Genesis of the giant Caixiashan Zn-Pb deposit in Eastern Tianshan, NW China: Constraints from geology, geochronology and S-Pb isotopic geochemistry

Journal Pre-proofs Genesis of the giant Caixiashan Zn-Pb deposit in Eastern Tianshan, NW China: Constraints from geology, geochronology and S-Pb isotopic geochemistry Rongzhen Gao, Chunji Xue, Guoxiang Chi, Junfeng Dai, Chen Dong, Xiaobo Zhao, Ronghao Man PII: DOI: Reference:

S0169-1368(19)30826-1 https://doi.org/10.1016/j.oregeorev.2020.103366 OREGEO 103366

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Ore Geology Reviews

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5 September 2019 15 December 2019 26 January 2020

Please cite this article as: R. Gao, C. Xue, G. Chi, J. Dai, C. Dong, X. Zhao, R. Man, Genesis of the giant Caixiashan Zn-Pb deposit in Eastern Tianshan, NW China: Constraints from geology, geochronology and S-Pb isotopic geochemistry, Ore Geology Reviews (2020), doi: https://doi.org/10.1016/j.oregeorev.2020.103366

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Genesis of the giant Caixiashan Zn-Pb deposit in Eastern Tianshan, NW China: Constraints from geology, geochronology and S-Pb isotopic geochemistry

Rongzhen Gaoa, Chunji Xuea*, Guoxiang Chib, Junfeng Daic, Chen Dongd, Xiaobo Zhaoa, Ronghao Mana

a State Key Laboratory of Geological Processes and Mineral Resource, School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China b Department of Geology, University of Regina, Regina S4S 0A2, Canada c Key Laboratory on Nuclear Resources and Environment, East China University of Technology, Nanchang 330013, China d Jiangxi Nonferrous Metals Geological Exploration Bureau, Nanchang 330025, China

* Corresponding author: email, [email protected]

Abstract: The Caixiashan Zn-Pb deposit is the largest carbonate-hosted Zn-Pb deposit in Eastern Tianshan, NW China. The deposit comprises the No. Ⅰ, Ⅱ, Ⅲ and Ⅳ ore zones with a proven reserve of 131 Mt ore at 3.95% Pb+Zn. The orebodies generally occur as irregular lenses and pods in altered carbonate rocks of the Mesoproterozoic Kawabulake Group near faults. The mineralization is characterized by massive, disseminated and vein/veinlet sulfides including pyrite, pyrrhotite, sphalerite and galena with minor arsenopyrite and chalcopyrite, as well as sulfosalt minerals of Ag, As, Sb and Pb. The mineralization is associated with tremolite, chlorite, silica and carbonate alterations. Rb-Sr isotopic dating of sphalerite and pyrrhotite yields an isochron age of 337.2 ± 5.7 Ma, which is interpreted as the mineralization age. Zircon U-Pb dating reveals that stocks of diorite, quartz diorite, K-feldspar granite and monzonitic granite that occur in the deposit area were emplaced at 348.2 ± 3.7 Ma, 351.9 ± 3.5 Ma, 333.6 ± 3.6 Ma and 330.0 ± 3.6 Ma, respectively. These age data suggest that the mineralization is coeval with Carboniferous granitic magmatism. The δ34SV-CDT values of sulfides (excluding the syn-sedimentary pyrite) range from -2.42‰ to 19.1‰, suggesting that the reduced sulfur was mainly derived from thermal sulfate reduction (TSR) of seawater-derived sulfates in the marine sedimentary basement rocks

and minor contribution by replacement of syn-sedimentary pyrite, as well as a possible input of magmatic sulfur. The Pb isotopic compositions of sulfides, with 15.422 to 15.614, and

208Pb/204Pb

206Pb/204Pb

ranging from 17.074 to 17.361,

207Pb/204Pb

from

from 36.685 to 37.303, partly overlap with those of basement rocks of the

Mesoproterozoic Kawabulake Group and the Carboniferous intrusions, suggesting that the ore metals were derived from both the basement and Carboniferous magmatism. On the basis of the spatio-temporal relations between hydrothermal alterations/mineralization and Carboniferous magmatism, we conclude that the Caixiashan Zn-Pb deposit is a high-temperature carbonate replacement deposit related to concealed granitic intrusions, which were formed in an arc environment related to the subduction of the South Tianshan Ocean plate underneath the Central Tianshan massif during the Carboniferous time. The results of this study indicate that there is a great potential of finding more large-scale Zn-Pb deposits similar to Caixiashan in Eastern Tianshan.

Keywords: Sulfide Rb-Sr dating; Zircon U-Pb ages; S-Pb isotopes; Caixiashan Zn-Pb deposit; Eastern Tianshan

1. Introduction The Central Asian Orogenic Belt (CAOB) is regarded as the largest accretionary orogen on earth (Fig. 1a; Windley et al., 2007; Xiao et al., 2013) and hosts a great variety of base and precious metal deposits that formed during its tectonic evolution in the Paleozoic (Mao et al., 2005; Chai et al., 2008; Pirajno, 2010; Goldfarb et al., 2014). While the Cu-Mo-Au mineralization associated with porphyry systems and the related magmatism have been extensively studied and fairly well understood (Goldfarb et al., 2014; Seltmann et al., 2014; Xue et al., 2016), relatively little has been known about the distal Zn-Pb mineralization without direct connection with the magmatic intrusions and their potential genetic relationship with magmatism (Li et al., 2010; Turamuratov et al., 2011; Dai et al., 2019). This is in part because magmatic hydrothermal fluids may migrate over a long distance (Meinert et al., 2005) and it is generally difficult to identify the causative magmatic intrusions for such distal mineralization. Determining the spatio-temporal relationships of magmatic and hydrothermal events and tracing the source of ore-forming materials are essential for revealing the ore genesis of these Zn-Pb deposits and

increasing our capabilities to discover new deposits of similar origin (ÖZTÜRK et al., 2005; Wang et al., 2014; Vezzoni et al., 2016; Zhao et al., 2018a). The Eastern Tianshan Orogen, located between the Tarim and Junggar basins in the southern part of CAOB (Fig. 1a), is characterized by complex tectonic evolution and extensive magmatism during the Paleozoic (Chen et al., 2012). Many Zn-Pb deposits with similar geological characteristics, including Caixiashan, Yuxi, Hongyuan, Jiyuan and Hongxingshan, were recently discovered in the Mesoproterozoic carbonate rocks of the Central Tianshan massif in Eastern Tianshan (Fig. 1b; Peng et al., 2006; Xiao et al., 2009; Ding et al., 2010). Of these carbonate-hosted Zn-Pb deposits, the Caixiashan deposit is the only large-scale one with a proven reserve of 131 Mt ore at 3.95% Pb+Zn (Cao et al., 2012, 2013; Li et al., 2016a). The regional Zn-Pb mineralization may be related to Late Paleozoic magmatism (Gao et al., 2007a, 2007b; Ding et al., 2010, 2016; Cao et al., 2012, 2013; Lu et al., 2018). Recently, skarn Zn-Pb mineralization closely related to the Late Carboniferous magmatism was identified based on typical skarn minerals such as garnet, pyroxene and magnetite and fluid inclusion studies in the Hongyuan Zn-Pb deposit (Fig. 1b; Lu et al., 2018). However, compared to the genesis of the large-scale distal skarn Zn-Pb deposits found in Western Tianshan, including Kurgashigan (Turamuratov et al., 2011), Altyntopkan (Li et al., 2010), Tuyke (Li et al., 2010), Keregetash (Li et al., 2010) and Arqiale (Dai et al., 2019), the degree of study about the relationship between the Zn-Pb mineralization and Paleozoic magmatism in Eastern Tianshan is relatively low. A number of studies have been carried on the Caixiashan Zn-Pb deposit, including the ore deposit geology (Peng et al., 2006; Gao et al., 2007a; Cao et al., 2013; Sun et al., 2013), S-Pb-C-H-O isotopes (Liang et al., 2005; Gao et al., 2007a, 2007b; Cao et al., 2013; Li et al., 2018), fluid inclusions (Gao et al., 2006; Peng et al., 2007; Li et al., 2016b) and mineralization age (Li et al., 2016a). However, there are still many unanswered questions regarding the mineralization age and source of ore-forming materials. The mineralization age was proposed to be Early Neoproterozoic based on a laminated pyrite Re-Os isochron age of 859 ± 79 Ma (MSWD=6.7) and an euhedral pyrite Re-Os isochron age of 837 ± 39 Ma (MSWD=6.5) with high MSWD values (Li et al., 2016a). However, these pyrite grains may be initially formed as early syn-sedimentary colloform/framboidal pyrite and inherit some of the initial Re-Os compositions, and it is thus difficult to extract pure hydrothermal pyrite samples related to the main mineralization. Furthermore, precipitation of these pyrite grains was not necessarily coeval

