Paleoproterozoic SEDEX-type stratiform mineralization overprinted by Mesozoic vein-type mineralization in the Qingchengzi Pb-Zn deposit, Northeastern China

Journal Pre-proofs Paleoproterozoic SEDEX-type stratiform mineralization overprinted by Mesozoic vein-type mineralization in the Qingchengzi Pb-Zn deposit, Northeastern China Jian Li, Wen-yan Cai, Bin Li, Ke-yong Wang, Han-lun Liu, Yassa Konare, Ye Qian, Gill-Jae Lee, Bong-Chul Yoo PII: DOI: Reference:

S1367-9120(19)30361-X https://doi.org/10.1016/j.jseaes.2019.104009 JAES 104009

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Journal of Asian Earth Sciences

Received Date: Revised Date: Accepted Date:

12 November 2018 1 September 2019 1 September 2019

Please cite this article as: Li, J., Cai, W-y., Li, B., Wang, K-y., Liu, H-l., Konare, Y., Qian, Y., Lee, G-J., Yoo, BC., Paleoproterozoic SEDEX-type stratiform mineralization overprinted by Mesozoic vein-type mineralization in the Qingchengzi Pb-Zn deposit, Northeastern China, Journal of Asian Earth Sciences (2019), doi: https://doi.org/ 10.1016/j.jseaes.2019.104009

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Paleoproterozoic SEDEX-type stratiform mineralization overprinted by Mesozoic vein-type mineralization in the Qingchengzi Pb-Zn deposit, Northeastern China

Jian Li1, Wen-yan Cai1, Bin Li2, Ke-yong Wang1, 3*, Han-lun Liu1, Yassa Konare1, 4, Ye Qian1, 3, Gill-Jae Lee5, Bong-Chul Yoo5

1 College of Earth Sciences, Jilin University, Changchun 130061, China 2 Liaoning Dandong Qingchengzi Mining Co., Ltd, Dandong, Liaoning, 118107, China 3 Key Laboratory of Mineral Resources Evaluation in Northeast Asia, Ministry of Land and Resources of China, Changchun, 130061, China 4 IAMGOLD Exploration Mali Sarl, Bamako 2699, Mali 5 Convergence Research Center for Development of Mineral Resources, Korea Institute of Geoscience and Mineral Resources, Daejeon 34132, Republic of Korea

*Corresponding author:

Tel: 86-13069004095 E-mail: [email protected]

E-mail addresses:

[email protected] (J.-Li) 1

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[email protected] (W.-Y. Cai) [email protected] (B.-Li) [email protected] (K.-Y. Wang) [email protected] (H.-L. Liu) [email protected] (K.-Yassa) [email protected] (Y.-Qian) [email protected] (G.-J. Lee) [email protected] (B.-C. Yoo)

Postal address: 2199 Jianshe Street, College of Earth Sciences, Jilin University, Changchun 130061, China.

Abstract The Qingchengzi Pb–Zn deposit is located in the northeastern Jiao–Liao–Ji Belt (JLJB), North China Craton (NCC). Field observation and age dating indicate that the 2

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deposit was formed from Paleoproterozoic sedimentary exhalative (SEDEX) stratiform mineralization overprinted by Late Triassic hydrothermal vein-type mineralization. Five types of fluid inclusions (FIs) are identified in the quartz grains, based on petrography and laser Raman spectroscopy: liquid-rich two-phase (type 1), vapor-rich two-phase (type 2), CO2-bearing (types 3a and 3b), and CO2-pure (type 4). Quartz from the SEDEX stratiform ores contains only type 1 FIs, and hydrogen-oxygen isotopic compositions indicate that the ore-forming fluids were magmatic water-derived. The ore-forming fluids were likely of medium-temperatures and low-salinity, and belonged to a NaCl–H2O hydrothermal system. Quartz from the vein-types contains all five types of FIs, and the ore-forming fluids may have belonged to a medium-temperature, lowsalinity NaCl–H2O–CO2 hydrothermal system. Hydrogen-oxygen isotopes indicate that the vein-type ore-forming fluids were derived from magmatic-meteoric mixed source. Rare-earth element (REE) and sulfur-lead isotopic compositions indicate that oreforming materials of the SEDEX stratiform mineralization were derived from the wallrocks and magma, wheres those of the vein-type mineralization were derived from Late Triassic granitic magma, wall-rocks, and the Paleoproterozoic SEDEX ores. Based on field geological and geochronological data, we propose the following regional metallogenic model: (1) SEDEX mineralization occurred during the Paleoproterozoic post-collisional extension in the JLJB; (2) vein-type mineralization was generated by the north-dipping subduction of the Yangtze Craton beneath the NCC, which led to continent-continent collision and slab break-off in the Late Triassic. Keywords: Fluid inclusion; Ore REE; H–O–S–Pb isotopes; SEDEX; Hydrothermal 3

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vein-type mineralization; Jiao–Liao–Ji Belt.

1. Introduction The Paleoproterozoic Jiao–Liao–Ji Belt (JLJB; also called the Liaoji Belt; Zhai and Santosh, 2011) is a narrow, elongate domain that trends NE–SW for 700 km from eastern Shandong, through eastern Liaoning and southern Jilin, in China, and extends into northern North Korea (Fig. 1). The belt is located in the eastern North China Craton (NCC, Fig. 1c) and is one of the most important and oldest tectonic/metallogenic belts within the NCC (Liu et al., 2014a; Cai et al., 2017; Xu et al., 2018). This belt records a long and complicated history of magmatism, tectonic deformation, multi-stage metamorphic evolution, and crustal reworking (Liu et al., 2014b; Xu et al., 2018). In recent decades, magmatic–hydrothermal Au–Ag deposits (e.g., Xiaotongjiapuzi, Baiyun, and Gaojiapuzi; Zhang et al., 2016a, 2019; Liu et al., 2019), stratiform–vein Pb–Zn deposits (e.g., Qingchengzi; Yu et al., 2009; Ma et al., 2016; Duan et al., 2017), and non-metallic deposits (e.g., talc, borate, and magnesite in the Dashiqiao area, southern Liaoning, China; Tang et al., 2009; Misch et al., 2018) have been discovered in the JLJB. The Qingchengzi Pb–Zn deposit is one of the largest deposits in the JLJB (located in the northeastern part of the belt, Fig. 1c) and consists of at least 10 ore blocks, including the Zhenzigou, Xiquegou, Diannan, Benshan, Nanshan, Mapao, and Erdao blocks (Dong, 2012; Ma et al., 2016). This deposit contains >85,000 tons of Pb and 69,000 tons of Zn (LDQMCL, 2016), and exhibits stratiform and vein mineralization types. 4

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The mining history of the Qingchengzi Pb–Zn deposit extends back to the Ming dynasty (>400 years ago; K.Y. Wang et al., 2016; Ma et al., 2016), and relevant theoretical research began during the 1900s. Many studies have investigated the geological characteristics of the deposit (X.F. Wang et al., 2010; Dong, 2012), the sources of ore-forming fluids and materials (Ma et al., 2012a, 2012b, 2013a, 2013b; Yang et al., 2015a, 2016; Duan et al., 2017), diagenesis, and metallogenic geochronology (Yu et al., 2009; Duan et al., 2012, 2014; Ma et al., 2016). However, the ore genesis and metallogenic models of the deposit are still debated, partly because of inaccuracies in the dating methods employed in previous isotopic studies, and this limits our understanding of the ore-forming fluids and materials. Several metallogenic models have been proposed for the Qingchengzi Pb–Zn deposit. Zhang (1984) proposed a metamorphic origin. Jiang (1987, 1988) studied the O, C, Pb, and S isotopes of ore bodies and wall-rocks, and proposed that the initial source of ore-forming materials was mainly from seafloor volcanic eruptions, classifying the deposit as a sedimentary–metamorphic–hydrothermal stratabound Pb– Zn deposit. Liu and Ai (2001), Xue et al. (2003), and Duan et al. (2017) proposed various versions of a Mesozoic hydrothermal mineralization model based on isotopic data and trace-element analyses. Liu et al. (2007) studied the genesis of siliceous rocks and syngenetic faults in the Qingchengzi deposit and suggested that seafloor exhalative sedimentation and mineralization occurred during the early stage of the formation of the deposit. Two different types of mineralization (stratiform and vein-type) have been 5

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identified in the Qingchengzi Pb–Zn deposit, but data from previous studies are insufficient to clearly constrain the ore genesis. We therefore, investigated the stratiform and vein-type mineralization to determine the ore genesis of this deposit. In this study, three representative ore blocks (Zhenzigou, Diannan, and Xiquegou) were selected for systematic analysis of ore deposits. Here, we present the results of fluid inclusion microthermometry and laser Raman spectroscopy, stable (H–O–S) and radiogenic (Pb) isotopic analyses, and ore rare-earth element (REE) analyses of the stratiform and vein-type mineralization in the Qingchengzi Pb–Zn deposit. These new datasets allow us to explore the sources of ore-forming fluids and materials, discuss the mineral precipitation mechanism, and ascertain the ore genesis of the two different mineralization types, with the aim of providing a better understanding of Pb–Zn metallogenesis in the northeastern JLJB. 2. Geological background 2.1 Geological setting The NCC is the largest cratonic block in China and contains rocks as old as ca 3.8 Ga (Liu et al., 1992; Song et al., 1996; Lu et al., 2006; X.P. Wang et al., 2017). It covers ~1.5  106 km2 in northern China, the southern part of northeastern China, Inner Mongolia, Bohai Bay, and the northern Yellow Sea (Fig. 1a; Zhao et al., 2005). The NCC is surrounded by several large orogenic belts, namely, the Central Asian Orogenic Belt in the north, the Central China Orogen in the southwest, the Qinling–Dabie Belt in the south, and the Su–Lu Ultrahigh-Pressure Metamorphic Belt in the east (Fig. 1a, b). The Archean-Paleoproterozoic basement of the NCC can be divided into the 6

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Western Block (WB) and Eastern Block (EB), which amalgamated/collided along the Trans-North China Orogen (TNCO) at ca 1.85 Ga (Zhao et al., 2001, 2005). The WB consists of two microcontinental blocks (the Yinshan and Ordos blocks) that collided along the Khondalite Belt (KB) at ca 1.95 Ga (Zhao et al., 2005, 2011). The KB is dominated by graphite-bearing sillimanite–garnet gneiss, garnet quartzite, felsic paragneiss, calc-silicate rock, and marble (Zhao et al., 2005, 2011). The Yinshan Block consists of a series of Neoarchean tonalitic–trondhjemitic–granodioritic (TTG) gneisses and minor supracrustal rocks, and was metamorphosed to the greenschist to granulite facies at ca 2.5 Ga (Zhao et al., 2011). The Ordos Block is covered by the Mesozoic– Cenozoic Ordos Basin and comprises Late Archean granulite-facies basement (according to drilling data; Zhao et al., 2011). The EB also consists of two microcontinental blocks: the Longgang Block (also known as the northern Liaoning– southern Jilin Complex) in the northwest of the EB is separated from the Namgrim Block (also referred to as the southern Liaoning–Langrim Complex) in the southeast (Liu et al., 2014b) by the JLJB (Fig. 1b; Zhao et al., 1998, 2001, 2005, 2011, 2012). The Nangrim Block is composed of intensively deformed Late Archean diorite– tonalite–granodiorite suites (Chai et al., 2016) that yield laser ablation-inductively coupled plasma–mass spectrometry (LA–ICP–MS) zircon U–Pb ages of 2.55–2.45 Ga (Lu et al., 2004). The Longgang Block consists of Late Archean tonalitic– trondhjemitic–granodioritic (TTG) gneisses and minor pyroxene granitoids (with calcalkaline geochemistry) that yield an Nd isotopic model age of 2.84 Ga, which represents the age of crust formation (Wu et al., 1997). 7

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In summary, the aggregation of several microcontinental blocks and the formation of important tectonic belts (i.e., TNCO, KB, and JLJB) in the NCC were completed during the Archean–Proterozoic. The region thus records the assembly, accretion, and break-up of the Columbia supercontinent (Zhao et al., 2011). 2.2. Regional geology Tectonically, the JLJB is considered part of the eastern EB (Fig. 1b, c) and represents the suture zone of the collision between the Longgang and Nangrim blocks. The JLJB comprises greenschist- to lower- amphibolite-facies sedimentary and volcanic successions with associated granitic and mafic intrusions (Zhao et al., 2005, 2011). The sedimentary and volcanic successions include the Macheonayeong Group (North Korea), the Ji’an and Laoling groups in southern Jilin (northeastern China), the Liaohe Group (including the South and North Liaohe groups) in eastern Liaoning Peninsula (northeastern China), and the Fenzishan and Jingshang groups in the Jiaobei Massif (northern China) (Fig. 1c; Tam et al., 2011; Liu et al., 2014a, 2014b). The Liaohe Group (particularly the Dashiqiao Formation) is considered to contain the main orebearing strata, which are spatially related to the mineralization (e.g., gold, silver, lead, zinc, borate, and magnesite deposits; Zhai and Santosh, 2013). In eastern Liaoning, >72% of Pb–Zn deposits occur in the Liaohe Group (Dong, 2005). The Liaohe Group is enriched in Pb and Zn to levels that are much higher than the crustal Clark value. For example, the Gaixian Formation contains average 27 ppm Pb and 51 ppm Zn, the Dashiqiao Formation contains average 48 ppm Pb, and 58 ppm Zn, and the Langzishan Formation contains average 28 ppm Pb and 40 ppm Zn (Ding et al., 1992). 8

