Decratonic gold mineralization: Evidence from the Shangzhuang gold deposit, eastern North China Craton

Accepted Manuscript Decratonic gold mineralization: Evidence from the Shangzhuang gold deposit, eastern North China Craton

Ya-Chun Cai, Hong-Rui Fan, M. Santosh, Fang-Fang Hu, KuiFeng Yang, Xian-Hua Li PII: DOI: Reference:

S1342-937X(17)30318-0 doi:10.1016/j.gr.2017.09.009 GR 1871

To appear in: Received date: Revised date: Accepted date:

8 May 2017 8 July 2017 13 September 2017

Please cite this article as: Ya-Chun Cai, Hong-Rui Fan, M. Santosh, Fang-Fang Hu, Kui-Feng Yang, Xian-Hua Li , Decratonic gold mineralization: Evidence from the Shangzhuang gold deposit, eastern North China Craton. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Gr(2017), doi:10.1016/j.gr.2017.09.009

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Decratonic gold mineralization: evidence from the Shangzhuang gold deposit, eastern North China Craton

Ya-Chun Caia, Hong-Rui Fana,b*, M. Santoshc,d, Fang-Fang Hua,b, Kui-Feng

SC

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Yanga,b, Xian-Hua Lib,e

a

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Key Laboratory of Mineral Resources, Institute of Geology and Geophysics,

Chinese Academy of Sciences, Beijing 100029, China College of Earth Science, University of Chinese Academy of Sciences, Beijing

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b

100049, China

D

c

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School of Earth Sciences and Resources, China University of Geosciences

Beijing, 29 Xueyuan Road, Beijing 100083, China Department of Earth Sciences, University of Adelaide, Adelaide SA 5005,

Australia e

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d

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State Key Laboratory of Lithospheric Evolution, Institute of Geology and

Geophysics, Chinese Academy of Sciences, Beijing 100029, China

*Corresponding author. E–mail: [email protected], Address: as above; Phone: (+86) 10 82998218; Fax: (+86) 10 62010846

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Abstract The Jiaodong Peninsula in the eastern North China Craton (NCC) hosts some of the world-class gold deposits. Among these, the Shangzhuang gold deposit

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represents a typical fault-zone hosted disseminated- and stockwork-style gold mineralization. The mineralization is characterized by intense hydrothermal

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alteration halos in the wallrocks with the mineralized veins intruding into

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altered wallrocks. Zircon U-Pb isotope dating constrains the timing of

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emplacement of the Guojialing granodiorite as 130 ± 1 Ma. Five molybdenite samples from the main mineralization stage veins yielded a well-fitted isochron

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age of 126 ± 2 Ma (MSWD=1.3), marking the timing of gold mineralization. Four types of fluid inclusions are identified at Shangzhuang, and their

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petrographic and microthermometric features suggest fluid immiscibility followed by fluid mixing. This inference is also supported by oxygen and

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hydrogen isotopic data of quartz veins from stage III. The measured δ18O values of quartz are +12.3 to +13.7‰ for stage II and +11.7 to +12.0‰ for stage III,

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with calculated δ18Ofluid values for stage II ranging from +5.9 to +7.3‰ and for stage III from +3.4 to +3.7‰. δD values for stage II and III quartz range from -65.3 to -75.2‰ and -70.6 to -74.7‰, respectively. The data suggest that the ore-forming fluids were initially derived from magmatic sources, followed by mixing with meteoric water. SIMS in-situ sulfur isotope analyses of two types of pyrite (Py I and Py II) from different mineralization stages show different sulfur isotope features. The δ34S values for Py I (+10.2 to +11.3‰,

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mean=+10.8‰, n=25) are higher than those of the later mostly gold-related Py II (+4.1 to +6.8‰, mean=+5.4‰, n=27). The higher δ34S values of Py I are correlated to degassing of mantle wedge metasomatized by the slab fluids. The relatively lower δ34S values of Py II might suggest increasing of fO2 through

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fluid mixing between ore-forming fluids and meteoric water.

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The temporal, spatial and tectonic relations between the giant gold

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mineralization and destruction of the NCC suggest a genetic linkage. The gold

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mineralization between 126 and 117 Ma at Jiaodong was probably initiated at the peak of decratonization (ca. 125 Ma) of the eastern NCC. Phanerozoic

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craton margin orogeny also played a critical role in the generation of the early Cretaceous giant gold deposits in the eastern NCC. Integrated geological mineralization

features,

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characteristics,

metallogenic

age,

sources

of

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ore-forming fluids and sulfur, and tectonic settings favor a decratonic gold mineralization model for the Shangzhuang gold deposit. The geodynamic

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scenario proposed for the early Cretaceous giant gold mineralization event in

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the eastern NCC includes the paleo-West Pacific plate subduction, asthenospheric upwelling, multiple subduction-collision processes along the margins.

Keywords: Fluid inclusion; Re-Os geochronology; SIMS sulfur isotope; Shangzhuang gold deposit; Jiaodong

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1. Introduction Gold deposits in the Jiaodong peninsula have attracted considerable attention in the recent studies, particularly in the light of the world-class gold deposits in

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this region that raised the status of China as the largest gold producer of the world (Yang and Zhou, 2001; Qiu et al., 2002; Fan et al., 2003; Li et al., 2003,

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2006; Chen et al., 2005; Mao et al, 2008; Zhai and Santosh, 2013; Goldfarb and

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Santosh, 2014; Yang et al., 2014a, b, c; Mills et al., 2015a, b; Santosh and

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Pirajno, 2015; Zhu et al., 2015; Groves and Santosh, 2016; Yang et al., 2016). Although previous studies have addressed the nature and origin of the

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ore-forming fluids and sulfur, ore genesis, and the association between the early Cretaceous granitoid intrusions and gold metallogeny, the relationship between

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gold mineralization and decratonization in the North China Craton (NCC) continue to be ambiguous and controversial (Goldfarb and Santosh, 2014; Li

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and Santosh, 2014; Zhu et al., 2015; Deng and Wang, 2016; Deng et al., 2017). The Shangzhuang gold deposit is located in the northwestern Jiaodong

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Peninsula, and is a typical disseminated- and stockwork-style mineralization in the Zhaoyuan-Laizhou gold belt. Mineral assemblages and petrographic analyses show that some features of the Shangzhuang deposit are in contrast with some of the other Jiaojia-type deposits at Jiaodong that are dominated by disseminated- and stockwork-style ores. One of the most important and unique aspects of this deposit is the appearance of molybdenite in the

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quartz-pyrite-polymetallic sulfide-gold stage. Another aspect is the presence of multiphase H2O-CO2-NaCl-solid inclusions in the early mineralizing stage. These features provide further constrains for understanding the genesis of the giant Jiaodong gold deposits.

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The age range of gold mineralization at Jiaodong has been generally constrained

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as 126-117 Ma corresponding to the early Cretaceous based on recent Ar-Ar,

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Rb-Sr and U-Pb geochronology (e.g., Yang and Zhou, 2001; Li et al., 2003,

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2006; Zhang et al., 2003; Li et al., 2008; Cai et al., 2011; Hu et al., 2013; Bi and Zhao, 2017; Ma et al., 2017). However, most of these results were obtained

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from analyses of hydrothermal minerals and pyrite. Hydrothermal minerals such as sericite are presumed to have formed contemporaneously with sulfides and

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were used to constrain the mineralization age of the gold deposits. However, the

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isotopic systematics in hydrothermal minerals may be disturbed by geologic events after sulfides deposition, such as later hydrothermal fluids. These

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minerals are assumed that they formed at the same time as the sulfide or gold

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(Selby and Creaser, 2001). The Rb-Sr isotopic ages of sulfide minerals might correspond to the ages of inclusions in the sulfide minerals and may not reflect the formation age of the sulfides (Suzuki et al., 1996). However, Re-Os molybdenite geochronology offers a powerful tool to better constrain the timing of mineralization (Stein et al., 1997; Spencer et al., 2015). This geochronometer is ideal because the ore mineral that is closed to post-mineralization hydrothermal alteration is dated directly (Spencer et al., 2015). Though there is

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a general consensus on the age of gold mineralization at Jiaodong, the direct Re-Os dating of molybdenite offers a more robust constraint. Sources of ore-forming sulfur in the gold deposits at Jiaodong remain debated. Previous sulfur isotope analyses of pyrite separates from the Jiaodong gold

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deposits have yielded δ34S values between 1.9‰ and 14.1‰ (Qiu et al., 2002;

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Mao et al., 2008; Zhu et al., 2015; Wen et al., 2016 and references therein), and

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are mostly between 3.4‰ and 13.5‰. Wide ranges in the sulfur isotope values

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from ore-related pyrite in the Jiaodong gold deposits has led to different interpretations for the sources of ore-forming sulfur, such as mantle-derived

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materials mixed with crust-derived sulfur (Wen et al., 2016), mixed sources related to processes of mantle-crust interaction (Mao et al., 2008; Lan et al.,

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2010), sources from wallrocks (Wang et al., 2002; Cai et al., 2011) and

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seawater-derived sulfur (Sun et al., 2006). Most of these analyses were carried out on mineral separates of texturally complex pyrite from variable stages. Data

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obtained from these conventional analyses may not precisely constrain the

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source of sulfur because of the overlapping sulfur isotopes from multiple geological processes and recrystallization of pyrite, and potentially useful information preserved at the grain-scale may be neglected. In order to resolve these issues, we provide new sulfur isotope data through in-situ spot analyses of pyrite from different gold mineralization stages using secondary ion mass spectrometry (SIMS). Although the gold mineralization at Jiaodong was previously considered as

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―orogenic type‖, the nearly two billion year gap between gold mineralization and the latest regional metamorphism, together with the sources of ore-forming fluids and tectonic settings have raised doubt on the orogenic gold deposit model (Zhai et al., 2004; Li et al., 2013, 2015; Zhai and Santosh, 2013; Yang et

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al., 2014b; Zhu et al., 2015). Recently, based on geological characteristics,

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mineralizing features, metallogenic ages, sources of ore-forming fluids and

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materials, and tectonic background, the gold deposits have been named as Jiaodong type (Zhai et al., 2004; Yang et al., 2014b; Li et al., 2015) and

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decratonic type (Zhu et al., 2015). In this study, we present detailed field and

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petrographic studies to investigate the ore paragenetic sequence and the spatial zoning of wallrock alteration in the Shangzhuang gold deposit at Jiaodong.

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Re-Os geochronology on gold-related molybdenite and U-Pb ages of zircons

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from the wallrock Guojialing granodiorite are also presented with a view to elucidate the timing of magmatism and gold mineralization. Additionally, we

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present results from fluid inclusion studies and oxygen and hydrogen isotopes to

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gain insights on the origin and evolution of the ore-forming fluids. We also report new in-situ SIMS sulfur isotopes of pyrite in order to constrain the sources of ore forming sulfur. Based on the new results, and in conjunction with published data, we attempt to formulate a genetic model for the gold mineralization and its link with decratonization of the NCC. 2. Regional geologic setting The Jiaodong Peninsula marks the southeast margin of the NCC and close to the

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collisional margin of the NCC with the Yangtze Craton (YC) (Fig. 1). The region is bound by the Tan-Lu fault in the west and the Pacific Plate in the east. The Jiaodong region is separated by the Wulian-Yantai fault into two terrains, the Jiaobei terrain in the north and Sulu orogenic belt in the south (Zheng et al.,

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2003) (Fig. 2). The Sulu belt was formed by the Triassic northward subduction

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of the YC beneath the NCC (Cong, 1996; Liou et al., 1996; Zheng et al., 2003).

