Insights into the formation of the Dasuji porphyry Mo deposit (North China Craton) gained from mineral chemistry data

Journal Pre-Proof Insights into the formation of the Dasuji porphyry Mo deposit (North China Craton) gained from mineral chemistry data Peiwen Chen, Qingdong Zeng, Weikang Guo, Junqi Chen PII: DOI: Reference:

S0169-1368(19)30076-9 https://doi.org/10.1016/j.oregeorev.2019.103072 OREGEO 103072

To appear in:

Ore Geology Reviews

Received Date: Revised Date: Accepted Date:

28 January 2019 27 July 2019 10 August 2019

Please cite this article as: P. Chen, Q. Zeng, W. Guo, J. Chen, Insights into the formation of the Dasuji porphyry Mo deposit (North China Craton) gained from mineral chemistry data, Ore Geology Reviews (2019), doi: https:// doi.org/10.1016/j.oregeorev.2019.103072

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Insights into the formation of the Dasuji porphyry Mo deposit (North China Craton) gained from mineral chemistry data

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

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a Key

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Peiwen Chena,b,c, Qingdong Zenga,b,c,*, Weikang Guoa,b,c, Junqi Chend

b Institutions

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

of Earth and Planetary Sciences, University of Chinese Academy of

Mongolia Zhongxi Mining Co., Ltd, Inner Mongolia 012300, China

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d Inner

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Sciences, Beijing 100049, China

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c Collage

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Academy of Sciences, Beijing 100029, China

*Corresponding author at: NO. 19, Beitucheng Western Road, Chaoyang district,

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100029 Beijing, China. Tel.: +86 10 82998175; Fax: +86 10 62010846.

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E-mail address: [email protected] (Q.D. Zeng).

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[email protected] (P.W. Chen); [email protected] (Q.D. Zeng); [email protected] (W.K. Guo); [email protected] (J.Q. Chen)

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Abstract The Dasuji Mo deposit is located within the northern margin of the North China Craton. Based on vein cross-cutting relationships, mineral assemblages and alteration

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characteristics, the formation of the deposit can be divided into four stages: stage 1,

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consisting of two vein types developed in deep, is characterized by K-feldspathization

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with minor molybdenum mineralization; stage 2, containing four distinct vein types,

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is the main stage of molybdenum mineralization accompanied by sericitization and silicification; stage 3 is involved in lead-zinc mineralization associating with

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carbonatization and fluorination; and stage 4 is characterized by no mineralization.

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This paper presents new mineral (magnetite, rutile, molybdenite, and pyrite) chemistry data that provide new insights into the formation of this deposit. The

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magnetites within veins in the deposit have chemical compositions that are indicative

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of a magmatic origin, suggesting that these magnetites hosted in quartz were captured from syn-mineralization granites in the area. Molybdenite W, Pb, Zn, and Cu

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concentrations increase with the decreasing temperature of formation, suggesting the

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initiation of W, Pb, Zn, and Cu precipitation at the end of the second stage of mineralization. The stage 3 pyrite within the deposit contains the highest concentrations of Pb, Zn, and Cu, consistent with the Pb–Zn–(Cu) mineralization that formed during this stage. The majority of the F ion deposition occurred at the end of stage 3, and the fluids associated with stage 4 were meteoric water dominated. Keywords: Mineral chemistry; Ore-forming process; Dasuji Mo deposit; Northern

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margin of NCC.

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Introduction The Central Asian Orogenic Belt (CAOB) is located between Siberia and the North China Craton (NCC) and is one of the largest known accretionary collage

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systems on Earth. The belt records significant crustal growth and long-lived

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magmatism that is associated with metallogenesis including a series of porphyry

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deposits (Gao et al., 2018; Jahn et al., 2000; Sengör et al., 1993; Windley et al., 2007;

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Xiao et al., 2003, 2018). These deposits include those of the Yanliao Mo belt, which is located on the northern margin of the NCC and contains more than 20 Mo deposits

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(Nie et al., 2012; Wu et al., 2017; Zeng et al., 2009, 2012, 2013). The Mo

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mineralization in this region is divided into porphyry, porphyry–skarn, skarn, and vein types of mineralization, with the first two of these types being the most economically

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important (Jiang et al., 2014; Zeng et al., 2013). Three periods of Mo mineralization

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have been identified based on geochronological research in this area (Liu et al., 2010; Zeng et al., 2011, 2012, 2013; Zhang et al., 2009), namely, during the Triassic (245–

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220 Ma), the Jurassic (189–145 Ma), and the Early Cretaceous (144–130 Ma). The

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Triassic Mo mineralization is regarded to be related to the tectonic evolution of the Paleo-Asian Ocean, during which the Early Triassic Mo mineralization formed in a syn- to post-collisional setting associated with the collision between Siberia and the NCC, and the Middle–Late Triassic Mo mineralization formed in a post-collisional extensional setting (Chen et al., 2018, 2019; Sun et al., 2015; Zeng et al., 2012, 2013). Porphyry type deposits, related to intermediate–acid intrusions, have significant

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economic importance that provide 60% and 95% of global Cu and Mo production and ~10% of world Au production (Bodnar, 1995; Sillitoe, 1972; Sinclair, 2007). Such deposits contain variable but massive veinlets that provide evidence of high fluxes of

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ascending ore-forming fluids that carry and transport metals within these systems. It is

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therefore critical to understand the enrichment process of metals in such type of

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deposits. To trace the source and evolution of those metals, Laser ablation–

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inductively coupled plasma–mass spectrometry (LA–ICP–MS) spot analysis and mapping has proven to be critical to reveal the concentration and distribution of the

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metals in sulfide and oxide minerals such as pyrite, arsenopyrite, sphalerite,

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molybdenite, magnetite, and rutile (Cook et al., 2009; Rabbia et al., 2009; Thomas et al., 2011; Winderbaum et al., 2012; Ciobanu et al., 2013; Large et al., 2014; Huang,

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2015; Pašava et al., 2016; Kovalenker et al., 2018; Ren et al., 2018). Hence, it is

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possible to precisely constrain the evolution of ore-forming fluids by the information from LA-ICPMS elemental analysis.

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For this study, we take the Dasuji porphyry Mo deposit, which is located within

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the northern NCC and was discovered in 2006 (Yu et al., 2008), as a case study. The deposit contains 0.144 Mt of Mo reserves at an average grade of 0.133% Mo (IMZM, 2012). The ore-forming and hydrothermal alteration processes that are recorded within the deposit have been constrained to some extent, as shown in the work of Yu et al (2008), Nie et al. (2012) and Wang et al (2014) describing the geology of the deposit. Further work by Zhang et al (2009), Wu et al. (2014) and Chen et al. (2018)

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determined the timing of ore formation, whereas Chen et al. (2019) reported the evolution of ore-forming fluids associated with the deposit based on fluid inclusion studies, and Wu et al. (2018), Chen et al. (2018) and Zhang et al. (2019) described the

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geochemical characteristics of the deposit. However, previous studies for the division

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of veins are very rough, and the mineralogy of each vein generation is also relatively

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poor. The present study provides detailed descriptions of the characteristics of veins

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and ore petrogenesis within the Dasuji deposit using extensive field observations and petrographic thin-section observations. We identified twelve different types of veins

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from four stages and discussed the mineralogy generation, and carried out in-situ LA–

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ICP–MS analysis of magnetite, rutile, molybdenite, and pyrite from the different veins. These data allow for precise determination of the distribution of trace elements and

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metallogenic process of the deposit. Furthermore, this study presents new pyrite He–

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Ar isotopic data to determine the source of the ore-forming fluids associated with the deposit. All of these are helpful for understanding the formation of the deposit and

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even other porphyry Mo deposits in the northern margins of the NCC.