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The Jingshan Group consists of high-grade pelitic gneisses, pelitic granulites, felsic paragneisses, quartzites, siliceous rocks, marbles, and minor mafic granulites (Zhou et al., 2003), and is distributed in the southern JLJB (Fig. 1c). The Fenzishan Group is exposed mainly in the northern and western Jiaobei Massif (Fig. 1c), and consists of pelitic schists, fine-grained paragneisses, calc-silicate marbles, marble, and minor amphibolites (Tam et al., 2011). The Liaohe Group is located in the central and northern JLJB (Fig. 1c), and the metamorphic–sedimentary rocks are subdivided into the Langzishan, Li’eryu, Gaojiayu, Dashiqiao, and Gaixian formations (Zhang, 1988). The Ji’an Group occurs predominantly in the northeastern JLJB (Fig. 1c) and comprises volcanic rocks metamorphosed to amphibolite facies (Lu et al., 2006), including twomica schists, mica–staurolite schists, marble, quartzofeldspathic gneisses, granulitefacies pelitic metamorphic rocks, and minor mafic granulite (Cai et al., 2017). The Laoling Group is exposed in the northeastern JLJB (Fig. 1c) and consists of mica schist, phyllite, sericite phyllite, a thick layer of marble, and phyllitic schist with thin marble horizons (Xing et al., 2011). The Macheonayeong Group occurs near North Korea (Fig. 1c), and the lithological assemblage is unknown. Granitoids and mafic intrusions are associated with the sedimentary and volcanic successions in the JLJB. The granitoid plutons include deformed A-type granites and undeformed alkaline syenites and rapakivi granites (Li et al., 2005; Zhao et al., 2005). Mafic intrusions are gabbro and dolerite, most of which have been metamorphosed to amphibolite facies, although original igneous textures are locally preserved (Faure et al., 2004). The area is covered by thick sequences of Meso-Neoproterozoic to Paleozoic 9

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sediments and is intruded by large volumes of Mesozoic granitoids (Lu et al., 2006). 3. Ore deposit geology 3.1. Ore district geology 3.1.1. Stratigraphy The Qingchengzi Pb–Zn ore district is located in the northeastern JLJB (Fig. 1c). The strata exposed within the ore district are mainly sedimentary–metamorphic rocks of the Paleoproterozoic Liaohe Group and Quaternary sediments (Fig. 2). Within the ore district, the Liaohe Group consists of the Langzishan, Gaojiayu, Dashiqiao, and Gaixian formations (from bottom to top; the Li’eryu Formation is missing). The Langzishan Formation is not exposed in the ore district and consists mainly of graphitized banded marble and biotite schist (Ma et al., 2016). The Gaojiayu Formation is composed of graphitized marble, hornblende schist, and wollastonite mica schist, and occurs in the central and southern parts of the ore district (Fig. 2). The Dashiqiao Formation hosts the main Pb–Zn mineralization (e.g., the Zhenzigou, Diannan, and Xiquegou ore blocks; Dong et al., 2010; Sha et al., 2011; Ma et al., 2012a, 2013a, 2013b, 2016). It is distributed in the central part of the ore district (Fig. 2). The different lithological assemblages can be divided into three units, D1, D2, and D3. Unit D1 contains banded marble, hornblende schist, and garnet–mica schist; unit D2 comprises mainly garnet–mica schist; and unit D3 consists primarily of banded marble, dolomite marble, graphitized banded marble, and garnet–mica schist. The Gaixian Formation is located in the eastern and northwestern parts of the ore district (Fig. 2). It is the main host of Au–Ag deposits (e.g., the Xiaotongjiapuzi Au, Gaojiapuzi Ag, and Baiyun Au), 10

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and contains mica schist interlayered with diopside granulite. 3.1.2. Structures The Qingchengzi ore district records multiple periods of tectonic and magmatic activities. The faults in the Qingchengzi ore district can be divided into three groups (NW–SE-, E–W- and NE–SW-trending faults) based on orientation (Fig. 2). The NW– SE-trending faults, which dip to NE at 20–60°, and secondary fractures control the form and scale of vein-type mineralization (e.g., the Diannan, Benshan, Mapao, and Xiquegou ore blocks). The folds are mainly E–W-trending, and include the Xinling anticline, the Sikeyangshu syncline, the Zhenzigou anticline, the Nanshan syncline, and the Qingchengzi anticline (Fig. 2). Among them, the Zhenzigou and Qingchengzi anticlines control the stratiform mineralization (e.g., the Zhenzigou ore block; Dong, 2012). The cores of the Zhenzigou and Qingchengzi anticlines consist of striped granite, and the fold axes plunge to the north at 70°. Fold limbs consist of the Dashiqiao and Gaixian formations. 3.1.3. Magmatic rocks The igneous intrusions in the Qingchengzi ore district can be categorized into three groups according to age, as follows: (1) Paleoproterozoic granitic intrusions are mostly striped granite and include the Dadingzi intrusion. Striped granite is distributed in the central part of the ore district (Fig. 2), including within the core of the Qingchengzi anticline. The granite yields sensitive high-resolution ion microprobe (SHRIMP) and LA–ICP–MS zircon U–Pb ages of 2176–2166 Ma (Li and Zhao, 2007; Li et al., 2017). The Dadingzi intrusion 11

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consists mainly of biotite monzogranite and medium- to fine-grained plagiogranite, is distributed in the southeast of the ore district (Fig. 2), and yields a SHRIMP zircon U– Pb age of 1869 ± 16 Ma (Song et al., 2017). (2) Early Yanshanian granitic rocks are found in the southern and northern parts of the Qingchengzi ore district (Fig. 2), and are represented by the Xinling and Shuangdinggou intrusions. These rocks include compositionally variable and complex granites and biotite monzogranites that yield LA–ICP–MS and SHRIMP zircon U–Pb ages of 225–220 Ma (Yu et al., 2009; Li et al., 2019) and 224–222 Ma (Duan et al., 2012, 2014; Li et al., 2019), respectively. According to aeromagnetic data, these intrusions are connected at depth and may therefore represent the same pluton (Fang et al., 1994; Dong et al., 2010). Early Yanshanian magmatism was accompanied by the intrusion of dikes, which include lamprophyre, gabbro, microdiorite, granite-porphyry, and quartz-porphyry that yield LA–ICP–MS zircon U–Pb ages of 227–211 Ma (Liu and Ai, 2002; Wu et al., 2005; Zhang et al., 2016b, 2016c). (3) Late Yanshanian intrusions are mainly granite, monzonite, diorite, and lamprophyre (Fig. 2) that yield LA–ICP–MS zircon U–Pb ages of 167–130 Ma (Liu and Ai, 2002; Zhang et al., 2016b; Zhou et al., 2017; Li et al., 2019). 3.2. Mineralization characteristics Field surveys indicate that the Qingchengzi Pb–Zn deposit contains both the stratiform and vein-type mineralization. The ages of the stratiform and vein-type mineralization are 1798 ± 8 Ma (Ma et al., 2016) and 221 ± 12 Ma (Yu et al., 2009) (sphalerite step-dissolution Rb–Sr dating), respectively, indicating that there were two 12

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episodes of mineralization in the Qingchengzi Pb–Zn ore district, reflecting the different origins of the ore. Zhenzigou, Diannan, and Xiquegou are the most important ore blocks in this ore district, representing up to 67% of the total reserves (Zhang, 1984; Ma et al., 2013a), and were thus selected for a systematic study of the deposits. 3.2.1. Zhenzigou ore block The Zhenzigou ore block is located in the eastern part of the Qingchengzi Pb–Zn deposit (Fig. 2) and comprises 113 ore bodies, including stratiform and vein-type mineralization hosted mainly by marble and mica schist of the Langzishan and Dashiqiao formations (Fig. 3a, b). A representative stratiform ore body is No. 2 (composed of 22 small ore bodies), which is hosted by graphitized banded marble, biotite schist, (mica) banded marble, dolomite marble, and garnet–mica schist. The ore body has the same orientation as the wall-rocks (Fig. 4a–d) and shows obvious striation/stratification and banded structures (Fig. 4e–h). This ore body is 10–61 m long and 1.0–8.2 m thick, trends NW–SE, dips NE at 40–50°, and contains an average of 6.04% Pb and 10.1% Zn (Sha et al., 2011). The ore minerals of the stratiform mineralization are massive, occur as densely disseminated veinlets, and include sphalerite, galena, pyrite, and chalcopyrite (Fig. 4e–l), with minor amounts of pyrrhotite, arsenopyrite, marcasite, and argentite (Ma et al., 2016). The main gangue minerals are dolomite, biotite, calcite, and minor quartz. Hydrothermal alteration (predominantly typical sedimentary exhalative (SEDEX) alteration) is weak in the stratiform mineralization, occurs within 3 m of the ore body (Jiang, 1988; Ding et al., 1992; Sun et al., 2006; Ma et al., 2012a), and consists of graphitization, tourmalinization, 13

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carbonatization, silicification, chloritization, and dolomitization. The vein ore body is represented by No. 319 (composed of 7 small ore bodies), which occurs in ore-bearing wall-rocks of Dashiqiao Formation dolomite marble and is controlled by NW–SE-trending fractures (Fig. 4m–n). This ore body is 14–64 m long and 1–6 m wide, dips SW at 22–42°, and contains an average of 5–7% Pb and 7–10% Zn (LDQMCL, 2016). The ore minerals of the vein-type mineralization are disseminated and massive or occur as veinlets, and include sphalerite, galena, pyrite, arsenopyrite, and pyrrhotite, with minor chalcopyrite and marcasite (Fig. 4m–t). The main gangue minerals are quartz, dolomite, and calcite. Hydrothermal alteration is well developed near the ore bodies and wall-rocks, and comprises mainly silicification, chloritization, and carbonatization, with lesser epidotization and sericitization. Silicification, chloritization, and sericitization are closely associated with the vein-type Pb–Zn mineralization. 3.2.2. Diannan and Xiquegou ore blocks The main vein-type mineralization is developed in the Diannan and Xiquegou ore blocks (Fig. 3c, d), which are located in the eastern and western parts of the Qingchengzi Pb–Zn deposit, respectively (Fig. 2). The Diannan ore block consists of 7 main ore bodies (Nos. 1–5, 7, and 13, of which No. 3 is the largest) that occur principally in the marble, granulite, and mica schist of the Dashiqiao Formation. The ore body is 18 m long with a mean thickness of 2.5 m, trends 320° and dips NE at 60°, and contains 4.22% Pb and 1.40% Zn (LDQMCL, 2016). Twelve ore bodies have been identified in the Xiquegou ore block, mainly in the 14

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marble and dolomite marble of the Dashiqiao Formation. No. X, which is the largest ore body and representative of the rest, is 195 m long and 1.1–1.6 m thick (mean of 1.3 m), dips NW at 70–75°, and has a mean Pb grade of 5.51% (LDQMCL, 2016). The vein-type mineralization at Diannan, Xiquegou, and Zhenzigou displays similar geological characteristics in each case, comprising disseminated and massive ore minerals (Fig. 5c–d and j–l) such as sphalerite, galena, pyrite, marcasite, and arsenopyrite, with minor chalcopyrite and tetrahedrite (Fig. 5e–h and m–t). The main gangue minerals are quartz, dolomite, and calcite. The wall-rock alteration is similar to that of the Zhenzigou vein-type mineralization, with silicification and chloritization being closely related to the vein-type Pb–Zn mineralization. 4. Sampling and analytical methods 4.1. Fluid inclusions Fluid inclusion (FI) petrography, microthermometry, and laser Raman spectroscopy were performed at the Laboratory of Geological Fluid, Jilin University (Changchun, China). Samples for FI study were collected from underground mine ore of the Qingchengzi Pb–Zn deposit (Nos. 2, 320, 319, and 289 ore bodies of the Zhenzigou ore block, No. 3 ore body of the Diannan ore block, and No. 426 ore body of the Xiquegou ore block). Doubly polished thin sections (~0.20 mm thick) were made from 54 quartz samples (24 from Zhenzigou, 13 from Diannan, 17 from Xiquegou) associated with the different mineralization types, and 18 thin sections were selected for laser Raman spectroscopy analysis (8 from Zhenzigou, 5 from Diannan, 5 from Xiquegou). Microthermometric analyses were conducted on a Linkam THMS-600 15

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heating–freezing stage with a temperature range of −196 to 600°C. The heating rates were 0.1°C min−1 when phase transitions were approached. The precision of the temperature measurement was ±0.2°C during freezing and ±2°C during heating. The salinities were calculated using the final melting temperature of ice (Tm-ice) for the aqueous two-phase inclusions (Bodnar, 1993), and the final melting temperature of CO2-clathrate (Collins, 1979) for the CO2-rich inclusions. To confirm the gas compositions of single inclusions, representative FIs were analyzed using an RM-2000 laser Raman microprobe with an argon ion laser and a laser source of 514 nm. The spectral region was 4500–100 cm−1, with a resolution of ±2 cm−1. Analyses were performed with an accumulation time of 60 s and a beam spot size of 1 μm. 4.2. Hydrogen and oxygen isotopic analyses Twelve quartz and calcite samples from the Zhenzigou ore block (stratiform and vein ore bodies) were selected for hydrogen and oxygen isotopic analyses, and crushed and ground into granules of 40–80 mesh. Hydrogen and oxygen isotopes were analyzed at the Analytical Laboratory of the Beijing Research Institute of Uranium Geology, China National Nuclear Corporation (CNNC) (Beijing, China), using a Finnigan MAT253 mass spectrometer. For hydrogen isotopic analysis, water from FIs was released from the samples by heating to ~500°C. The water then reacted with zinc powder at 410°C to generate hydrogen (Friedman, 1953). Oxygen was extracted from quartz by reaction with BrF5 and converted to CO2 on a platinum-coated carbon rod for oxygen isotopic analysis, following the method of Clayton and Mayeda (1963). The 16

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δ18O and δD values are reported in per mil notation (‰) relative to Vienna Standard Mean Ocean Water (V-SMOW) standards, with analytical uncertainties (1σ) of ±2‰ for δD and ±0.2‰ for δ18O. 4.3. Ore REE analysis After petrographic examination, nine samples (5 from Zhenzigou, 2 from Diannan, and 2 from Xiquegou) were crushed and powdered in an agate mill to ~200 mesh. The REE analyses were performed at ALS Minerals–ALS Chemex (Guangzhou, China). REE compositions were analyzed using an ICP–MS (ME-MS81) instrument. 4.4. Sulfur isotopic analysis Thirty-one sulfide samples (pyrite and galena) were collected from the Qingchengzi ore district (Zhenzigou, Diannan, and Xiquegou ore blocks) for sulfur isotopic analysis. All sulfide separates were further purified (>99% purity) by handpicking under a microscope. The sulfur isotopic analyses were performed using a MAT251 mass spectrometer at the Analytical Laboratory in Beijing Research Institute of Uranium Geology, CNNC (Beijing, China). Sulfur isotopic compositions of sulfide minerals were measured using the conventional combustion method (Robinson and Kasakabe, 1975). Sulfur isotope ratios are reported as δ34S relative to the Vienna Canyon Diablo Troilite (V-CDT), with an analytical reproducibility of ±0.2‰. 4.5. Lead isotopic analysis Twenty-four sulfide samples were chosen for lead isotopic analyses, which were performed using a MAT-261 thermal ionization mass spectrometer at the Analytical Laboratory in Beijing Research Institute of Uranium Geology, CNNC (Beijing, China). 17