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The ultrahigh-pressure (UHP) metamorphic rocks in the Sulu belt mainly include Neoproterozoic granitic gneisses with subordinate coesite-bearing

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eclogite, schist and quartzite (Zheng et al., 2003; Huang et al., 2006; Zhang et

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al., 2012). A syenite complex of age ~210 Ma has been identified at Shidao in the Sulu belt (Chen et al., 2003; Yang et al., 2005). Numerous Mesozoic plutons

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are exposed within the Sulu belt. The late Jurassic granitoids are mainly

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composed of the Duogushan, Wendeng, and Kunyushan plutons, varying in composition from granodiorite and monzogranite to garnet-bearing leucogranite

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(Guo et al., 2005). Zircon U-Pb dating of these intrusions reveals emplacement

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ages in the range of 142 to 161 Ma (Hu et al., 2004; Guo et al., 2005). The early Cretaceous magmatic rocks include sporadic mafic rocks and massive intermediate-felsic rocks (Zhao and Zheng, 2009), and are represented by the Liudusi pyroxene diorites (115 Ma), the Taiboding K-feldspar-porphyritic granites (114 Ma), Sanfoshan K-feldspar-porphyritic granites (113 Ma), Weideshan granites (113 Ma) (Guo et al., 2005) and widespread mafic-felsic dykes (108–129 Ma) (Guo et al., 2004; Yang et al., 2004; Liu et al., 2008a, b,

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2009a; Zhang et al., 2012; Cai et al., 2015a). The Jiaobei terrain is the southeastern boundary of the NCC and the Precambrian basement rocks in this area mainly consists of Neoarchean Jiaodong

Group

TTG

gneisses

(tonalite-trondhjemite-granodiorite),

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Paleoproterozoic Fenzishan and Jinshan Group metasedimentary sequences

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with ~1.8 Ga amphibolite- to granulite-facies metamorphic rocks, and the

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Meso-Neoproterozoic Penglai Group (Lu, 1998; Wallis et al., 1999; Zhai et al.,

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2000; Tang et al., 2007, 2008). The widely distributed Mesozoic magmatic rocks in the Jiaobei terrain are mainly composed of the late Jurassic Linglong

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biotite granites and Luanjiahe monzogranites (150–160 Ma) (Miao et al., 1997; Wang et al., 1998; Hou et al., 2007; Yang et al., 2012), the early Cretaceous

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Guojialing granodiorite (126–130 Ma) (Miao et al., 1997; Wang et al., 1998;

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Yang et al., 2012, 2014c), Yashan monzogranite (~113Ma) and Aishan granitoids (~116–125 Ma) (Goss et al., 2010), the Cretaceous Qingshan Group

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volcanic rocks (98–124 Ma) (Tang et al., 2008; Liu et al., 2009b), and

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widespread mafic dykes (86–132 Ma) (Yang et al., 2004; Liu et al., 2008b; Zhang et al., 2008; Cai et al., 2013). 3. Gold deposits in the Jiaodong Peninsula Although the Jiaodong gold province covers only ~0.2% of China‘s total landmass, the region accounts for ~30% of the total national gold reserves with an overall endowment of >4000 tons (t) Au and contributes more than 25% of

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total gold production per annum (Fan et al., 2007; Goldfarb et al., 2014; Santosh and Pirajno, 2015). This region is the most important gold producer in China, both in terms of gold reserves and production. The Jiaodong gold province can be divided into the Zhaoyuan–Laizhou, Penglai–Qixia and Muping–Rushan

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gold belts from west to east. More than 85% of the gold resources are

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concentrated in the Zhaoyuan–Laizhou gold belt (Fig. 2) within an area of about

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3500 km2 (Qiu et al., 2002; Fan et al., 2003).

veins-style

(Linglong-type)

and

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Gold deposits of the Jiaodong Peninsula can be divided into gold-bearing quartz fault-zone

hosted

disseminated-

and

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stockwork-style (Jiaojia-type) gold mineralization (Qiu et al., 2002; Fan et al., 2003; Deng et al., 2015). The Linglong-type quartz vein-style gold deposit are

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typically hosted in second- or third-order faults cutting Mesozoic granitoids,

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while the Jiaojia-type disseminated- and stockwork-style deposits occur along first-order faults surrounded by broad alteration halos (Qiu et al., 2002). The

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majority of deposits in this district are hosted by Mesozoic granitoids or, less

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commonly, in basement rocks (Goldfarb et al., 2014). Gold mineralization in this district was broadly contemporaneous and concentrated in 126-117 Ma as deduced from Ar-Ar and Rb-Sr dating of hydrothermal alteration minerals (e.g., Zhang et al., 2003; Li et al., 2003, 2006; Cai et al., 2011; Hu et al., 2013; Bi and Zhao, 2017), Rb-Sr isochron dating of pyrite (e.g., Yang and Zhou, 2001; Li et al., 2008), as well as by U-Pb dating of hydrothermal zircon and monazite (e.g., Hu et al., 2004; Ma et al., 2017). There

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are also a few possible outliers at ca. 109 Ma (Li et al., 2006) and ca. 130 Ma (Yang et al., 2014a). These ages of large-scale gold mineralization in the Jiaodong Peninsula are coincident with the peak period at 120–130 Ma (Wu et al., 2005) of the giant igneous event in the eastern NCC (Fig. 1, Fig. 3A) and

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destruction of NCC, suggesting that the mechanism of the gold metallogeny

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may be related to decratonization of NCC (Zhu et al., 2015).

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4. Geology of the Shangzhuang deposit

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The Shangzhuang gold deposit (37°26′10.04″ - 37°27′06.18″N, 120°09′44.24″ 120°11′00.26″), containing >35 t Au at an average grade of 3.78 g/t, is located

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30 km northwest of Zhaoyuan city (Fig. 2) and is a typical fault-zone hosted disseminated- and stockwork-style gold mine in the Zhaoyuan-Laizhou gold

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belt. The gold deposit is structurally controlled by the Wangershan fault and situated in the northern section of Wangershan fault (Fig. 4). Mineralization

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mainly occurs within the Guojialing porphyritic granodiorite intrusions.

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4.1 Orebody characteristics The disseminated and veinlet mineralization hosted by Guojialing granodiorite form lenticular orebodies extending 0-40 m from the main fault. The orebodies are broadly parallel to the Wangershan fault, striking 25°–45° NE and dipping 30°–40° NW. Disseminated- and stockwork-style mineralizations are generally sited in the hanging wall of the main fault (Figs. 5, 6B) and are hosted in the altered Guojialing porphyritic granodiorite. Some shallow-level orebodies are

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located in the foot wall of the fault (Figs. 5, 6A). The deposit is composed of eleven orebodies, among which no. III-1, VIII-1 and XI are the major ones. 4.2 Wallrocks

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The wallrocks in the Shangzhuang gold mine are mainly magmatic rocks, including late Jurassic Linglong biotite granite, early Cretaceous Guojialing

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porphyritic granodiorite and mafic to felsic dykes (Fig. 4). The petrographic

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features of Linglong and Guojialing granitic intrusions in the Shangzhuang area

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were described by Yang et al. (2012). The K-feldspar phenocrysts from Guojialing granodiorite at Shangzhuang are larger than those other areas (up to

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17cm×6cm) (Fig. 7A). The mafic to felsic dykes contain lamprophyre, dolerite, gabbro, diorite, aplite and pegmatite, which intrude into the granitic rocks and

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dominantly strike NE/NNE. The aplite and pegmatite are pre-mineralization dykes, whereas the mafic to intermediate dykes (Fig. 7B) occur through the

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whole mineralization stage and were emplaced during early to late Cretaceous (Cai et al., 2013, 2015a, b).

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4.3 Structural setting

Regional faults in the Jiaodong area predominantly trend NE/NNE and are subsidiary to the Tan-Lu fault zone (Qiu et al., 2002; Deng et al., 2015). The distribution of the main gold deposits in the Jiaodong Peninsula is regionally controlled by major fault zones (Qiu et al., 2002; Wang et al., 2015). For example, the major gold deposits in our study area, the Zhaoyuan-Laizhou gold

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belt, are structurally controlled by the Cangshang-Sanshandao, Jiaojia-Xincheng, and Zhaoyuan-Pingdu faults from west to east (Qiu et al., 2002; Wang et al., 2015; Yang et al., 2016). The NNE- to NE-trending Jiaojia-Xincheng fault (JXF), ~30 km long (Song et

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al., 2010), is the most prominent fault in the Jiaojia-Xincheng gold field,

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comprising more than 20 gold deposits including Shangzhuang, Jiaojia,

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Xincheng, Sizhuang, Wangershan, Matang, Jiehe, Hedong, and Hexi deposits

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with >1300 t gold resource (Deng et al., 2015; Yang et al., 2016). The JXF, striking 10–40° and dipping 10–45° NW, occurs partially along the contact

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between granitoids and the Jiaodong group amphibolites (Qiu et al., 2002; Song et al., 2010). The secondary N/NNE-trending faults in the footwall of the JXF,

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such as the Wangershan, Dongzhuangzi and Houjia faults, hosting different

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scales of gold deposits, are broadly parallel to the JXF, but converge into the

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later to the north (Fig. 4).

The Wangershan fault zone is about 12 km long, generally striking 10–40° and

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dipping 30–65° NW. It controls the occurrence and distribution of the Shangzhuang gold deposit. In the Shangzhuang gold field, it is 1800 m long and 20–120 m wide, striking 25–45° and dipping 30–40° NW. It occurs partially along the contact between the Linglong biotite granite and Guojialing porphyritic granodiorite, or entirely within the Linglong granite. The central part of the fault zone contains a black fault gouge zone having 2–10 cm thickness with adjacent silicified mylonites. The continuous and sustained wavy

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gouge indicates a structural feature of compression-shear. 4.4 Hydrothermal alteration Multiple hydrothermal alteration halos are observed in the Shangzhuang gold

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deposit. They occur along the Wangershan fault and show regular spatial zonation (Fig. 8). The mineralization-related alteration styles include potassic

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alteration, sericitization, silicification, pyrite-sericite-quartz alteration. Small

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scales of carbonation, chloritization, albite alteration and argillic alteration are

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also observed. The alteration patterns and alteration mineral assemblages are similar to those in other gold deposits of the Zhaoyuan-Laizhou belt (Qiu et al.,

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2002; Li et al., 2013).

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Potassic alteration occurs in the most distal part of the alteration zone (Fig. 8),

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and at some places it is characterized by distinct veinlets containing pyrite-quartz veins along the joint fissure in the Guojialing granodiorite (Fig.