Geological setting The NCC is located in northern China and is separated from the CAOB to the

north by the Chifeng–Kaiyuan Fault (Fig. 1A; Hou et al., 2010; Jiang et al., 2014). The Precambrian basement of the NCC is split into the Western Block (WB), the Trans-North China Orogen (TNCO), the Eastern Block (EB), and the Jiao–Liao–Ji

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Belt (JLJB). The WB and EB consist of Archean to Paleoproterozoic rocks, whereas the TNCO and JLJB contain solely Paleoproterozoic rocks (Zhao et al., 2005). The Archaean basement near the northern margin of the NCC is dominated by biotite

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granulite, biotite–plagioclase gneiss, magnetite quartzite, garnet gneiss, and

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plagioclase hornblendite units (Nie et al., 2012). The Proterozoic–Mesozoic cover

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rocks in this northern NCC region consist predominantly of carbonate and clastic

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sedimentary rocks (IBGM, 1991; Zeng et al., 2012). This region also contains diorite, granodiorite, monzogranite, syenogranite, monzonite, and syenite intrusives (Zhang et

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al., 2014; Li et al., 2017; Xiao et al., 2018). The Triassic Mo mineralization in this

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region formed during two separate stages at 250–235 and 235–220 Ma (Chen et al., 2019). The early-formed deposits are generally porphyry type (e.g., the deposits of

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Chaganhua, Chagandeersi, Baituyingzi, Chehugou, and Sadaigoumen), although

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minor quartz vein-hosted deposits also formed at this time (e.g., Yuanbaoshan). This stage of Mo mineralization is always associated with Cu or W (Sun et al., 2013; Cai et

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al., 2011). The late stage of mineralization generated porphyry (e.g., Dasuji),

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porphyry–skarn (e.g., Hekanzi), and quartz vein (e.g., Xishadegai) Mo deposits that contain significant Mo without any other notable mineralization (Jiang et al., 2014; Zhang et al., 2009; Chen et al., 2018). The Jining region is located within the northeastern WB close to the TNCO (Fig. 1A). The area contains units of the Paleoarchean Xinghe and Mesoarchean Jining and Wulashan groups, the early Permian Zahuaigou Formation, and other Mesozoic and

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Cenozoic rocks (Fig. 1B; IBGM, 1991; IMZM, 2012). The Dasuji porphyry Mo deposit is located close to the Daihai–Huangqihai Fault. The Jining region also contains numerous intrusions, including Mesoarchean granitoids that are dominated

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by tonalites, trondhjemites, and granodiorites (Yu et al., 2008; IMZM, 2012);

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Neoproterozoic granitoids consisting of biotite granite, rapakivi granite, and

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granodiorite intrusions (Wang et al., 2017); late Paleozoic intrusive granodiorite and

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monzogranites as well as minor gabbroic dikes (Nie et al., 2012); and Mesozoic granitoids that are dominated by alkali feldspar granites, porphyritic granites, and

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quartz porphyry intrusions (Chen et al., 2018).

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The Dasuji Mo deposit is located 26 km to the southeast of Zhuozi County and is located within garnet plagioclase gneisses of the Mesoarchean Jining Group (Fig. 1C).

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The area of and around the deposit contains Mesozoic intrusive rocks, including alkali

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feldspar granite, granite porphyry, and quartz porphyry intrusions as well as minor diabase and diorite porphyrite dikes. The Mesozoic granites are the main host of the

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Mo mineralization at this area. Chen et al. (2018) reported zircon U–Pb ages of 227.6

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± 1.5 Ma, 225.7 ± 1.5 Ma, 224.3 ± 1.8 Ma for alkali feldspar granite, granite porphyry, and quartz porphyry, and all of them are syn-mineralization granites. Although the geochronological data cannot be used to determine the order of emplacement of these bodies considering the uncertainties, Chen et al. (2018) proposed that the alkali feldspar granite was emplaced first and followed by the two porphyries based on the cross-cutting relationships and geochemical characteristics. The molybdenite Re–Os

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isochron age of 223.9 ± 1.5 Ma (Chen et al., 2018) suggest that Mo mineralization was synchronous, and genetically more closed related to the emplacement of two porphyries. The barren granite porphyry (Fig. 2A) is a post-mineralization granite

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(203.0 ± 4.4 Ma; Chen et al., 2018). The Mo orebodies within the Dasuji deposit do

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not crop out, but instead are lenticular (Fig. 2) and host mineralization that is

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dominantly present as veins and stockworks (Fig. 3), with minor amounts of

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brecciated and disseminated mineralization. The deposit contains molybdenite and pyrite and minor amounts of magnetite, rutile, galena, sphalerite, and chalcopyrite

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(Fig. 4) that are hosted within dominated gangue minerals of quartz, K-feldspar, and

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plagioclase. Minor amounts of sericite, kaolinite, fluorite, calcite, and epidote also exist. The Dasuji deposit is also characterized with well-developed hydrothermal

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alterations that can be divided into three zones based on field observation and

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microscopy work, namely, a deep intense K-feldspar alteration zone, a moderate- to shallow-depth sericite alteration zone, and a near-surface and peripheral fluorite and

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carbonate alteration zone (Fig. 2). Specific vein types developed in different alteration

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zone, and the altered mineral assemblages of each zone will be described in the next section.

Vein and mineral characteristics The veins within the Dasuji Mo deposit can be divided into four stages of development (Chen et al., 2019) based on morphology, structure, mineralogy,

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alteration halos, cross-cutting relationships, and modes of occurrence (Seedorff et al., 2005). Each of these stages of vein development has a different mineral assemblage (Fig. 5). Fluid inclusions are well developed in all vein types at Dasuji, and Wu et al.

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(2014) and Chen et al. (2019) selected the primary inclusions for microthermometry

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and get the result of homogenization temperatures decreasing from early to late stages,

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with stages 1–4 having homogenization temperatures of 468–375, 435–271, 318–206,

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and 222–142 °C, respectively. Stage 1 and 2 veins are also associated with significant silicification.

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Stage 1 veins, including K-feldspar–quartz (Vein 1.1; Fig. 3A) and barren quartz

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veins (Vein 1.2; Fig. 3B), usually occur in the deep and enveloped by potassic alteration (Fig. 2) containing K-feldspar, quartz, biotite, and minor sericite. Type 1.1

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veins are dominated by K-feldspar and quartz (Fig. 3A) and contain minor amounts of

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molybdenite (Fig. 4D), pyrite, magnetite, rutile, plagioclase, and biotite. Type 1.2 veins only a few millimeters wide and dominated by quartz and locally contain minor

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amounts of molybdenite (Fig. 3B), and they cut earlier Type 1.1 veins somewhere.

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And the Stage 1 veins are cut by later Type 2.1 veins. Stage 2 veins host the majority of Mo mineralization within the deposit and are

hosted by quartz porphyry, porphyritic granite, and alkali feldspar granite units. All Stage 2 veins are best developed at moderate to shallow depths and associated with intense sericite alteration and silicification. The veins are always bordered by quartz and sericite, and at places minor K-feldspar, sometimes a little calcite and chlorite.

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Four types of stage 2 veins are recognized: quartz–molybdenite veins (Vein 2.1; Fig. 3C), quartz–molybdenite stockworks (Vein 2.2; Fig. 3C–E), quartz–molybdenite– fluorite veins (Vein 2.3; Fig. 3E), and quartz–molybdenite–pyrite veins (Vein 2.4; Fig.

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3F). Although type 2.2 veins are much thinner (<5mm) than others, they are the

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dominant vein type at Dasuji and their alteration envelopes can reach up to 50 cm in

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width. Type 2.2 veins always cut the earlier Vein 2.1 (Fig. 3C), and it is also common

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for Vein 2.2 to be cut by the later Vein 2.3 (Fig. 3E) and Vein 2.4. All stage 2 veins are dominated by quartz and molybdenite (Fig. 4F–I). Type 2.3 and 2.4 veins contain

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minor amounts of fluorite, and type 2.4 veins contain more pyrite than the other stage

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2 veins. Type 2.1 (Fig. 4F) and 2.2 veins contain minor amounts of magnetite (Fig. 5), and rutile is present in all type stage 2 veins (Figs. 4E, I, 5). It should be noted that the

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magnetite within the syn-mineralization granites is usually euhedral (Fig. 4A),

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whereas the magnetite within the veins in the deposit in all cases has a xenomorphic structure and has margins that are uniformly replaced by molybdenite (Fig. 4F).