with Zn-Pb mineralization, as some hydrothermal pyrite was partially replaced by sphalerite and galena (Li et al., 2016a). Owning to geochemical complexities of pyrite grains in the Caixiashan Zn-Pb deposit and lack of direct determination of mineralization age, it remains unclear whether the pyrite Re-Os isochron age of Li et al. (2016a) can represent the main phase Zn-Pb mineralization age. Controversies may also exist regarding the sources of the ore-forming materials. Some proposed the Mesoproterozoic basement rocks as the main sources (Li et al., 2018), whereas others suggested mixed sources with an input of Carboniferous magmatic origin or mantle sources (Liang et al., 2005; Gao et al., 2007a, 2007b; Cao et al., 2012, 2013; Li et al., 2016a). Consequently, the Caixiashan Zn-Pb deposit has been variably classified as MVT type (Peng et al., 2007), stratabound type (Xiao et al., 2009; Ding et al., 2010), mesothermal type of magmatic origin (Cao et al., 2012, 2013), Irish type (Li et al., 2016b) and carbonate replacement type (Li et al., 2018). In this paper, we present new zircon U-Pb ages of diorite and quartz diorite stocks, sphalerite and pyrrhotite Rb-Sr isochron age and S-Pb isotopic compositions of sulfides and possible source rocks in the Caixiashan ZnPb deposit. With these new data and previous results, we aim to reevaluated the Zn-Pb mineralization age and the source of ore-forming materials, and then to constrain the genesis of the Caixiashan Zn-Pb deposit. The implications of the new data and genetic model for further exploration of similar carbonate-hosted Zn-Pb deposits in Eastern Tianshan are also discussed. 2. Geological setting The Eastern Tianshan Orogen is an important part of the southern segment of the Central Asian Orogenic Belt (Fig. 1a), which was formed from tectonic evolution of the paleo-Asian Ocean with remarkable crustal growth and formation of various mineral deposits (Fig. 1b; Ma et al., 1997; Windley et al., 1990; Xiao et al., 2004). Tectonically, Eastern Tianshan includes the Dananhu-Tousuquan island arc, Kangguer-Huangshan ductile shear zone, Aqishan-Yamansu island arc and Central Tianshan massif from north to south, which are separated by the E-trending Kangguer, Yamansu and Aqikekuduke-Shaquanzi faults, respectively (Fig. 1b; Qin et al., 2002; Xiao et al., 2004; Su et al., 2011). The Dananhu-Tousuquan island arc is characterized by intrusions and volcanic rocks of Devonian to Carboniferous (Mao et al., 2005), and hosts several important porphyry Cu deposits including Tuwu, Yandong, Linglong and Chihu (Shen et al., 2014; Xiao et al., 2017; Wang et al., 2018) and hydrothermal vein Cu deposits

including Xiaoerquanzi and Kalatage (Mao et al., 2005; Deng et al., 2016). The Kangguer-Huangshan ductile shear zone comprises greenschist-facies metamorphosed volcaniclastic rocks of Carboniferous, intruded by Permian mafic-ultramafic intrusions (Xiao et al., 2004) and Late Carboniferous-Late Permian granites (Shen et al., 2014; Huang et al., 2014). It hosts some orogenic Au deposits (e.g., Kangguer), epithermal Au deposits (e.g., Shiyingtan) and magmatic Cu-Ni sulfide deposits (e.g., Xiangshan, Huangshan) (Rui et al., 2002; Zhou et al., 2004; Chen et al., 2012). The shear zone was interpreted as a result of deformation of an inter-arc basin (Ma et al., 1997; Shu et al., 2002). The Aqishan-Yamansu island arc belt is composed of Carboniferous-Permian volcanic-, volcaniclastic- and clastic rocks, intruded by Late Paleozoic arc-related granitoids (Zhou et al., 2010; Zhao et al., 2018b; Jiang et al., 2018). It contains many skarn Fe deposits (e.g., Hongyuntan, Bailingshan, Chilongfeng, Kumutage and Yamansu; Chen et al., 2018b; Zhang et al., 2018), VMS Cu-Zn deposits (e.g., Yinbangshan; Jiang et al., 2018) and porphyry Mo deposits (e.g., Donggebi; Wang et al., 2018). The Central Tianshan massif mainly comprises Precambrian metamorphic basement intruded by Carboniferous felsic intrusions including diorite, quart diorite, granite and granodiorite with zircon U-Pb ages of 299-375 Ma (Fig. 1b; Xiao et al., 2004; Mao et al., 2005; Jiang et al., 2018). The Precambrian basement rocks are represented by gneiss, quartz schist, migmatite, siltstone, mudstone and carbonate rocks of the Mesoproterozoic Xingxingxia and Kawabulake groups. The Kawabulake Group, which has been dated with a single zircon U-Pb age of 1141 ± 60 Ma (Xiu et al., 2002), conformably overlies the Xingxingxia Group, which was interpreted to have formed in a passive continental margin environment as indicated by the formation of carbonate platform (Xiao et al., 2009; Cai et al., 2013). The magmatic arc system was then formed in the Central Tianshan massif as a result of the subduction of the South Tianshan Ocean plate during the Late Paleozoic (Xiao et al., 2009). The Central Tianshan massif hosts various types of ore deposits, including carbonate-hosted Zn-Pb deposits (e.g., Caixiashan, Yuxi, Hongyuan and Tianyu; Li et al., 2016a, 2016b; Lu et al., 2018), skarn Zn-Pb deposits (e.g., Liujiaquanxi, Qianluzi; Ding et al., 2010), magmatic hydrothermal W-Mo deposits (e.g., Shadong; Chen et al., 2018a), magmatic Cu-Ni sulfide deposits (e.g., Baishiquan; Chai et al., 2008), sedimentation reformation Fe deposits (e.g., Tianhu; Huang et al., 2015), magmatic V-Ti magnetite deposits (e.g., Weiya; Shi et al., 2016) and orogenic Au deposits (e.g., Jinwozi; Zhang et al., 2015). 3. Geology of the Caixiashan Zn-Pb deposit

3.1 Local geology The Caixiashan Zn-Pb deposit is situated in the western part of the Central Tianshan massif, about 3 km south of the Aqikekuduke Fault (Fig. 1b). The strata outcropped include the Mesoproterozoic Xingxingxia and Kawabulake groups (Fig. 2). The former comprises a series of metamorphic complex including granulite and schist while the latter consists of interbedded siltstone, mudstone and chert with lentoid dolomite marble in the lower lithologic member, which is the main ore-bearing horizon, and mylonitic quartz sandstone in the upper lithologic member. The Mesoproterozoic carbonate rocks have been locally subject to dynamic metamorphism during the Permian-Carboniferous period, having generated mylonites along shear zones in the southern part of the mining area (Chen et al., 2019; Li et al., 2016b). The structural framework of the deposit area is characterized by an ENE-trending overturned anticline that plunges to the SSE. The northern limb dips about 82°-89° to the south while the southern limb dips 65°-73° southward. The anticline was formed before mineralization, which is controlled by interlayer fractures in both limbs. A series of NW-, ENE- and NNE-trending faults occur as secondary faults of the Aqikekuduke Fault, and three principle episodes of activities of these faults have been identified based on their crosscutting relationships (Fig. 2). The earliest episode includes NW-trending reverse faults (F4, F9), whereas the second episode comprises ENE-trending normal faults (F1, F2), which are parallel to the bedding and mylonitic foliations and contain breccia zones that host Zn-Pb mineralization (Li et al., 2016b; Cao et al., 2012). The third episode is characterized by NNE-trending sinistral strike-slip faults (F5, F6, F7, F8, F10) that crosscut those of the early episodes as well as the orebodies. Magmatic intrusions in the Caixiashan deposit area consist of an exposed diorite-quartz diorite stock and a number of dykes of various compositions including diorite, quartz diorite and diabase (Cao et al., 2012). The stock was emplaced in the Mesoproterozoic Xingxingxia and Kawabulake groups in the northern mining area and has a whole rock Rb-Sr isochron age of 323 Ma (Fig. 2; Gao et al., 2006; Wang et al., 2010). Hornfels and hydrothermal alterations of tremolite, chlorite, silica, carbonate and actinolite were observed in the contact zones between the stock and the Kawabulake Group (Fig. 2; Cao et al., 2012, 2013). A concealed monzonitic granite intrusion was also intersected at ca. 500 m underground by deep drilling (Cao et al., 2012). Similar K-feldspar

granite and monzogranite stocks near the Caixiashan deposit (outside Fig. 2) yield zircon U-Pb ages of 333.6 ± 3.6 Ma and 330.0 ± 3.6 Ma, respectively, which were formed in an active continental margin arc environment related to the northward subduction of the South Tianshan Ocean plate (Chen et al., 2019). The diorite dykes have been dated at 353.0 ± 2.5 Ma, 352.0 ± 1.6 Ma, 348.2 ± 2.0 Ma and 352.2 ± 2.7 Ma (Li et al., 2016c). 3.2 Characteristics of orebodies A total of 182 orebodies in the form of irregular lenses and pods have been delineated in the Caixiashan Zn-Pb deposit, and these orebodies are mainly located in the lower lithologic member of the Mesoproterozoic Kawabulak Group near lithological contacts and faults (Fig. 3). The deposit is divided into the four ore zones (No. Ⅰ, Ⅱ, Ⅲ and Ⅳ) based on the distribution of orebodies (Fig. 2). The No. Ⅰ ore zone is mainly hosted in the siltstone breccia near the F1 fault in the northern limb of the anticline, whereas the No. Ⅱ, Ⅲ, Ⅳ ore zones are all mainly located in the dolomite marble near interlayer fractures in the southern limb. The siltstone is much less mineralized than the dolomite marble and only comprises a minor proportion of the total Zn-Pb resource. The No. Ⅱ ore zone accounts for the largest portion of the reserves and is characterized by relatively high grades of Zn-Pb and some useful elements such as Ag (with an average grade of 13.48 ppm and highest grade of 87.50 ppm), Cd (with an average grade of 57.53 ppm) and Ga (with an average grade of 4.9 ppm). The mineralization styles include massive, laminated, disseminated sulfides and those in veins and veinlets (Cao et al., 2013). Ore and gangue minerals occur as open-space filling of voids, cementation of breccias and replacement of the dolomite marble, as readily seen in drill core, hand specimens and thin sections (Cao et al., 2013; Li et al., 2016b). The high-grade orebodies are generally associated with fractures and breccia zones, which are also marked by various hydrothermal alterations of quartz, calcite, sericite, chlorite, tremolite and actinolite (Cao et al., 2012). 3.3 Ore mineralogy and paragenetic sequences The primary ores mainly comprise sphalerite, galena, pyrite and pyrrhotite with minor amounts of arsenopyrite, chalcopyrite, tetrahedrite, argentite and other Pb-Sb-Ag sulfosalts , whereas the oxidized and mixed ores have complex assemblages of anglesite, cerussite, smithsonite, jarosite, limonite, hematite and malachite with various amounts of sulfides (Fig. 4; Gao et al., 2007a, 2007b; Li et al., 2018). Based on textural characteristics and paragenetic associations observed within the Caixiashan deposit, mineralization is divided