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7C). This marks the earliest alteration stage and is characterized by the appearance of K-feldspar that replaces or overgrows primary plagioclase

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imparting a pink to reddish colour (Fig. 7C, D), which is likely the result of disseminated hematite nanoparticles in feldspar crystals (Putnis et al., 2007). Potassic alteration becomes more pervasive and intense proximal to the orebodies and main fault. Weakly altered wallrocks are characterized by plagioclase partly replaced by K-feldspar (Fig. 9A) or remnant plagioclase within recrystallized K-feldspar. In strongly altered rocks, recrystallized

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K-feldspar totally replaces plagioclase with minor muscovite filling fractures, and biotite and amphibole have been virtually obliterated (Fig. 9B). Minor amounts of recrystallized quartz are also observed as narrow undulated quartz ribbons surrounding feldspars (Fig. 9C), indicating the early ductile deformation

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of the wallrocks. Only limited sulfide minerals are developed in the potassic

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alteration. Accessory minerals are magnetite, monazite, titanite, apatite, zircon,

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and ilmenite.

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In the middle zone, alteration is dominantly sericitization accompanied by silicification (i.e., phyllic alteration) and characterized by green to gray

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appearance (Fig. 7E). Phyllic alteration becomes more pervasive proximal to the main fault. Weak phyllic alteration is typified by partial or total replacement of

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biotite by sericite and transformation of plagioclase to sericite (Fig. 9D). The

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K-feldspar crystals experienced only minor degree of alteration. Strongly phyllic altered rocks have lost all their primary features and have been

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extensively leached, with resultant increase of porosity, and was later filled by

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secondary quartz (Fig. 9E). In some case, sericite veinlets fill fractures within secondary K-feldspar or cut the K-feldspar crystals, indicating that phyllic alteration is later than potassic alteration (Fig. 9F). A few isolated and euhedral pyrite (Py I) grains were developed in this alteration zone. Pyrite-sericite-quartz alteration nearest to the main fault marks the inner part of the alteration zone, and is closely associated with gold mineralization. The alteration is characterized by gray to dark gray appearance and mainly

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composed of quartz, sericite and pyrite (Fig. 7F). Alteration in this zone is most intense and strong. Pyritization, sericitization and silicification have heavily overprinted the former alterations. The feldspars are almost completely altered to sericite and newly formed quartz also appears (Fig. 9G, H). Sericite occurs as

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veinlets filling fractures, or as scaly aggregate coexisted with fine-grained

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quartz (Fig. 9G, H). Two generations of quartz are observed. The first (Qtz I) is

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magmatic and represented by anhedral grains with undulose extinction (Fig. 9G). The second (Qtz II) type is composed of recrystallized quartz filling

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fractures within the hydrothermal or altered minerals (Fig. 9G). Pyrite is

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disseminated and euhedral to subhedral with quartz in the phyllic assemblage (Fig. 9H), and contains inclusions of Ag-rich grains similar to those included in

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pyrite from the quartz-pyrite vein (see below). Some chalcopyrite and sphalerite

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grains coexist with pyrite or are included in pyrite grains. Sericite and quartz in the alteration zone nearby the fault have been strongly brecciated, indicating the

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brittle deformation of the wallrocks. The dark black fault gouge, as boundary of

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alteration zone, is composed of clay minerals, mylonite and minor pyrite. Carbonation is a late-stage alteration and not associated with gold mineralization. Carbonate minerals generally exist as veins together with late-stage quartz (Fig. 9I). 4.5 Mineral paragenesis As mentioned above, the Shangzhuang gold deposit consists of disseminatedand stockwork-style mineralization. The disseminated mineralization is mainly

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developed in the pyrite-sericite-quartz altered granite (Fig. 7F). The stockwork-style

mineralization

is

hosted

in

potassic,

phyllic

and

pyrite-sericite-quartz alterations, and mineralized veinlets crosscut these alterations (Figs. 8 and 10).

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The mineral assemblages and ore types in the Shangzhuang deposit lead us to

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find two distinct features in this deposit which are different from those in the

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other Jiaojia-type deposits at Jiaodong. The first is the appearance of

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molybdenite in the quartz-pyrite-polymetallic sulfide-gold stage which is even unique for other gold deposits in Jiaodong. The second is the more common

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development of vein mineralization as compared to the other Jiaojia-type deposits in Jiaodong.

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Four mineralization stages (Fig. 11) have been recognized based on the vein crosscutting relationships and the textural relationships between minerals within

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the veins (Fig. 10). These are, from early to late, quartz-K-feldspar-sericite stage (I), quartz-pyrite-gold stage (II), quartz-pyrite-polymetallic sulfide-gold stage

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(III), quartz-carbonate stage (IV). The mineralization stage II and III typically occur as veins crosscutting stage I mineral assemblages (Fig. 10A, B, D-F), indicating that the two stages postdate the stage I. The second and third mineralization stages were defined based on the feature that the outer part (stage II) of the veins is intruded by the inner part (stage III) (Fig. 10A, D-F). Quartz-carbonate veins of stage IV cut the mineral assemblages and veins of all other stages. Stage II and III are gold deposition stages. A schematic summary

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of the paragenetic sequence of vein minerals is shown in Fig. 11. Stage I, which is defined by clouded white quartz with K-feldspar and variable amounts of sericite in the surrounding alteration zones, is related to the early stage hydrothermal alterations. Clouded white quartz, with compact, coarse

PT

grained and translucent in hand specimen (Fig. 10C), makes up more than 75%

RI

of the total volume. The petrographic characteristics of K-feldspar and sericite

SC

have been described above. Small amounts of euhedral to subhedral pyrite (Py I)

NU

grains are developed (Fig. 10C). Gold was not deposited during this stage. A few hydrothermal monazites replacing hydrothermal K-feldspar from stage I are

MA

included in the pyrite vein of stage III (Fig. 12A). Stage II is characterized by banded milky white quartz veins containing pyrite

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D

(Fig. 10A, D-F), with small amounts of gold/electrum. Pyrite (Py I) occurs as coarse euhedral cubes and subhedral aggregates. Gold occurs as small grains (<

CE

10 μm) found as inclusions within Py I grains (Fig. 12B). According to previous studies on gold included in Py I from Jiaojia-type deposit (Jiang, 2011; Wen,

AC

2015), gold in this stage generally occurs as electrum (Ag content up to 25%–30%), and gold fineness in stage II is lower than that from stage III (Table 1). Stage III is characterized by precipitation of abundant polymetallic sulfide minerals (pyrite, molybdenite, galena, sphalerite and chalcopyrite) with dark grey quartz forming bands or veinlets intruding veins of the stage II (Fig. 10A,

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D-F). This stage is the main gold deposition stage. Pyrite (Py II) occurs as fine-grained subhedral to anhedral aggregates (Fig. 10A, D-F). Compared with the composition of Py I, Py II generally contains Te contents and some of the grains

contain

Au

(Table

2).

Molybdenite

commonly

occurs

as

PT

molybdenite-pyrite-quartz vein (Fig. 12C) or molybdenite-quartz vein (Fig. 12D)

RI

containing native gold grains (Fig. 12E). Gold in this stage is primary native

SC

gold with fineness ranging from 864 to 888 (Table 1). It is mainly hosted as inclusions (Fig. 12F-H) or in fractures in Py II (Fig. 12F). Some gold grains

NU

occur along pyrite or quartz grain boundaries (Fig. 12H, I) and occasionally as

MA

free grains in quartz (Fig. 12F, H). Importantly, gold in this stage is associated with molybdenum (Table 1), and some of the molybdenite grains also show

D

significant gold contents (Table 3), which is a unique feature as compared to the

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other gold deposits in Jiaodong. Galena is characterized by exsolution (Fig. 12J) and filling fractures (Fig. 12K) in pyrite. Sphalerite is often intergrown with

CE

pyrite II (Fig. 12L).

AC

The last stage (stage IV) marks the waning of hydrothermal activity, and is characterized by quartz-carbonate/carbonate veins, with only very minor pyrite. 5. Analytical methods 5.1 Microthermometry and Raman spectroscopy Microthermometric measurements and Raman spectroscopic analyses of fluid inclusions were carried out at the Fluid Inclusion Laboratory, Institute of

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Geology and Geophysics, Chinese Academy of Sciences (IGGCAS). Microthermometry data were obtained using a Linkam THMS 600 programmable heating and freezing stage combined with a Zeiss microscope. The thermocouple was calibrated using synthetic fluid inclusion standards at

PT

0.0°C, -56.6°C, and 374.1°C. The reproducibility of measurements was ±0.2°C

RI

for ice melting temperatures and ±2°C for homogenization temperatures.

SC

Raman spectroscopic analyses of fluid inclusions were carried out on the

NU

LabRam HR800 Raman microspectrometer coupled with a Zeiss microscope. An argon ion laser with a wavelength of 532 nm and a source power of 44 mW

MA

was used in detection.

D

5.2 Electron microprobe (EMP) and Scanning Electron Microscope (SEM)

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Major element compositions of ore minerals were measured on a JEOL JXA-8100 electron microprobe at IGGCAS. The acceleration voltage and beam

CE

current were 15 kV and 12 nA, respectively. Beam diameter was 5 μm and counting time was 10 seconds on peaks, and 5 seconds on each background.

AC

Well-defined natural mineral standards are applied for calibration. Mineral phases and back-scattered electron (BSE) images were obtained using a LEO 1450VP Scanning Electron Microscope (SEM) coupled with an INCA ENERGY-300 Energy Dispersive X-ray Spectrometer (EDS) at IGGCAS. 5.3 Geochronology 5.3.1 Zircon U-Pb dating

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U-Pb dating analyses of zircon from Guojialing granodiorite were performed using LA-ICP-MS at the State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan. Detailed operating conditions for the laser ablation system, the ICP-MS instrument, and

PT

the data reduction process are described by Liu et al. (2008, 2010). Zircon

RI

91500 was used as external standard for U-Pb dating. Off-line selection and

SC

integration of background and analytic signals, time-drift correction and U-Pb dating were performed by ICPMSDataCal (Liu et al., 2008, 2010). Concordia

NU

diagrams and weighted mean calculations were made using Isoplot/Ex ver3

5.3.2 Molybdenite Re-Os dating

MA

(Ludwig, 2003).

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Re-Os isotope analyses of molybdenite were carried out by ICP-MS at the Re-Os Laboratory, National Research Center of Geo-analysis, at the Chinese

CE

Academy of Geological Sciences in Beijing. Detailed chemical separation procedure, the ICP-MS measurement condition and operating conditions were

AC

described by Du et al. (1994, 2004). 5.4 Stable isotopes

5.4.1 Bulk sulfur isotope analysis Conventional bulk sulfur isotope analyses were carried out on hand-picked separates of pyrite and molybdenite at the Analytical Laboratory of the Beijing Research Institute of Uranium Geology. Isotopic compositions of six pyrite

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samples and two molybdenite samples from stage III were measured. The analytical uncertainties of sulfur isotope measurements are better than ±0.2‰. 5.4.2 SIMS sulfur isotope analysis

PT

In-situ sulfur isotope (32S, 33S and 34S) analyses of pyrite were performed using a Cameca IMS-1280 SIMS at IGGCAS, following the analytical procedures

RI

given in Chen et al. (2015). Sonora and Qinghu pyrite was used as running

SC

standards for sulfur isotope analysis sessions. Every 5 Shangzhuang pyrite

NU

analyses were bracketed by one Sonora and Qinghu standard analysis. Instrumental bias for δ34S and δ33S were determined by average values and 2

MA

standard deviation (SD) of these bracketing standard analyses.