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Stage 3 veins are mainly developed in the shallow depths and periphery of the

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deposit, including quartz–carbonate–galena–pyrite (Vein 3.1; Fig. 3G) and quartz– pyrite–carbonate–fluorite (Vein 3.2; Fig. 3H) veins. The stage 3 is characterized by the appearance of lead-zinc mineralization, associating with carbonatization and fluorination different from the stage 2. Pyrite is the main sulfide mineral in these veins (Fig. 5). Type 3.1 veins are typical veins in stage 3 containing some galena (Fig. 4K) and minor amounts of sphalerite and chalcopyrite. Type 3.2 veins cut earlier vein

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types, and local fluorite is highly enriched (Fig. 3I). The final hydrothermal activity recorded within the Dasuji Mo deposit formed the stage 4 carbonate ± quartz veins (Fig. 3J), which are dominated by carbonates

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with minor amounts of quartz and rare accessory minerals (Fig. 5).

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Samples

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Sampling and analytical methods

The samples used for trace-element analysis during this study were collected

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from drillholes and exposures within open pits (Figs 1C, 2), and the details of sample

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locations are given in Table 1. During this study, trace-element compositions were determined for four magnetite samples collected from open-pit exposures and drill

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hole ZK111, five rutile samples collected from open-pit exposures and drill holes

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ZK105 and ZK111, eight molybdenite samples collected from the six different types of veins, and eight pyrite samples collected from a granite and the six different types

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of veins (Fig. 1C, 2A; Table 1). Thin-section preparation and mineral separation were

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undertaken at the Langfang Institute of Regional Investigation, Hebei Province, China. Trace-element analysis Mineral trace-element compositions were determined by LA–ICP–MS at the

Wuhan Sample Solution Analytical Technology Co., Ltd., Wuhan, China. Detailed operating conditions for the LA system and the ICP–MS instrument and the data reduction approaches used are given in Zong et al. (2017). Laser ablation was

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undertaken using a GeolasPro LA system consisting of a 193 nm COMPexPro 102 ArF excimer laser with a maximum energy setting of 200 mJ and a MicroLas optical system. This LA system was coupled to an Agilent 7700e ICP–MS instrument that

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was used to acquire ion-signal intensities. Helium was used as a carrier gas with argon

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used as a make-up gas that was mixed with the carrier gas via a T-connector before

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entering the ICP. A “wire” signal smoothing device is included within this LA system

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(Hu et al., 2015). The LA–ICP–MS analyses undertaken during this study used a 32m-diameter spot size and a laser frequency of 5 Hz. Magnetite and rutile trace-

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element compositions were calibrated using BHVO-2G, BCR-2G, and BIR-1G

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standards without internal standardization, whereas molybdenite and pyrite traceelement concentrations were calibrated using NIST 610 and NIST 612 standards

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without internal standardization (Liu et al., 2008). A USGS MASS-1 sulfide reference

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material was used to assess the accuracy of the calibration methods used for the unknowns analyzed during this study. Each analysis incorporated a background

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acquisition of approximately 20–30 s followed by 50 s of data acquisition from the

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sample. The Excel-based ICPMS Data Cal software package was used to perform the off-line selection and integration of background and analyzed signals and time-drift corrections as well as the quantitative calibration of trace-element analyses (Liu et al., 2008). The accuracy is generally better than 5–10% for most trace elements (Liu et al., 2008).

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Results Magnetite The concentrations of 38 trace elements (Al, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn,

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Ga, Ge, Y, Zr, Nb, Mo, Ag, Cd, Cs, Hf, Ta, W, Pb, Th, and 14 rare-earth elements

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(REEs)) were determined in magnetite by LA–ICP–MS during this study (Tables 2,

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S1). The granite-hosted (6 spots) and vein-hosted (4 spots) magnetites have similar

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concentrations of REEs as well as of some other elements (Table 2), and both types of magnetite share common “seagull”-shaped chondrite-normalized REE diagram

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patterns (Sun and McDonough, 1989; Fig. 6A) that are similar to the patterns of the

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Dasuji granites (Chen et al., 2018). The magnetites from the Dasuji deposit have elevated siderophile element concentrations relative to the lower crust (Taylor and

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Mclennan, 1985; Fig. 7A) and contain 1143–4598 ppm Ti, 958–3092 ppm V, 456–

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2045 ppm Cr, and 462–1419 ppm Mn. They also contain 589–2068 ppm Al, 362– 1458 ppm Ca, and 517 –2673 ppm Nb. These magnetites also contain 0.2–41 ppm Mo,

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0.06–3 ppm Cu, 0.02–687 ppm Pb, 108–853 ppm Zn, and 0.01–0.3 ppm Ag.

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Compared with the Dasuji granites (Chen et al., 2018), these magnetites contain more Nb, Ta, Ti, V, Cr, Co, Ni, and W (Fig. 7A), with all other elements being present in relatively low concentrations (Tables 2, S1). Rutile The concentrations of a total of 37 elements (the same suite as for magnetite barring Ti) within granite-hosted (4 spots) and vein-hosted (14 spots) rutile were

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determined during this study (Tables 2, S1). The rutile is similar to the magnetite from the study area in that both granite- and vein-hosted rutile have similar chondritenormalized REE diagram patterns (Sun and McDonough, 1989; Fig. 6B) and similar

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ranges in the concentrations of some other elements (Table 2). All of the rutile

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analyzed during this study contain elevated concentrations of Nb (7.7–14.2 wt.%) and

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Ta (0.4–1.1 wt.%) as well as the other high-field-strength elements (HFSEs),

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including 161–1055 ppm Zr, 17–126 ppm Hf, 0.1–288 ppm Y, and 0.3–176 ppm Ce, with heavy REE (HREE) values of 0.1–195 ppm. In comparison, the granite-

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hosted rutile contains 86.4–155 ppm Zr, 4.06–10.70 ppm Hf, 13.0–34.6 ppm Y, and

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21.7–186 Ce, and has HREE values of 6.13–15.41 ppm (Chen et al., 2018). The rutile therefore contains elevated concentrations of V, Mn, Zr, Nb, Hf, Ta, W, and

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HREEs relative to the lower crust (Taylor and McLennan, 1985) and the Dasuji

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granites (Fig. 7B; Chen et al., 2018), as well as 1–78 ppm Mo. Molybdenite

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Molybdenite within different veins in the deposit (Table 1) has highly variable

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metal concentrations (Tables 3, S1). All of the molybdenite analyzed during this study has chondrite-normalized REE diagram patterns with negative Eu anomalies (Fig. 6). The type 1.1 vein-hosted molybdenite has a “seagull" REE pattern that is similar to those of the Dasuji granites (Fig. 6C), whereas the other molybdenite patterns record weak REE fractionation (Fig. 6D, E). Compared with the lower crust (Taylor and McLennan, 1985), the molybdenite in the study area is enriched in Ag, Cd, W, Re, Bi,

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and Pb (Fig. 7C, D). The Re concentrations of molybdenite vary widely (0.0616– 29.04 ppm), and all of the molybdenite contains measurable concentrations of Cu (0.4418–76.58 ppm), Zn (0.1414–121.7 ppm), W (1.188–178.4 ppm), and Pb (10.96–

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315.2 ppm; Tables 3, S1).

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Pyrite

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Twenty three of the 36 pyrite spot analyses undertaken during this study yielded

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measurable concentrations of Mo (Table 4, S1). The majority of the pyrite from stage 3 veins have elevated concentrations of Mo (0.3643–22.38 ppm; Table 5) relative to

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the lower crust (Taylor and McLennan, 1985). Pyrite Pb concentrations vary over

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several orders of magnitude (0.0019–75.08 ppm), with pyrite from the granite and from type 3.1 veins containing much more Pb compared with other type of pyrite in

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the study area. The type 3.1 vein-hosted pyrite also contains high concentrations of

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Ag (0.9959–14.18 ppm; Fig. 7E, F). Both Co and Ni are the common trace elements in pyrites and their concentration range from 0.2 to 1637 ppm (Co) and from 0.05 to

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1544 ppm (Ni) (Tables 4, S1), most likely as a result of substitution of Fe into the

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pyrite lattice.