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Each sample weighting 10–50 mg was first leached in acetone to remove surface contamination, then washed in distilled water and dried in an oven at 60°C. Washed sulfides were dissolved in a mixture of dilute nitric and hydrofluoric acids. Following ion-exchange chemistry, the Pb in the solution was loaded onto Re filaments using a phosphoric acid–silica gel emitter. The measured Pb isotope ratios were corrected for instrumental mass fractionation of 0.11% per atomic mass unit with reference to repeated analyses of the NBS-981 Pb standard. The analytical precision of Pb isotopes was better than ±0.09‰. 5. Results 5.1. Fluid inclusions Petrographic studies and inclusion analyses focused on fluid inclusion assemblages (FIAs, Goldstein and Reynolds, 1994). A group of inclusions trapped synchronously represents a true FIA if the inclusions were trapped along the same primary growth zone in quartz, or along the same healed fracture (Goldstein and Reynolds, 1994; Goldstein, 2001, 2003). In the Qingchengzi deposit, it is difficult to identify FIs in quartz grains that meet these criteria (especially as the stratiform mineralization has a long and complex history). Quartz with euhedral growth zones is rare, and FIs located along primary growth zones in euhedral quartz are extremely rare. Most FIs occur in scattered groups and clusters without unambiguous evidence for contemporaneous trapping. Moreover, the number of CO2-bearing inclusions is small, with few displaying groups or clusters. Most inclusions (both CO2-bearing and aqueous) studied here occur in groups or clusters and show similar liquid/vapor ratios in a single 18

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grain or in several nearby grains of quartz. Where groups or clusters of inclusions exhibit similar heating and freezing behavior, we infer that they were trapped from similar fluids under similar conditions and so have a common origin (e.g., Rusk et al., 2008; Hennings et al., 2017; Y.H. Wang et al., 2018). 5.1.1. Fluid inclusion petrography FIs in quartz of the two mineralization types were identified in the selected samples from the Qingchengzi Pb–Zn deposit, and only primary inclusions were analyzed, according to the criteria of Goldstein and Reynolds (1994). Five types of FI were distinguished based on phases at room temperature (25°C) (i.e., liquid–vapor, LH2O–LCO2, and VH2O–VCO2), observed phase transitions during heating and freezing runs, and laser Raman spectroscopy data of the studied quartz samples: liquid-rich twophase (type 1), vapor-rich two-phase (type 2), CO2-bearing (type 3, including types 3a and 3b), and CO2-pure (type 4) inclusions. Type 1 inclusions consist of two phases (vapor and liquid water) at room temperature, with VH2O/(VH2O + LH2O) <50 vol.% (mostly 10–30 vol.%). These inclusions generally have oval, rounded, or irregular shapes, and are 4–13 μm in size (Fig. 7a, f, i, k–m). They are commonly distributed as FIAs (Fig. 7l–m). Type 2 inclusions consist of two phases (vapor and liquid water) at room temperature, with VH2O/(VH2O + LH2O) >50 vol.% (mostly 60–80 vol.%). These FIs are round or oval in shape, and generally 5–13 μm in size (Fig. 7b, f). Type 3 CO2-bearing inclusions consist mainly of two components, an aqueous solution and CO2. They can be divided into two subtypes, 3a and 3b, according to the 19

20

proportion of CO2. Most type 3a and 3b inclusions are composed of three or two phases, (LH2O + LCO2 + VCO2) or (LH2O + LCO2), at room temperature, and the latter change into three phases with the appearance of CO2 bubbles that freeze at ~10°C. Type 3 inclusions are commonly distributed as FIAs, clusters, or isolated inclusions. Type 3a inclusions consist of two or three phases, (LH2O + LCO2) or (LH2O + LCO2 + VCO2), at room temperature with (VCO2 + LCO2)/(VCO2 + LCO2 + LH2O) <50 vol.% (mostly 20–35 vol.%). These inclusions are round or oval in shape, generally 6–15 μm in size (Fig. 7c, f), and commonly coexist with type 1 and 2 inclusions (Fig. 7f), indicating fluid immiscibility (H.Z. Lu et al., 2004). Type 3b inclusions consist of two or three phases, (LH2O + LCO2) or (LH2O + LCO2 + VCO2), at room temperature. Type 3b inclusions have (VCO2 + LCO2)/(VCO2 + LCO2 + LH2O) >50 vol.% (mostly 65–85 vol.%), are generally oval or round in shape, and are 7–12 μm in size (Fig. 7d, g–j). Type 4 inclusions consist of gaseous and liquid CO2 phases at room temperature, or a single liquid CO2 phase, with the latter changing to two phases as CO2 bubbles appear when cooling to <10°C. The type 4 inclusions are generally 6–15 μm in size (Fig. 7e, g). 5.1.2. Microthermometry and salinity Microthermometric measurements were obtained from 313 inclusions. In most cases, the measurements were performed on FIAs. Results are presented in Table 1 and Figure 8, which show the association between mineral assemblages, physicochemical conditions, and ore genesis.

20

21

SEDEX stratiform mineralization Only type 1 inclusions were identified in the quartz from the stratiform ores. They yielded melting temperatures of ice (Tm-ice) of −4.3 to −2.4°C, with calculated salinities of 4.0–6.9 wt.% NaCl eq., and homogenized to the liquid phase at temperatures (Th-v) of 221–246°C (Fig. 8a, b). Vein-type mineralization Type 1, 2, 3a, 3b, and 4 inclusions were identified in the quartz from the vein ores. The type 1 inclusions yielded Tm-ice of −6.0 to −3.1°C, with salinities of 5.1–9.2 wt.% NaCl eq., and homogenized to the liquid phase at temperatures (Th-v) of 281–312°C (Fig. 8c, d). Type 2 inclusions yielded Tm-ice of −5.3 to −2.3°C, with calculated salinities of 3.9–8.3 wt.% NaCl eq., and homogenized to the vapor phase at temperatures (Th-v) of 270–318°C (Fig. 8c, d). Type 3a inclusions yielded final melting temperatures of solid CO2 (Tm-CO2) of −57.6 to −56.9°C. These values are slightly lower than the critical point for pure CO2 (−56.6°C), indicating the presence of small amounts of N2 and CH4 (identified by laser Raman spectroscopy; Fig. 9). Clathrate melting temperatures (Tm-cla) are 5.8–7.9°C, corresponding to salinities of 4.1–7.8 wt.% NaCl eq., and the CO2 phase homogenized to a liquid phase at temperatures (Th-CO2) of 26.4–29.9°C. Type 3a inclusions are completely homogenized to the liquid phase of CO2 at temperatures (Th-total) of 270– 316°C (Fig. 8c, d). Type 3b inclusions gave final melting temperatures of solid CO2 (Tm-CO2) of −57.8 21

22

to −56.7°C. These values are slightly lower than the critical point for pure CO2 (−56.6°C), indicating the presence of a subordinate amount of other volatiles (e.g., N2 and CH4, as identified by laser Raman spectroscopy; Fig. 9). Clathrate melting (Tm-cla) occurred at 5.4–7.5°C, corresponding to salinities of 4.9–8.5 wt.% NaCl eq. The CO2 phase homogenized to liquid or a vapor CO2 phase at temperatures (Th-CO2) of 26.3– 30.6°C, and all type 3b inclusions totally homogenized to liquid H2O at temperatures (Th-total) of 279–325°C (Fig. 8c, d). Type 4 inclusions yielded melting temperatures (Tm-CO2) for solid CO2 of −56.9 to −56.7°C, close to the CO2 critical point of −56.6°C. Raman analyses confirmed that these inclusions are almost pure CO2. Most type 4 inclusions homogenized to the vapor phase (Th-CO2) at 30.1 to 30.8 °C. 5.1.3. Laser Raman spectroscopy To constrain the gas compositions of single inclusions, representative samples of the stratiform and vein-type mineralization were examined using laser Raman microspectroscopy. Results for individual inclusions from various quartz samples are shown in Figure 9. Type 1 and 2 inclusions from the stratiform and vein-type mineralization are composed of H2O, with a notable absence of CO2 (Fig. 9a, b). Type 3a and 3b inclusions from the vein-type mineralization contain a vapor phase of CO2 (Fig. 9c–h) with minor amounts of CH4 and N2 (Fig. 9c–e, g), and a liquid phase with a large amount of water (Fig. 9c–e). 5.2. Hydrogen and oxygen isotopic analysis Oxygen and hydrogen isotopic data are listed in Table 2 and plotted in Figure 10, 22

23

and include the results of this study (n = 16) and those of earlier work (n = 18; Ding et al., 1992; Dong et al., 2010; Ma et al., 2012a; K.Y. Wang et al., 2016; Song et al., 2017). The measured δ18O values are 5.7–15.1‰. The oxygen isotopic composition of oreforming fluids can be calculated from the oxygen isotopic compositions of quartz. This calculation uses the quartz–water fractionation equations (δ18OH2O = δ18Oquartz–water – (3.38 × 106 × T−2) + 3.40) (Clayton et al., 1972), together with the mean homogenization temperatures calculated from the FIA data (Table 1). The resulting δ18OH2O values of the ore-forming fluids are −9.4 to 4.5‰ for vein-type mineralization, 4.6 to 7.5‰ for stratiform mineralization, and 9.1 to 9.3‰ for Yanshanian granites. The hydrogen isotopic compositions, represented by δD values, are −99.3 to −78.0‰ for vein-type mineralization, −105.1 to −103.3‰ for stratiform mineralization, and −116.0 to −112.0‰ for Yanshanian granites. 5.3. Ore REE analysis The stratiform ore samples are characterized by enrichment in light REEs (LREEs), depletion in heavy REEs (HREEs) (LREEs/HREEs = 3.79–16.02; LaN/YbN = 3.88−20.89), and pronounced negative to positive Eu anomalies (Eu/Eu* = 0.46–3.34, mean = 1.34). These characteristics are consistent with those of the wall-rocks, but differ from seawater (Fig. 11a). The total REE (ΣREE) content of vein-type mineralization is slightly higher than that of stratiform mineralization (Table 3), which also exhibits enrichment in LREEs, depletion in HREEs (LREEs/HREEs = 5.22–30.75; LaN/YbN = 5.52−62.76), and moderate to weak negative Eu anomalies (Eu/Eu* = 0.48– 0.99, mean = 0.71), consistent with the characteristics of Yanshanian granites (Fig. 11b). 23

24

5.4. Sulfur isotope analysis Sulfur isotopic data are listed in Table 4 and plotted in Figure 12, and include the results of this study (sulfide ore; n = 31) and those of earlier work (sulfide ore, marble, and Yanshanian granite; n = 132; Ding et al., 1992; Chi, 2002; Sha et al., 2006; Ma et al., 2013b, 2016; Song et al., 2017). The δ34S values of stratiform and vein-type mineralization sulfide ore, marble (wall-rocks), and Yanshanian granites (Xinling and Shuangdinggou intrusions) from the Qingchengzi ore district are −0.2 to 14.4‰ (mean = 6.2‰), 3.2 to 7.9‰ (mean = 5.4‰), −0.5 to 13.2‰ (mean = 6.6‰), and 5.6 to 7.6‰ (mean = 6.6‰), respectively. The sulfur isotopic compositions of stratiform mineralization and marble have similar ranges and means, and the wide range of δ34S values indicates the involvement of multiple sources. In contrast, the δ34S values of vein-type mineralization sulfide ore and Yanshanian granites show similar ranges and means, indicating a homogeneous sulfur source. 5.5. Lead isotopic analysis The Pb isotopic compositions of 84 sulfide samples and 11 whole-rock samples obtained from this study (n = 24) and previous studies (n = 71; Ding et al., 1992; Yu et al., 2009; Ma et al., 2016; Duan et al., 2017; Song et al., 2017) are listed in Table 5 and plotted in Figure 13. Lead isotopic compositions of the sulfides from the stratiform mineralization (206Pb/204Pb = 17.643–18.333, 208Pb/204Pb

207Pb/204Pb

= 15.538–15.641, and

= 37.667–38.185) and vein-type mineralization (206Pb/204Pb = 17.511–

17.800, 207Pb/204Pb = 15.524–15.660, and 208Pb/204Pb = 37.648–38.178) are similar and variable, and overlap those of Dashiqiao Formation marble (206Pb/204Pb = 17.866– 24

25

19.599,

207Pb/204Pb

= 15.579–15.843, and

208Pb/204Pb

= 35.858–38.347) and

Yanshanian granites (i.e., the Shuangdinggou and Xinling intrusions with 206Pb/204Pb = 16.417–17.410, 207Pb/204Pb = 15.471–15.535, and 208Pb/204Pb = 35.494–38.082). 6. Discussion 6.1. Sources and nature of the ore-forming fluids 6.1.1. Stratiform mineralization The FI study shows that hydrothermal quartz grain from the stratiform ores contain only type 1 inclusions, which exhibit medium-temperatures (221–246°C, mean = 234°C) and low-salinities (4.0–6.9 wt.% NaCl eq.), as determined by observations of phase transitions during heating experiments. Results indicate that the ore-forming fluids of stratiform mineralization belonged to a NaCl–H2O system characterized by mediumtemperatures and low-salinities (Fig. 8 and Table 1). The salinities of type 1 inclusions are close to the average value of seawater (3.5 wt.% NaCl eq.; Vanko et al., 1991), indicating that the ore-forming fluids may have originated from seawater. However, in the δD–δ18O diagram (Fig. 10), all of the analyzed quartz plots below the primary magmatic water field, indicating that the ore-forming fluids were derived from primary magmatic water. Furthermore, the REE pattern of the stratiform mineralization sulfide ore differs significantly from that of seawater near hydrothermal vents (Fig. 11), indicating that ore-forming fluids of the stratiform mineralization were derived from primary magmatic water rather than seawater. Ore-forming fluids of the stratiform mineralization belong to a mediumtemperature and low-salinity NaCl–H2O hydrothermal system, and only contain type 1 25