into three stages, namely pre-ore stage, syn-ore stage and post-ore stage (Fig. 5). The pre-ore stage is characterized by massive syn-sedimentary pyrite with fine-grained dolomite and calcite in the laminated ores (Figs. 4a, 4b; Li et al., 2016b). The syn-sedimentary pyrite (Py1) has a colloform or framboidal texture and it is locally recrystallized and occurs as hydrothermal pyrite (Py2), which were both replaced by later sulfides such as sphalerite and galena (Figs. 4b, 4c). The syn-ore stage is divided into three substages with different characteristic mineral assemblages: tremolite-graphite (Ⅱ-1), sphalerite-pyrrhotite (Ⅱ-2), and galena-sulfosalt (Ⅱ-3). Stage II-1 is represented by the formation of tremolite, graphite, quartz and recrystallized dolomite and calcite in the hydrothermal carbonate-replacement ores (Fig. 4d). The long columnar euhedral tremolite was generally crosscut and replaced by later sulfides such as galena, sphalerite and medium- to coarse-grained hydrothermal pyrite (Figs. 4e, 4f). Stage II-2 is characterized by large volumes of massive sphalerite and pyrrhotite coexisting with hydrothermal quartz after precipitation of slightly earlier pyrite and arsenopyrite (Figs. 4g, 4h). Small pyrrhotite inclusions locally occur in sphalerite with a linear distribution pattern, which may have resulted from solid solution or that the pyrrhotite and sphalerite were precipitated from the ore-forming fluid at the same time (Figs. 4b, 4g). The overall contemporaneousness of sphalerite and pyrrhotite is also manifested by their mutual crosscutting relationship (Fig. 4h). Stage II-3 is represented by anhedral inclusions and/or veins of galena, which replace massive sphalerite (Fig. 4g). Locally tetrahedrite, argentite, chalcopyrite and other PbSb-Ag sulfosalts including kilbrickenite (Pb9Sb22S42), tetrahedrite (Cu12Sb4S13), boulangerite (Pb5Sb4S11), bournonite (CuPbSbS3) and pyrargyrite (Ag3SbS3) are associated with galena (Peng et al., 2006; Liang et al., 2008). Pyrrhotite is also locally surrounded by galena-chalcopyrite-tetrahedrite-argentite association (Fig. 4i). The post-ore stage includes two substages, i.e. dynamic deformation (Figs. 4j, 4k) and supergene oxidation (Fig. 4l). The early dynamic deformation of sulfides, especially galena, may be related to tectonic activities during the Permian-Carboniferous (Chen et al., 2019), whereas the later supergene oxidation, characterized by a mineral assemblage of cerussite, smithsonite, anglesite, jarosite, limonite, hematite and malachite (Fig. 4l), may have occurred after the area was uplifted and eroded and the orebodies were close to the surface. 4. Samples and analytical methods 4.1 Zircon LA-ICP-MS U-Pb dating

In order to better ascertain the emplacement ages of the felsic intrusions in the Caixiashan deposit area, two samples, one quartz diorite (C-220) and one diorite (C-113), were selected to separate zircon grains for zircon U-Pb dating (Fig. 2). These grains were collected via conventional density and magnetic techniques before being handpicked under a binocular microscope, and they were then mounted in an epoxy resin and polished to about half of their diameter. All these zircon grains were documented with transmitted and reflected microscopy images to examine exterior textures, and with cathodoluminescence (CL) images to examine internal textures before selecting points for analysis. Zircon U-Pb analyses were conducted by LA-ICP-MS at the Institute of Mineral Resources, Chinese Academy of Geological Sciences (IMR-CAGS), Beijing, and were performed with a NewWave UP 213nm Nd-YAG laser coupled to a Finniagan Neptune multi-collector ICP-MS at IMR-CAGS. Analyses of standard zircon GJ-1 (Elhlou et al., 2006) were interspersed between the samples to ensure analytical accuracy. Concentrations of U, Th and Pb were calibrated using international standard M127 (U=923ppm; Th=439ppm; Th/U=0.475; Nasdala et al., 2008). Data were calculated using the ICPMSDataCal program (Liu et al., 2008), and the common Pb calculations were carried out by using the ComPbCorr#_151 program (Anderson, 2002). Data processing was performed using the Isoplot/Ex v. 3.0 program to draw LA-ICP-MS zircon U-Pb concordant diagrams and weighted average age schematic diagrams (Ludwig, 2003). Uncertainties in individual analyses are reported at the 1σ level; errors on the ages are quoted at the 95% confidence level. 4.2 Sphalerite and pyrrhotite Rb-Sr dating Five sphalerite and one pyrrhotite samples in laminated ores were collected from the No. II ore zone of the Caixiashan Zn-Pb deposit. The pure sulfides of the same shape, color, and granularity were handpicked to fulfill as much as possible the same origin requirement for Rb-Sr dating. The Rb-Sr isotopic analyses were performed on a VG-354 Thermal Ionization Mass Spectrometer at the State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil Science, Chinese Academy of Science. The sphalerite and pyrrhotite separates (representing the 40-60 mesh size fraction) were soaked in 10% acetic acid to remove any remaining carbonate, and then crushed to size of 200-400 mesh in a boron-carbide mortar and leached with deionized water to remove fluid inclusions. The sulfide residues were then prepared for Rb-Sr dating. The details of this analytical method were described by Wang et al. (2007) and Guo et al. (2018). Rb and Sr concentrations were obtained by isotope dilution. Sr isotope ratios were measured on Thermal Ionization Mass Spectrometer with five collectors. The

total procedure blanks for Rb and Sr were ＜20 pg and 50 pg, respectively. The average measured 87Sr/86Sr ratio for the NBS-987 standard in this study was 0.710223 ± 0.000006. The 87Rb/86Sr analytical error is < 0.5%, and the 87Sr/86Sr analytical error is 0.01-0.005%. The Rb-Sr isochron age and initial isotopic ratios were calculated using the Isoplot/Ex v. 3.0 program (Ludwig, 2003). 4.3 S-Pb isotopic analysis Seven ore samples (C-25, C-71, C-72, C-199, C-202, C-206, C-212) from the No. Ⅱ ore zone of the Caixiashan Zn-Pb deposit were collected for S and Pb isotopic analysis. These ore samples were obtained from syn-sedimentary stage (C-72), sphalerite-pyrrhotite stage (C-71, C-212) and galena-sulfosalt stage (C-25, C-199, C-202, C-206). Separate pyrite, sphalerite, pyrrhotite and galena grains were extracted from crushed material (40-60 mesh-size) and concentrated by hand-picking under a binocular microscope to a purity higher than 99%, followed by cleaning in doubly distilled water. Eleven whole rock samples of dolomitized marble, sandstone and quartzite from the Mesoproterozoic Kawabulake Group were also selected for Pb isotopic analysis; samples with mineralization and strong hydrothermal alteration were avoided. The sulfide separates and whole rock samples were all powdered to ＜200 mesh using an agate mortar. The powdered sulfide and whole rock samples were then sent to the analytical laboratory at the Beijing Research Institute of Uranium Geology for S and Pb isotopic analysis. Sulfur in the sulfides was first converted to SO2 by reacting with Cu2O using a continuous flow device, and then analyzed with a Finnigan MAT-251 mass spectrometer. The accuracy of the S isotope analyses is better than ± 0.2‰. Lead in the sulfides and wholerock samples was extracted by reacting with HF + HClO4 solutions, followed by ion exchange processes, and then analyzed with an ISOPROBE-T surface ionization mass spectrometer. The analytical error for 1 μg Pb is less than 0.05% for 206Pb/204Pb and less than 0.005% for 208Pb/206Pb. 5. Results 5.1 Zircon U-Pb ages Zircon grains from the quartz diorite (C-220) are mostly colorless or yellowish brown without any visible inclusions. These grains are commonly 80-110 µm long and 30-70 µm wide, euhedral crystals showing clear oscillatory zoning as revealed by CL images (Fig. 6a). Analytical data of 23 zircon grains from this sample are