Discussion Ore-forming fluid sources Pyrite is an important mineral within the Dasuji deposit and is present in significant amount (Fig. 5). The Co and Ni contents of pyrite can provide insights into

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the processes involved in and the geological setting of pyrite formation (Bajwah et al., 1987; Bralia et al., 1979; Brill, 1989; Cook et al., 2009). The LA–ICP–MS analysis yield Co/Ni ratios of pyrite within the syn-mineralization granites, that represent the

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magmatic origin, in the study area range from 0.35 to 1.91 (average of 1.39; Fig. 8),

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and this pyrite contains 121–819 ppm Co and 97–1544 ppm Ni (Tables 4, S1). The

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pyrite within type 1.1 and 2.3–3.1 veins has Co/Ni ratios of 1.76–29.08 (average of

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9.90) with a value of 136.6 (Tables 4, S1). These pyrites also contain similar concentrations of Co (100.8–1174 ppm) but lower concentrations of Ni (7.37–289.5

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ppm) compared with the pyrite within the granite (Fig. 8). These values indicate that

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these pyrites have a hydrothermal origin, consistent with the results of the H and O isotopic analyses reported by Chen et al. (2019). In contrast, the pyrite within the type

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3.2 veins contains variable and lower concentrations of Co (0.24–155.0 ppm) and Ni

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(0.05–22.79 ppm) than the pyrite within other veins (Fig. 8). This Co and Ni depletion may relate to the addition of large amount of meteoric water to the system (Chen et al.,

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2019).

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Primary vein mineral assemblages The four stages of mineralization recorded within the Dasuji Mo deposit

generated nine different types of vein, each with distinctive mineral assemblages (Fig. 5). Wu et al. (2014) and Chen et al. (2019) suggested that the presence of magnetite in type 1.1, 2.1, and 2.2 veins indicates that high-oxygen-fugacity conditions prevailed during the formation of these veins. The origin of rutile in type 1.1 and stage 2 veins

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within the Dasuji deposit is also not clear. In situ analysis indicates that the granitehosted magnetite has very similar chondrite-normalized REE (Fig. 6A) and traceelement (Fig. 7A) diagram patterns to those of the hydrothermal-vein magnetite. In

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addition, the overall distribution patterns of elements within the magnetite (barring

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several siderophile elements) are similar to the distribution patterns of elements

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within the syn-mineralization Dasuji granites (Fig. 6A, 7A), suggesting a similar

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origin. The Ti concentrations of magnetite are interpreted to be controlled by formation temperatures (Nadoll et al., 2014; Van Baalen, 1993), whereas the

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concentrations of V within magnetite are controlled by fO2 conditions (Balan et al.,

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2006; Bordage et al., 2011; Sievwright et al., 2017). The fact that the two types of magnetite in the study area have similar Ti and V contents (Tables 2, S1) means that

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they were formed in a similar environment. All of the magnetite analyzed during this

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study plots in the porphyry field of a (Ti + V)–(Ca + Al + Mn) diagram (Dupuis and Beaudoin, 2011; Fig. 9A), indicating that the magnetite within the Dasuji area is

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related to porphyry-type mineralizing systems. The Cr and Ni concentrations of

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magnetite can be used to effectively discriminate between magmatic and hydrothermal magnetite, and all of our samples plot in the magmatic magnetite field (Dare et al. 2014; Fig. 9B). All of the magnetite from the study area also contains elevated concentrations of Ti, V, and Cr, all of which are indicative of a magmatic origin (Dare et al., 2014; Mollo et al., 2013; Nadoll et al., 2012, 2014). Finally, our samples have uniform Y/Ho and Nb/Ta values (Fig. 9C) that are indicative of a

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common origin (Jang and Naslund, 2003; Yaxley, 1998; Zheng et al., 2011). All of these data indicate that the vein-hosted magnetites all have a magmatic origin and were sourced from the surrounding granitic host rocks.

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Calc-alkaline porphyry-related systems rarely contain magmatic rutile (Williams

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and Cesbron, 1977). However, rutile is present within both the syn-mineralization

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granites and the mineralized veins in the Dasuji area. Rutile can form as a result of the

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dissolution of Ti-bearing minerals (biotite, ilmenite, titanite, and hornblende, among others) during hydrothermal alteration (Gerald et al., 1981; Keith, 2005; Lewis et al.,

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1975) or can crystallize directly from Ti-bearing hydrothermal systems (Williams and

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Cesbron, 1977). The Dasuji granites have A-type affinities and do not contain magmatic biotite or hornblende (Chen et al., 2018). These granites are also free of

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ilmenite and contain generally unaltered titanite. However, the Ti-rich magnetites

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within the granites (1143–4598 ppm; Tables 2, S1) may have provided a source of Ti to form the rutile in the study area (Fig. 4B). The fact that there is little rutile

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surrounding this magnetite and that the majority of the rutile in the study area is

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granular (Fig. 4B, E, F, I) both support the derivation of rutile from a Ti-bearing hydrothermal system, a process that is supported by the composition of the rutile in the study area. The rutile in the study area is compositionally uniform (Table 2, S1), although the vein-hosted rutile contains lower concentrations of REEs compared with the rutile within the syn-mineralization granites (Figs 6B, 7B). Both Y and Ho have similar ionic radii and electrovalencies, meaning that Y/Ho ratios in magmatic

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systems should remain stable unless the system has been disturbed by processes such as fluid migration (Yaxley, 1998; Zheng et al., 2011), and the same applies to Nb and Ta. The rutile within the study area has variable Y/Ho ratio values (Fig. 9C) that are

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suggestive of a hydrothermal origin. In addition, the rutile from the study area

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contains significant concentrations of Nb (8.1–14.2 wt.%) and Ta (0.4–1.1 w.t%)

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(Tables 2, S1), meaning that the variation in rutile Nb/Ta ratios is far lower than the

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Y/Ho variation (Fig. 9C). Ore-forming processes

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Type 1.1–2.3 veins contain molybdenite with Re contents (1–29 ppm) that are

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higher than those of the molybdenite within the type 2.4 veins (0.06–0.15 ppm; Tables 3, S1), recording changes in the sourcing of the ore-forming fluids (Berzina et al.,

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2005; Mao et al., 1999; Shirey and Walker, 1998; Voudouris et al., 2013). However,

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molybdenite Re contents can also be affected by temperature (Giles and Schiling, 1972; Ren et al., 2018; Todorov and Staikov, 1985) because more ReS2 can be

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dissolved in melts or fluids at higher temperatures (Xiong and Wood, 2002), leading

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to lower Re content in molybdenite at a higher temperature. The higher-temperature type 1.1 veins within the Dasuji deposit (390–460 °C; Chen et al., 2019) contain molybdenite with lower Re contents compared with the molybdenite of type 2.1–2.3 veins, suggesting the Re content in molybdenite controlled by temperature; whereas molybdenite from type 1.1 veins have higher lower Re contents than lowertemperature type 2.4 veins, implying that other factors besides temperature also play a

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role such as the composition of parent magmas themselves and/or fractionation, variations of physical and chemical conditions of crystallization (Berzina et al., 2005). The pyrite within the granites in the study area contains more Mo (3–22 ppm) than

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does the pyrite within the type 1.1–2.4 veins (Tables 4, S1). In addition, the pyrite

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within the type 3.1–3.2 veins contains less than 0.01 ppm Mo, indicating that the

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formation of the type 3.1 veins.