26

inclusions, indicating that there was no fluid immiscibility or boiling. Therefore, we conclude that ore-forming fluids of the stratiform mineralization belonged to a homogeneous system (H.Z. Lu et al., 2004). 6.1.2. Vein-type mineralization Hydrothermal quartz grains from the vein ores contain five types of FI (based on petrography, microthermometry analyses, and laser Raman spectroscopy): types 1, 2, 3a, 3b, and 4. The results of our study of FIs, in combination with studies of deposit geology, allow inferences to be made about the nature of ore-forming fluids. The FIs indicate that the ore-forming fluids related to vein-type mineralization were characterized by medium-temperatures (270–325°C, mean = 297°C) and low-salinities (3.9–9.2 wt.% NaCl eq.), and belonged to a NaCl–H2O–CO2 hydrothermal system. Fluid immiscibility occurred during vein-type mineralization of the Qingchengzi Pb–Zn deposit, as inferred from the following observations regarding FIs: (1) four FI types (types 2, 3a, 3b, and 4) were identified with markedly different FIAs distributed within the same plane (Fig. 7f), suggesting a close genetic relationship; (2) the FIs exhibit the same homogenization temperatures (mainly 280–300°C); and (3) the FIs display different homogenization behavior (i.e., some homogenized to a vapor phase, and others to a liquid phase). Results of component analyses of FIs show that the gas phase component comprises H2O, CO2, N2, O2, and CH4 (± C2H2, C2H4, and C2H6) (Ma et al., 2012a), consistent with the results of laser Raman spectroscopic analysis (this study, Dong et al., 2010; K.Y. Wang et al., 2016; Song et al., 2017). The high H2O content (>50%; indicating that the ore-forming fluids were water-rich) may reflect 26

27

mixing with meteoric water during mineralization process (Ma et al., 2012a). The liquid phase component comprises H2O, cations of Na+, K+, and Ca2+, and anions of Cl− and SO42− (with minor NO3−, F−, and Br−), with contents of Ca2+ > Cl− > SO42− > K+ > Na+ > F− (Ma et al., 2012a). In general, the Na+/K+ ratio of the magmatic hydrothermal fluid is less than 1 (Ma et al., 2012a), and the Na+/K+ ratios of the vein-type mineralization ore-forming fluids are 0.79–2.28 (mean 1.32), indicating that the ore-forming fluids have the characteristics of both magmatic hydrothermal fluids and meteoric water. The above analysis indicates that the ore-forming fluids have complex compositions and are characterized by fluid immiscibility, implying that they were derived from mixed sources. Quartz from the vein ores show a wide range of δ18OH2O (−9.4 to 4.5‰) and δD (−99.3 to −78‰) values (Table 3), indicating that the ore-forming fluids were derived from a mixture of fluids from multiple sources. This inference is also supported by the presence of N2 in the FIs (this study; Ma et al., 2012a; K.Y. Wang et al., 2016). In a δD–δ18O diagram (Fig. 10), the quartz plots in the region between the primary magmatic water field and to a lesser degree along the meteoric water line. Carbon isotopic analysis of vein-type mineralization quartz and calcite yields δ13C values of −12.6 to −4.4‰ (K.Y. Wang et al., 2016), which also indicate that the ore-forming fluids were derived from the mixing of water from magmatic and meteoric sources. There are numerous Au–Ag deposits (e.g., Xiaotongjiapuzi and Gaojiapuzi) on the periphery of the Qingchengzi Pb–Zn ore district, and their mineralization ages (233– 225 Ma; Xue et al., 2003; Zhang et al., 2016a) are consistent with the age of 27

28

Qingchengzi Pb–Zn vein-type mineralization. The source of the ore-forming fluids of the gold and silver deposits have been shown to be mixed magmatic water and meteoric water (Liu et al., 2019; Zhang et al., 2019), indicating that large-scale mineralization related to meteoric water occurred during the Middle–Late Triassic. 6.2. Sources of ore-forming materials 6.2.1. Ore REEs The REEs have the same, or similar, charges and ionic radii (R(REE3+) = (0.977– 1.16) × 10−10; Shannon, 1976), and are not significantly separated during geological processes. This enables them to be used as an important tracer of the sources of oreforming material (Mills and Elderfield, 1995; Ding et al., 2000). Stratiform ores and stratiform wall-rocks display the same REE patterns in Figure 11a, with LREE enrichment and HREE depletion, indicating that they were derived from the same source. Their ΣREE contents are lower than that of the vein ores, which indicates that the stratiform mineralization formed during hydrothermal activity (Ding et al., 2000) and was affected by hot water (Klinkhammer et al. 1994; Yan et al., 2008). Stratiform mineralization and stratiform wall-rocks exhibit mostly positive Eu anomalies, which are attributed to (a) inheritance from ore-forming hydrothermal fluids during precipitation (Ding et al., 2003a, 2003b); and (b) metamorphic deformation or fluid action (e.g., water–rock interaction) after ore formation, which resulted in the separation of Eu from REEs. Leaching of fluid can cause REE patterns to change. LREEs are more likely to be removed from the rock than HREEs (owing to their larger ionic radii), which would result in LREE depletion (Ding et al., 2003a, 2003b); however, 28

29

the ore is enriched in LREEs. When Eu in ores is mostly divalent (the Eu2+ radius is larger than that of other trivalent REEs), it is much easier to remove from the oreforming fluids, and fluid action subsequent to ore precipitation does not result in positive Eu anomalies (Ding et al., 2003a, 2003b; Ma et al., 2013a). The metallic minerals associated with stratiform mineralization in the study area are mainly sulfides, with characteristics that indicate formation in a reducing environment (see Section 6.2.2), in which Eu exists in the form of Eu2+. Therefore, the strong enrichment in LREEs and positive Eu anomalies in the Qingchengzi stratiform mineralization are inherited from ore-forming fluids during initial ore precipitation, rather than being the result of later geological processes. This also indicates that the stratiform mineralization and stratiform wall-rocks were formed at similar times (i.e., Paleoproterozoic; Ma et al., 2016). The ΣREE content of the vein-type mineralization is higher than that of stratiform mineralization (Table 3), and displays similar distribution patterns to the Yanshanian granites, indicating a genetic relationship between the vein-type mineralization and the granites (Fig. 11b). Vein-type mineralization also has similar REE patterns to those of vein wall-rocks, indicating that the host stratigraphy also contributed to vein-type mineralization, which is further supported by their negative Eu anomalies (Table 3, Fig. 11b) and similar S–Pb isotopic compositions. The REE pattern of the vein Pb–Zn ore is similar to that of the stratiform Pb–Zn ore, with the exception that the positive Eu anomaly is almost absent and ΣREE is higher in the former. Therefore, we conclude that the vein Pb–Zn ore had the same source as the stratiform Pb–Zn ore and that vein29

30

type mineralization had a ‘reforming effect’ (i.e., causing the re-enrichment of oreforming materials) on the Paleoproterozoic stratiform mineralization. This conclusion is also supported by the overlapping Y/Ho ratios, which are 15.1–50.0 for the ore in the Qingchengzi ore district, 15.1–42.3 for vein-type mineralization, and 20.5–50.0 for stratiform mineralization (this study; Ma et al., 2013a). This further explains the reforming effect of later vein-type mineralization on stratiform mineralization. The above features indicate that vein-type mineralization REEs were derived from Mesozoic magmatic hydrothermal fluids, stratiform ore, and wall-rocks. 6.2.2. Sulfur The mineral assemblage of the Qingchengzi Pb–Zn deposit comprises metallic sulfides such as pyrite (FeS2), galena (PbS), sphalerite (ZnS), and chalcopyrite (CuFeS2). The lack of sulfate (SO42−), magnetite (Fe3O4), and hematite (Fe2O3) indicates that the ore-forming fluids formed in a low-oxygen-fugacity environment and that sulfur existed mainly in the form of HS− and S2− (Ohmoto and Goldhaber, 1997). This means that the values of δ34S represent the sulfur isotopic compositions of the oreforming fluids (i.e., δ34SΣS = δ34Ssulfide; Ohmoto, 1972). The δ34S values of metallic sulfide samples of the stratiform mineralization are −0.2 to 14.4‰ (mean 6.2‰; Fig. 12). The wide range of isotopic values (with two peaks at 1–5‰ and 6–10‰) indicates that the sulfur isotopes were derived from two sources. The narrow δ34S range of 1–5‰ indicates a magmatic source for the sulfur (Ohmoto and Rye, 1979; Faure, 1986); the range of 6–10‰ overlaps with values of sedimentary rocks, metamorphic rocks, and marble of the Dashiqiao Formation (mostly 9–10‰; Fig. 30

31

12a; Ding et al., 1992), indicating that the Dashiqiao Formation also provided sulfur isotopes. The δ34S values of stratiform mineralization in Figure 12b are clustered at 7– 8‰. Field observations show that the ore bodies are in conformable contact with the wall-rocks and are characterized by “syn-sedimentary deposits”, indicating that the sulfur isotopes of the stratiform mineralization were derived predominantly from the Dashiqiao Formation. Therefore, the sulfur isotopes of stratiform mineralization represent a mixture of magmatic- and sedimentary-derived sulfur, and are comparable with those of SEDEX deposits elsewhere, where the sulfur isotopes are derived mainly from sediments and magma, such as the Dengjiashan Zn–Pb deposit (−7.2 to 30.1‰; Ma et al., 2007); Changba Pb–Zn deposit in the Qinling Belt, China (8.1–31.5‰; Ma et al., 2004); the Erlihe Zn–Pb deposit in Shanxi Province, China (mean of −8.4‰; Zhang et al., 2011); and the Chahmir Zn–Pb deposit in the early Cambrian Zarigan– Chahmir Basin, Iran (10.9–29.8‰; Rajabi et al., 2014). The sulfur isotope values of the sulfides in the vein-type mineralization (3.2–7.9‰, mean of 5.4‰; Fig. 12) are lower than those of the stratiform mineralization, and overlap with those of the Yanshanian intrusions (Xinling and Shuangdinggou granites with 5.6–7.6‰, mean of 6.6‰; Ding et al., 1992), indicating a genetic relationship between the Yanshanian granites and vein-type mineralization. The sphalerite of the vein-type mineralization yields a step-dissolution Rb–Sr age of 221 ± 12 Ma (Yu et al., 2009), which is within error of the LA–ICP–MS and SHRIMP zircon U–Pb ages for the Xinling and Shuangdinggou granitoids of 225–220 Ma (Yu et al., 2009; Duan et al., 2012, 2014; Li et al., 2019). Therefore, the sulfur isotopes of the vein-type 31

32

mineralization originated mostly from Yanshanian granitic magma. Furthermore, the sulfur isotope values of the vein-type mineralization also overlap with those of stratiform mineralization and wall-rocks (marble), indicating that they were also derived from the Paleoproterozoic stratiform ores and wall-rocks. 6.2.3. Lead Sulfide minerals usually contain very low concentrations of U and Th, and insignificant radiogenic Pb isotopes (Zhang, 1992; Zhang et al., 2000). Therefore, the isotopic compositions of Pb in sulfide minerals from hydrothermal ore deposits are an effective tracer of the source of metals (Sato and Sasaki, 1980; Browning et al., 1987; Stuart et al., 1999; Tosdal et al., 2003). The lead isotopic compositions of sulfides from the stratiform mineralization are tightly clustered, indicating that these sulfides share similar Pb isotopic compositions and have the same Pb source. In 206Pb/204Pb

207Pb/204Pb

vs.

206Pb/204Pb

and

208Pb/204Pb

vs.

diagrams (Fig. 13), most of the data points are distributed in the domain

between the mantle and the lower/upper crust evolution curve, indicating complex Pb sources. These features indicate that primitive Pb in the stratiform mineralization was derived mainly from two-component mixing between relatively high- and lowradiogenic end-members (Zhao et al., 2007; Ding et al., 2014). The high-radiogenic end-member can be correlated with an upper-crustal Pb reservoir (Zartman and doe, 1981), possibly the sedimentary–metamorphic host rocks, because the sulfide compositions of stratiform mineralization partly overlap with those of the marble (Fig. 13). The low-radiogenic end-member is probably associated with magmatic activity. 32

33

Consequently, the Pb isotopic compositions of different sulfide minerals in the stratiform mineralization can be interpreted to reflect a mixture of two different Pb sources: wall-rocks and magmatic. The Pb isotopic compositions of vein-type mineralization show a broad correlation between

206Pb/204Pb

and

207Pb/204Pb

or

208Pb/204Pb

(Fig. 13). We suggest that the

differences in Pb isotopes between the two mineralization types record systematic spatial and temporal changes in isotope ratios during sulfide ore formation. Most of the data are distributed in the domain between the upper/lower- crustal and mantle evolution curves in Figure 13. The primitive Pb in the vein-type mineralization is derived mainly from two-component mixing between relatively high- and lowradiogenic end-members, showing similar characteristics to stratiform mineralization. The high-radiogenic end-member is similar to the upper- crustal Pb reservoir (Zartman and doe, 1981) and could possibly be represented by the Liaohe Group sedimentary– metamorphic rocks (the vein-type mineralization sulfides overlap with the marble field in Figure 13). The low-radiogenic end-member may be represented by the Yanshanian granitic magma. The feldspars of the Xinling and Shuangdinggou granitoids are characterized by 206Pb/204Pb = 17.12–17.41, 207Pb/204Pb = 15.47–15.54, and 208Pb/204Pb = 37.51–37.89 (Table 5; Fig. 13). The two granites show similar Pb isotopic ratios, indicating that they formed coevally from the same source. The ages of vein-type mineralization are consistent with the granite ages (225–220 Ma; Yu et al., 2009; Duan et al., 2012, 2014; Li et al., 2019). The Hf(t) values of zircons from the biotite monzogranite (Shuangdinggou) are −15.4 to −17.6, indicating that these granites were 33

34

derived from partial melting of thickened lower crust with a minor mantle-derived component (Duan et al., 2014), which in turn indicates that vein-type mineralization Pb isotopes were sourced from deep magma. Furthermore, Pb isotopic compositions of sulfide minerals from the vein-type mineralization ores overlap with those of stratiform mineralization. Similar to the sulfur, the Pb in the vein-type mineralization ores may have been derived from stratiform mineralization ores. Therefore, we conclude that the vein-type mineralization Pb isotopes were derived from wall-rocks, Paleoproterozoic stratiform ore, and Yanshanian granitic magma. Ma et al. (2016) and Yu et al. (2009) reported 87Sr/86Sr values of 0.7156–0.8689 and 0.7085–0.9487 for stratiform and vein-type mineralization in the Zhenzigou and Xiquegou ore blocks, respectively. Comparison with the Dashiqiao Formation (marble), Gaixian Formation (schist), and Yanshanian granites indicates that the stratiform mineralization Sr isotopes were derived mainly from the Liaohe Group (particularly from Dashiqiao Formation marble and Gaixian Formation schist; Ma et al., 2016) and that the vein-type mineralization Sr isotopes were derived from Yanshanian granites and metamorphic rock (Yu et al., 2009). The sources of the ore-forming materials of the Qingchengzi Pb–Zn deposit can be summarized as follows. The ore-forming materials of stratiform mineralization were derived directly from wall-rocks and magma, whereas those of vein-type mineralization were derived mainly from Yanshanian granitic magma, with some contributions from the host sediments and Paleoproterozoic stratiform ores.