summarized in Table 1. Th content is between 47.1 ppm and 192.6 ppm, while U content is between 55.5 ppm and 260.9 ppm. The Th/U ration varies from 0.66 to 1.10. These characteristics are indicative of a typical magmatic genesis for all the analyzed zircon grains. All the results are plotted on the U-Pb concordant diagram within analytical errors (Fig. 6b), yielding a weighted mean 206Pb/238U age of 351.9 ± 3.5 Ma (MSWD = 0.091, n = 23). The mean age is interpreted to be the crystallization age of the quartz diorite. Zircon grains from the diorite (C-113) are mostly colorless or yellowish brown without any inclusions. These grains are generally 50-90 µm long and 30-50 µm wide, euhedral crystals with low length-width ratios showing clear oscillatory zoning as revealed by CL images (Fig. 6c). Analytical data of 24 zircon grains from this sample are also summarized in Table 1. Th content is between 34.1 ppm and 319.6 ppm, while U content is between 61.9 ppm and 303.5 ppm. The Th/U ration varies from 0.53 to 1.04. These data also indicate a typical magmatic origin for all the analyzed zircon grains. All the results are plotted on the U-Pb concordant diagram within analytical errors (Fig. 6d), yielding a weighted mean 206Pb/238U age of 348.2 ± 3.7 Ma (MSWD = 0.30, n = 24). The mean age is interpreted to be the crystallization age of the diorite. 5.2 Rb-Sr isochron age The Rb-Sr isotope data of the sphalerite and pyrrhotite samples are listed in Table 2, and plotted in isochron diagram in Fig. 7. Rb content is between 0.0157 ppm and 1.589 ppm, while Sr content is between 0.4561 ppm and 3.256 ppm. The 87Rb/86Sr and 87Sr/86Sr ratios range from 0.0854 to 1.683, and from 0.712562 ± 0.000009 to 0.720217 ± 0.000009, respectively. All the analytical data yield a Rb-Sr isochron age of 337.2 ± 5.7 Ma and an initial 87Sr/86Sr ratio of 0.712148 ± 0.000064 (Fig. 7a), while the sphalerite data alone yield a Rb-Sr isochron age of 344 ± 29 Ma and an initial 87Sr/86Sr ratio of 0.71213 ± 0.00017. The sphalerite and pyrrhotite samples have variable 87Sr/86Sr ratios without covariance between 1/Sr and 87Sr/86Sr (Fig. 7b), indicating that the value of (87Sr/86Sr)i has remained constant. 5.3 S isotopic compositions The S isotopic compositions of 48 sulfide samples obtained from the Caixiashan Zn-Pb deposit during both this study and previous studies are listed in Table 3 and shown in Fig. 8. The δ34SV-CDT values of pyrite vary

broadly from -25.3‰ to 19.1‰. Syn-sedimentary pyrite has very negative δ34SV-CDT values of -22.9‰ in this study and from -25.3‰ to -8.6‰ reported by Li et al. (2018), whereas the hydrothermal pyrite has positive δ34SVCDT

values ranging from 8.3‰ to 19.1‰. The pyrrhotite, sphalerite and galena display similar S isotopic

composition, with the δ34SV-CDT values ranging from -2.42 ‰ to 12.2‰ for pyrrhotite, 6.5‰ to 16.02‰ for sphalerite, and 1.2‰ to 13.88‰ for galena (Fig. 8). 5.4 Pb isotopic compositions The Pb isotopic compositions of sulfides (including pyrite, pyrrhotite, galena and sphalerite), Carboniferous intrusive rocks (including diorite and granite) and rocks of the Mesoproterozoic Kawabulake Group from the Caixiashan Zn-Pb deposit, obtained from this study and previous studies, are summarized in Table 4 and Table 5 and shown in Fig. 9. The contents of U and Th for the sulfides are too low to influence the Pb isotopic compositions, whereas for whole rocks of diorite, granite, dolomite marble, carbonaceous slate, chert and sandstone, the Pb isotope compositions at the time of mineralization were adjusted using the U, Th, and Pb concentrations of the samples and a mineralization age of 337 Ma in this study (e.g., Carr et al., 1995; Zhang et al., 2002; Gao et al., 2019). The twenty-six sulfide samples have relatively homogeneous Pb isotopic compositions with

206Pb/204Pb, 207Pb/204Pb,

and

208Pb/204Pb

values ranging from 17.074 to 17.361, 15.422 to

15.614 and 36.685 to 37.303, respectively. However, the seventeen whole-rock samples of the Mesoproterozoic Kawabulake Group show large variations in

206Pb/204Pb, 207Pb/204Pb

and

208Pb/204Pb

ratios of 16.958-17.966,

15.386-15.581 and 36.467-38.673, respectively. However, whole rock samples of dolomite marble and some sandstone yield similar Pb isotopic ratios as the sulfides (Fig. 9 and Table 5). Whole-rock samples of diorite and granite also have Pb isotopic compositions that partly overlap with those of the sulfides, with ratios for 206Pb/204Pb, 207Pb/204Pb

and 208Pb/204Pb in the ranges of 16.802 - 18.091, 15.467 - 15.547, and 36.560 - 37.821,

respectively (Fig. 9 and Table 5). 6. Discussion 6.1 Age of mineralization and related magmatism Although some geochronological studies have been conducted to date the mineralization of the Caixiashan Zn-Pb deposit (Li et al., 2016a, 2016c; Chen et al., 2019), the temporal relationship between mineralization and Carboniferous magmatism remains uncertain. Li et al (2016a, 2016b, 2018) suggested that the magmatism

postdates the mineralization, because the pyrite Re-Os isochron ages of 859 ± 79 Ma (MSWD=6.7) and 837 ± 39 Ma (MSWD=6.5), interpreted to be the Zn-Pb mineralization ages, are much older than the zircon U-Pb ages of 353.0 ± 2.5 Ma, 352.0 ± 1.6 Ma, 348.2 ± 2.0 Ma and 352.2 ± 2.7 Ma for the high-Mg diorite dykes that are widely distributed in the deposit area. However, it is possible that the pyrite Re-Os isochron ages do not accurately represent the mineralization age, because it is impossible to extract pure hydrothermal pyrite samples related to the main mineralization, as these pyrite grains may have been initially formed as early syn-sedimentary colloform/framboidal pyrite and inherited some of the initial Re-Os compositions, and precipitation of hydrothermal pyrite grains during syn-ore stage may be earlier than Zn-Pb mineralization (Li et al., 2016a). The possibility of spurious Re-Os isochron ages therefore cannot be ruled out, due to possible mixing effects and complexities within these pyrite samples. Similar phenomena and interpretations have been recently reported in carbonate-hosted Zn-Pb deposits (Hnatyshin et al., 2020). The sulfide Rb-Sr isotopic dating method has been regarded as one of the best isotopic dating methods to directly determine the accurate mineralization age, and has been successfully applied to date the mineralization in many hydrothermal Zn-Pb deposits (Nakai et al., 1990, 1993; Christensen et al., 1995; Saintilan et al., 2015; Ostendorf et al., 2017; Guo et al., 2018; Dai et al., 2019). In the Caixiashan Zn-Pb deposit, the sphalerite and pyrrhotite Rb-Sr isochron age of 337.2 ± 5.7 Ma obtained in this study and interpreted to represent the main phase mineralization age is close to the zircon U-Pb ages of 348.2 ± 3.7 Ma and 351.9 ± 3.5 Ma for the dioritequartz diorite stock in the northern deposit area. These ages are also similar to the zircon U-Pb ages of 333.3 ± 3.6 Ma and 330.0 ± 3.6 Ma reported for the K-feldspar granite and monzonitic granite stocks in the surrounding area (Chen et al., 2019). The similarity of emplacement ages of granitic intrusions and the mineralization age (Fig. 10) suggests that the Carboniferous granitic magmatism is coeval with the Zn-Pb mineralization, although the relatively early diorite-quartz diorite stock may not be directly related to the mineralization, because the age gap is much larger than 2 Ma (the maximal lifespan of a magmatic-hydrothermal system; Sillitoe and Mortensen, 2010; Zhao et al., 2018a). This inference, however, is based on the assumption that the sphalerite and pyrrhotite Rb-Sr dating is reliable, which need to be further discussed here. Several basic requirements must be met for reliable sulfide Rb-Sr dating, including same origin of sulfides,

constant initial 87Sr/86Sr ratio under the closed mineralization system and variable 87Rb/86Sr ratio of sulfides. In the Caixiashan deposit, sphalerite and pyrrhotite samples with the same shape, color and granularity were carefully collected from the laminated ore without evident deformation and supergene oxidation to fulfill as much as possible the experiment requirements. Petrographic observations reveal that pyrrhotite and sphalerite display solid solution exsolution texture and mutual crosscutting relationship (Fig. 5), indicating that they were precipitated from the ore-forming fluid at the same time (Hutchison and Scott, 1981). The sphalerite Rb-Sr isochron age (344 ± 29 Ma) is similar to the isochron age (337.2 ± 5.7 Ma) with pyrrhotite included, which also suggest that pyrrhotite is indeed contemporaneous with sphalerite. There is no linear relationship between 1/Sr and 87Sr/86Sr (Fig. 7b), suggesting that the initial (87Sr/86Sr)i value has remained constant, because plot of 1/Sr 87Sr/86Sr

was a widely used test method for Rb-Sr isotopic dating (Petke and Diamond, 1996; Guo et al., 2018).