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majority of the Mo within the ore-forming fluids in this area precipitated before the

The W content of molybdenite is dominated by the volume of W available for

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mechanical mixing and the presence of W-bearing inclusions within molybdenite

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(Uzkut, 1974). The W content of molybdenite therefore reflects the abundance of W within associated magmatic systems. The chemical bonding of W is dependent on S/O

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activity ratios, with oxygen fugacity conditions controlling whether W forms oxide or

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sulfide bonds (Drábek, 1982). Ciobanu et al. (2013) reported W contents of 39–619 and 8–536 ppm in molybdenite from the Hilltop porphyry Au and Boddington Cu–Mo

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(Au) deposits in Western Australia, respectively, suggesting that W formed a

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predominantly isomorphous bond within molybdenite. Pašava et al. (2015) found that W concentrations of up to 5000 ppm within low-Re and inclusion-free molybdenite from the greisen-type W mineralization at Vítkov are also characterized by isomorphous structures. Pašava et al. (2016) reported that molybdenite within porphyry Cu–Mo–(Au) deposits in Uzbekistan contain W contents of 1–5471 ppm in the form of nanometer- to micrometer-scale inter-lamellar impurities and/or

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intergrowths of tungstenite with molybdenite. In the present study, the higher W values within the type 2.4 veins (25–138 ppm W; Fig. 10C) indicate that the W in the fluids that formed the Dasuji deposit decreased during stage 3 mineralization and may

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have formed minor amounts of W-bearing mineralization, consistent with the research

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undertaken by Chen et al. (2019). The decreasing W content of these fluids is likely to

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relate to a reduction in temperature (from 280–460 °C to 210–320 °C; Fig. 5) and

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variations in the oxygen fugacities of these fluids (Ren et al., 2018).

The porphyry Mo systems of western North America, northeastern China, and

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the eastern Qinling region of China are commonly associated with hydrothermal Pb–

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Zn deposits and paragenetic late Pb–Zn veins (e.g., Climax, Stein and Hannah, 1985; Daheishan, Liu et al., 2014; Shapinggou, Ren et al., 2018). Jones (1992) and Sillitoe

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(2010) suggested that porphyry mineralization is genetically related to base- and

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precious-metal skarn–hydrothermal veins as well as epithermal precious-metal deposits. The third stage of the genesis of the Dasuji deposit is associated with the

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formation of Pb–Zn mineralization. Molybdenite Pb (Fig. 10B) concentrations are

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negatively correlated with Re concentrations in a similar fashion to the data reported by Ciobanu et al. (2013) and Pašava et al. (2016) for global porphyry deposits. The similarity of the relationships of Pb to Re also suggests that the geochemical behavior of these elements is similar within the Dasuji system. The molybdenite within the type 2.4 veins contains higher concentrations of Pb and Zn compared with the earlierformed molybdenite (Fig. 10B, D), indicating that Pb and Zn started to deposit during

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the end of mineralization stage 2. The pyrite within the type 3.1 veins also contain the highest Pb and Zn concentrations of any pyrite analyzed during this study (Fig. 11B, C), suggesting that this Pb–Zn mineralizing event, which is associated with the

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formation of galena (Fig. 4K) and sphalerite, led to a rapid decrease in Pb and Zn

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concentrations within the stage 3 fluids (Chen et al., 2019). The type 3.1 veins also

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contain only small amounts of exsolution of chalcopyrite in sphalerite (Chen et al.,

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2019). Molybdenite and pyrite within type 2.4 and 3.1 veins, respectively, contain the most Cu of any molybdenite and pyrite analyzed during this study, with these Cu

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concentrations being positively correlated with Zn (Figs 10D, 11B). The precipitation

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of Pb–Zn–Cu minerals within the type 3.1 veins most likely reflects the addition of meteoric water to the system, which is proposed by Chen et al, (2019) based on the

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evidence of H–O isotopes and fluid inclusion composition. Ciobanu et al. (2013)

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suggested that porphyry Mo deposits containing Pb–Zn minerals have Pb + Zn values (241–1260 ppm) that are higher than those of porphyry Mo–(Cu) deposits with no

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Pb–Zn minerals (148–239 ppm). The molybdenite within the Dasuji deposit has Pb +

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Zn values of 11–430 ppm (average of 122 ppm; Table S1), which are a little lower than the values of other porphyry Mo deposits that contain Pb–Zn minerals (Ciobanu et al., 2013). These lower molybdenite Pb + Zn values may reflect (1) the low abundances of Pb–Zn minerals within the deposit or (2) the fact that molybdenite formed much earlier than the Pb–Zn minerals within the deposit. The pyrite within the deposit also contains low concentrations of Ag (<1 ppm) barring the pyrite within

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type 3.1 veins (1–14 ppm; Tables 4, S1), which contain Ag concentrations that are positively correlated with Pb (Fig. 11C). Metallogenic model

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Seedorff and Einaudi (2004a, b) used evolutionary tree diagrams to illustrate the

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spatial and temporal linkages that define the evolution of mineralizing systems.

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Constructing this type of space–time diagram (Fig. 12) for the Dasuji deposit

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illustrates element migration, mineral assemblages, and alteration zones along a vertical line in the center of the hydrothermal system during the entirety of the

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magmatic–hydrothermal processes that formed the deposit. The syn-mineralization

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Dasuji granites were emplaced at 227.6–224.3 Ma, slightly earlier than the formation of the Mo mineralization in this area at 223.9 ± 1.5 Ma (Chen et al., 2018). Primary

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ore-forming fluids were exsolved from these granites during mineralization stage 1,

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yielding fluid inclusions that homogenize at temperatures of up to 470 °C (Chen et al., 2019). These fluids carried Na, K, Mn, Fe, Mo, Pb, Zn, Cu, Ti, Ca, Cl, F, and S ions

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that caused deep and intense potassic alteration (Fig. 2) and the formation of K-

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feldspar–quartz and barren quartz veins with potassic halos, both of which are associated with the deposition of minor amounts of molybdenite. The second stage of mineralization was associated with the deposition of the majority of the Mo within the deposit from fluids at temperatures of 300–400 °C (Chen et al., 2019; Wu et al., 2014). Compared with stage 1 fluids, the stage 2 fluids contained less Mo, K, W, and HREEs, and more F and were associated with widespread silicification and sericite alteration

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and the precipitation of molybdenite within quartz–molybdenite veins and stockworks, quartz–molybdenite–fluorite veins, and quartz–molybdenite–pyrite veins. The third stage of mineralization involved the incorporation of meteoric water into the

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magmatic–hydrothermal system, leading to a drop in temperature to 210–320 °C and

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the development of carbonatization and fluorination (Chen et al., 2019; Wu et al.,

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2014). The majority of the Pb, Zn, and Cu mineralization within the deposit was

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deposited within type 3.1 veins, with these Pb–Zn–Cu veins developing distally around the main Mo orebody. The stage 4 mineralizing fluids were dominated by

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meteoric water, contained only rare ore minerals, and yielded fluid inclusions that

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Conclusion

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homogenize at temperatures of 140–220 °C (Chen et al., 2019; Wu et al., 2014).

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(1) The Dasuji mineral deposit records four metallogenic stages associated with the development of nine different types of vein. The deposit is also associated with

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silicic–potassic, silicic–sericite, fluorite, and carbonate types of alteration.

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(2) The magnetite within the hydrothermal veins in the deposit was derived from

the surrounding syn-mineralization granites, indicating that the hydrothermal systems that formed the deposit were active under low oxygen fugacity conditions. (3) The Pb, Zn, and Cu within the deposit initially began to be precipitated during the formation of the type 2.4 veins, with the majority of these metals being deposited within type 3.1 veins that were formed as a result of the incorporation of

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meteoric water into the mineralizing system.

Acknowledgments

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This work was financially supported by the National Natural Science Foundation of

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China (Grant No. 41390443), the National Key Research and Development Program

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of China (Grant No.2017YFC0601306), and State Key Laboratory of Lithospheric

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Evolution (S201605). We are grateful to Dr. Lingli Zhou, Prof. Guang Wu, Prof.

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Huaiyu He, and one anonymous reviewer for constructive suggestions.