D

5.4.3 Oxygen and hydrogen isotopes

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Oxygen and hydrogen isotopes were carried out at the Beijing Research Institute of Uranium Geology. Isotopic compositions of four quartz crystals

CE

from stage II and two quartz crystals from stage III were measured.

AC

Reproducibility of oxygen isotopes for isotopically homogeneous pure quartz is about ±0.2‰. Analyses of standard water samples suggest a precision for δD of ±2‰.

6. Analytical results 6.1 Geochronology 6.1.1 Zircon U-Pb dating of Guojialing granodiorite

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Zircon grains from the Guojialing granodiorite (sample 08G30) are generally euhedral and prismatic, and range in size from 80 to 200 μm, with length to width ratio of 1.5:1 to 6:1. A total of 18 spots were analyzed on 15 representative grains (Table 4). Three zircon grains show core-rim structure, and

PT

clear oscillatory growth zoning in the rim but the core domains are unzoned.

RI

The cores of three grains yield 207Pb/206Pb ages of 2515 Ma, 2603 Ma and 2513

SC

Ma (Table 4), which are likely to be inherited zircons from the basement of the Jiaobei terrain (Tang et al., 2008; Tam et al., 2011). The rim ages of the three

NU

grains are all around 129 Ma. Two grains with oscillatory growth zoning yield Pb/238U ages of 161 Ma and 159 Ma (Table 4), which may be inherited from

MA

206

the late Jurassic granites in the Jiaobei terrain (Yang et al., 2012). The remaining

206

Pb/238U age of 129.8±0.5 Ma (n=13, MSWD=0.1) (Table 4

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weighted mean

D

zircons showing clear oscillatory growth zoning are concordant and yield a

and Fig. 13A, B), which is considered to represent the crystallization age of the

CE

Guojialing granodiorite at Shangzhuang.

AC

6.1.2 Re-Os isotope dating of molybdenite Re-Os concentrations and isotope data for five molybdenite samples from the Shangzhuang gold deposit are reported in Table 5 and Fig. 14. All the molybdenite samples show relatively high Re contents and low common Os contents, ranging from 162.56 to 422.42 parts per million (ppm) and 0.0197 to 0.1280 parts per billion (ppb), respectively.

187

Re and

187

Os concentrations vary

from 102.17 to 265.50 ppm and 213.94 to 556.30 ppb, respectively. The

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isochron age of molybdenite was computed using ISOPLOT 4.15 software of Ludwig (2012). A well-fitting 187Re vs. 187Os isochron produces an age of 126 ± 2 Ma (MSWD=1.3; Fig. 14A). The model ages are calculated with the decay constant of λ187Re=1.666×10-11 yr-1 with an uncertainty of 0.017×10-11 (1%)

PT

(Smoliar et al., 1996). Model age uncertainty includes the uncertainty of the

RI

decay constant and is given as 2σ (Table 5). Calculated Re-Os molybdenite

SC

model ages range from 125.32 to 126.91 Ma, yielding a weight average Re-Os molybdenite model age of 126 ± 1 Ma (MSWD=0.67; Fig. 14B), which is in

NU

good agreement with the five-point 187Re vs. 187Os isochron age.

MA

6.2 Fluid inclusion

Fluid inclusion studies were carried out in quartz selected from representative

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D

mineralized veins and altered wallrocks from different mineralization stages described above. After detailed petrographic examination of 28 doubly polished

CE

thick sections, quartz grains from 17 representative samples containing adequate fluid inclusions were selected for microthermometric measurements and Raman

AC

spectroscopic analyses. Petrographic studies and microthermometry analyses focused on fluid inclusion assemblages (FIAs, Goldstein and Reynolds, 1994). 6.2.1 Fluid inclusion petrography Four types of fluid inclusions are identified based on their petrographic characteristics at room temperature and their Raman analyses. These include: type 1 vapor-dominant CO2 inclusions (>90 vol% vapor, VCO2±LCO2), type 2

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two-

and

three-phase

H2O-CO2-NaCl

inclusions

(LH2O+VCO2

and

LH2O+LCO2+VCO2), type 3 two-phase H2O-NaCl inclusions (LH2O+VH2O) and

type

4

multiphase

H2O-CO2-NaCl-solid

inclusions

(LH2O+LCO2+VCO2+S).

PT

Type 1 comprises primary mono-phase vapor-only CO2 inclusions and

RI

two-phase CO2 inclusions containing >90 vol% vapor (Fig. 15A, F). These

SC

inclusions are rare, quadrangular or ellipsoidal, 3 to 8 μm in diameter and were

NU

only identified in quartz from stage I.

Type 2 consists of primary two- and three-phase H2O-CO2-NaCl inclusions

MA

(Type 2a and Type 2b, respectively) (Fig. 15B, C, F) at room temperature. Type 2a inclusions are generally ellipsoidal and 6 to 12 μm in size with volumetric

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D

V-L proportion ranging from 35% to 50%. Type 2b inclusions display negative crystal or ellipsoidal shapes, varying from 10 to 19 μm in size and with V-L

CE

proportion between 30% and 60%. Type 2 fluid inclusions are commonly distributed as FIAs, clusters or isolated inclusions and occur in samples from

AC

stage I to III.

Type 3 aqueous inclusions (6–17 μm in diameter) contain a liquid phase (LH2O) and a vapor bubble (VH2O) that typically occupies 5 to 20 vol% of the inclusions at room temperature (Fig. 15D, H). They display negative crystal, ellipsoidal or rounded forms and occur in almost all the samples especially those from stage III and IV. They are commonly distributed as FIAs (Fig. 15G,

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H). Type 4 inclusions are characterized by the presence of an additional transparent solid phase (S) within three-phase H2O-CO2-NaCl inclusions (Fig. 15E, F, I-K). They show a size range of 8 to17 μm diameter, contain 10 to 30 vol% vapor and

PT

have negative crystal, ellipsoidal or irregular shapes. The solids from type 4

RI

inclusions are inert in the Raman spectroscopy. Some of them look like

SC

melt-fluid inclusions (Fig. 15K) and commonly occur in quartz from stage I.

NU

Mono-phase liquid-only H2O inclusions were also identified and occur as

MA

secondary trails.

6.2.2 Fluid inclusion microthermometry and Raman spectroscopic results

D

Microthermometric measurements were obtained from 318 inclusions and in

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most cases the measurements were done on fluid inclusion assemblages (FIAs). A summary of microthermometric data on the measured fluid inclusions and the

CE

corresponding mineralization stages in the Shangzhuang gold deposit are shown

AC

in Table 6. The results are plotted in Fig. 16. Fluid inclusions in Stage I: Freezing temperatures of carbonic and aqueous-carbonic inclusions are generally between -98 and -100 °C. For type 1 inclusions, the melting temperatures of solid CO2 (TmCO2) range from -56.7 to -56.6 °C, close to the CO2 critical point of -56.6 °C. Raman analyses confirmed that these inclusions are almost pure CO2. The majority of type 1 inclusions homogenize into the vapor phase (ThCO2) from 30.5 to 30.7 °C.

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Type 2a fluid inclusions in quartz from stage I exhibit final melting temperatures of CO2 clathrate (Th(Cl)) between 5.0 and 7.0 °C, corresponding to salinities in the range of 5.7 to 9.0 wt % NaCl equiv (Collins, 1979). The total homogenization of type 2a fluid inclusions occurs in the liquid phase between

PT

298 and 325 °C.

RI

For type 2b fluid inclusions, temperatures of solid CO2 melting range from

SC

-57.2 to -56.6 °C but are mainly between -56.9 and -56.6 °C. The CO2 clathrates

NU

finally melted at from 5.1 to 6.8 °C, corresponding to salinities in the range of 6.0 to 8.8 wt % NaCl equiv (Collins, 1979). Partial homogenization of type 2b

MA

fluid inclusions occurs between 30.1 and 31.0 °C. Type 2b fluid inclusions finally homogenized into liquid phase between 316 and 350 °C.

PT E

D

In the type 4 inclusions, the gas bubble was the last phase to disappear, and the multiphase inclusions did not homogenize even at temperature as high as

CE

600 °C (limit of the Linkam thermometric apparatus). No daughter minerals homogenized even when the inclusion was heated past its expected

AC

homogenization temperature for several minutes. These solid phases are most likely carbonates (as also reported in Wen et al., 2015) or silicate minerals, and they represent heterogeneous trapping. Fluid inclusions in Stage II: In this stage, type 2 inclusions are the most dominant inclusion type. Type 2a fluid inclusions exhibit Th(Cl) between 5.9 and 7.2 °C, corresponding to salinities of 5.3 to 7.5 wt % NaCl equiv (Collins, 1979).

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The total homogenization into liquid varies from 271 to 305 °C. In type 2b fluid inclusions, the TmCO2 was recorded between -57.2 and -56.3 °C but are mainly between -56.8 and -56.6 °C. Th(Cl) is in the 6.2 to 8.6 °C range, corresponding to salinities of 2.8 to 7.1 wt % NaCl equiv, and the ThCO2 mainly

PT

into the vapor phase varied from 29.0 to 31.1 °C. The final homogenization,

RI

occurring both to the liquid and gaseous phases, ranges from 301 to 328 °C.

SC

Fluid inclusions in Stage III: Type 2b and type 3 inclusions are the main

NU

inclusion type in Stage III. Type 2b inclusions show T mCO2 between -56.9 and -56.4 °C. The melting temperatures of a few fluid inclusions are slightly above

MA

that of pure CO2, possibly due to kinetic factors in the inclusions. CO2 clathrates finally melted between 6.6 and 7.8 °C and reflect salinities between 4.3 and 6.4

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D

wt % NaCl equiv. The ThCO2 mainly into the vapor occurred between 29.6 to 31.0 °C. The total homogenization temperatures (Th) data of these inclusions is

CE

observed from 246 to 298 °C.

Most of the type 3 aqueous inclusions froze completely at temperatures between

AC

-75 and -90 °C. Upon heating, the first melting temperatures (or eutectic temperatures; Te) were recorded, but only a few measurements could be made precisely due to their small size and metastablity. The type 3 inclusions show T e between -36.9 and -21.6 °C, which is interpreted to indicate that the fluids were NaCl-rich (Diamond, 2003), perhaps with variable concentrations of KCl and minor divalent Fe chlorides. Final ice melting temperatures (Tm(ice)) for type 3

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inclusions occur between -6.3 and -3.6 °C, equivalent to salinities of 5.9 to 9.6 wt % NaCl (Bodnar, 1993). The final homogenization of type 3 inclusions, mostly to the liquid phase, varies from 228 to 286 °C. Fluid inclusions in Stage IV: Type 3 aqueous inclusions are dominant in this

PT

stage. They show final ice melting temperatures from -3.2 to -0.5 °C,

RI

corresponding to salinities of 0.9 to 5.3 wt % NaCl equiv (Bodnar, 1993). The

SC

Th of Type 3 inclusions mainly into the vapor phase ranges from 156 to 203 °C.