The sphalerite and pyrrhotite Rb-Sr isochron age in this study is therefore geologically significant and reliable. 6.2 Sources of reduced sulfur and ore metals Sulfur isotopic compositions of the sulfides and possible geological reservoirs are important indicators to constrain the source of reduced sulfur (Rye and Ohmoto, 1974; Ohmoto and Goldhaber, 1997). By comparation with the δ34SV-CDT values of seawater sulfates in the Mesoproterozoic Kawabulake Group (~20‰, Strauss, 1993) and magmatic intrusions of mantle source (0 ± 3‰, Ohmoto and Goldhaber, 1997), the wide range of δ34SV-CDT values of sulfides obtained in this study and previous studies (-2.42 ‰ to 19.1 ‰; Fig. 8) suggests that the reduced sulfur for mineralization may have been derived from multiple sources including those from reduction of sulfates. Most of the sulfur with high positive δ34SV-CDT values may indicate that thermal sulfate reduction (TSR) of seawater-derived sulfates in the marine sedimentary basement rocks, with the largest S isotope fractionations of less than 15 ‰ (Kiyosu, 1980; Kiyosu and Krouse, 1990; Machel et al., 1995), may account for the predominant reduced sulfur source, which is favored by the elevated temperatures of the oreforming fluids (180 ℃ - 370 ℃) and presence of CH4 and SO42- coexisting in individual fluid inclusions (Peng et al., 2007; Li et al., 2016a, 2018). In contrast, the low δ34SV-CDT values of syn-sedimentary pyrite ranging from -8.6 ‰ to -25.3 ‰ may have been derived from bacterial sulfate reduction processes (BSR), which is consistent with framboidal and colloidal pyrite, generally interpreted to be the products of bacterial activity (Donald and

Southam, 1999). Syn-sedimentary pyrite may have contributed some reduced sulfur to the main phase mineralization through recrystallization and replacement of pyrite by sphalerite and galena, thus lowering the δ34SV-CDT values of hydrothermal sulfides to some extent. Furthermore, magmatic fluids as an important possible contributor of reduced sulfur for mineralization cannot be ruled out, as some of the δ34SV-CDT values also fall in the range of magmatic sulfur. Pb isotopes are a powerful tool for tracing source of Pb and, by inference, of the other ore metals (Carr et al., 1995; Mirnejad et al., 2011; Gromek et al., 2012). The similarities and differences between the Pb isotopic compositions of sulfides and those of possible source rocks are shown in Fig. 9. The sulfides of galena, pyrite, sphalerite and pyrrhotite from the Caixiashan Zn-Pb deposit have similar Pb isotopic compositions as dolomite marble, sandstone and chert of the Kawabulake Group, suggesting that ore metals were mainly sourced from these basement rocks. This inference is supported by the high abundance of ore elements (Pb-Zn-Ag-Cu-As) in the basement rocks of the Kawabulake Group, especially in the dolomite marble (Lu et al., 2012). Similarly, the Carboniferous diorite and granite intrusions are located in a large cluster partly overlapping with the sulfides, suggesting that the Carboniferous magmatism may provide some ore metals. Moreover, the Pb isotopic compositions of sulfides are close to the evolution curve of orogen (Fig. 9), indicating that the source of ore metals has mixed attributes of the mantle and crust. This inference is consistent with the low initial Os values of hydrothermal pyrite, which was interpreted to reflect the contribution of the Carboniferous mantle-derived magmatism with a mantle Os signature (Li et al., 2016a, 2016c). The initial

87Sr/86Sr

ratio of sphalerite and

pyrrhotite (0.712148) is also compatible with a mixed origin of the metals from the mantle (87Sr/86Sr = 0.707; Fature, 1986) and continental crust (87Sr/86Sr = 0.719; Fature, 1986). 6.3 Mineralization model and its implication The Caixiashan Zn-Pb deposit shares many similarities with intrusion-related carbonate replacement deposits elsewhere (Titley, 1996; Megaw, 1998; Vikre, 1998; Bonsall et al., 2011). Although the carboniferous stocks do not have direct spatial relationship with the orebodies (Gao et al., 2007a), the hydrothermal alterations of tremolite, chlorite, silica and carbonate have been identified in the contact zone between the dolomite marble of the Kawabulake Group and these stocks (Peng et al., 2006; Gao et al., 2007a, 2007b; Cao et al., 2012, 2013). The location of Zn-Pb mineralization controlled by faults/interlayer fractures and dolomite marble (Cao et al.,

2012, 2013) and the presences of Cu-Ag-Sb-As-Pb sulfosalts such as tetrahedrite, ramdohrite, pyrargyrite and

argentite (Gao et al., 2007a) in the Caixiashan Zn-Pb deposit are all commonly found in the reported intrusionrelated carbonate replacement deposits (Sharp and Buseck, 1993; Lueth et al., 2000; Voudouris et al., 2008). The relatively high ore-forming temperature (180 ℃ to 370 ℃ and concentrated around 270 ℃; Peng et al., 2007; Li et al., 2016b) is similar to those of the distal high-temperature intrusion-related carbonate replacement deposits, such as the Zn-Pb-Ag mineralization in the Lavrion District, Attica, Greece (Voudouris et al., 2008; Bonsall et al., 2011), which is higher than those ascribed to MVT deposits (90 ℃ - 200 ℃; Leach et al., 2005). It is consistent with the three-dimensional model of ore-forming temperature based on systematic fluid inclusion studies that the intrusions account for the high-temperature mineralization zones (Sun et al., 2012), and the CO-H isotope tracing results that the ore-forming fluids are initially magmatic origin with gradual more connate brine addition accompanying with the Zn-Pb mineralization (Peng et al., 2007; Gao et al., 2007a, 2007b; Cao et al., 2013). A plot of homogenization temperatures versus silver grade for carbonate-hosted Zn-Pb deposits on the earth (Fig. 11; Titley, 1996; Bonsall et al., 2011) also displays that the Caixiashan deposit is part of hightemperature intrusion-related carbonate replacement deposits rather than MVT or Irish type deposits.

Based on above discussion, we therefore proposed that the Caixiashan deposit was a high-temperature carbonate replacement type deposit related to the coeval Carboniferous granitic intrusions buried at depth (Fig. 12), which may be a distal magmatic hydrothermal product formed in an arc environment related to the

subduction of the Southern Tianshan Ocean plate beneath the Middle Tianshan massif (Dong et al., 2011; Han et al., 2011; Li et al., 2016c; Chen et al., 2019). During the Mesoproterozoic period, the Central Tianshan massif was likely in a relatively stable passive margin setting (Li et al., 2016b; Lu et al., 2018), and the syn-sedimentary pyrite precipitated simultaneously within the fertile basement rocks of the Kawabulake Group yielding a Re-Os isochron age of 1019 ± 70 Ma (MSWD=3.5) in the Caixiashan deposit (Li et al., 2016b, 2018). It may provide favorable ore-forming conditions such as some sources of reduced sulfur and ore metals, forming the critical pre-ore stage. During the Carboniferous period, extensive felsic magmatism and related precious and base metal mineralization were formed as a result of the subduction

of the South Tianshan Ocean plate (Fig. 12a; Li et al., 2016c; Lu et al., 2018; Chen et al., 2019). The magmatic fluids enriched in ore metals and sulfur were derived from the causative granitic intrusions and migrated away along the regional Aqikekuduke Fault and its secondary faults such as F1, F2, F3, F4 (Fig. 12b). The high-temperature magmatic fluids facilitate the mobilization and extraction of ore-forming elements from the basement rocks of the Kawabulake Group during the long-distance transportation, resulting in the formation of ore-forming fluids, and then the fluids flow into interlayer fractures and breccia zones with high permeabilities, where they were mixed with the carbonaceous dolomite marble or slate (Fig. 12b). Accompanying with progressive fluid-rock reaction, organic matter acted as an important reducing agent indicative of the CH4 component in the fluid inclusion and C-O isotopic compositions (Gao et al., 2007a, 2007b; Cao et al., 2012, 2013; Li et al., 2018), and large amounts of H2S were formed from the connate seawater sulfates by the process of thermal sulfate reduction (TSR), resulting in sulfide precipitation at the deposition site. Syn-sedimentary pyrite replacement and magmatic origin sulfur may also provide some reduced sulfur. At the same time, hydrothermal alteration of tremolite is gradually changed to relatively low-temperature hydrothermal alterations of silica and carbonate with the flowing of the fluids from deep concealed intrusions escaping to the shallow parts (Cao et al., 2012). After the Carboniferous period, the deposit experienced post-ore stages of dynamic deformation and supergene oxidation to some extent. Extensive arc-related Carboniferous magmatism related to the subduction of the South Tianshan Ocean plate and carbonate rock of the Kawabulake Group were reported in the Middle Tianshan Massif of Eastern Tianshan (Fig. 1b; Chen et al., 2019; Dong et al., 2011; Han et al., 2011; Nijat et al., 2015; Li et al., 2016c). Although some distal carbonate replacement Zn-Pb deposits including Jiyuan, Yuxi, Hongyuan and Hongxingshan, which are similar to the giant Caixiashan deposit, and coeval skarn Zn-Pb deposits including Liujiaquanxi and Qianluzi have been discovered in the Kawabulake Group of Eastern Tianshan (Gao et al., 2007a, 2007b; Ding et al., 2010, 2016; Cao et al., 2012, 2013; Lu et al., 2018), the number of large-scale Zn-Pb deposits is limited. However, many large-scale distal skarn Zn-Pb-(Ag-Cu) deposits related to Carboniferous arc-related magmatism in the similar metallogenic setting, such as Kurgashingan (Turamuratov et al., 2011), Altyntopkan (Li et al., 2010), Tuyke (Li et al., 2010), Keregetash (Li et al., 2010) and Arqiale (Dai et al., 2019), have been discovered in western Tianshan. Moreover, regional Aqikekuduke Fault and its secondary faults (F1,

F2, F3, F4) widely detected in the Middle Tianshan Massif provide favorable ore-forming conditions. These all may indicate that there is a great potential of finding more similar large-scale carbonate-hosted Zn-Pb deposits like Caixiashan in Eastern Tianshan. 7. Conclusions (1) Rb-Sr isotopic dating of paragenetic association of sphalerite and pyrrhotite yields an isochron age of 337.2 ± 5.7 Ma, which was interpreted as the direct mineralization age, and then the mineralization was coeval with the Carboniferous granitic magmatism. (2) S isotopic compositions of sulfides reveal that reduced sulfur was mainly derived from thermal sulfate reduction (TSR) of seawater-derived sulfates in the marine sedimentary basement rocks and minor contribution by replacement of syn-sedimentary pyrite, as well as a possible input of magmatic sulfur. (3) Pb isotopic compositions of sulfides and possible source rocks indicate that the ore metals are mainly sourced from some rocks of the Mesoproterozoic Kawabulake Group and Carboniferous felsic intrusions. (4) The Caixiashan Zn-Pb deposit is a distal high-temperature carbonate replacement deposit related to concealed granitic intrusions, which were formed in an arc environment related to the subduction of the South Tianshan Ocean plate underneath the Central Tianshan massif during the Carboniferous time.