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Figure Captions

Figure 1. A. The tectonic characteristics and distribution of major Mo deposits in

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north margin of NCC (after Zhao et al., 2005; Jiang et al., 2014; Wang et al., 2017;

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Chen et al., 2019). B. Sketch geological map of the Jining area, Inner Mongolia

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(modified after Nie et al., 2012; Chen et al., 2019). C. Geological map of the Dasuji

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deposit (modified after IMZM, 2012). Porphyry Mo (Cu) deposit on north margin of NCC: 1–Caosiyao, 2–Dazhuangke, 3–Sadaigoumen, 4–Dacaoping, 5–yangjiazhangzi, 7–Xiaojiayingzi,

8–Baituyingzi,

9–Kulitu,

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6–Lanjiagou,

10–Jiguanshan,

11–

Chamuhan,

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Yuanbaoshan, 12–Nianzigou, 13–Chehugou, 14–Xiaodonggou, 15–Hongshanzi, 16– 17–Nailinggou,

18–Hashitu,

19–Yangchang,

20–Banlashan,

21–

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Laojiagou, 22–Haolibao, 23–Aolunhua, 24–Chaganhua, 25–Chagande’ersi, 26–

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Zhunsujihua, 27–Wurinitu, 28–Wulandele, 29–Diyanqin’amu.

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Figure 2. Geological cross sections along (A) No. 1 and (B) No. 13 exploration lines

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of the Dasuji deposit (modified after IMZM, 2012).

Figure 3. Vein types from Dasuji: A. K-feldspar–quartz vein (Vein 1.1) from Stage 1; B. barren quartz vein (Vein 1.2) with potassic alteration zoon from Stage 1; C. quartz–molybdenite vein (Vein 2.1) cut by quartz–molybdenite stockwork (Vein 2.2) from Stage 2; D. quartz–molybdenite stockwork (Vein 2.2) from Stage 2; E. quartz–

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molybdenite–fluorite vein (Vein 2.3) cutting quartz–molybdenite stockwork (Vein 2.2) from Stage 2; F. quartz–molybdenite–pyrite vein (Vein 2.4) from Stage 2; G. quartz– carbonate–galena–pyrite vein (Vein 3.1) from Stage 3; H. quartz–pyrite–car–fl vein

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(Vein 3.2) from Stage 3 and cut the earlier quartz–molybdenite veins; I.. local highly

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enriched fluorite vein (Vein 3.2) from Stage 3 and cut earlier quartz–molybdenite

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veins; J. carbonate±quartz vein from Stage 4.

Figure 4. Microscopic photographs of ore minerals from Dasuji: A. magnetite from

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granite; B. rutile from granite; C. pyrite from granite; D. molybdenite in Vein 1.1; E.

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granular rutile in Vein 2.1; F. molybdenite replacing magnetite along the margin in Vein 2.1; G. molybdenite in Vein 2.2; H. molybdenite in Vein 2.3; I. molybdenite,

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pyrite and rutile in Vein 2.4; J. molybdenite replacing pyrite along the margin in Vein

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3.1; K. galena and pyrite in Vein 3.2; L. pyrite in Vein 3.3.

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Figure 5. Minerals paragenetic sequence for the Dasuji porphyry Mo deposit.

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*Homogenization temperatures are from Chen et al. (2019).

Figure 6. Chondrite-normalized REE patterns for the minerals from Dasuji deposit. A. magnetite; B. rutile; C. molybdenite in Vein 1.1 and 2.1; D. molybdenite in Vein 2.2 and 2.3; E. molybdenite in Vein 2.4 and 3.1; F. average values of molybdenite in all veins; G. pyrite in granite and Vein 2.4; H. pyrite in Vein 3.1–3.3. The normalizing

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values of chondrite are from Sun and McDonough (1989), and the whole-rock data are from Chen et al. (2018).

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Figure 7. Lower crust-normalized trace element spider diagrams for the minerals from

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Dasuji deposit. A. magnetite in granite and veins; B. rutile in granite and veins; C.

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molybdenite in different veins; D. average values of molybdenite in different veins; E.

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pyrite in granite and different veins; F. average values of pyrite in granite and different veins. The normalizing values of lower crust are from Taylor and Mclennan

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(1985), and the whole-rock data are from Chen et al. (2018).

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Figure 8. Diagram of Ni vs. Co in pyrite from Dasuji deposit.

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Figure 9. A. Diagram of (Ti+V) vs. (Ca+Al+Mn) in magnetite (after Dupuis and Beaudoin, 2011). B. Ni/Cr vs. Ti diagram in magnetite to discriminate magnetite from

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magmatic and hydrothermal environments (after Dare et al., 2014). C. Plot of Y/Ho vs.

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Nb/Ta in magnetite and rutile from Dasuji deposit. BIF: banded iron formation, Skarn: Fe–Cu skarn deposits, IOCG: iron oxide–copper–gold deposits, Porphyry: porphyry Cu (Mo) deposits, Kiruna: Kiruna apatite–magnetite deposits, Fe–Ti, V: magmatic Fe–Ti-oxide deposits.

Figure 10. Different inter-element correlations in the set of molybdenite samples from

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Dasuji deposit.

Figure 11. Different inter-element correlations in the set of pyrite samples from

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Dasuji deposit.

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fluids and formation of the multiple spatial zones.

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Figure 12. Simplified space-time diagram for Dasuji shows inferred flow paths of

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Table Captions

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Table 1. Detailed information of all samples in this study.

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Table 2. Summary of magnetite and rutile chemistry from different samples.

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Table 3. Summary of molybdenite chemistry from different samples.

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Table 4. Summary of pyrite chemistry from different samples.

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References Anderson, D.L., 2000. The statistics and distribution of helium in the mantle. Int. Geol. Rev. 42, 289–311.

F

Bajwah, Z.U., Seccombe, P.K., Offler, R., 1987. Trace element distribution, Co:Ni

O

ratios and genesis of the Big Cadia iron-copper deposit, New South Wales,

O

Australia. Miner. Deposita 22, 292–300.

PR

Balan, E., Villiers, J.P.R.D., Eeckhout, S.G., Glatzel, P., Toplis, M.J., Fritsch, E., 2006. The oxidation state of vanadium in titanomagnetite from layered basic

E-

intrusions. Am. Mineral. 91(5–6), 953–956.

PR

Ballentine, C.J., Burgess, R., Marty, B., 2002. Tracing fluid origin, transport and interaction in the crust. Rev. Miner. Geochem. 47, 539–614.

AL

Berzina, A.P., Sotnikov, V.I., Economou-Eliopoulos, M., Eliopoulos, D.G., 2005.

R N

Distribution of rhenium in molybdenite from porphyry Cu–Mo and Mo–Cu deposits of Russia (Siberia) and Mongolia. Ore Geol. Rev. 26, 91–113.

U

Blevin, P.L., 2004. Redox and compositional parameters for interpreting the granitoid

JO

metallogeny of Eastern Australia: implications for gold-rich ore systems. Resour. Geol. 54(3), 241–252.

Bodnar, R.J., 1995. Fluid inclusion evidence for a magmatic source for metals in porphyry copper deposits, in Thompson, J. ed., Magmas, fluids, and ore deposits. Mineralogical Association of Canada Short Course 23, 139–152. Bordage, A., Balan, E., Villiers, J.P.R., Cromarty, R., Juhin, A., Carvallo, C., Calas,

JOURNAL PRE-PROOF

G., Sunder Raju, P.V., Glatzel, P., 2011. V oxidation state in Fe–Ti oxides by high-energy resolution fluorescence-detected x-ray absorption spectroscopy. Phys. Chem. Miner. 38(6), 449-458.

F

Bralia, A., Sabatini, G., Troja, F., 1979. A revaluation of the Co/Ni ratio in pyrite as

O

geochemical tool in ore genesis problems. Miner. Deposita 14, 353–374.

O

Brill, B.A., 1989. Trace-element contents and partitioning of elements in oreminerals

PR

from the CSA Cu–Pb–Zn deposit, Australia. Can. Mineral. 27, 263–274.

Geochemistry, 1–403.