34

35

6.3. Ore genesis The ore genesis of the Qingchengzi Pb–Zn deposit is unresolved, with two main types having been proposed: The first is the SEDEX-type related to Paleoproterozoic JLJB (Ma et al., 2016; K.Y. Wang et al., 2016; Yang et al., 2015a, 2015b); The second is the hydrothermal-vein-type controlled by fractures (Liu and Ai, 2001; Xue et al., 2003; Duan et al., 2017). The results of our study, in combination with those of recent studies, indicate that there are two mineralization types in the Qingchengzi Pb–Zn deposit. A detailed comparison of the two types is presented in Table 6. Several lines of evidence indicate that stratiform mineralization belongs to the SEDEX-type, while vein mineralization is more applicable to the medium-temperature hydrothermal-veintype, as discussed here. The first line of evidence is based on spatial distributions: (a) the stratiform ore body is parallel to the wall-rock, being controlled by interlayer fractures, and displays obvious stratification in the ore body (Fig. 14); (b) lamprophyre, granite porphyry dikes, and the vein ore body are controlled mainly by NW–SEtrending fractures that crosscut the strata and/or stratiform ore body (Fig. 15). The second line of evidence is based on temporal relationships: the Rb–Sr isotopic data show that the ages of stratiform and vein-type mineralization are 1798 ± 8 Ma (Paleoproterozoic; Ma et al., 2016) and 221 ± 12 Ma (Late Triassic; Yu et al., 2009), respectively. The third line of evidence indicates that the Paleoproterozoic stratiform mineralization is a typical SEDEX-type deposit, as follows: (a) the presence of typical exhalite characteristics (mainly siliceous, banded tourmaline, and tourmaline rocks; Liu 35

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et al., 2007); (b) the stratiform ore bodies are controlled by strata, with comformable contacts with wall-rocks (have the same orientation as wall-rocks), and display stratification structures similar to sedimentary characteristics (Fig. 14f–n); (c) the stratiform ore body has a typical “double-layer” structure: the upper part is a stratiform ore body (SEDEX system), and the lower part comprises stockwork veins (hydrothermal system); and (d) the ore-forming fluids of the stratiform mineralization belonged to a NaCl–H2O system characterized by medium-temperatures and lowsalinities, were derived from primary magmatic water, and are analogous to those of SEDEX deposits (e.g., the Gacun volcanic-hosted massive sulfide polymetallic deposit in Sichuan, China (Hou et al., 2001); the Mt Chalmers VHMS deposit in central Queensland, Australia (Zaw et al., 2003); the Pingshui VMS Cu–Zn deposit in SE China (Chen et al., 2015); and the Laochang Pb–Zn–Ag–Cu VMS deposit in SW China (Li et al., 2015)). The Qingchengzi Pb–Zn deposit wall-rocks are sedimentary–metamorphic rocks of the Liaohe Group and were metamorphosed to greenschist to amphibolite facies at ca 1800 Ma (Fang et al., 1994; Yu et al., 2009). The stratiform mineralization belongs to a SEDEX-type deposit. Finally, the FIs and isotopic (H–O–S–Pb–Sr) compositions of the Late Triassic vein-type mineralization are significantly different from those of the stratiform mineralization. The following features indicate that the vein-type mineralization represents a typical hydrothermal-vein-type deposit: (a) the ore bodies occur mainly as veins or are lenticular in shape and controlled by fractures; (b) wall-rock alteration is characterized by silicification, sericitization, chloritization, and carbonatization, and 36

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silicification and sericitization are closely associated with the vein-type Pb–Zn mineralization; (c) the FIs in quartz are type 1, 2, 3a, 3b, and 4 inclusions characterized by fluid immiscibility, and the ore-forming fluids belonged to a NaCl–H2O–CO2 hydrothermal system characterized by medium-temperatures and low-salinities; and (d) the ore-forming fluids were derived from the mixing of magmatic water and meteoric water, similar to typical hydrothermal-vein-type deposits in Inner Mongolia (China) such as the Hua’naote Pb–Zn (Han et al., 2013; G.F. Chen et al., 2016), Hua’aobaote Pb–Zn (W. Chen et al., 2008; Y.Q. Chen et al., 2014), and Aerhada Pb–Zn–Ag (Ke et al., 2016, 2017) deposits. The vein mineralization thus represents a mediumtemperature hydrothermal-vein-type deposit. 6.4 Metallogenic model 6.4.1. Stratiform mineralization Liu et al. (2018) proposed that the JLJB experienced an integrated introversion tectonic process that was initiated at 2.2–2.0 Ga during an intra-continental rifting event, and transitioning to an active continental margin at 2.0–1.9 Ga, followed by arc– continent collision at ca 1.9 Ga and post-collisional extension at 1.9–1.8 Ga. Rb–Sr isotopic data yield an age for the stratiform mineralization of ca 1.8 Ga (Ma et al., 2016), indicating that the SEDEX mineralization in the Qingchengzi ore district occurred during the post-collision extension stage (Liu et al., 2018). The Qingchengzi Pb–Zn deposit is located in the northeastern JLJB (Fig. 1c), and wall-rocks comprise Paleoproterozoic sedimentary–metamorphic rocks of the Liaohe Group. The ore-forming fluids of the stratiform mineralization belonged to a NaCl– 37

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H2O system characterized by medium-temperatures (homogenization temperatures of 221–246°C) and low-salinities (4.0–6.9 wt.% NaCl eq.). Hydrogen and oxygen isotopic data (δD, −105.1 to −103.3‰; δ18OH2O, 4.6 to 7.5‰) indicate that the fluids were derived from primary magmatic water. Ore REE contents and S, Pb, and Sr isotopic compositions suggest that the sedimentary–metamorphic rocks of the Liaohe Group were the primary source of ore-forming materials in the massive sulfide deposit. The metallogenic process envisaged for the Qingchengzi SEDEX mineralization is illustrated in Figure 16. During the Paleoproterozoic (ca 1.8 Ga), volcanic activity occurred in the Qingchengzi area. Fluids that accumulated during fractional crystallization in the magma chamber (Shinohara and Kazahaya, 1995; Li et al., 2015) subsequently phase-separated from magma and vented onto the seafloor. The separated fluids were enriched in ore metals (especially Cu, Pb, and Zn). Modern seafloor hydrothermal systems show that when the depth of seawater is <1500 m, shallow seawater does not exert sufficient pressure to keep the fluid in its original state, thereby ebabling fluid boiling or immiscibility (Bischoff and Rosenbauer, 1984; Bischoff and Pitzer, 1985; Peter and Mark, 1995; H.Z. Lu et al., 2004; Ni et al., 2005). Only type 1 FIs in quartz crystals are observed in the stratiform mineralization, indicating the absence of boiling or immiscibility in the ore-forming fluids and a water depth of >1500 m. In our model, the hydrothermal fluid separated from the shallow magma chamber, ascended along the stockwork, and leached ore-forming materials from the wall-rocks (i.e., the Liaohe Group). During fluid migration to weak zones between strata, the decrease in temperature and release of pressure reduced the transport efficiency of Pb2+, 38

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Zn2+, and Cu2+ in the ore-forming fluid. With the change in temperature and pressure, the fluid system destabilized, which led to sulfur ions combining with metal ions to precipitate abundant metal sulfides and form stratiform ore bodies (Fig. 16a). SEDEX-type deposits are characterized by the strong involvement of hydrothermal fluids in mineralization and multi-stage fluid activity, as illustrated in the metallogenic model shown in Figure 16b. 6.4.2. Vein-type mineralization Based on geological features, characteristics of the ore-forming fluid, ore REEs, and C–H–O–S–Pb–Sr isotope systematics, we propose that the vein-type mineralization is a hydrothermal-vein-type deposit, formed during the Late Triassic (ca 221 Ma; Rb– Sr isotopic data; Yu et al., 2009). This Triassic age precludes the possibility that the vein-type mineralization formed by metamorphic processes or Paleoproterozoic seafloor exhalation. Magmatic activity occurred frequently in the Qingchengzi area during the Triassic. Yu et al. (2009) reported a SHRIMP zircon U–Pb age of 225 Ma for the Xinling granite, which is consistent with previous K–Ar ages (227–218 Ma; Fang et al., 1994). Duan et al. (2014) obtained LA–ICP–MS zircon U–Pb ages of 227–210 Ma and 224 Ma for lamprophyres and the Shuangdinggou biotite monzogranite, respectively. Zhang et al. (2016b) reported a LA–ICP–MS zircon U–Pb age of 227 Ma for lamprophyre from the Qingchengzi ore district. These data indicate that voluminous Late Triassic intrusive activity occurred in the Qingchengzi ore district, with Late Triassic magmatism controlling the formation of ore deposits in the area. Furthermore, the step-dissolution 39

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Rb–Sr age of sphalerite from vein-type mineralization (221 ± 12 Ma; Yu et al., 2009) is within error of the LA–ICP–MS and SHRIMP zircon U–Pb ages of the Shuangdinggou and Xinling granitoids (225–220 Ma; Yu et al., 2009; Duan et al., 2012, 2014; Li et al., 2019). It suggests a genetic connection between the Late Triassic granites and vein-type mineralization. Combined with the geochemical characteristics of the magmatic rocks and the regional geological setting, we consider that the Late Triassic granites were formed in a syn/post-collisional setting (also supported by the large volumes of mafic rocks; Hall and Fahrig, 1987; Zhao and McCulloch, 1993) of the Yangtze Craton (YZC) and NCC (Duan et al., 2014; Li et al., 2019). During the Late Triassic, northward subduction of the YZC beneath the NCC resulted in continental collision, ultrahigh-pressure conditions, thickened lower crust, and eclogite formation (Fig. 17a). Slab break-off during deep subduction led to asthenospheric flow through fissures and caused partial melting of the upper mantle, forming basaltic magma. The mantle-derived magma underplated the base of the thickened lower crust and induced partial melting to produce granitic magma, forming the abundant contemporaneous lamprophyre, diorite, and granite in the area. Post-magmatic hydrothermal fluids derived from the granitic magma mixed with circulating meteoric water during magma upwelling along the fault (Fig. 17b), resulting in the immiscibility of the ore-forming fluids. The ore REE and C–S–Pb–Sr isotopic compositions indicate that the ore-forming materials were derived mainly from magma and that the Late Triassic granitic magma provided the main ore-forming materials for vein-type mineralization. The magma chamber degassed Cl–, which is the most 40

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abundant anion in the ore-forming fluids (Ma et al., 2012a). Pb, Zn, and Cu are strongly partitioned into magmatic fluids as chloride complexes (Hemley and Hunt, 1992; Hedenquist and Lowenstern, 1994; Li et al., 2015). Owing to the continuous supply of meteoric water, the temperature and pressure of the ore-forming fluid decreased, and fluid immiscibility occurred. Escape of CO2 caused the fluid system to become unbalanced, and chloride became unstable, resulting in the combining of metal and sulfur ions to precipitate abundant metal sulfides. However, we cannot completely rule out the involvement of a small amount of metals leached from the overlying Liaohe Group and Paleoproterozoic stratiform ore during the ascent of magmatic fluid. 7. Conclusions Our comprehensive study of FIs, ore REEs, and H–O–S–Pb isotopic systematics of the Qingchengzi Pb–Zn deposit leads to the following conclusions. (1) The ore bodies are divided into two types: stratiform and vein. Ore-forming fluids of the SEDEX stratiform mineralization belonged to a NaCl–H2O system characterized by medium-temperatures and low-salinities, and were derived from primary magmatic water with the involvement of material from wall-rocks and magma. Stratiform mineralization occurred during the Paleoproterozoic post-collision extensional stage of the Jiao–Liao–Ji Belt, and the ore genesis is similar to that of a SEDEX-type deposit. (2) Ore-forming fluids of the vein-type mineralization are characterized by medium-temperatures and low-salinities, belonged to a NaCl–H2O–CO2 hydrothermal system, and were derived from the mixing of magmatic water and meteoric water. The 41

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ore-forming materials were derived mainly from Yanshanian granitic magma, with contributions from the host sediments and Paleoproterozoic stratiform ores. Vein-type mineralization was generated by the north-dipping subduction of the Yangtze Craton beneath the North China Craton, which resulted in continent-continent collision and slab break-off in the Late Triassic. The ore genesis is a medium-temperature, hydrothermal-vein-type deposit, controlled by fractures.

Acknowledgments

We gratefully acknowledge three anonymous reviewers for their insightful comments, which greatly improved the quality of this manuscript. We thank Prof. Khin Zaw and Miss Diane Chung for handling of the manuscript and editorial input. We are grateful to Juliana Useya from University of Zimbabwe and Chunkit Lai from the Universiti Brunei Darussalam for kindly helping with English editing. We are also grateful to the staff of the Analytical Laboratory at the Beijing Research Institute of Uranium Geology, China National Nuclear Corporation, for their advice and assistance with the isotopic analyses. We thank ALS Minerals–ALS Chemex, Guangzhou, China, for their assistance in the rare-earth element analyses. This work was financially supported by the National Key R&D Program of China (2018YFC0603804).