Acknowledgments: This research was jointly supported by the National Key Research and Development Program of China (2017YFC0601202), the National Science and Technology Support Program of China (No. 2011BAB06B02), Natural Science Foundation of China (41902067), China Postdoctoral Science Foundation Grant (2019M650784), the Fundamental Research Funds for the Central Universities (2652016072) and Foreign Experts' Recruiting Program from the State Administration of Foreign Experts Affairs of China (G20190001238). The authors would like to thank the First Brigade of Xinjiang Geology and Mineral Resources Bureau and Xinjiang Institute of Geological Survey for their support of our fieldwork. Great appreciation is extended to two anonymous reviewers for their reviews and constructive suggestions, and to Prof. Franco Pirajno and Prof. Wenjiao Xiao for their editorial handling.

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Figure Captions: Fig. 1 (a) Simplified tectonic map of the Central Asian Orogenic Belt (modified after Sengör et al., 1993) showing the location of the Eastern Tianshan; (b) Geological map of the Eastern Tianshan and major ore

deposits distribution (modified after Wang et al., 2006a, 2006b; Lu et al., 2018). Zircon U-Pb ages of Carboniferous intrusions in the Middle Tianshan massif are also presented (Sun et al., 2006; Wang et al., 2006a, 2006b; Zhang et al., 2010; Nijat et al., 2015; Li et al., 2016c; Lu et al., 2018; Chen et al., 2019).

Fig. 2 Geological map of the Caixiashan Zn-Pb deposit (modified after Cao et al., 2013; Li et al., 2016b). The locations of cross-section line 36 and line 38 have been outlined. The alteration zones including tremolitization and hornfels were drawn after Geological Team 1 of Xinjiang Bureau of Geology and Mineral Resources (2005).

Fig. 3 Geological cross sections of the NO. Ⅱ ore zone in the Caixiashan Zn-Pb deposit along line 36 (a) and line 38 (b) and the location is shown in Fig. 2 (modified after Geological Team 1 of Xinjiang Bureau of Geology and Mineral Resources, 2005).

Fig. 4 Photographs and photomicrographs of ore features and paragenetic sequences in the Caixiashan Zn-Pb deposit. (a) Laminated ore and massive pyrite replaced by sphalerite and galena; (b) Crushed pyrite replaced by sphalerite and solid solution exsolution texture of sphalerite-pyrrhotite; (c) colloform pyrite (Py1) recrystallized to be hydrothermal pyrite (Py2) and replaced by sphalerite, galena and pyrrhotite veinlets; (d) Mesh-vein ore and dolomite marble fragments replaced by massive sphalerite; (e) Tremolite replaced by pyrite and sphalerite; (f) Tremolite replaced by galena, sphalerite and pyrrhotite; (g) Sphalerite, pyrrhotite and arsenopyrite replaced by galena; (h) Sphalerite and pyrrhotite showing mutual crosscutting relationship and euhedral arsenopyrite surrounded by pyrrhotite; (i) Pyrrhotite surrounded by late galena, tetrahedrite and argentite; (j) Deformed massive ore and galena crosscut the whole ore; (k) Edge of massive sphalerite grains locally deformed showing directional arrangement of sericite; (l) Outcrop of oxidized ore with the occurrence of smithsonite, limonite and malachite. Mineral abbreviations: Sph sphalerite, Gn - galena, Py - pyrite, Py1 - colloform pyrite, Py2 - recrystallized hydrothermal pyrite, Po pyrrhotite, Apy - arsenopyrite, Ccp - chalcopyrite, Td - tetrahedrite, Arg - argentite, Cal - calcite, Ser sericite, Tr - tremolite, Lm - limonite, Sm - smithsonite, Ma - malachite.

Fig. 5 Paragenetic sequence of ore and gangue minerals from the Caixiashan Zn-Pb deposit.

Fig. 6 Zircon cathodoluminescence (CL) images and U-Pb concordant diagrams and weighted average ages of the quartz diorite (a, b) and diorite (c, d) samples from the Caixiashan Zn-Pb deposit.

Fig. 7 Rb-Sr isochron diagram and 1/Sr vs. 87Rb/86Sr diagram for sphalerite and pyrrhotite from the Caixiashan Zn-Pb deposit. A complete list of data is presented in Table 2.

Fig. 8 Histogram of δ34SV-CDT values of sulfide minerals including pyrite, pyrrhotite, sphalerite and galena from the Caixiashan Zn-Pb deposit. A complete list of data is presented in Table 3.

Fig. 9 Pb isotopic compositions of sulfide minerals including pyrite, pyrrhotite, sphalerite and galena, host rocks of the Mesoproterozoic Kawabulake Group, and Carboniferous magmatic rocks from the Caixiashan ZnPb deposit and adjacent areas. (a) 207Pb/204Pb-206Pb/204Pb diagram; (b)208Pb/204Pb-206Pb/204Pb diagram. The evolution lines for the mantle, orogen, upper crust and lower crust are from Zartman and Doe (1981), and a complete list of data is presented in Table 4 and Table 5.

Fig. 10 Compiled ages of mineralization age and Carboniferous felsic magmatic intrusions in the Caixiashan ZnPb deposit. A complete list of data is presented in Table 6. Arabic numerals stand for the reference number.

Fig. 11 Homogenization temperature vs. silver grade diagram of carbonate-hosted deposits worldwide, including high-temperature carbonate replacement, Mississippi Valley type (MVT) and Irish type ore deposits (modified after Titley, 1993; Bonsall et al., 2011). A shaded area for the Caixiashan Zn-Pb deposit shows that it has values of homogenization temperature (Peng et al., 2007; Li et al., 2016b) and silver grade that are within the field of high-temperature carbonate-replacement type deposits.

Fig. 12 Proposed genetic model for the Caixiashan Zn-Pb deposit. (a) extensive coveal felsic intrusions were emplaced during the Carboniferous, which were related to the subduction of the South Tianshan Ocean plate (modified after Chen et al., 2019); (b) the concealed causative granitic intrusion was emplaced and generated the large-scale Zn-Pb mineralization at ca. 337 Ma, providing an important source of ore-forming materials and heat for fluid flow (modified after Peng et al., 2007). The schematic diagram of the metallogenic model is inferred based on Gao et al. (2006, 2007a, 2007b) and Cao et al. (2012, 2013).

Table Captions: Table 1 LA-ICP-MS U-Pb data of zircon grains for the quartz diorite and diorite intrusions from the Caixiashan Zn-Pb deposit

Table 2 Rb-Sr isotope compositions of sphalerite and pyrrhotite from the Caixiashan Zn-Pb deposit

Table 3 S isotopic compositions of sulfide minerals from the Caixiashan Zn-Pb deposit

Table 4 Pb isotopic compositions of sulfide minerals from the Caixiashan Zn-Pb deposit

Table 5 Pb isotopic compositions of host rocks of the Mesoproterozoic Kawabulake Group and Carboniferous intrusions from the Caixiashan Zn-Pb deposit

Table 6 Compiled ages of mineralization and Carboniferous felsic magmatic intrusions from the Caixiashan ZnPb deposit

Fig. 1

Fig. 2

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Fig. 8

Fig. 9

Fig. 10

Fig. 11

Fig. 12

Table 1 LA-ICPMS U-Pb data of zircon grains for the quartz diorite and diorite intrusions from the Caixiashan Zn-Pb deposit Spot number