E-

Burnard, P., 2012. The noble gases as geochemical tracers. Advances in Isotope

PR

Burnard, P.G., Hu, R.Z., Turner, G., Bi, X.W., 1999. Mantle, crustal and atmospheric noble gases in Ailaoshan gold deposits, Yunnan province, China. Geochim.

AL

Cosmochim. Acta 63, 1595–1604.

R N

Cai, M.H., Zhang, Z.G., Qu, W.J., Peng, Z.A., Zhang, S.Q., Xu, M., Chen, Y., Wang, X.B., 2011. Geological characteristics and Re–Os dating of the Chaganhua

U

molybdenum deposit in Urad Rear Banner, western Inner Mongolia. Acta Geosci.

JO

Sinica 32, 64–68 (in Chinese with English abstract).

Campbell, F.A., Ethier, V.G., 1984. Nickel and cobalt in pyrrhotite and pyrite from the Faro and Sullivan orebodies. Can. Mineral. 22, 503–506.

Čech, F., Riede,r M., Vrána, S., 1973. Drysdallite, MoSe2, a new mineral. Neues Jahrbuch Fur Mineralogie Monatshefte: 433–442. Chen, P.W., Zeng, Q.D., Wang, Y.B., Zhou, T.C., Yu, B., Chen, J.Q., 2018.

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Petrogenesis of the Dasuji porphyry Mo deposit at the northern margin of North China Craton: Constrains from geochronology, geochemistry and isotopes characteristics. Lithos 322, 87–103.

F

Chen, P.W., Zeng, Q.D., Zhou, T.C., Wang, Y.B., Yu, B., Chen, J.Q., 2019. Evolution

O

of fluids in the Dasuji porphyry Mo deposit on the northern margin of the North

PR

fluid inclusions. Ore Geol. Rev. 104, 26–45.

O

China Craton: Constraints from Microthermometric and LA-ICP-MS analyses of

Ciobanu, C.L., Cook, N.J., Kelson, C.R., Guerin, R., Kalleske, N., Danyushevsky,

E-

L.V., 2013. Trace element heterogeneity in molybdenite fingerprints stages of

PR

mineralization. Chem. Geol. 347, 175–189.

Cook, N.J., Ciobanu, C.L., Mao, J., 2009. Textural controls on gold distribution in

AL

As-free pyrite from the Dongping, Huangtuliang and Hougou gold deposits,

R N

North China Craton (Hebei Province, China). Chem. Geol. 264, 101–121. Cox, R.A., Bédard, L.P., Barnes, S.J., Constantin, M., 2007. Selenium Distribution in

U

Magmatic Sulfide Minerals. DIVEX Rapport Annuel 2007, Project SC 26,

JO

Québec, Canada, 11 pp.

Dare, S.A.S., Barnes, S.J., Beaudoin, G., Méric, J., Boutroy, E., Potvin-Doucet, C., 2014. Trace elements in magnetite as petrogenetic indicators. Miner. Deposita 49(7), 785–796. Ding, Z.J., Yao, S.Z., Liu, C.Q., 2003. The characteristics of exhalation-sedimentary deposit of donggouba polymetal deposit: evidence from ore' s ree composition.

JOURNAL PRE-PROOF

Acta Petrol. Sinica 19(4), 792–798 (in Chinese with Enhlish abstract). Drábek, M., 1982. The system Fe-Mo-S-O and its geologic applications. Econ. Geol. 77, 1053–1056.

F

Drábek, M., 1995. The Mo-Se-S and Mo-Te-S systems. Neues Jahrbuch Fur

O

Mineralogie Monatshefte 169, 255–263.

O

Dupuis, C., Beaudoin, G., 2011. Discriminant diagrams for iron oxide trace element

PR

fingerprinting of mineral deposit types. Miner. Deposita 46, 1–17.

Gao, J., Klemd, R., Zhu, M.T., Wang, X.S., Li, J.L., Wan, B., Xiao, W.J., Zeng, Q.D.,

E-

Shen, P., Sun, J.G., Qin, K.Z., Campos, E., 2018. Large-scale porphyry-type

PR

mineralization in the Central Asian metallogenic domain: a review. J. Asian Earth Sci. 165(1), 7–36.

AL

Gerald, K.C., 1981. Some geologic and potential resource aspects of rutile in

R N

porphyry copper deposits. Econ. Geol. 76, 2240–2256. Giles, D.L., Schiling, J.H., 1972. Variation in rhenium content of molybdenite. In:

U

24th International Geological Congress. Section 10. Geochemistry, Montreal,

JO

145–152.

Haas, J.R., Shock, E.L., Sassani, D.C., 1995. Rare earth elements in hydrothermal systems: estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures. Geochim. Cosmochim. Acta 59(21), 4329–4350. He, H.Y., Zhu, R.X., Saxton, J., 2011. Noble gas isotopes in corundum and peridotite

JOURNAL PRE-PROOF

xenoliths from the eastern North China Craton: implication for comprehensive refertilization of lithospheric mantle. Phys. Earth Planet. In. 189, 185–191. Heinrich, C.A., 2005. The physical and chemical evolution of low-salinity magmatic

F

fluids at the porphyry to epithermal transition: a thermodynamic study. Miner.

O

Deposita 39, 864–889.

PR

formation. Rev. Mineral. Geochem. 65, 363–387.

O

Heinrich, C.A., 2007. Fluid-fluid interactions in magmatic-hydrothermal ore

Hou, W.R., Nie, F.J., Xu, B., Li, W., Fan, Y.W., Zhao, C.R., 2010. Geological

E-

features and geodynamic background of the molybdenum polymetallic deposits

English abstract).

PR

in central-western Inner Mongolia. Geol. Explor. 46, 751–764 (in Chinese with

AL

Hu, R.Z., Bi, X.W., Jiang, G.H., Chen, H.W., Peng, J.T., Qi, Y.Q., Wu, L.Y., Wei,

R N

W.F., 2012. Mantle-derived noble gases in ore-forming fluids of the graniterelated Yaogangxian tungsten deposit, Southeastern China. Miner. Deposita 47,

U

623–632.

JO

Hu, Z.C., Zhang, W., Liu, Y.S., Gao, S., Li, M., Zong, K.Q., Chen, H.H., Hu, S.H., 2015. “Wave” signal smoothing and mercury removing device for laser ablation quadrupole and multiple collector ICP-MS analysis: application to lead isotope analysis. Anal. Chem. 87, 1152–1157. Huang, D.H., 2015. Discussion with Prof. Mao Jingwen on types, ore-forming material source of some deposits and geological significance of rhenium content

JOURNAL PRE-PROOF

in molybdenite. Geol. Rev. 61(5), 990–1000 (in Chinese with English abstract). Huang, F., Chen, Y.C., Wang, D.H., 2013. Research on Part of Typical Molybdenum Deposits of Mesozic in eastern China. Geological Publishing House, Beijing, pp.

F

1–272 (in Chinese).

O

Inguaggiato, C., Burbano, V., Rouwet, D., Garzón, G., 2017. Geochemical processes

O

assessed by rare earth elements fractionation at “laguna verde” acidic-sulphate

PR

crater lake (azufral volcano, colombia). Appl. Geochem. 79, 65–74.

Inner Mongolia Autonomous Region Bureau of Geology and Mineral Resource

E-

(IBGM) (1991) Regional Geology of Inner Mongolia Autonomous Region,

PR

Geological Publishing House, Beijing, 32–71 (in Chinese). Inner Mongolia Zhongxi Mining Limited Company (IMZM), 2012. Prospecting

AL

report of Dasuji Mo deposit at Zhuozi County, the Inner Mongolia Autonomous

R N

Region County (in Chinese).

Jahn, B.M., Wu, F., Chen, B., 2000. Granitoids of the Central Asian orogenic belt and

U

continental growth in the Phanerozoic: Transactions of the Royal Society of

JO

Edinburgh. Earth Sci. 91, 181–193.

Jaireth, S., Hoatson, D.M., Miezitis, Y., 2014. Geological setting and resources of the major rare-earth-element deposits in australia. Ore Geol. Rev. 62, 72–128.