NU

6.3 Stable isotopes

MA

6.3.1 Sulfur isotope

The results of conventional sulfur isotope analyses of minerals are presented in

D

Table 7. The complete isotopic data (n=52) for in-situ sulfur isotope analyzed

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by SIMS is provided in Supplementary Table A1. The δ34S values for pyrite and molybdenite from molybdenite-pyrite-quartz

CE

veins in stage III are 4.8‰, 4.6‰ (δ34S(Py II)) and 5.5‰, 5.3‰ (δ34S(Mo)) (Table

AC

7), respectively. For pyrite from pyrite-quartz veins in stage III, δ34S values range from 5.6‰ to 6.5‰ (Table 7). Two types of pyrite (Py I and Py II) mentioned above from different mineralized stages were analyzed by SIMS. The results of SIMS and EMPA analyses show lack of any isotopic and compositional zoning in the pyrite grains. The spatial variation of sulfur isotope is also very small for single pyrite grains or veins from each stage. Notably, the two types of pyrite show obviously different

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sulfur isotope features (Fig. 17; Table A1). The δ34S values of Py I from the early mineralization stage have a narrow range between +10.2 and +11.3‰, with an average of +10.8‰ (n=25) (Fig. 17), while the δ34S values of most gold-related Py II from main mineralization stage range from +4.1 to +6.8‰,

PT

with an average of +5.4‰ (n=27) (Fig. 17).

RI

6.3.2 Oxygen and hydrogen isotopes

SC

The results of oxygen and hydrogen isotope analyses for 4 stage II quartz

NU

samples and 2 stage III quartz samples are presented in Table 7. The measured δ18O values are +12.3 to +13.7‰ for stage II quartz and +11.7 to +12.0‰ for

MA

stage III quartz (Table 7). δD values for stage II and III quartz range from -65.3 to -75.2‰ and -70.6 to -74.7‰, respectively (Table 7). The values of δ18O and

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δD for the fluids were calculated using the formation temperature obtained in primary fluid inclusions within quartz from stage II and III. The oxygen isotope

CE

fractionation factor as reported in Clayton et al. (1972) for quartz-water was employed. The calculated δ18Ofluid values for stage II are +5.9 to +7.3‰ (Fig. 18;

AC

Table 7), using a formation temperature of 328 °C. The δ18Ofluid values for stage III range from +3.4 to +3.7 ‰ (Fig. 18; Table 7), according to a formation temperature of 275°C. 7. Discussion 7.1 Timing of gold mineralization of Shangzhuang deposit Several lines of evidences in our study suggest that the gold and molybdenite

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mineralization in the Shangzhuang deposit is contemporaneous and that the Re-Os molybdenite age can represent the timing of gold mineralization. Firstly, the field and petrographic observation shows that all molybdenite formed during the main gold mineralization stage (Figs. 10A, B and 11), with higher gold

PT

content and grade where molybdenite-pyrite-quartz vein occurs. Secondly,

RI

petrographic and SEM observations of the molybdenite-pyrite-quartz veins

SC

show the close association of native gold grains with molybdenite (Fig. 12E). Thirdly, electron microprobe analyses show substantial molybdenum contents in

NU

the gold grains from main mineralization stage (Table 1). Some of the

MA

molybdenite grains also have significant gold contents (Table 3). Therefore, the direct Re-Os dating of molybdenite provides a better constraint on the timing of

D

gold mineralization.

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Our Re-Os molybdenite model ages on five molybdenite samples from the Shangzhuang gold deposit range from 125.3 to 126.9 Ma (mean=126 Ma) and

CE

yield a well-fitting and consistent isochron age of 126 ± 2 Ma (MSWD=1.3),

AC

suggesting that the gold mineralization occurred at ca. 126 Ma. This newly reported age from our study is within the duration (126‒117 Ma) (Fig. 3C) of large-scale gold mineralization in the Jiaodong Peninsula as reported in previous studies (Yang and Zhou, 2001; Qiu et al., 2002; Zhang et al., 2003; Li et al., 2003, 2006, 2008; Cai et al., 2011; Hu et al., 2013; Bi and Zhao, 2017; Ma et al., 2017). Although the age of gold mineralization in Jiaodong is not controversial, our new geochronological data provides a robust constraint on the

ACCEPTED MANUSCRIPT P a g e | 32

timing of metallogeny. The ca. 126 Ma age for the gold mineralization also coincides with the peak of the early Cretaceous extensional tectonics (Fig. 3B) and destruction of the NCC (see discussion below).

PT

7.2 Characteristics, origin and evolution of ore-forming fluids Fluid inclusion studies indicate that the early mineralization stage fluid system

RI

was characterized by relatively high temperature and moderate salinity and was

SC

a CO2-rich H2O-CO2-NaCl hydrothermal system. With time, the fluids evolved

NU

towards moderate to high temperature with varying salinities, and were a H2O-CO2-NaCl hydrothermal system with continuous depletion in CO2 and

MA

enrichment in H2O. Towards the final phase of mineralization, the temperature and salinity decreased to minimum levels and the hydrothermal fluid was

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D

dominantly a H2O-NaCl system.

Many previous studies have interpreted ore-forming fluids at Jiaodong as a

CE

H2O-CO2-NaCl hydrothermal system which underwent immiscibility or boiling. However, in the Shangzhuang deposit, our fluid inclusion data suggest a more

AC

complex scenario. For stage I, four types of fluid inclusions were identified with notably different FIAs distributed within the same plane (Fig. 15F). This feature can be explained by one or more of the following mechanisms: (1) multiple hydrothermal fluid events; (2) phase separation through fluid immiscibility; (3) fluid mixing; and (4) heterogeneous trapping. Among these the first one can be excluded because of the various types of inclusions occurring as primary FIAs

ACCEPTED MANUSCRIPT P a g e | 33

in stage I quartz. The major inclusion types show similar salinities, gaseous compositions and CO2 homogenization temperature ranges (Fig. 16 and Table 6), implying a genetic relationship, which excludes fluid mixing. Evidence of fluid immiscibility was observed in quartz from stage I, where primary CO 2-rich

PT

FIAs occur along with primary type 2a and 2b inclusions (Fig. 15F) and the two

RI

major coexisting fluid types (2a and 2b) have similar homogenization

SC

temperature (Fig. 16 and Table 6). Remarkably, in stage I quartz also shows heterogeneous trapping of type 4 inclusions that coexist with other types of

NU

inclusions. Thus, inclusion types from stage I are interpreted to be products of

MA

fluid immiscibility and coeval partial heterogeneous trapping. From petrographic and microthermometric studies of fluid inclusions, it appears that

D

the fluid immiscibility started from the late part of stage I and continued

fluid

inclusion

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through most of stage II. For stage III, type 2b inclusions, one of the two major types,

possess

similar

gaseous

compositions,

CO2

CE

homogenization temperature, total homogenization temperature and slightly

AC

lower salinities compared with the earlier fluids (Fig. 16 and Table 6), suggesting a genetic relationship. The type 3 inclusions, another major fluid inclusion type in stage III, sometimes show salinities and total homogenization temperature which are distinct from those of type 2b inclusions (Fig. 16) even within the same fluid inclusion plane. This feature does not match with the criteria for fluid immiscibility (Ramboz et al., 1982), and instead, may be attributed to some degree of fluid mixing occurring in stage III. This is also

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confirmed by oxygen and hydrogen isotope data of stage III quartz (Fig. 18). Oxygen and hydrogen isotope data can be applied to investigate the possible origin of ore-forming fluids. As quartz from stage I was mostly overprinted by subsequent fluids and recrystallized, only quartz from stage II and III

PT

mineralized veins was analyzed for oxygen and hydrogen isotopes for the

RI

present study. Figure 18 shows that the ore-forming fluids were initially derived

SC

from magmatic fluids, and then evolved towards mixing of magmatic fluids

NU

with meteoric water. There are some clues on the parent magmatic fluids of the Shangzhuang deposit, such as the occurrence of heterogeneous trapping of

MA

inclusions containing carbonate or silicate daughter minerals (Fig. 15I) and the presence of some melt-fluid inclusions (Fig. 15K), both of which imply

D

ore-forming fluids may be related to magmatic fluids (Moura et al., 2006). The

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influx of meteoric water into the system is consistent with the fluid mixing and decline of temperature and salinity. The oxygen and hydrogen isotope

CE

compositions of ore-forming fluids from Shangzhuang and other early

AC

Cretaceous gold deposits in the eastern NCC, when compared with typical orogenic gold deposits of mostly metamorphic origin (Zhu et al., 2015, and references therein), show significant difference (Fig. 18). Previous studies have emphasized the magmatic affiliation of ore-forming fluids in the early Cretaceous gold deposits at Jiaodong (Yang and Zhou, 2001; Mao et al., 2008; Li et al., 2013) and elsewhere in the NCC (Li et al., 2012; Zhu et al., 2015). Issues related to the sources of ore-forming fluids/parent magmatic fluids of

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gold mineralization at Jiaodong remain debated. However, there is a general consensus that both crustal and mantle fluids participated in the gold metallogenetic process.

PT

7.3 Sources of ore-forming sulfur Sulfur is one of the most abundant elements in the Jiaodong gold deposits. Most

RI

researchers concur that gold was transported in the ore fluids as bisulfide

SC

complexes (Hayashi and Ohmoto, 1991; Benning and Seward, 1996; Loucks

NU

and Mavrogenes, 1999) and co-precipitated with sulfide, especially pyrite. Therefore, knowledge of the sulfur isotopic composition of auriferous pyrite is

MA

important to improve the understanding of the source of ore-forming materials,

D

and the genesis of the deposits (Kesler et al., 2005; Chang et al., 2008).