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Figure captions

Fig. 1 (a) Map showing the distribution of major structures in China; (b) simplified geological map of the North China Craton; (c) geological map of the Paleoproterozoic Jiao–Liao–Ji Belt in the Eastern Block of the North China Craton (after Zhao et al., 2005). Fig. 2 Geological map of the Qingchengzi ore district (modified after LDQMCL, 2016). Fig. 3 Geological cross-section of exploration lines (a) 33 and (b) 9 in the Zhenzigou ore block, and lines (c) 412 and (d) 46 in the Diannan and Xiquegou ore blocks, respectively. Fig. 4 Characteristics of the mineral assemblages of the Qingchengzi Pb–Zn deposit in the Zhenzigou ore block, (a–l) Stratiform mineralization; (m–t) vein-type mineralization. (a–d) Stratabound ore body and comfortable contact with wall-rocks; 62

63

(e–h) striped and striated dolomite–pyrite–galena–sphalerite–chalcopyrite ore in stratabound ore body; (i) pyrite and galena replaced by sphalerite; (j) sphalerite intergrown with chalcopyrite and pyrrhotite; (k) sphalerite intergrown with galena; (l) galena replaced by sphalerite; (m–n) vein ore body cutting wall-rocks; (o–p) massive quartz–pyrite ore; (q) sphalerite intergrown with chalcopyrite, and galena replaced by sphalerite; (r) euhedral and subhedral pyrite; (s) galena replaced by sphalerite; (t) sphalerite intergrown with chalcopyrite and pyrite. Abbreviations: Apy = Arsenopyrite; Ccp = Chalcopyrite; Dol = Dolimite; Gn = Galena; Po = Pyrrhotite; Py = Pyrite; Qtz = Quartz; Sp = Sphalerite. Fig. 5 Characteristics of the mineral assemblages in the Diannan and Xiquegou ore blocks of the Qingchengzi Pb–Zn deposit, (a–l) Diannan ore block; (m–t) Xiquegou ore block. (a–b) Vein ore body (quartz–pyrite–galena); (c–d) quartz–pyrite ore; (e) chalcopyrite and pyrrhotite intergrown with galena, and pyrite replaced by galena; (f– g) pyrite intergrown with marcasite; (h) euhedral pyrite; (i) wall-rock (marble) cut by a quartz–pyrite–galena vein; (j–l) quartz–pyrite–galena ore; (m) arsenopyrite and galena showing graphic texture; (n) pyrite–arsenopyrite–chalcopyrite vein; (o) euhedral and subhedral pyrite scattered in a quartz vein; (p) pyrite intergrown with marcasite, and arsenopyrite replaced by pyrite; (q) tetrahedrite and pyrite intergrown with chalcopyrite and arsenopyrite, and chalcopyrite replaced by galena; (r–s) chalcopyrite replaced by sphalerite and galena; (t) euhedral and subhedral arsenopyrite intergrown with chalcopyrite. Abbreviations: Apy = Arsenopyrite; Ccp = Chalcopyrite; Gn = Galena; Mrc = Marcasite; Po = Pyrrhotite; Py = Pyrite; Qtz = Quartz; Sp = Sphalerite; Td = 63

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Tetrahedrite. Fig. 6 Paragenetic sequence of the two mineralization types in the Qingchengzi Pb–Zn deposit. Fig. 7 Microphotographs of representative FIs in quartz from the Qingchengzi Pb–Zn deposit. (a) Type 1 liquid-rich two-phase inclusions; (b) Type 2 vapor-rich two-phase inclusions; (c–d) Type 3 CO2-bearing inclusions; (e) Type 4 CO2-pure inclusions; (f–k) The representative primary FIs in quartz crystals; (l–m) Oriented FIAs of type 1 from vein mineralization. Abbreviations: VCO2 = CO2 vapor; LCO2 = CO2 liquid; VH2O = H2O vapor; LH2O = H2O liquid. Fig. 8 Histograms of total homogenization temperatures and salinities of FIs in (a–b) stratiform and (c–d) vein-type mineralization of the Qingchengzi Pb–Zn deposit. Fig. 9 Representative Raman spectra of FIs in the Qingchengzi Pb–Zn deposit for (a) stratiform mineralization, and (b–h) vein-type mineralization. (a–b) H2O of the vapor phase of type 1 and 2 inclusions; (c–e) CO2 of the vapor phase and H2O spectra of the liquid phase of type 3a and 3b inclusions, with minor vapor phase amounts of CH4 and N2; (f–h) CO2 of the vapor phase spectra of type 3a and 3b inclusions. Fig. 10 Plot of δD versus δ18O (after Taylor, 1974) for stratiform and vein-type mineralization of the Qingchengzi Pb–Zn deposit, in comparison with Yanshanian granites and the fields of primary magmatic and metamorphic water. Fig. 11 Chondrite-normalized REE patterns of (a) stratiform mineralization, stratiform wall-rocks, and seawater near hydrothermal vents; and (b) vein-type mineralization, vein wall-rocks, and Yanshanian granites. Data sources are as follows: chondrite values 64

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used for normalization are from Sun and McDonough (1989); some of the stratiform, vein-type mineralization and wall-rock data are from Ma et al. (2013a); data of seawater near hydrothermal vents are from Klinkhammer et al. (1983). Fig. 12 (a) Sulfur isotopic compositions of rock and mineralization types, and (b) histogram of the sulfur isotopes of sulfides from the Qingchengzi Pb–Zn deposit. Stratiform and vein mineralization isotopic data are from this study, Ding et al. (1992), Chi (2002), Sha et al. (2006), Ma et al. (2013a, 2016), Duan et al. (2017), and Song et al. (2017). Data of Yanshanian granites and marble are from Ding et al. (1992). Fig. 13 Lead isotopic compositions of sulfides, wall-rocks, and Yanshanian granites in the Qingchengzi Pb–Zn deposit. (a) 206Pb/204Pb.

207Pb/204Pb

vs.

206Pb/204Pb;

(b)

208Pb/204Pb

vs.

Abbreviations: UC = Upper crust; O = Orogen; M = Mantle; LC = Lower

crust. The average growth lines are from Zartman and Doe (1981). Fig. 14 (a) Idealized model of the stratiform mineralization in the Qingchengzi Pb–Zn deposit (the dotted rectangle indicates the area shown in the other panels); (b) banded marble; (c) banded mica schist; (d–e) stratiform ore body; (f–k) stratabound ore body in conformable contact with wall-rocks, and stratification structures visible in the ore body; (l–n) typical SEDEX mineralization characteristics, with the upper part being a stratiform ore body with a stratification structure, and the lower part a vein channel. Abbreviations: Dol = Dolimite; Gn = Galena; Py = Pyrite; Sp = Sphalerite. Fig. 15 (a) Idealized model of vein-type mineralization in the Qingchengzi Pb–Zn deposit (dotted rectangles indicate the locations shown in the other panels); (b–d, h) lamprophyre dikes cutting wall-rocks; (e–g) lamprophyre dike cutting a stratiform ore 65

66

body; (i–m) vein mineralization cutting wall-rocks. Note: the age of the lamprophyre dikes (227–224 Ma; LA–ICP–MS zircon U–Pb data; Duan et al., 2014; Zhang et al., 2016b) is consistent with the age of vein mineralization (~221 Ma; sphalerite stepdissolution Rb–Sr dating; Yu et al., 2009). Abbreviations: Py = Pyrite; Qtz = Quartz. Fig. 16 Metallogenic model of the stratiform mineralization in the Qingchengzi Pb–Zn deposit. (a) Seafloor hydrothermal exhalation, followed by (b) multiple metallogenic activity of the stratiform mineralization. Fig. 17 Metallogenic model of the vein-type mineralization in the Qingchengzi Pb–Zn deposit. (a) North-dipping subduction of the YZC beneath the NCC resulted in continent-continent collision and slab break-off. (b) The post-magmatic hydrothermal fluids of the granitic magma mixed with circulating meteoric water, resulting in the immiscibility of the ore-forming fluids and the precipitation of metallic sulfides along the fault to form the vein ore body.

66

67

Table 1 Microthermometric data for FIs from the Qingchengzi Pb–Zn deposit Mineralization type

Stratiform

Vein

Host minerals

Qtz

Qtz

Inclusion types

Type 1

Tm-CO2 (°C)

/

Tm-cla (°C)

/

Th-CO2 (°C)

/

Th-total (°C)

Tm-ice (°C)

Th-v (°C)

Salinity (wt.% NaCl eq.)

/

−4.3 to −2.4

221–246 (93)/234a

4.0–6.9

281–312 (72)/296

5.1–9.2

270–318 (64)/293

3.0–5.9

−6.0 to −3.1 −3.7 to −1.8

Type 1

/

/

/

/

Type 2

/

/

/

/

5.8–7.9

26.4–29.9

270–316 (45)/299

/

/

4.1–7.8

5.4–7.5

26.3–30.6

279–325 (38)/303

/

/

4.9–8.5

/

30.1–30.8

/

/

/

/

Type 3a

Type 3b

Type 4

−57.6 to −56.9 −57.8 to −56.7 −56.9 to −56.7

Abbreviations: Tm-CO2 = final melting temperature of solid CO2; Tm-cla = final melting temperature of CO2–H2O clathrate; Th-CO2 = homogenization temperature of CO2 phases; Th-total = total homogenization temperature of CO2 fluid inclusions; Tm-ice = temperature of final ice melting; Th-v = homogenization temperature of vapor-rich and liquid-rich two-phase fluid inclusions; Qtz = quartz. a Range

(number)/average

67

68

Table 2 Oxygen and hydrogen isotopic compositions of FIs in quartz from the Qingchengzi Pb– Zn deposit Samp le no.

Locati on

ZZ-21 ZZ-22 ZZ-41 ZZ-42

Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Zhenzi gou Bensha n

ZZ-7 ZZ10 ZZ11 ZZ12 ZZ11-1 ZZ11-2 ZZ12-1 ZZ12-2 ZZ14-1 ZZ14-2 ZZ14-3 ZZ14-4 Bs4

Host miner als

δ18OVSMOW/‰

δDVSMOW/‰

T/(° C)

δ18OH2OSMOW/‰

Ore body shape

Qtz

10.7

−97.5

297

3.7

Vein

Qtz

9.2

−99.3

297

2.2

Vein

Qtz

9.8

−96.5

297

2.8

Vein

Qtz

10.5

−98.5

297

3.5

Vein

Qtz

9.5

−97.9

297

2.5

Vein

Qtz

10.0

−94.6

297

3.0

Vein

Qtz

9.7

−95.7

297

2.7

Vein

Qtz

9.6

−95.1

297

2.6

Vein

Qtz

15.1

−103.3

234

5.4

Qtz

14.0

−104.5

234

7.0

Qtz

14.5

−105.1

234

7.5

Qtz

13.9

−103.9

234

6.9

Qtz

14.7

−103.8

234

5.0

Qtz

15.0

−104.1

234

5.3

Qtz

14.3

−104.6

234

4.6

Qtz

14.8

−103.9

234

5.1

Qtz

6.6

−94.4

211

−4.4

68

Stratifo rm Stratifo rm Stratifo rm Stratifo rm Stratifo rm Stratifo rm Stratifo rm Stratifo rm Vein

Data source This study This study This study This study This study This study This study This study This study This study This study This study This study This study This study This study Song et al.,

69

2017 Bs5

Bensha n

Qtz

9.7

−79.9

211

−1.3

Vein

Xqg3

Xiqueg ou

Qtz

10.0

−83.0

237

0.4

Vein

Song et al., 2017 Song et al., 2017

Table 2 (Continued) Oxygen and hydrogen isotopic compositions of FIs in quartz from the Qingchengzi Pb– Zn deposit Sam ple no.

Location

Host miner als

δ18OVSMOW/‰

δDVSMOW/‰

T/(° C)

δ18OH2OSMOW/‰

Ore bod y sha pe

Xqg4

Xiquegou

Qtz

5.7

−89.3

238

−3.9

Vei n

QD15

Diannan

Qtz

/

−78.0

/

−6.0

Vei n

QZ11

Zhenzigou

Qtz

/

−91.0

/

−6.7

Vei n

QD-9

Diannan

Qtz

/

−81.0

/

−9.4

Vei n

ZZ01

Zhenzigou

Qtz

11.8

−86.0

/

1.9

Vei n

ZZ02

Zhenzigou

Qtz

14.4

−85.0

/

4.5

Vei n

69

Data sour ce Song et al., 2017 Don g et al., 2010 Don g et al., 2010 Don g et al., 2010 Ma et al., 2012 a Ma et al.,

70

ZZ03

Zhenzigou

Qtz

12.8

−90.0

/

2.9

Vei n

86JS3

Shuangding gou granite

Qtz

11.1

−116.0

/

9.3

/

86JX2

Xinling granite

Bi

6.5

−112.0

/

9.1

/

QCZ4

Zhenzigou

Qtz

/

−95.4

227

−0.6

Vei n

QCZ5

Zhenzigou

Qtz

/

−96.5

250

0.0

Vei n

2012 a Ma et al., 2012 a Ding et al., 1992 Ding et al., 1992 K.Y. Wan g et al., 2016 K.Y. Wan g et al., 2016

Abbreviations: Qtz = quartz; Bi = Biotite

Table 3 REE contents of stratiform and vein mineralization of the Qingchengzi Pb–Zn deposit Sample no.

ZH-1

ZH-2

Mineralization-type

ZH3-1

ZH3-2

ZH3-3

DN-4

DN-5

Stratiform

XQ-1

XQ-4

Vein

La

5.50

1.30

4.90

2.70

2.50

7.30

12.20

2.20

1.00

Ce

9.80

2.30

9.90

4.70

5.60

14.90

24.60

3.70

1.70

Pr

0.89

0.21

1.03

0.40

0.61

1.52

2.65

0.31

0.13

Nd

3.20

0.80

3.90

1.30

2.50

6.80

11.30

1.10

0.50

Sm

0.58

0.22

0.64

0.17

0.47

1.51

2.37

0.16

0.07

70

71

Eu

0.23

0.10

0.55

0.08

0.23

0.49

0.56

0.04

0.03

Gd

0.61

0.24

0.54

0.08

0.33

1.69

2.30

0.14

0.12

Tb

0.09

0.04

0.06

0.01

0.04

0.25

0.33

0.02

0.02

Dy

0.60

0.23

0.38

0.06

0.26

1.69

2.11

0.12

0.16

Ho

0.14

0.05

0.08

0.01

0.05

0.38

0.45

0.03

0.04

Er

0.42

0.14

0.21

0.03

0.14

1.06

1.23

0.07

0.12

Tm

0.06

0.02

0.03

0.01

0.02

0.15

0.17

0.01

0.02

Yb

0.38

0.13

0.19

0.04

0.13

0.89

0.98

0.07

0.13

Lu

0.06

0.02

0.03

0.01

0.02

0.12

0.14

0.01

0.02

Y

6.40

1.50

2.80

0.50

1.70

16.10

15.60

1.00

1.50

ΣREE

22.56

5.80

22.44

9.60

12.90

38.75

61.39

7.98

4.06

LREE

20.20

4.93

20.92

9.35

11.91

32.52

53.68

7.51

3.43

HREE

2.36

0.87

1.52

0.25

0.99

6.23

7.71

0.47

0.63

LREE/HREE

8.56

5.67

13.76

37.40

12.03

5.22

6.96

15.98

5.44

LaN/YbN

10.38

7.17

18.50

48.42

13.79

5.88

8.93

22.54

5.52

Table 3 (Continued) REE contents of stratiform and vein mineralization of the Qingchengzi Pb–Zn deposit Sample no.