Content (ppm) Th

U

Th/U

Isotopic ratios

Calc

207Pb/206Pb

1σ

207Pb/235U

1σ

206Pb/238U

1σ

207Pb/206Pb

1σ

C-220 Quartz diorite C-220-1

91.2

104.9

0.87

0.0547

0.0030

0.4175

0.024

0.0560

0.0017

466.7

124.1

C-220-2

94.4

99.5

0.95

0.0527

0.0026

0.4043

0.023

0.0557

0.0018

322.3

104.6

C-220-3

62.9

74.6

0.84

0.0618

0.0058

0.4718

0.048

0.0567

0.0022

733.3

201.8

C-220-4

102.0

95.2

1.07

0.0612

0.0095

0.4605

0.066

0.0560

0.0023

655.6

338.9

C-220-5

58.6

70.1

0.84

0.0566

0.0043

0.4295

0.031

0.0558

0.0012

476.0

168.5

20

C-220-6

89.6

88.6

1.01

0.0547

0.0031

0.4067

0.021

0.0556

0.0013

466.7

93.5

C-220-7

59.9

90.4

0.66

0.0607

0.0049

0.4502

0.030

0.0556

0.0020

631.5

169.4

C-220-8

47.1

60.8

0.78

0.0511

0.0079

0.4137

0.067

0.0567

0.0019

255.6

309.2

C-220-9

50.8

63.5

0.80

0.0549

0.0042

0.4114

0.028

0.0558

0.0011

409.3

170.4

C-220-10

118.1

112.9

1.05

0.0567

0.0028

0.4357

0.022

0.0558

0.0012

479.7

109.2

C-220-11

192.6

260.9

0.74

0.0514

0.0024

0.3997

0.019

0.0565

0.0016

261.2

107.4

C-220-12

106.1

111.2

0.95

0.0569

0.0032

0.4367

0.023

0.0565

0.0011

487.1

119.4

C-220-13

125.4

114.3

1.10

0.0532

0.0045

0.3989

0.032

0.0556

0.0015

338.9

158.3

C-220-14

67.8

77.8

0.87

0.0567

0.0033

0.4300

0.023

0.0565

0.0013

479.7

129.6

C-220-15

115.1

105.7

1.09

0.0595

0.0042

0.4568

0.031

0.0566

0.0011

583.4

147.2

C-220-16

62.0

67.1

0.92

0.0544

0.0054

0.4101

0.037

0.0563

0.0016

387.1

225.9

C-220-17

71.1

81.8

0.87

0.0611

0.0044

0.4667

0.032

0.0563

0.0014

642.6

155.5

C-220-18

100.4

106.0

0.95

0.0565

0.0052

0.4282

0.039

0.0558

0.0012

472.3

203.6

C-220-19

93.0

94.7

0.98

0.0577

0.0039

0.4432

0.032

0.0560

0.0015

520.4

146.3

C-220-20

48.9

55.5

0.88

0.0523

0.0052

0.4086

0.039

0.0573

0.0017

298.2

234.2

C-220-21

79.3

88.4

0.90

0.0612

0.0054

0.4406

0.034

0.0560

0.0016

655.6

192.6

C-220-22

92.0

95.7

0.96

0.0572

0.0039

0.4268

0.027

0.0561

0.0011 9

498.2

150.0

C-220-23

70.3

74.8

0.94

0.0593

0.0039

0.4430

0.028

0.0556

0.0013

588.9

144.5

C-113 Diorite C-113-1

162.3

268.7

0.60

0.0521

0.0037

0.4091

0.031

0.0558

0.0016

300.06

167.6

3

C-113-2

107.3

138

0.78

0.0573

0.0031

0.4451

0.024

0.0560

0.0011

501.89

113.9

3

C-113-3

78.1

89.5

0.87

0.0573

0.0079

0.4331

0.055

0.0560

0.0023

501.89

310.1

3

C-113-4

73.5

86.7

0.85

0.0593

0.0048

0.4445

0.031

0.0551

0.0013

588.915

175.9

3

C-113-5

106.1

113.6

0.93

0.0540

0.0048

0.4030

0.035

0.0546

0.0019

368.57

203.7

3

C-113-6

48.7

65.4

0.74

0.0545

0.0066

0.4166

0.053

0.0557

0.0024

390.79

274.0

3

C-113-7

86.9

105.5

0.82

0.0564

0.0046

0.4364

0.033

0.0564

0.0013

477.82

181.5

3

C-113-8

85

104.7

0.81

0.0513

0.0052

0.3966

0.040

0.0556

0.0018

253.77

36.1

3

C-113-9

119

108.6

1.09

0.0590

0.0047

0.4502

0.030

0.0561

0.0010

568.55

158.3

3

C-113-10

80.8

85.7

0.94

0.0572

0.0034

0.4405

0.028

0.0558

0.0010

501.89

133.3

3

C-113-11

75.6

85.3

0.89

0.0536

0.0063

0.3949

0.053

0.0536

0.0019

353.76

260.2

3

le er

C-113-12

117.6

83.2

0.73

0.0597

0.0044

0.4645

0.035

0.0566

0.0013

594.47

156.5

3

C-113-13

34.1

141.2

0.68

0.0559

0.0076

0.4040

0.043

0.0533

0.0029

455.6

300.9

3

C-113-14

206.8

178.5

0.53

0.0581

0.0048

0.4297

0.031

0.0544

0.0016

600.025

179.6

3

C-113-15

94.5

61.9

0.72

0.0594

0.0097

0.4549

0.078

0.0559

0.0025

583.36

356.9

3

C-113-16

44.8

90.4

0.85

0.0602

0.0045

0.4556

0.035

0.0557

0.0014

612.98

161.9

3

C-113-17

319.6

109.2

1.04

0.0511

0.0055

0.3879

0.048

0.0533

0.0021

255.62

220.4

3

C-113-18

96.1

127.4

0.74

0.0521

0.0046

0.3893

0.034

0.0553

0.0016

300.06

201.8

3

C-113-19

94.4

75.4

0.91

0.0589

0.0041

0.4470

0.029

0.0559

0.0018

561.145

150.0

3

C-113-20

68.9

303.5

0.60

0.0515

0.0036

0.3927

0.032

0.0541

0.0017

261.175

158.3

3

C-113-21

87.5

67.8

0.87

0.0579

0.0118

0.4314

0.090

0.0539

0.0027

524.11

260.2

3

C-113-22

59.1

80.8

0.70

0.0534

0.0070

0.4059

0.055

0.0549

0.0011 8

346.35

301.8

3

C-113-23

56.6

183.4

0.82

0.0531

0.0045

0.4041

0.031

0.0557

0.0012

344.5

195.5

3

C-113-24

49.9

130

1.01

0.0545

0.0063

0.4180

0.044

0.0558

0.0020

390.79

261.1

3

Table 2 Rb-Sr isotope compositions of sphalerite and pyrrhotite from the Caixiashan Zn-Pb deposit. Locatio n

1/Rb Ore mineral

Rb/ppm

Sr/ppm

87Rb/86Sr

Sphalerite

0.0539

1.864

0.0854

0.005

0.712609±11

0.00005

Sphalerite

0.3081

1.762

0.5137

0.005

0.714592±9

Sphalerite

0.2634

1.128

0.6943

0.005

Sphalerite

0.0157

0.4561

0.1014

8

Sphalerite

0.3593

3.256

2

Pyrrhotite

1.589

2.763

1

4

Ore zone II

2σ

87Sr/86Sr

2σ

(87Sr/86Sr)

i

1/

（1/ppm）

（1/p

0.7122

18.55288

0.53

0.00005

0.71213

3.245699

0.56

0.715551±10

0.00005

0.71218

3.796507

0.88

0.005

0.712562±9

0.00005

0.71208

63.69427

2.19

0.3259

0.005

0.713733±12

0.00005

0.71217

2.78319

0.30

1.683

0.005

0.720217±9

0.00005

0.71214

0.629327

0.36

Notes: (87Sr/86Sr)i= 87Sr/86Sr-87Sr/87Rb(eλt-1), λ87Rb=1.42×10−11/yr., t=337.2 ± 5.7 Ma.

Table 5 Pb isotopic compositions of host rocks of the Mesoproterozoic Kawabulake Group and Carboniferous intrusions from the Caixiashan Zn-Pb deposit

Sample number.