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The results obtained from in-situ and conventional analyses of sulfur isotopes for pyrite from the Shangzhuang gold deposit in this study show that the δ34S

CE

values for Py I (+10.2 to +11.3‰, mean=+10.8‰) are higher than those (+4.1 to +6.8‰, mean=+5.4‰) of the later gold-related Py II (Fig. 17). Zhu et al. (2015)

AC

used He-Ar isotopes from the early Cretaceous gold deposits in the NCC to show that the ore-forming fluids were dominantly derived from the mantle. Hydrothermal fluids exsolved from mantle-derived magmas are enriched in H2S, and H2S is the predominant aqueous sulfur species (Ohmoto and Rye, 1979; Zheng and Chen, 2000). If the sulfur in the fluids is dominated by one species (i.e., H2S), sulfide minerals (e.g., pyrite) precipitating from solution would

ACCEPTED MANUSCRIPT P a g e | 36

exhibit δ34S values similar to the value of the ore fluids (δ 34SΣS) owing to very small relative isotopic enrichment factor between pyrite and the aqueous species (~ -0.2 at 350°C, Kajiwara and Krouse, 1971) (Ohmoto, 1972). In addition, δ34S values of magmatic fluids are almost equal to those of parental mafic magma,

PT

i.e., δ34Sfluids=δ34S H2S≈δ34SPy I≈δ34Smelt (Ohmoto and Rye, 1979; Zheng and Chen,

RI

2000). The δ34S values of early Py I are obviously higher than that of chondrite

SC

(δ34S=~0‰) and contemporaneous mantle-derived intermediate-mafic dykes (5.3 to 10.8‰, mean=6.9‰, Huang, 1994), indicating the presence of a more S-rich source, which may be related to degassing of mantle wedge

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34

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metasomatized by slab fluids. Zhu et al. (2015) suggested that during the westward subduction of the paleo Pacific plate in early Cretaceous, parts of the

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subducted slab became stagnant in the mantle transition zone under eastern

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NCC, leading to intense metasomatism of lithospheric mantle and an increase in oxygen fugacity. This process could give rise to enrichment of 34S (Ionove et al.,

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1992). Fluids released by the subducted slab and overlying sediments have also

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been suggested to be potential carriers of Au and S (Goldfarb and Santosh, 2014). Meanwhile, since H2S is generally enriched in light S, H2S degassing of magmatic fluids will also increase the heavy S (e.g.,

34

S) of the fluid. When

ore-forming fluids transformed to stage III, marking the main period of gold precipitation, fluid mixing between magmatic fluids and relatively high oxygen fugacity (fO2) and low temperature meteoric water took place, leading to decreasing temperature and increasing fO2 of the ore-forming fluids. Meanwhile,

ACCEPTED MANUSCRIPT P a g e | 37

the aqueous sulfur species was no longer the H2S species, and comprised S2-, HS-, and H2S, among which the former two sulfur species were responsible for gold transport. In this condition where several aqueous species are present in significant proportions, a slight change in pH and/or fO2 can change the δ34SPy

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value drastically (Ohmoto, 1972). For example, at 250°C, an increase in fO2 by 1

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log unit, or an increase of pH by 1 unit could decrease δ34S value by nearly 20%

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(Ohmoto, 1972). As the pH changed in a narrow range because of CO2 buffering, increasing of fO2 attributed to fluid mixing may be the main reason for the

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decline of δ34S values of Py II. Given the fluid transport distance and the

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different wallrocks (composed of metamorphic rocks and granitoids), sulfidation must have taken place simultaneously along fluid pathways with ore

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deposition.

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7.4 A decratonic gold mineralization model for the Shangzhuang gold deposit

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It is difficult to apply the conventional classification schemes for common ore deposit types (e.g. Cox et al., 1986) to define the formation of the Shangzhuang

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gold deposit. Integrated geological characteristics, mineralization and alteration features, metallogenic age, sources of ore-forming fluids and materials, and tectonic settings favor a decratonic gold mineralization model as defined by Zhu et al. (2015) for the Shangzhuang gold deposit. Petrological, geological and geophysical evidence shows that the NCC, particularly its eastern part, underwent extensive decratonization (or destruction)

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and thinning of the lithospheric during Mesozoic and Cenozoic (Fan and Menzies, 1992; Griffin, et al., 1998; Gao et al., 2004, 2009; Wu et al., 2005; Zhu and Zheng, 2009; Li and Santosh, 2014), which culminated during the early Cretaceous (130‒110 Ma) (Zhu et al., 2012; Zhai and Santosh, 2013), with

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large-scale deformation, magmatic activities, widespread rift basins and

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metamorphic core complexes, and formation of large-scale metal deposits and

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oil-gas resources (Yang et al., 2003, 2008; Wu et al., 2005; Gao et al., 2009; Wang et al., 2011; Charles et al., 2012; Zhu et al., 2015). Geochronological data

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suggest that the decratonization and lithospheric thinning of the NCC was

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diachronous (Zhang et al., 2014 and references therein), and the mineralization age at ~126 Ma of the Shangzhuang gold deposit is remarkably consistent with

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the peak age of decratonization at ca. 125 Ma (Zhu et al., 2012, 2015) in the

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eastern NCC. Taking into the account the age range of 126‒117 Ma for metallogeny in Jiaodong (Fig. 3), the gold mineralization might have been

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initiated at the peak of decratonization of the eastern NCC and the duration of

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gold precipitation was ca. 10 Ma. It has been well established that the dominant compressive tectonic regime linked to Paleozoic marginal orogeny switched to an extensional tectonic regime in the NCC during the early Cretaceous (Zhai et al., 2004). The dominantly NW-SE extension during this period is broadly similar to that of the NE Asian region (Wang et al., 2011; Zhou et al., 2012). This extensional tectonic

event

was

associated

with

the

formation

of

widespread

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mafic-intermediate dykes, extensive felsic magmas and large-scale metallic mineral deposits, together with the development of rift basins (e.g. Ren et al., 2002; Zhu et al., 2012a) and metamorphic core complexes (MCCs) (e.g. Davis et al., 1996, 2002; Liu et al., 2005; Wang et al., 2011; Charles et al., 2012; Lin et

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al., 2013, 2015) (Fig. 1). Geochronologic data show that these MCCs were

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nearly coeval and show similar cooling ages, ranging from 130 to 115 Ma and

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dominantly at 130 to 120 Ma (Fig. 3B) (Wang et al., 2011; Zhu et al., 2012a, b; Lin et al., 2013, 2015), with a peak of ~126 Ma (Fig. 3B, Lin et al., 2013, 2015).

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Thus, the timing of extension is consistent with ages of most gold deposits in

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the eastern NCC. Moreover the peak age of extension remarkably coincides with the onset of gold mineralization (Fig. 3), linking the mineralization with

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the peak of decratonization. In addition, almost at the same time (ca. 127 Ma),

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the Tan-Lu fault and its subsidiary structures, which strongly structurally controlled gold deposits in Jiaodong, witnessed sinistral transcurrent

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displacement (Mercier et al., 2007).

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Gold deposits are distributed along the northern, southern and eastern margins of the eastern NCC (Fig. 1). Zhang et al. (2014) integrated geochronological, geochemical and structural data in the NCC and proposed that the decratonization of the NCC initially started from its northern and eastern margins and the intensity of the Mesozoic magmatism and deformation in the NCC became much weaker from craton margins to its inland regions. They considered

that

the

craton

margin

destruction

is

a

result

of

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post-collision/post-orogenic lithospheric delamination, as also confirmed by Xu et al. (2009). These conclusions suggest that the orogeny and delamination along the margins of the NCC weakened the lithospheric zones, leading to intense crust-mantle interaction and a strongly convective asthenosphere, which

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led to the destruction and lithospheric thinning. These processes fuelled the

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reactivation and pre-concentration of ore-forming materials such as gold (Fig.

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19). The eastern NCC is surrounded by Phanerozoic orogens. To the north lies the Xing-Meng orogen formed as a result of the closure of Paleo-Asian Ocean;

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to the south is the Qinling-Dabie orogen; to the east is the Sulu orogen resulting

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from subduction of the Yangtze Block beneath the NCC, and to the west is the Paleoproterozoic Trans-North China orogen (Xu et al., 2009). Windley et al.

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(2010) also proposed that multiple late Paleozoic to early Mesozoic subduction

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along the southern and northern margins of the NCC has important bearing on the hydration and weakening the mantle lithosphere. Santosh (2010) suggested

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that a combination of subduction erosion, thermal and chemical destruction was

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instrumental in eroding the root of the eastern NCC. Thus, it is evident that Phanerozoic orogeny played a critical role in generating the early Cretaceous giant gold deposits in the eastern NCC. The origin of ore-forming fluids and materials also exhibits a close connection to craton destruction. Ore-forming fluids of the gold deposits in the eastern NCC were enriched in CO2. Mantle xenoliths and geophysical studies reveal that the lithosphere of the eastern NCC underwent significant thinning and

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decratonization during the early Cretaceous (Menzies et al., 1993; Griffin, et al., 1998). Therefore, the thinned and hot lithosphere provided a favorable setting for the large-scale influx of CO2 (Zhang et al., 2017). It was demonstrated that in the early Cretaceous the mantle wedge of the destroyed NCC experienced

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continuous hydration and extensive metasomatism (Fig. 19), the partial melting

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of which produced voluminous hydrous, Au- and S-bearing mafic magmas (Zhu

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et al., 2015). This mantle-derived melt together with crust-derived components

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might have provided the source of ore-forming fluids and materials. Thus, the spatial and tectonic coincidence between the giant gold mineralization

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and destruction of the NCC confirms a genetic linkage between the two. The large scale lithospheric delamination, asthenospheric upwelling, multiple

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orogenic processes along the craton margins, and associated seismicity provided

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an optimal setting for the gold mineralization (Fig. 19) (Yang et al., 2003; Chen et al., 2005; Wu et al., 2005; Zhu and Zheng, 2009; Goldfarb et al., 2014;

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8. Conclusions

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Peterson and Mavrogenes, 2014; Zhu et al., 2015).

The Shangzhuang gold deposit is composed of disseminated and veinlet mineralization hosted within the Guojialing granodiorite. Zircon U-Pb dating shows that the Guojialing granodiorite was emplaced at ca. 130 Ma. Our study reveals that molybdenite appeared in the quartz-pyrite-polymetallic sulfide-gold stage of the Shangzhuang gold deposit. Geologic and mineralogical

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characteristics confirm that gold and molybdenite are contemporaneous and the Re-Os molybdenite age of 126 Ma provides a reliable estimate of the timing of gold mineralization. Based on petrographic and microthermometric studies of fluid inclusions, it is

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inferred that fluid inclusions from stage I correspond to fluid immiscibility and

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coeval partial heterogeneous trapping. The fluid immiscibility started from the

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later part stage I and continued through most of stage II. Subsequently, fluid

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mixing occurred in stage III. Oxygen and hydrogen isotope data also suggest that the initially magmatic ore-forming fluids were later mixed with meteoric

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water.

Sulfur isotope analyses using in-situ and conventional methods on pyrite from

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different stages reveal markedly higher δ34S values of Py I from the early mineralization stage suggesting degassing of mantle wedge metasomatized by

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slab fluids. The decline of δ34S values from Py I to Py II was related to increasing fO2 attributed to fluid mixing. Wallrock sulfidation must have taken

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place simultaneously along fluid pathways and during ore-depositional processes.

Integrated geological characteristics, mineralization features, metallogenic age, sources of ore-forming fluids and sulfur, and tectonic settings favor a decratonic gold mineralization model for the Shangzhuang gold deposit. The geodynamic scenario proposed for the early Cretaceous giant gold mineralization event in

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the eastern NCC includes the paleo-West Pacific plate subduction, asthenospheric upwelling, multiple collision/orogen along the margins, and seismicity.

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Acknowledgments We thank Lei Chen and Hongxia Ma for their assistances in SIMS sulfur isotope

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analyses of pyrite, Limin Zhou for helps with Re-Os isotope analyses of

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molybdenite, Xin Yan, Saihong Yang and Di Zhang for their helps with BSE

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imaging and EMP analysis, and Zhaochu Hu for helps with zircon LA-ICP-MS U–Pb dating. We are indebted to staffs of Shandong Zhaojin Group and the

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Canzhuang Gold Mine for their logistic and technical support during sampling in the mining areas. We are grateful to Drs. Ting-Guang Lan, Xuan Liu,

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Wen-Gang Xu, Xiao-Chun Li and Bo-Jie Wen for valuable discussions. Two anonymous referees are thanked for their constructive and valuable comments

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which greatly contributed to the improvement of the manuscript. This study is supported by the fund from the Ministry of Science and Technology of People‘s

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Republic of China (No. 2016YFC0600105), the National Natural Science Foundation of China (No. 41672094) and China Postdoctoral Science Foundation (No. 2015M571113).