ZH-1

ZH-2

Mineralization-type

ZH3-1

ZH3-2

ZH3-3

DN-4

DN-5

Stratiform

XQ-1

XQ-4

Vein

δEu

1.17

1.32

2.78

1.84

1.70

0.93

0.72

0.80

0.99

δCe

0.98

0.98

1.03

0.98

1.08

1.04

1.01

0.96

0.99

Note: δEu = Eu/Eu* = EuN/Sqrt (SmN × GdN); δCe = Ce/Ce* = 2CeN/(LaN + PrN)

71

72

Table 4 Sulfur isotopic compositions of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit δ34 S ‰

Ore body

Pyrit e

7.3

Strati form

Zhen zigou

Pyrit e

7.9

Strati form

ZH-9

Zhen zigou

Pyrit e

6.2

Strati form

ZH10

Zhen zigou

Pyrit e

8.6

Strati form

ZH11

Zhen zigou

Gale na

8.2

Strati form

ZH12

Zhen zigou

Gale na

7.7

Strati form

ZH13

Zhen zigou

Gale na

7.6

Strati form

ZH14

Zhen zigou

Gale na

7.8

Strati form

ZZ1-1

Zhen zigou

Pyrit e

8.7

Vein

Sam ple no.

Locat ion

Min erals

ZH-7

Zhen zigou

ZH-8

Dat a sour ce This pape r This pape r This pape r This pape r This pape r This pape r This pape r This pape r This pape r

72

δ34 S ‰

Sam ple no.

Locat ion

QCZ -16b

Zhen zigou

Galena

4.7

Vein

DN-6

Diann an

Pyrite

6.9

Vein

DN-7

Diann an

Pyrite

7.4

Vein

DN-8

Diann an

Pyrite

7.3

Vein

DN-9

Diann an

Pyrite

6.5

Vein

XQ-8

Diann an

Pyrite

5.7

Vein

XQ-9

Diann an

Pyrite

5.3

Vein

XQ10

Diann an

Pyrite

5.0

Vein

XQ11

Diann an

Pyrite

5.7

Vein

Miner als

Ore body

Data sour ce This pape r This pape r This pape r This pape r This pape r This pape r This pape r This pape r This pape r

73

ZZ1-2

Zhen zigou

Pyrit e

4.6

Vein

ZZ-7

Zhen zigou

Gale na

4.0

Vein

ZZ-8

Zhen zigou

Gale na

5.1

Vein

QCZ4a

Zhen zigou

Gale na

7.2

Vein

QCZ4b

Zhen zigou

Gale na

6.6

QCZ13a

Zhen zigou

Gale na

6.6

QCZ13b

Zhen zigou

Gale na

QCZ13c

Zhen zigou

Gale na

QCZ16a

Zhen zigou

Gale na

5.2

4.4

4.4

This pape r This pape r This pape r This pape r

XQ12

Diann an

Galena

5.0

Vein

XQ13

Diann an

Galena

4.7

Vein

XQ14

Diann an

Galena

4.4

Vein

XQ15

Diann an

Galena

4.0

Vein

Vein

This pape r

2011 1481

Zhen zigou

Pyrite

5.0

Strati form

Vein

This pape r

2011 1482

Zhen zigou

Galena

6.8

Strati form

Vein

This pape r

ZKC -11

Zhen zigou

Chalco pyrite

6.9

Strati form

Vein

This pape r

ZKC -13

Zhen zigou

Pyrite

8.2

Strati form

Vein

This pape r

ZKC -15

Zhen zigou

Pyrite

9.0

Strati form

ZKC -18

Zhen zigou

Pyrite

6.3

Strati form

KZ2

Zhen zigou

Galena

4.6

Strati form

ZKC02B

Zhen zigou

Pyrit e

7.7

Strati form

ZKC04A

Zhen zigou

Pyrit e

7.5

Strati form

Ma et al., 2016 Ma et al., 2016 73

This pape r This pape r This pape r This pape r Ma et al., 2013 b Ma et al., 2013 b Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Sha et al., 2006

74

Table 4 (Continued) Sulfur isotopic compositions of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sam ple no.

Locat ion

Mine rals

δ34S ‰

Ore body

ZKC05A

Zhenz igou

Pyrit e

7.3

Strati form

ZKC06

Zhenz igou

Pyrit e

14.4

Strati form

ZKC08

Zhenz igou

Pyrrh otite

14.4

Strati form

ZKC09

Zhenz igou

Pyrit e

8.2

Strati form

ZKC10

Zhenz igou

Pyrit e

7.0

Strati form

ZKC17

Zhenz igou

Pyrit e

7.6

Strati form

LZZ0 02

Zhenz igou

Pyrit e

5.0

Strati form

LZZ0 03

Zhenz igou

Gale na

6.8

Strati form

Xqg5

Xiqug ou

Pyrit e

4.8

Strati form

Data sour ce Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Song et 74

Samp le no.

Locat ion

Mine rals

δ34S ‰

Ore body

KZ12

Zhenz igou

Pyrit e

7.2

Strati form

KZ311

Zhenz igou

Sphal erite

6.1

Strati form

Zzg2

Zhenz igou

Gale na

5.9

Strati form

Zzg1

Zhenz igou

Pyrit e

5.6

Strati form

ZZ39 0-16

Zhenz igou

Sphal erite

8.0

Strati form

ZZ39 0-1

Zhenz igou

Sphal erite

8.2

Strati form

ZZ39 0-8-2

Zhenz igou

Sphal erite

8.2

Strati form

3904-2

Zhenz igou

Sphal erite

7.3

Strati form

3906-1

Zhenz igou

Sphal erite

8.0

Strati form

Data sour ce Sha et al., 2006 Sha et al., 2006 Sha et al., 2006 Sha et al., 2006 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et

75

Xqg6

Xiqug ou

Pyrit e

5.4

Strati form

Xqg8

Xiqug ou

Pyrit e

5.0

Strati form

Xqg9

Xiqug ou

Pyrit e

5.0

Strati form

KX37

Xiqug ou

Gale na

5.0

Strati form

KX52

Xiqug ou

Gale na

5.2

Strati form

KX15-2

Xiqug ou

Pyrit e

4.6

Strati form

KX25

Xiqug ou

Pyrit e

2.8

Strati form

KX26

Xiqug ou

Pyrit e

6.5

Strati form

ZZ39 0-15

Zhenz igou

Gale na

5.2

Strati form

330-6

Zhenz igou

Gale na

3.9

Vein

al., 2017 Song et al., 2017 Song et al., 2017 Song et al., 2017 Sha et al., 2006 Sha et al., 2006 Sha et al., 2006 Sha et al., 2006 Sha et al., 2006 Dua n et al., 2017 Dua n et al., 2017 75

39010-1

Zhenz igou

Sphal erite

7.8

Strati form

39010-5

Zhenz igou

Sphal erite

7.9

Strati form

ZZW1

Zhenz igou

Sphal erite

7.3

Strati form

DNA-2

Diann an

Sphal erite

6.9

Vein

DN-6

Diann an

Sphal erite

6.3

Strati form

DN15 0-5

Diann an

Sphal erite

5.7

Vein

DN15 0-4

Diann an

Sphal erite

5.6

Vein

DNB Y

Diann an

Sphal erite

6.3

Vein

ZZ39 0-12

Zhenz igou

Gale na

5.4

Strati form

BS-4

Bensh an

Gale na

4.7

Vein

al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017 Dua n et al., 2017

76

Table 4 (Continued) Sulfur isotopic compositions of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit δ34 S ‰

Ore body

Gale na

5.6

Strati form

Zhen zigou

Gale na

3.5

Vein

390-7

Zhen zigou

Gale na

4.8

Strati form

NS-12

Nans han

Gale na

5.8

Vein

NS60-1

Nans han

Gale na

5.2

Vein

NS60-6

Nans han

Gale na

5.4

Vein

NS10

Nans han

Gale na

6.4

Vein

XQ18 0-2

Xiqu gou

Gale na

3.2

Vein

XQ36 0-1

Xiqu gou

Gale na

3.9

Vein

XQA 360-7

Xiqu gou

Gale na

3.9

Vein

Samp le no.

Locat ion

Min erals

39060-1

Zhen zigou

3305-1

Data sour ce Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017

76

δ34 S ‰

Ore body

Pyrit e

6.7

Stratif orm

Zhen zigou

Pyrit e

9.1

Stratif orm

XQ18 0-2

Xiqu gou

Pyrit e

6.0

Vein

XQA 360-1

Xiqu gou

Pyrit e

5.2

Vein

XQA 180-1

Xiqu gou

Pyrit e

6.1

Vein

DN-6

Diann an

Pyrit e

6.4

Stratif orm

DNB Y

Diann an

Pyrit e

7.2

Vein

NS11

Nans han

Pyrit e

7.9

Vein

NS10

Nans han

Pyrit e

7.9

Vein

NS-13

Nans han

Pyrit e

7.6

Vein

Samp le no.

Locat ion

Mine rals

33012

Zhen zigou

ZZ39 0-8-1

Data sour ce Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017

77

XQ36 0-3

Xiqu gou

Gale na

3.4

Vein

DN1-1

Diann an

Gale na

4.3

Vein

DN13-2

Diann an

Gale na

6.4

Vein

DN36 0-2

Diann an

Gale na

4.6

Vein

DN36 0-3

Diann an

Gale na

4.7

Vein

DN36 0-4

Diann an

Gale na

3.7

Vein

BS-1

Bens han

Gale na

4.6

Vein

BS-4

Bens han

Gale na

4.7

Vein

Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017

QC23

Zhen zigou

Pyrit e

6.3

Stratif orm

QC23

Zhen zigou

Sphal erite

3.7

Stratif orm

QC23

Zhen zigou

Gale na

4.9

Stratif orm

QC20

Zhen zigou

Sphal erite

8.0

Stratif orm

320-2

Zhen zigou

Gale na

8.6

Stratif orm

320-4

Zhen zigou

Sphal erite

8.6

Stratif orm

320-5

Zhen zigou

Gale na

6.4

Stratif orm

/

Xingl ing granit e

6.3

Whole -rock

XDB1

Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992

Table 4 (Continued) Sulfur isotopic compositions of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sa mpl e no.

XD B-2

Locat ion

/

Mineral s

Xingling granite

δ34 S ‰

5.6

Ore body

Dat a sou rce

Sam ple no.

Locat ion

Mine ral

δ34 S ‰

Ore body

Data sourc e

Whole -rock

Din g et al., 199 2

Z62 10

Zhen zigou

Pyrit e

6.0

Strati form

Chi, 2002

77

78

/

Shuangd inggou granite

7.0

Whole -rock

/

Shuangd inggou granite

7.6

Whole -rock

/

Wallrock marble

9.4

Whole -rock

/

Wallrock marble

13. 2

Whole -rock

/

Wallrock marble

11. 4

Whole -rock

/

Wallrock marble

9.1

Whole -rock

/

Wallrock marble

– 0.5

Whole -rock

QZ161

/

Wallrock marble

0.4

Whole -rock

Z32 10

Zhen zigou

Pyrite

8.6

Stratif orm

SD B-2

SD B-5

QZ2

QZ10

QZ25

QZ1

QZ24

Din g et al., 199 2 Din g et al., 199 2 Din g et al., 199 2 Din g et al., 199 2 Din g et al., 199 2 Din g et al., 199 2 Din g et al., 199 2 Din g et al., 199 2 Chi, 200 2 78

Z62 10

Zhen zigou

Sphal erite

3.5

Strati form

Chi, 2002

Z62 10

Zhen zigou

Gale na

3.4

Strati form

Chi, 2002

Z89 1

Zhen zigou

Pyrit e

7.0

Strati form

Chi, 2002

Z89 1

Zhen zigou

Gale na

3.8

Strati form

Chi, 2002

Z32 892

Zhen zigou

Pyrit e

6.1

Strati form

Chi, 2002

Z32 892

Zhen zigou

Sphal erite

3.6

Strati form

Chi, 2002

Z32 8914

Zhen zigou

Pyrit e

7.6

Strati form

Chi, 2002

Z32 8914

Zhen zigou

Sphal erite

5.1

Strati form

Chi, 2002

Z62 892

Zhen zigou

Pyrit e

8.4

Strati form

Chi, 2002

79

Table 4 (Continued) Sulfur isotopic compositions of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sam ple no. Z32 10 Z32 13 Z32 13 Z32 13 Z63 2 Z63 2 Z63 2 Z63 206 Z63 206 Z61 88 Z61 88 Z61 89 Z61 89 Z6-1 Z6-1

Locat ion

Mine rals

δ34S ‰

Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou

Sphal erite

4.8

Pyrite

8.8

Sphal erite Galen a Pyrite Sphal erite Galen a

4.6 2.0 7.2 3.9 1.7

Pyrite

6.9

Sphal erite

3.1

Pyrite

9.1

Galen a

2.0

Pyrite

9.1

Galen a Sphal erite Galen a

0.9 2.8 1.7

Ore body

Data sourc e

Sam ple no.

Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm

Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002

Z62 892 Z62 897 Z62 897 Z62 897 Z92 011 Z92 011 Z92 011 Z92 012 Z92 012 Z61 88

79

Z6-2 Z6-2 Z-63 Z-64 /

Locat ion

Mine ral

δ34S ‰

Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou Zhenz igou

Galen a

1.4

Pyrite

6.0

/

Sphal erite Galen a Pyrite Sphal erite Galen a Pyrite Sphal erite Sphal erite Sphal erite Galen a

5.0 –0.2 6.0 2.9 5.0 5.7 2.4 6.8 3.3 2.9

Pyrite

5.0

Galen a

6.8

/

/

Ore body

Data sourc e

Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm Stratif orm

Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002 Chi, 2002

/

/

80

Table 5 Lead isotope ratios of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sample no.

