.L., Liu, J.J., Zhai, D.G., Yang, Y.Q., Wang, J.P., Zhang, Q.B., Zhang, A.L., Li, Y.L., Wang, X.L., Yang, Z.H., 2014c. Mineral composition of Bianjiadayuan Pb-Zn-Ag polymetallic deposit in inner Mongolia and its origin significance. Journal of China University of Geosciences 28, 73e86 (in Chinese with English abstract). Ward, J., Mavrogenes, J., Murray, A., Holden, P., 2017. Trace element and sulfur isotopic evidence for redox changes during formation of the Wallaby Gold Deposit, Western Australia. Ore Geology Reviews 82, 31e48. Wohlgemuth-Ueberwasser, C.C., Viljoen, F., Petersen, S., Vorster, C., 2015. Distribution and solubility limits of trace elements in hydrothermal black smoker sulfides: an in-situ LA-ICP-MS study. Geochimica et Cosmochimica Acta 159, 16e41. Wu, F.Y., Sun, D.Y., Ge, W.C., Zhang, Y.B., Grant, M.L., Wilde, S.A., Jahn, B.M., 2011. Geochronology of the Phanerozoic granitoids in northeastern China. Journal of Asian Earth Sciences 41 (1), 1e30.

15

Xiao, W.J., Mao, Q.G., Windley, B.F., Han, C.M., Qu, J.F., Zhang, J.E., Ao, S.J., Guo, Q.Q., Cleven, N.R., Lin, S.F., Shan, Y.H., Li, J.L., 2010. Paleozoic multiple accretionary and collisional processes of the Beishan orogenic collage. American Journal of Science 310 (10), 1553e1594. Xu, B., Zhao, P., Wang, Y.Y., Liao, W., Luo, Z.W., Bao, Q.Z., Zhou, Y.H., 2015. The preDevonian tectonic framework of Xing’aneMongolia orogenic belt (XMOB) in north China. Journal of Asian Earth Sciences 97, 183e196. Yuan, M.W., Li, S.R., Li, C.L., Santosh, M., Alam, M., Zeng, Y.J., 2018. Geochemical and isotopic composition of auriferous pyrite from the Yongxin gold deposit, Central Asian Orogenic Belt: implication for ore genesis. Ore Geology Reviews 93, 255e267. Zhai, D.G., Liu, J.J., Yang, Y.Q., Wang, J.P., Ding, L., Liu, X.W., Zhang, M., Yao, M.J., Su, L., Zhang, H.Y., 2012. Petrogenetic and metallogentic ages and tectonic setting of the Huanggangliang Fe-Sn deposit, Inner Mongolia. Acta Petrologica et Mineralogica 31, 513e523 (in Chinese with English abstract). Zhai, D.G., Liu, J.J., Zhang, H.Y., Yao, M.J., Wang, J.P., Yang, Y.Q., 2014. SePb isotopic geochemistry, UePb and ReeOs geochronology of the Huanggangliang FeeSn deposit, Inner Mongolia, NE China. Ore Geology Reviews 59, 109e122. Zhai, D.G., Liu, J.J., Zhang, A.L., Sun, Y.Q., 2017. U-Pb, Re-Os and 40Ar/39Ar geochronology of porphyry Sn
Cu
Mo and polymetallic (Ag- Pb-Zn-Cu) vein mineralization at Bianjiadayuan, inner Mongolia, northeast China: implications for discrete mineralization events. Economic Geology 112, 2041e2059. Zhai, D.G., Liu, J.J., Cook, N.J., Wang, X.L., Yang, Y.Q., Zhang, A.L., Jiao, Y.C., 2018a. Mineralogical, textural, sulfur and lead isotope constraints on the origin of AgPb-Zn mineralization at Bianjiadayuan, Inner Mongolia, NE China. Mineralium Deposita 4, 1e20. Zhai, D.G., Liu, J.J., Zhang, H.Y., Tombros, S., Zhang, A.L., 2018b. A magmatic-hydrothermal origin for Ag-Pb-Zn vein formation at the Bianjiadayuan deposit, inner Mongolia, NE China: evidences from fluid inclusion, stable (C-H-O) and noble gas isotope studies. Ore Geology Reviews 101, 1e16. Zhang, J., Deng, J., Chen, H.Y., Yang, L.Q., Cooke, D., Danyushevsky, L., Gong, Q.J., 2014a. LA-ICP-MS trace element analysis of pyrite from the Chang’an gold deposit, Sanjiang region, China: implication for ore-forming process. Gondwana Research 26 (2), 557e575. Zhang, J., Li, L., Gilbert, S., Liu, J.J., Shi, W.S., 2014b. LA-ICP-MS and EPMA studies on the Fe-S-As minerals from the Jinlongshan gold deposit, Qinling Orogen, China: implications for ore-forming processes. Geological Journal 49, 482e500. Zhang, P., Huang, X.W., Cui, B., Wang, B.C., Yin, Y.F., Wang, J.R., 2016. Re-Os isotopic and trace element compositions of pyrite and origin of the Cretaceous Jinchang porphyry Cu-Au deposit, Heilongjiang Province, NE China. Journal of Asian Earth Sciences 129, 67e80. Zhang, X.B., Wang, K.Y., Fu, L.Y., Zhang, M., Konare, Y., Peng, D.W., Cai, W.Y., 2017. Fluid inclusions, C-H-O-S isotope and geochronology of the Bujinhei Pb-Zn deposit in the southern Great Xing’an range of northeast China: implication for ore genesis. Resource Geology 67 (2), 207e227. Zhang, Y., Shao, Y.J., Chen, H.Y., Liu, Z.F., Li, D.F., 2016. A hydrothermal origin for the large Xinqiao Cu-S-Fe deposit, Eastern China: evidence from sulfide geochemistry and sulfur isotopes. Ore Geology Reviews 88, 534e549. Zhao, H.X., Frimmel, H.E., Jiang, S.Y., Dai, B.Z., 2011. LA-ICP-MS trace element analysis of pyrite from the Xiaoqinling gold district, China: implications for ore genesis. Ore Geology Reviews 43 (1), 142e153. Zhou, Y.T., Lai, Y., Meng, S., Shu, Q.H., 2018. Controls on different mineralization styles of the Dongbulage Mo and Taibudai Cu-(Mo) porphyry deposits in the Great Xing’an range, NE China. Journal of Asian Earth Sciences. https://doi.org/ 10.1016/j.jseaes.2018.01.028. Zwahlen, C., Stefania, C., Thomas, W., Roger, R., Christoph, H., 2014. The porphyry Cu-(Mo-Au) deposit at altar (Argentina): Tracing gold distribution by vein mapping and LA-ICP-MS mineral analysis. Economic Geology 109 (5), 1341e1358.

Please cite this article as: Song, K.-R et al., Genesis of the Bianjiadayuan PbeZn polymetallic deposit, Inner Mongolia, China: Constraints from insitu sulfur isotope and trace element geochemistry of pyrite, Geoscience Frontiers, https://doi.org/10.1016/j.gsf.2019.02.004