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Figure captions Fig. 1. A simplified geologic map showing distribution of the early Cretaceous gold deposits, magmatic rocks, and metamorphic core complexes (MCCs) in the eastern North China Craton (NCC) (modified after Wang et al., 2011; Li et al.,

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2012; Zhu et al., 2015).

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Fig. 2. Geological map of the Jiaodong gold province, showing the distribution

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of major fault zones, basements, Mesozoic igneous rocks, UHP metamorphic

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rocks, and gold deposits. Modified after Fan et al. (2003).

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Fig. 3. Age probability diagram showing summary of ages of the Mesozoic magmatic rocks (A), extensional structures (B) and gold mineralization of

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Jiaodong gold deposits (C) in the eastern NCC. Geochronological data of the

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Mesozoic magmatic rocks and extensional structures are from Zhang et al. (2014) and references therein, and Wang et al. (2011), Lin et al. (2015) and

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references therein, respectively. Ages of gold mineralization of Jiaodong gold deposits were collected from Chen et al. (2005), Li et al. (2015) and Ma et al.

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(2017), and references therein. Fig. 4. Geologic map of the Shangzhuang gold field. Fig. 5. The spatial distribution of orebodies at different levels in the Shangzhuang gold deposit (after unpublished geological data of Canzhuang Gold Mine; Yu, 2011). Fig. 6. Vertical geologic cross sections illustrating the structural controls on

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hydrothermal alteration and mineralization. Location of drill hole after unpublished geological data of Canzhuang Gold Mine. Fig. 7. Field photographs of wallrocks and ore-related hydrothermal alterations in the Shangzhuang gold deposit.

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A. Fresh Guojialing granodiorite with large K-feldspar phenocrysts. B. Mafic

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dyke intruded into potassic alteration and granodiorite, and was intruded by

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pyrite-quartz vein. C. Potassic alteration occurring as veinlets containing

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pyrite-quartz veins intruded wallrock. And a sketch picture illustrating the style of veined potassic alteration. D. Potassic alteration adjacent to fresh Guojialing

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granodiorite. E. Potassic alteration + Silicification adjacent to Sericitization + Silicification along a fault. F. Pyrite-sericite-quartz alteration characterized by

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gray to dark gray appearance and mainly composed of quartz, sericite and

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pyrite.

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Fig. 8. A measured sectional sketch, illustrating hydrothermal alteration zonation in the Shangzhuang gold deposit.

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Fig. 9. Photomicrographs of hydrothermal alteration features. A. Weakly potassic altered wallrocks characterized by plagioclase partly replaced by K-feldspar. B. Strongly potassic altered rocks, with recrystallized K-feldspar totally replaced plagioclase, minor muscovite filling fractures, and biotite and amphibole obliterated. C. Recrystallized quartz observed as narrow undulated quartz ribbons surrounding the feldspars within potassic alteration. D. Weakly

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phyllic alteration, typified by biotite partly or totally replaced by sericite and plagioclase transformed to sericite along polysynthetic twinning. E. Strongly phyllic altered rocks have lost all primary textures and been extensively leached. F. Sericite veinlets fill fractures within secondary K-feldspar or cut the

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K-feldspar crystals. G. and H. Pyritization, sericitization and silicification,

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feldspars completely altered to sericite and quartz, sericite appears as veinlets

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filling fractures or as scaly aggregate, and two generations of quartz are observed. I. Carbonation, carbonate minerals exist as vein with late-stage quartz.

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Abbreviations: Cal = calcite, Kfs = K-feldspar, Ms = muscovite, Pl =

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plagioclase, Py = pyrite, Qtz = quartz, Ser = sericite, Zrn = zircon. Fig. 10. Ore photographs showing vein mineralization paragenesis. A. Potassic

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altered wallrock was crosscut by Qtz-Py I vein from stage II, which was then

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intruded by Qtz-Py II-Mo vein from stage III. B. Mo vein crosscutting Qtz-Ser altered wallrock. C. Clouded white quartz with K-feldspar, sericite and a small

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amount of euhedral to subhedral Py I grains. D-F. Qtz-Py II-polymetallic sulfide

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vein intruding veins of the stage II and alteration mineral assemblages. Abbreviations: Kfs = K-feldspar, Mo = molybdenite, Py = pyrite, Qtz = quartz, Ser = sericite.

Fig. 11. Paragenesis sequence of ore, gangue, and alteration minerals of the Shangzhuang gold deposit. Fig. 12. Photomicrographs (D, I, and L) and BSE images (A-C, E-H, and J-K)

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of gold-related ore samples from the Shangzhuang gold deposit. A. Hydrothermal monazite replacing hydrothermal K-feldspar from stage I included in the Py II. B. Gold occurs as small grains found as inclusions within Py I. C-E. Molybdenite commonly occurs as molybdenite-pyrite-quartz vein or

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molybdenite-quartz vein containing native gold grains. F. Gold grains hosted as

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inclusions or in fractures in Py II. G. A secondary electron image showing gold

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grains formed as inclusions in Py II. H. Gold grains occur along pyrite or quartz grain boundaries, as inclusions or free gold grains. I. Reflected light photograph

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showing gold grains occur along pyrite or quartz grain boundaries. J. and K.

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Galena characterized by exsolutions and filling fractures in pyrite. L. Sphalerite intergrown with pyrite II. Abbreviations: Chr = chromite, Gn = galena, Kfs =

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K-feldspar, Mnz = monazite, Mo = molybdenite, Py = pyrite, Qtz = quartz, Ser

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= sericite, Sp = sphalerite, FF Au = fracture-fill gold, FG Au = free grains of gold, GB Au = grain-boundary gold, Inc Au = gold formed as inclusions.

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Fig. 13. U-Pb concordia diagram for zircons from Guojialing granodiorite

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analyzed by LA-ICPMS (A) and weighted average model age diagram (B). Fig. 14. (A). Re-Os isochron age diagram for molybdenite samples from the Shangzhuang gold deposit. (B). Re-Os weighted average model age diagram. Fig. 15. Transmitted light photomicrographs of fluid inclusions. A. Type 1 vapor-dominant CO2 inclusion. B. Type 2a two-phase H2O-CO2-NaCl inclusion. C. Type 2b three-phase H2O-CO2-NaCl inclusion. D. Type 3 two-phase

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H2O-NaCl inclusion. E. Type 4 multiphase H2O-CO2-NaCl-solid inclusion. F. Four various fluid inclusion types occurred in stage I quartz and different FIAs distributed in a same fluid inclusion plane. G. Fluid inclusion distributed as FIAs in stage III quartz. H. Sketch of distributions of oriented FIAs of type 3

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and total homogenization temperatures and salinities of these inclusions. I-K.

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Typical type 4 inclusions.

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Fig. 16. Histograms showing calculated salinities and total homogenization

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temperatures of different inclusion types from four stages of the Shangzhuang gold deposit.

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Fig. 17. Histograms of sulfur isotope compositions for different pyrite types and

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molybdenite in the Shangzhuang gold deposit.

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Fig. 18. Calculated δ18O and δD for fluids of stage II and III in the Shangzhuang gold deposit. Metamorphic water field, primary magmatic water

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field, and meteoric water line are from Taylor (1974). Oxygen and hydrogen isotope data of global orogenic gold deposit are from Zhu et al. (2015) and

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references therein.

Fig. 19. Schematic illustration of a genetic model for the gold mineralization in the Jiaodong and its link with decratonization of the NCC (modified from Huang et al., 2007; Li et al., 2012; Yang et al., 2012; Zhu et al., 2015). NCC = North China Craton, YC = Yangtze Craton.

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Table captions Table 1. Representative electron microprobe analyses of gold in Stage III from the Shangzhuang gold deposit Table 2. Representative electron microprobe analyses of pyrite I and pyrite II

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from the Shangzhuang gold deposit

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Table 3. Representative electron microprobe analyses of molybdenite from the

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Shangzhuang gold deposit

Table 4. LA-ICP-MS zircon U–Pb data for the Guojialing granodiorite

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Table 5. Re-Os isotope data of molybdenite

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Table 6. Microthermometric data of fluid inclusions for the Shangzhuang gold deposit

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Table 7. Oxygen, hydrogen, and sulfur isotope compositions of mineral

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separates from the Shangzhuang gold deposit

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Table 1 Representative electron microprobe analyses of gold in stage III from the Shangzhuang gold deposit Au1

Au2

Au3

Au4

Au5

Au6

Au7

Au8

Au9

Au10

Au11

Au12

Au13

Au14

Au15

Au16

wt % Au Ag Fe

81.93 10.63 0.14

80.33 10.78 1.24

56.10 7.65 14.11

77.71 10.99 0.84

81.04 10.50 1.14

80.57 10.62 0.14

82.53 10.97 0.30

82.05 10.60 0.20

76.14 10.40 3.24

79.62 11.02 6.00

77.14 10.47 1.36

73.75 10.87 2.97

75.26 10.95 3.12

71.29 11.26 4.11

83.70 11.73 1.02

S Mo Te Zn Cu Se As Ni Total

0.06 0.39 0.037 0.009 0.025 0 0.005 0.002 93.22

0.75 0.17 0.018 0.03 0.012 0.063 0.003 0.007 93.40

16.90 0.07 0.019 0.011 0.007 0 0 0.003 94.86

0.30 0.30 0.063 0 0 0 0 0 90.20

0.45 0.21 0.022 0.039 0.011 0 0 0 93.41

0.10 0.47 0.000 0.035 0 0 0 0.003 91.94

0.08 0.32 0.021 0 0 0 0 0.013 94.23

0.06 0.48 0.045 0.036 0.012 0.002 0.021 0 93.51

1.90 0.34 0.036 0.001 0 0 0 0.008 92.07

5.61 0.39 0.000 0 0 0.053 0 0 102.68

0.63 0.47 0.020 0.046 0 0.012 0 0 90.16

T P

81.99 10.35 3.41

1.80 0.40 0.004 0.041 0.011 0.016 0 0 89.86

2.23 0.47 0.039 0 0 0.007 0 0.001 98.49

1.82 0.47 0.000 0.022 0.027 0.011 0 0.012 91.68

2.97 0.87 0.000 0.024 0.041 0.017 0 0.006 90.58

0.83 0.41 0.023 0 0.022 0.031 0 0.01 97.76

885

882

880

876

885

884

886

880

878

880

872

888

873

864

877

Fineness

A

C C

T P E

D E 883

C S U

N A

M

I R

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Table 2 Representative electron microprobe analyses of pyrite I and pyrite II from the Shangzhuang gold deposit