Whole rocks

U

Th

Pb

Age

206Pb/204Pb

207Pb/204Pb

208Pb/204Pb

(206Pb/204Pb)t

FcxⅡzk3801-b10

Dolomite Marble

0.285*

0.094*

14.445*

337.2

17.184

15.527

37.013

17.119

15.52

C-151

Dolomite Marble

0.289

0.032

19.8

337.2

17.245

15.456

36.884

17.197

15.45

C-152

Dolomite Marble

0.281

0.156

9.19

337.2

17.533

15.462

37.103

17.432

15.45

11LCxS06

Dolomite Marble

0.285*

0.094*

14.445*

337.2

17.183

15.495

37.076

17.118

15.49

FcxⅡzk3801-b18

Carbonaceous slate

1.037*

7.381*

12.743*

337.2

17.226

15.531

37.083

16.958

15.51

11P29

Chert

-

-

-

337.2

17.187

15.387

37.121

17.187

15.38

11P48

Sandstone

1.037*

7.381*

12.743*

337.2

17.575

15.400

37.545

17.305

15.38

11P49

Sandstone

1.037*

7.381*

12.743*

337.2

17.661

15.451

37.617

17.390

15.43

C-95

Sandstone

0.311

0.973

3.84

337.2

17.432

15.464

37.182

17.165

15.45

C-96

Sandstone

0.36

0.951

3.79

337.2

17.478

15.483

37.327

17.164

15.46

c-97

Sandstone

0.343

0.962

3.63

337.2

17.750

15.511

38.964

17.429

15.49

c-180

Sandstone

1.63

12.5

20.8

337.2

18.065

15.562

38.778

17.798

15.54

c-181

Sandstone

1.62

14.6

19.6

337.2

18.090

15.596

39.057

17.807

15.58

c-182

Sandstone

1.96

14.3

24.8

337.2

18.233

15.595

38.992

17.962

15.58

C-187

Quartzite

0.034

0.044

1.51

337.2

18.041

15.568

38.371

17.965

15.56

C-188

Quartzite

0.037

0.025

0.972

337.2

18.095

15.504

38.270

17.966

15.49

C-189

Quartzite

0.024

0.011

1.11

337.2

17.884

15.519

37.976

17.811

15.51

FcxⅡzk3001-b15

Diorite

0.972*

3.588*

8.366*

337.2

17.184

15.527

37.016

16.802

15.50

FcxⅡzk3801-b6

Diorite

0.972*

3.588*

8.366*

337.2

17.206

15.544

37.079

16.824

15.52

Fcx-b19

Diorite

0.972*

3.588*

8.366*

337.2

17.303

15.544

37.188

16.920

15.52

Fcx-b20

Diorite

0.972*

3.588*

8.366*

337.2

17.547

15.568

37.545

17.161

15.54

FcxⅡzk3004-b6

Diorite

0.972*

3.588*

8.366*

337.2

17.285

15.536

37.159

16.902

15.51

ro-2

Diorite

0.95

3.38

9.43

337.2

18.405

15.485

38.201

18.063

15.46

ro-7

Diorite

0.88

2.3

8.98

337.2

18.297

15.494

38.057

17.966

15.47

ro-8

Diorite

0.95

3.65

6.51

337.2

18.488

15.530

38.296

17.992

15.50

ro-9

Diorite

1.24

4.24

8.8

337.2

18.523

15.498

38.352

18.043

15.47

ro-11

Diorite

0.84

4.37

8.11

337.2

18.442

15.490

38.184

18.091

15.47

Fcx-b7

Granite

0.972*

3.588*

8.366*

337.2

17.961

15.566

37.831

17.571

15.54

Note: “*” means mean value of the similar samples, “-” means no data

(207Pb/20

ple No.

Table 6 Compiled ages of mineralization and Carboniferous felsic magmatic intrusions from the Caixiashan Zn-Pb deposit

NO.

Sample number

1

C1603

2

Lithology/mineral

Age/Ma

Method

Monzonitic granite stock

330.0±3.6

LA-ICPMS zircon U-Pb

Chen et al., 2019

C1609

K-feldspar granite stock

333.3±3.6

LA-ICPMS zircon U-Pb

Chen et al., 2019

3

C-220

Quartz diorite stock

351.9±3.5

LA-ICPMS zircon U-Pb

This study

4

C-113

Diorite stock

348.2±3.7

LA-ICPMS zircon U-Pb

This study

5

γσ-2

353.0±2.5

LA-ICPMS zircon U-Pb

Li et al., 2016

6

γσ-7

352.0±1.6

LA-ICPMS zircon U-Pb

Li et al., 2016

7

γσ-9

348.2±2.0

LA-ICPMS zircon U-Pb

Li et al., 2016

8

γσ-11

352.2±2.7

LA-ICPMS zircon U-Pb

Li et al., 2016

9

C-2, C-5, C-201, C204, C-208, C-212

337.2±5.7

Sphaleite and pyrrhotite Rb-Sr

This study

High Mg dioritic dike

Sphalerite and pyrrhotite

Reference

Table 3 S isotopic compositions of sulfide minerals from the Caixiashan Zn-Pb deposit Mineral

δ34SV-CDT ‰

Sources

Sample No.

Mineral

δ34SV-CDT ‰

Source

71

Pyrite

18.3

This study

562m

Sphalerite

11.5

Li et al., 2

72

Pyrite

-22.9

This study

11cxs

Sphalerite

12.3

Li et al., 2

D-6-1

Pyrite

-21.11

Cao et al., 2013

657m

Sphalerite

11.3

Li et al., 2

KSD-20

Pyrite

19.1

Cao et al., 2013

535m

Sphalerite

10.1

Li et al., 2

KSD-21

Pyrite

15.3

Cao et al., 2013

147m

Sphalerite

10.7

Li et al., 2

SD-1-2

Pyrite

8.45

Cao et al., 2013

CXS-KSD-9

Sphalerite

14.89

Cao et al.,

K2501

Pyrite

15.38

Cao et al., 2013

CXS-KSD-13

Sphalerite

15.46

Cao et al.,

ple No.

Mineral

δ34SV-CDT ‰

Sources

Sample No.

Mineral

δ34SV-CDT ‰

K1502-2

Pyrite

14.91

Cao et al., 2013

CXS-KSD-18

Sphalerite

16.02

Cao et al.,

04-b1

Pyrite

-10.5

Gao et al., 2007

CXS-KSD-19

Sphalerite

15.3

Cao et al.,

02-b1

Pyrite

16.8

Gao et al., 2007

CXS-ZK2501

Sphalerite

12.23

Cao et al.,

82m

Pyrite

-25.3

Li et al., 2018

CXS-ZK1502-2

Sphalerite

14.21

Cao et al.,

3m

Pyrite

-10.1

Li et al., 2018

ZK4601-b3

Sphalerite

14.7

Gao et al.,

3-1m

Pyrite

-8.6

Li et al., 2018

ZK3801-b14

Sphalerite

7.6

Gao et al.,

87m

Pyrite

8.3

Li et al., 2018

ZK3402-b2

Sphalerite

6.5

Gao et al.,

.95m

Pyrite

11.8

Li et al., 2018

CXS-KSD-9

Galena

14.83

Cao et al.,

KSD-13

Pyrrhotite

-2.42

Cao et al., 2013

CXS-KSD-13

Galena

10.16

Cao et al.,

SD-1-1

Pyrrhotite

7.24

Cao et al., 2013

CXS-KSD-18

Galena

13.65

Cao et al.,

04-b3

Pyrrhotite

11.7

Gao et al., 2007

CXS-KSD-19

Galena

13.88

Cao et al.,

212

Pyrrhotite

12.2

This study

ZK3801-b12

Galena

11.8

Gao et al.,

.95m

Pyrrhotite

11.3

Li et al., 2018

ZK3004-b2

Galena

6.2

Gao et al.,

.71m

Pyrrhotite

5.7

Li et al., 2018

ZK3003-b7

Galena

1.2

Gao et al.,

0m

Pyrrhotite

4.6

Li et al., 2018

C-206

Galena

11.3

This stu

2m

Pyrrhotite

4.6

Li et al., 2018

C-199

Galena

8

This stu

.71m

Pyrrhotite

10

Li et al., 2018

286.71m

Galena

7.9

Li et al., 2

Table 4 Pb isotopic compositions of sulfide minerals from the Caixiashan Zn-Pb deposit Sample No.

Mineral

206Pb/204Pb

207Pb/204Pb

208Pb/204Pb

Sources

Source

FcxⅡzk3003-b7

Galena

17.176

15.525

37.002

Liang et al., 2005

FcxⅡzk3004-b2

Galena

17.180

15.528

37.013

Liang et al., 2005

FcxⅡzk3801-b12

Galena

17.171

15.521

36.992

Liang et al., 2005

FcxⅡzk3802-b12

Galena

17.175

15.525

37.000

Liang et al., 2005

FcxⅡTc50Rz1

Galena

17.177

15.526

37.008

Liang et al., 2005

FcxⅡTc46Rz1

Galena

17.176

15.525

37.003

Liang et al., 2005

CXS-KSD-19

Galena

17.156

15.522

37.005

Cao et al., 2013

CXS-KSD-18

Galena

17.074

15.422

36.685

Cao et al., 2013

C-25

Galena

17.112

15.446

36.764

This study

C-202

Galena

17.102

15.449

36.782

This study

83.87m

Galena

17.246

15.562

37.137

Li et al., 2018

FcxⅡzk4604-b1

Pyrite

17.203

15.527

37.071

Liang et al., 2005

FcxⅡzk3402-b1

Pyrite

17.185

15.526

37.019

Liang et al., 2005

c-71

Pyrite

17.175

15.453

36.822

This study

c-72

Pyrite

17.172

15.538

37.037

This study

485.95m

Pyrite

17.206

15.532

37.044

Li et al., 2018

286.71m

Pyrite

17.203

15.512

37.034

Li et al., 2018

513m

Pyrite

17.213

15.512

37.014

Li et al., 2018

FcxⅡzk3801-b14

Sphalerite

17.184

15.528

37.021

Liang et al., 2005

FcxⅡzk3402-b2

Sphalerite

17.181

15.527

37.014

Liang et al., 2005

FcxⅡzk4062-b3

Sphalerite

17.190

15.532

37.035

Liang et al., 2005

535m

Sphalerite

17.218

15.562

37.140

Li et al., 2018

FcxⅡzk3004-b3

Pyrrhotite

17.180

15.524

37.013

Liang et al., 2005

C-212

Pyrrhotite

17.251

15.500

36.997

This study

62.82m

Pyrrhotite

17.361

15.556

37.252

Li et al., 2018

269.71m

Pyrrhotite

17.313

15.614

37.303

Li et al., 2018

Research Highlights:

1. The Zn-Pb mineralization age of the Caixiashan deposit is 337.2 ± 5.7 Ma. 2. Reduced sulfur was mainly derived from thermal sulfate reduction (TSR) of seawater-derived sulfates and minor contribution by replacement of syn-sedimentary pyrite, as well as a possible input of magmatic sulfur. 3. Ore metals are mainly sourced from some rocks of the Mesoproterozoic Kawabulake Group and Carboniferous felsic intrusions. 4. The deposit is a distal high-temperature carbonate replacement deposit related to concealed granitic intrusions.

Conflicts of Interest: The authors declare no conflict of interest.

Graphical abstract：