Mineral

Location

208Pb/204Pb

207Pb/204Pb

206Pb/204Pb

Ore body

Data source

ZH-15

Galena

Zhenzigou

37.667

15.538

17.688

Stratiform

This paper

ZH-16

Galena

Zhenzigou

37.740

15.566

17.707

Stratiform

This paper

ZH-17

Galena

Zhenzigou

37.790

15.578

17.716

Stratiform

This paper

ZH-18

Galena

Zhenzigou

37.783

15.560

17.684

Stratiform

This paper

ZH-19

Pyrite

Zhenzigou

37.851

15.616

17.707

Stratiform

This paper

ZH-20

Pyrite

Zhenzigou

37.752

15.581

17.689

Stratiform

This paper

ZH-21

Pyrite

Zhenzigou

37.679

15.561

17.669

Stratiform

This paper

ZH-22

Pyrite

Zhenzigou

37.815

15.604

17.700

Stratiform

This paper

ZZ-7

Galena

Zhenzigou

38.156

15.622

17.881

Stratiform

This paper

ZZ-8

Galena

Zhenzigou

38.125

15.613

17.881

Stratiform

This paper

DN-10

Pyrite

Diannan

37.991

15.577

17.696

Vein

This paper

DN-11

Pyrite

Diannan

37.957

15.563

17.671

Vein

This paper

DN-12

Pyrite

Diannan

37.829

15.528

17.644

Vein

This paper

DN-13

Pyrite

Diannan

37.941

15.553

17.687

Vein

This paper

XQ-16

Galena

Xiquegou

37.994

15.536

17.675

Vein

This paper

XQ-17

Galena

Xiquegou

38.015

15.544

17.686

Vein

This paper

XQ-18

Galena

Xiquegou

37.956

15.528

17.668

Vein

This paper

XQ-19

Galena

Xiquegou

38.013

15.544

17.711

Vein

This paper

XQ-20

Pyrite

Xiquegou

37.968

15.531

17.709

Vein

This paper

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81

Table 5 (Continued) Lead isotope ratios of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sample no.

Mineral

Location

208Pb/204Pb

207Pb/204Pb

206Pb/204Pb

Ore body

Data source

XQ-21

Pyrite

Xiquegou

37.968

15.530

17.706

Vein

This paper

XQ-22

Pyrite

Xiquegou

37.987

15.538

17.708

Vein

This paper

XQ-23

Pyrite

Xiquegou

37.953

15.524

17.700

Vein

This paper

ZZ-1-1

Pyrite

Zhenzigou

38.127

15.660

17.847

Vein

This paper

ZZ-1-2

Pyrite

Zhenzigou

38.072

15.644

17.834

Vein

This paper

Bs1

Pyrite

Benshan

38.048

15.552

17.661

Vein

Bs2

Galena

Benshan

38.055

15.565

17.773

Vein

Xqg5

Pyrite

Xiquegou

38.116

15.582

17.880

Vein

Xqg6

Pyrite

Xiquegou

38.153

15.563

17.761

Vein

Xqg8

Pyrite

Xiquegou

37.731

15.569

17.566

Vein

Xqg9

Pyrite

Xiquegou

37.738

15.569

17.559

Vein

Dn3

Pyrite

Diannan

37.930

15.539

17.576

Vein

Dn4

Pyrite

Diannan

37.957

15.545

17.618

Vein

DN-1-2

Sphalerite

Diannan

38.003

15.593

17.865

Vein

Zzg1

Pyrite

Zhenzigou

37.902

15.576

17.697

Stratiform

Zzg2

Galena

Zhenzigou

38.002

15.581

17.832

Stratiform

ZKC-02B

Galena

Zhenzigou

37.800

15.591

17.747

Stratiform

ZKC-03B

Galena

Zhenzigou

38.012

15.580

17.820

Stratiform

ZKC-04A

Galena

Zhenzigou

38.020

15.584

17.849

Stratiform

ZKC-05A

Galena

Zhenzigou

38.024

15.585

17.852

Stratiform

81

Song et al., 2017 Song et al., 2017 Song et al., 2017 Song et al., 2017 Song et al., 2017 Song et al., 2017 Song et al., 2017 Song et al., 2017 Duan et al., 2017 Song et al., 2017 Song et al., 2017 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016

82

Table 5 (Continued) Lead isotope ratios of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sample no.

Mineral

Location

208Pb/204Pb

207Pb/204Pb

206Pb/204Pb

Ore body

ZKC-08

Galena

Zhenzigou

38.052

15.581

17.812

Stratiform

ZKC-09

Galena

Zhenzigou

38.054

15.580

17.804

Stratiform

ZKC-10

Galena

Zhenzigou

38.052

15.579

17.799

Stratiform

ZKC-11

Galena

Zhenzigou

38.045

15.587

17.851

Stratiform

ZKC-12

Galena

Zhenzigou

38.049

15.579

17.804

Stratiform

ZKC-13

Galena

Zhenzigou

38.053

15.582

17.814

Stratiform

ZKC-14

Galena

Zhenzigou

38.051

15.580

17.807

Stratiform

ZKC-15

Galena

Zhenzigou

38.050

15.582

17.816

Stratiform

ZKC-18

Galena

Zhenzigou

38.049

15.581

17.820

Stratiform

LZZ002

Pyrite

Zhenzigou

37.727

15.575

17.643

Stratiform

LZZ003

Galena

Zhenzigou

38.000

15.577

17.819

Stratiform

LZZ007-1

Pyrite

Zhenzigou

38.185

15.641

18.317

Stratiform

LZZ007-2

Pyrite

Zhenzigou

38.181

15.640

18.333

Stratiform

ZZ390-12

Sphalerite

Zhenzigou

38.005

15.578

17.833

Stratiform

ZZ390-16

Sphalerite

Zhenzigou

37.982

15.569

17.799

Stratiform

ZZ390-1

Sphalerite

Zhenzigou

38.044

15.593

17.872

Stratiform

ZZ390-11

Sphalerite

Zhenzigou

38.066

15.598

17.849

Stratiform

82

Data source Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Ma et al., 2016 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017

83

ZZ390-8-2

Sphalerite

Zhenzigou

38.011

15.581

17.847

Stratiform

ZZW-1

Sphalerite

Zhenzigou

38.054

15.591

17.847

Stratiform

390-10-5

Sphalerite

Zhenzigou

38.025

15.571

17.883

Stratiform

Duan et al., 2017 Duan et al., 2017 Duan et al., 2017

Table 5 (Continued) Lead isotope ratios of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sample no.

Mineral

Location

208Pb/204Pb

207Pb/204Pb

206Pb/204Pb

Ore body

390-10-1

Sphalerite

Zhenzigou

38.015

15.58

17.825

Stratiform

DN-6

Sphalerite

Diannan

38.017

15.573

17.749

Stratiform

ZZ390-12

Galena

Zhenzigou

38.030

15.588

17.853

Stratiform

ZZ390-15

Galena

Zhenzigou

38.019

15.583

17.861

Stratiform

330-12

Pyrite

Zhenzigou

38.140

15.591

17.781

Stratiform

DN-6

Pyrite

Diannan

38.073

15.589

17.759

Stratiform

DN150-5

Sphalerite

Diannan

37.941

15.557

17.666

Vein

DNBY

Sphalerite

Diannan

37.766

15.600

17.795

Vein

DN-13-2

Galena

Diannan

38.004

15.578

17.773

Vein

DN1-1

Galena

Diannan

38.121

15.608

17.775

Vein

DN360-3

Galena

Diannan

37.791

15.607

17.829

Vein

DN360-4

Galena

Diannan

37.648

15.568

17.651

Vein

NS-1-2

Galena

Nanshan

37.993

15.558

17.662

Vein

NS60-6

Galena

Nanshan

38.026

15.574

17.737

Vein

83

Data source Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017

84

330-5-1

Galena

Zhenzigou

38.030

15.566

17.789

Vein

330-6

Galena

Zhenzigou

38.085

15.574

17.775

Vein

330-7

Galena

Zhenzigou

38.063

15.564

17.728

Vein

XQ180-2

Galena

Xiquegou

37.670

15.549

17.511

Vein

XQA360-7

Galena

Xiquegou

37.731

15.563

17.559

Vein

XQ360-3

Galena

Xiquegou

38.083

15.589

17.880

Vein

Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017

Table 5 (Continued) Lead isotope ratios of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Sample no.

Mineral

Location

208Pb/204Pb

207Pb/204Pb

206Pb/204Pb

Ore body

XQA360-2

Pyrite

Xiquegou

38.046

15.575

17.800

Vein

DN13-2

Pyrite

Diannan

38.063

15.596

17.781

Vein

DNBY

Pyrite

Diannan

37.827

15.617

17.798

Vein

NS-1-3

Pyrite

Nanshan

37.980

15.574

17.755

Vein

NS-11

Pyrite

Nanshan

38.178

15.640

17.751

Vein

04LN676

Feldspar

37.874

15.525

17.410

/

37.863

15.483

17.121

/

Shuangdinggou 04LN677

Feldspar

84

Data source Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Duan et al., 2017 Yu et al., 2009 Yu et al., 2009

85

04LN678

Feldspar

37.841

15.471

17.201

/

04LN679

Feldspar

37.885

15.495

17.159

/

04LN681

Feldspar

Xinling

37.510

15.535

17.208

/

XDB-2

Feldspar

Xinling

37.322

15.500

17.087

/

XDB-1

Feldspar

Xinling

37.340

15.529

17.031

/

SDB-6

Feldspar

38.082

15.514

17.217

/

35.494

15.477

16.417

/

Shuangdinggou SDB-2

Feldspar

QZ-10

Marble

/

38.015

15.579

17.866

/

QZZ-24

Marble

/

38.347

15.632

18.091

/

Yu et al., 2009 Yu et al., 2009 Yu et al., 2009 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992 Ding et al., 1992

Table 6 Comparison of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Mineralization-type

Stratiform mineralization

Vein mineralization

Ore body

Stratiform, controlled by strata, comfortable contact with wall-rocks, and there are stratification structures similar to sedimentary characteristics.

Mainly as veins or are lenticular in shape, and are controlled by NW-trending fractures.

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Wall-rock

Graphitized banded marble, biobite schist, banded marble, dolomite marble, and garnet-mica schist of the Langzishan Formation, and the Dashiqiao Formation.

Mineral assemblage

The ore minerals are massive, veinlets, dense disseminated and include sphalerite, galena, pyrite, and chalcopyrite (Fig. 4e–l), with minor amounts of pyrrhotite, arsenopyrite, marcasite, and argentite. The main gangue minerals are dolomite, mica, calcite, and minor quartz.

Metallogenic age

Paleoproterozoic (sphalerite Rb–Sr age of 1798 ± 8 Ma; Ma et al., 2016).

Mainly occur in the marble, granulite and mica schist of Dashiqiao Formation. The ore minerals are disseminated and massive (Fig. 5c–d, and j–l), and include sphalerite, galena, pyrite, marcasite, arsenopyrite, and minor chalcopyrite and tetrahedrite (Fig. 5e–h and m–t). The main gangue minerals are quartz, dolomite, and calcite. Late Triassic (sphalerite Rb– Sr age of 221 ± 12 Ma; Yu et al., 2009).

Table 6 (Continued) Comparison of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Mineralization-type

Stratiform mineralization

Vein mineralization

Fluid inclusions

Contain only type 1 inclusions, with salinities of 4.0–6.9 wt.% NaCl eq. They were homogenized to the liquid phase at temperatures (Th-v) of 221–246°C (mean = 234°C). Results indicate that the stratiform mineralization ore-forming fluid belonged to a NaCl–H2O system characterized by moderate temperature and low salinity, and that the ore-forming fluids of

Type 1, 2, 3a, 3b, and 4 inclusions were identified in the quartz crystals of vein mineralization. Results of FIs studies indicate that the vein mineralization oreforming fluids was characterized by moderate temperature (270–325°C, mean = 297°C) and low

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87

stratiform mineralization are homogeneous system (no fluid immiscibility or boiling).

Hydrogen and oxygen isotopic

δ18OH2O = 4.6 to 7.5‰, δD = −105.1 to −103.3‰; ore-forming fluids of stratiform mineralization were derived from primary magmatic water.

Sulfur isotopic

δ34S = −0.2 to 14.4 ‰; derived from the wall-rocks and magma.

salinities (3.9–9.2 wt.% NaCl eq.) and was a NaCl–H2O–CO2 hydrothermal system, and the occurrence of fluid immiscibility. δ18OH2O = −9.4 to 4.5‰, δD = −99.3 to −78.0‰; ore-forming fluids comes from the mixing of primary magmatic water and meteoric water. δ34S = 3.2 to 7.9‰; derived from the Paleoproterozoic stratiform ore, Yanshanian granitic magma and wallrocks.

Table 6 (Continued) Comparison of stratiform and vein mineralization in the Qingchengzi Pb–Zn deposit Mineralization-type

Lead isotopic

Ore genesis

Geological setting

Stratiform mineralization

Vein mineralization

Mixture of two different lead sources: the wall-rocks and the magmatic source.

Derived from wallrocks, Paleoproterozoic stratiform ore and Yanshanian granitic magma.

SEDEX-type deposit.

Moderate-temperature hydrothermal-vein-type deposit

Post-collisional extension stage in the Jiao–Liao–Ji Belt.

Northward subduction of the Yangtze Craton beneath the North China Craton resulted in continental collision and slab break-off.

87

88

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89

Highlights 

Ore-forming fluids of stratiform mineralization belong to a NaCl-H2O system, and those of vein-type mineralization are attributed to a NaCl-H2O-CO2 system.



Ore-forming materials of vein-type mineralization were partly from the stratiform ores.



Paleoproterozoic stratiform mineralization is typical of SEDEX-type deposits.



Late Triassic vein-type mineralization represents a moderate-temperature hydrothermal-vein-type deposit.

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90

Graphical abstract

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Declaration of Interest Statement

We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted

Keyong Wang on behalf of coauthors May.17.2019

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