wt % Fe S Pb Ni Co Se As Cu Te Au Zn Ag Total

1

2

3

4

5

6

7

8

9

10

11

12

13

14

Py I

Py I

Py I

Py I

Py II

Py II

Py II

Py II

Py II

Py II

Py II

Py II

Py II

Py II

46.23 53.21 0.28 0.001 0 0 0 0.009 0 0 0.004 0.001 99.73

46.30 53.22 0.31 0.010 0 0 0 0 0 0 0 0.022 99.87

46.30 53.63 0.21 0.005 0 0.009 0 0.027 0 0 0.007 0 100.19

46.25 53.67 0.33 0.018 0 0 0.014 0 0 0 0 0 100.29

31.37 38.81 28.81 0.017 0.086 0.016 0 0 0.015 0 0 0 99.12

46.08 53.65 0.40 0.014 0.205 0.019 0 0.009 0.018 0 0.009 0.006 100.41

46.28 53.16 0.28 0.020 0 0 0 0 0.005 0.02 0.018 0 99.78

45.87 52.99 0.32 0.022 0 0.022 0 0 0.007 0.127 0.052 0.01 99.42

46.02 53.41 0.36 0.023 0 0 0 0.007 0.015 0 0 0.009 99.84

45.89 52.78 0.37 0.000 0 0.01 0.013 0.004 0 0 0.012 0.022 99.11

46.11 52.95 0.38 0.017 0 0.019 0 0 0.014 0 0 0 99.48

45.95 52.62 0.33 0.000 0 0.004 0.006 0 0.039 0.091 0 0.007 99.05

45.80 53.04 0.32 0.014 0 0.037 0.004 0 0.013 0 0.015 0 99.24

A

C C

T P E

D E

M

N A

C S U

I R

T P

46.25 53.30 0.46 0.005 0 0 0.025 0 0.003 0 0 0 100.04

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Table 3 Representative electron microprobe analyses of molybdenite from the Shangzhuang gold deposit

wt % Mo S Fe Pb Au Ag Te Se As Co Ni Cu Zn Total

2

3

4

5

6

7

Mo

Mo

Mo

Mo

Mo

Mo

Mo

45.67 35.18 0.22 0.28 0.004 0 0 0.01 0 0.059 0.007 0.023 0.062 81.52

57.21 40.83 0.14 0.35 0 0 0.031 0.005 0.014 0.047 0.015 0.009 0.016 98.66

44.07 32.99 0.22 0.33 0 0.018 0.007 0.015 0 0.047 0.027 0 0.014 77.74

52.55 38.86 0.13 0.30 0 0.022 0 0.001 0 0.024 0 0 0.011 91.89

57.71 41.63 0.16 0.38 0 0.008 0.048 0.002 0 0.036 0.018 0.007 0.03 100.02

56.06 40.90 0.33 0.60 0.026 0 0.004 0.017 0 0.005 0.029 0 0 97.97

57.49 41.70 0.20 0.35 0 0.045 0 0.02 0 0.012 0.004 0.021 0.035 99.88

D E

T P E

C C

A

1

M

N A

C S U

I R

T P

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Table 4 LA-ICP-MS zircon U–Pb data for the Guojialing granodiorite Concentrations(ppm)

Isotopic ratios

Isotopic ages(Ma) 207

Spot Pb(ppm)

Th(ppm)

U(ppm)

Th/U

207

Pb/206Pb

1σ

207

Pb/235U

1σ

206

Pb/238U

1σ

206

Pb/ Pb

207

1σ

T P

(Ma) 08G30(Guojialing granodiorite)

08G30-01

13.83

105.65

717.30

0.1473

0.04837

0.00146

0.13505

0.00384

0.02034

0.00018

08G30-02

8.12

50.61

425.80

0.1189

0.04943

0.00247

0.13793

0.00667

0.02034

0.00024

08G30-03

6.71

41.02

353.33

0.1161

0.04930

0.00224

0.13803

0.00620

0.02034

0.00021

08G30-04

13.41

96.81

694.18

0.1395

0.04843

0.00176

0.13571

0.00487

0.02034

08G30-05

114.15

33.97

228.42

0.1487

0.16571

0.00263

10.85920

0.16932

0.47382

08G30-06

8.62

111.07

435.51

0.2550

0.04897

0.00202

0.13565

0.00531

08G30-07

21.32

213.85

1072.06

0.1995

0.05022

0.00161

0.14155

0.00481

08G30-08

7.50

43.52

392.42

0.1109

0.05022

0.00268

0.14036

I R

Pb/235U

206

1σ

(Ma)

Pb/238U

1σ

(Ma)

116.8

65.7

128.6

3.4

129.8

1.2

168.6

112.0

131.2

6.0

129.8

1.5

161.2

105.5

131.3

5.5

129.8

1.3

0.00019

120.5

89.8

129.2

4.4

129.8

1.2

0.00317

2514.5

27.3

2511.1

14.5

2500.3

13.9

0.02034

0.00022

146.4

91.7

129.2

4.7

129.8

1.4

0.02034

0.00025

205.6

75.9

134.4

4.3

129.8

1.6

0.00738

0.02035

0.00027

205.6

124.1

133.4

6.6

129.9

1.7

C S U

N A

M

08G30-09

3.95

19.04

166.14

0.1146

0.05023

0.00280

0.17367

0.00937

0.02532

0.00032

205.6

126.8

162.6

8.1

161.2

2.0

08G30-10

16.10

390.28

570.04

0.6846

0.05071

0.00175

0.17470

0.00580

0.02500

0.00022

227.8

79.6

163.5

5.0

159.2

1.4

08G30-11

10.98

85.82

556.56

0.1542

0.05072

0.00176

0.14245

0.00501

0.02034

0.00020

227.8

79.6

135.2

4.5

129.8

1.3

08G30-12

6.20

34.39

325.17

0.1058

0.04844

0.00235

0.13409

0.00629

0.02034

0.00027

120.5

-84.3

127.8

5.6

129.8

1.7

08G30-13

4.82

42.33

260.17

0.1627

0.04919

0.00266

0.13475

0.00716

0.02034

0.00034

166.8

123.1

128.4

6.4

129.8

2.1

08G30-14

58.82

110.10

89.48

1.2304

0.17473

0.00286

11.52761

0.18869

0.47731

0.00371

2603.4

27.6

2566.8

15.3

2515.5

16.2

08G30-15

7.71

48.27

399.38

0.1209

0.04959

0.00199

0.13873

0.00549

0.02034

0.00020

176.0

126.8

131.9

4.9

129.8

1.3

08G30-16

11.52

89.75

592.34

0.1515

0.04909

0.00168

0.13688

0.00443

0.02034

0.00017

153.8

76.8

130.3

4.0

129.8

1.1

08G30-17

7.12

43.01

371.60

0.1157

0.04839

0.00211

0.13451

0.00583

0.02034

0.00021

116.8

101.8

128.1

5.2

129.8

1.3

08G30-18

106.98

467.81

97.07

4.8193

0.16557

0.00285

10.92732

0.19361

0.47805

0.00394

2513.3

29.0

2517.0

16.5

2518.8

17.2

PT

E C

C A

D E

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Table 5 Re-Os isotope data of molybdenite Re (ppm)

187

Common Os (ppb)

187

Re (ppm)

Os (ppb)

Model age (Ma)

Sample no.

weight (g)

Measured

±2σ

Measured

±2σ

Measured

±2σ

Measured

±2σ

47

0.05440

422.42

4.0693

0.0197

0.1104

265.50

2.5577

556.30

4.61

125.64

1.89

47-2

0.02050

303.73

2.3840

0.1269

0.1422

190.90

1.4984

403.14

3.55

126.62

1.81

47-5

0.02060

280.93

2.0501

0.1280

0.1434

176.57

1.2885

373.73

2.98

126.91

1.71

47-8

0.02270

162.56

1.2823

0.1153

0.2585

102.17

0.8060

213.94

1.70

125.55

1.73

47-9

0.02660

359.95

2.6302

0.0992

0.2223

226.24

1.6531

472.83

3.89

125.32

1.71

U N

D E

T P E

A

C C

A M

T P

I R

SC

Measured

±2σ

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Table 6 Microthermometric data of fluid inclusions for the Shangzhuang gold deposit Stage

FI type

Tm(CO2) (°C)

I

Type 1

-56.7 to -56.6 (14)/-56.61

Te (°C)

Tm(ice) (°C)

II

III

Th (°C)

Salinity(wt.% NaCl)

(°C)

298 to 325 (42)/313

5.7 to 9.0 (42)/7.3

316 to 350 (38)/333

6.0 to 8.8 (38)/7.6

271 to 305 (47)/291

5.3 to 7.5 (47)/6.4

29.0 to 31.1 (24)/30.1

301 to 328 (31)/315

2.8 to 7.1 (31)/5.2

29.6 to 31.0 (30)/30.1

246 to 298 (35)/280

4.3 to 6.4 (33)/5.5

228 to 286 (68)/261

5.9 to 9.6 (65)/8.0

156 to 203 (26)/179

0.9 to 5.3 (26)/3.2

T P

5.0 to 7.0 (42)/6.0 -57.2° to -56.6 (20)/-56.7

5.1 to 6.8 (38)/5.8

Type 2a Type 2b

-57.2 to -56.3 (23)/-56.8

6.2 to 8.6 (31)/7.3

Type 2b

-56.9 to -56.4 (30)/-56.7

6.6 to 7.8 (33)/7.1 36.9 to -21.6

-6.3 to -3.6

(6)/-30.5

(65)/-5.1

(26)/-1.9

D E

SC

U N

A M

-3.2 to -0.5

Type 3

I R

30.1 to 31.0 (24)/30.7

5.9 to 7.2 (47)/6.6

Type 3

IV

Th(CO2)

30.5 to 30.7 (16)/30.6

Type 2a Type 2b

Tm(cl) (°C)

Note: 1 = Range (number)/average. Abbreviations: FI = fluid inclusion, Te = eutectic temperature, Th = total homogenization temperature, Th(CO2) = homogenization temperature of the CO2 phases, Tm(cl) = final melting temperature of CO2-H2O clathrate, Tm(CO2) (°C) = final melting temperature of solid CO2, Tm(ice) = final melting temperature of ice.

T P E

A

C C

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Table 7 Oxygen, hydrogen, and sulfur isotope compositions of mineral separates from the Shangzhuang gold deposit Stage

Mineral

Sample no.

δDV-SMOW (‰)

δ18OV-SMOW (‰)

δ18Ofluid (‰)

II

Quartz

13SZ02 13SZ04 13SZ05 13SZ08

-75.2 -65.3 -70.0 -70.8

13.7 12.3 12.9 12.9

7.3 5.9 6.5 6.5

13SZ47-1 13SZ47-9 13SZ47-1 13SZ47-2 13SZ47-4 13SZ47-5 13SZ47-8 13SZ47-9 13SZ47-2 13SZ47-4

-70.6 -74.7

11.7 12.0

3.4 3.7

III

Quartz Pyrite II

Molybdenite

D E

A

C C

T P E

T P

I R

C S U

N A

M

δ 34SV-CDT (‰)

6.5 4.8 4.6 5.6 6.3 5.7 5.5 5.3

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AC

CE

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D

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SC

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Graphical abstract

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Research Highlights

 Re-Os dating of gold-related molybdenite implies timing of gold mineralization is 126 Ma.

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 Fluid immiscibility occurred in stage I, II; fluid mixing happened in stage

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III.

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 SIMS S isotopes reveal transformation of mineralization condition.  A decratonic gold mineralization model is proposed for Shangzhuang gold

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CE

PT E

D

MA

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deposit.