Jang, Y.D., Naslund, H.R., 2003. Major and trace element variation in ilmenite in the skaergaard intrusion: petrologic implications. Chem. Geol. 193(1–2), 109–125. Jiang, S.H., Liang, Q.L., Bagas, L., 2014. Re–Os ages for molybdenum mineralization

JOURNAL PRE-PROOF

in the Fengning region of northern Hebei Province, China: new constraints on the timing of mineralization and geodynamic setting. J. Asian Earth Sci. 79, 873– 883.

F

Jones, B.K., 1992. Application of metal zoning to gold exploration in porphyry

O

copper systems. J. Geochem. Explor. 43, 127–155.

O

Keith, M.S., 2005. Rutile geochemistry as a guide to porphyry Cu-Au mineralization,

PR

Northparkes, New South Wales, Australia. Geochem. Explor. Environ. Anal. 5(3), 247–253.

E-

Kendrick, M.A., Burgess, R., Pattrick, R.A., Turner, G., 2001. Fluid inclusion noble

PR

gas and halogen evidence on the origin of Cu-porphyry mineralizing fluids. Geochim. Cosmochim. Acta 65, 2651–2668.

AL

Keppler, H., 1996. Constraints from partitioning experiments on the composition of

R N

subduction-zone fluids. Nature 380(9), 16320–16330. Klemm, L.M., Pettke, T., Heinrich, C.A., 2008. Fluid and source magma evolution of

U

the Questa porphyry Mo deposit, New Mexico, USA. Miner. Deposita 43(5),

JO

533–552.

Klemm, L.M., Pettke, T., Heinrich, C.A., Campos, E., 2007. Hydrothermal evolution of the El Teniente deposit, Chile: Porphyry Cu-Mo ore deposition from lowsalinity magmatic fluids. Econ. Geol. 102(6), 1021–1045. Kovalenker, V.A., Trubkin, N.V., Abramova, V.D., Plotinskaya, O.Y., Kiseleva, G.D., Borisovskii, S.E., Yazykova, Y.I., 2018. Typomorphic characteristics of

JOURNAL PRE-PROOF

molybdenite from the Bystrinsky Cu–Au porphyry–skarn deposit, eastern Transbaikal region, Russia. Geol. Ore Deposits 60(1), 62–81. Large, R.R., Halpin, J.A., Danyushevsky, L.V., Maslennikov, V.V., Bull, S.W., Long,

F

J.A., Gregory, D.D., Lounejeva, E., Lyons, T.W., Sack, P.J., McGoldrick, P.J.,

O

Calver, C.R., 2014. Trace element content of sedimentary pyrite as a new proxy

O

for deep-time ocean–atmosphere evolution. Earth Planet. Sci. Lett. 389, 209–220.

PR

Lewis, B.G., John, P.H., 1975. The porphyry copper deposit at El Salvador, Chile. Econ. Geol. 70, 857–912.

E-

Li, G., Hua, R., Zhang, W., Hu, D., Wei, X., Huang, X.E., Xie, L., Yao, J., Wang, X.,

PR

2011. He–Ar isotope composition of pyrite and Wolframite in the Tieshanlong Tungsten Deposit, Jiangxi, China: implications for fluid evolution. Resour. Geol.

AL

61, 356–366.

R N

Li, S., Chung, S.L., Wilde, S.A., Jahn, B.M., Xiao, W.J., Wang, T., Guo, Q.Q., 2017. Early-Middle Triassic high Sr/Y granitoids in the southern Central Asian

U

Orogenic Belt: Implications for ocean closure in accretionary orogens. J.

JO

Geophys. Res. 122(3), 2291–2309.

Li, Z.L., Hu, R.Z., Yang JS, Peng JT, Li XM, Bi XW (2007) He, Pb and S isotopic constraints on the relationship between the A-type Qitianling granite and the Furong tin deposit, Hunan Province, China. Lithos 97: 161–173. Liu, J., Mao, J.W., Wu, G., Wang, F., Luo, D.F., Hu, Y.Q., 2014. Fluid inclusions and H–O–S–Pb isotope systematics of the Chalukou giant porphyry Mo deposit,

JOURNAL PRE-PROOF

Heilongjiang Province, China. Ore Geol. Rev. 59, 83–96. Liu, Y.S., Gao, S., Hu, Z.C., Gao, C.G., Zong, K.Q., Wang, D.B., 2010. Continental and oceanic crust recycling-induced melt-peridotite interactions in the Trans-

F

North China Orogen: U-Pb dating, Hf isotopes and trace elements in zircons of

O

mantle xenoliths. J. Petrol. 510, 537–571.

O

Liu, Y.S., Hu, Z.C., Gao, S., Günther, D., Xu, J., Gao, C.G., Chen, H.H., 2008. In situ

PR

analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard. Chem. Geol. 257, 34–43.

E-

Loftus-Hills, G., Solomon, M., 1967. Cobalt, nickel and selenium in sulphides as

PR

indicators of ore genesis. Miner. Deposita 2, 228–242.

Mao, J.W., Zhang, Z.C., Zhang, Z.H., Du, A.D., 1999. Re–Os isotopic dating of

AL

molybdenites in the Xiaoliugou W(Mo) deposit in the northern Qilian mountains

R N

and its geological significance. Geochim. Cosmochim. Acta 63, 1815–1818. McCandless, T.E., Ruiz, J., Campbell, A.R., 1993. Rhenium behavior in molybdenite hypogene

and

near-surface

environments:

implications

for

Re–Os

U

in

JO

geochronology. Geochim. Cosmochim. Acta 57, 889–905.

Migdisov, A., Williams-jones, A.E., Brugger, J., Caporuscio, F.A., 2016. Hydrothermal transport, deposition, and fractionation of the ree: experimental data and thermodynamic calculations. Chem. Geol. 439, 13–42. Mollo, S., Putirka, K., Iezzi, G., Scarlato, P., 2013. The control of cooling rate on titanomagnetite composition: implications for a geospeedometry model

JOURNAL PRE-PROOF

applicable to alkaline rocks from mt. etna volcano. Contrib. Miner. Petrol. 165(3), 457–475. Nadoll, P., Angerer, T., Mauk, J.L., French, D., Walshe, J., 2014. The chemistry of

F

hydrothermal magnetite: a review. Ore Geol. Rev. 61, 1–32.

O

Nadoll, P., Mauk, J.L., Hayes, T.S., Koenig, A.E., Box, S.E., (2012) Geochemistry of

O

magnetite from hydrothermal ore deposits and host rocks of the Mesoproterozoic

PR

Belt Supergroup, United States. Economic Geology 107: 1275–1292.

Nie, F.J., Liu, Y.F., Zhao, Y.A., Cao, Y., 2012. Discovery of Dasuji and Caosiyao

E-

large-size Mo deposits in central Inner Mongolia and its geological significances.

PR

Miner. Deposits 31(4), 930–940 (in Chinese with English abstract). Oreskes, N., Einaudi, M.T., 1990. Origin of rare earth element-enriched hematite

AL

breccias at the Olympic Dam Cu-U-Au-Ag deposit, Ｒ oxby Downs, South

R N

Australia. Econ. Geol. 85(1), 1–28. Ozima, M., Podosek, F.A., 2001. Noble gas geochemistry. Cambridge University

U

Press (367 pp.).

JO

Pašava, J., Svojtka, M., Veselovský, F., Ďurišová, J., Ackerman, L., Pour, O., Drábek, M., Halodová, P., Haluzová, E., 2016. Laser ablation ICPMS study of trace element chemistry in molybdenite coupled with scanning electron microscopy (SEM) – an important tool for identification of different types of mineralization. Ore Geol. Rev. 72, 874–895. Pašava, J., Veselovský, F., Drábek, M., Svojtka, M., Pour, O., Klomínský, J., Škoda,

JOURNAL PRE-PROOF

R., Ďurišová, J., Ackerman, L., Halodová, P., Haluzová, E., 2015. Molybdenite– tungstenite association in the tungsten-bearing topaz greisen at Vítkov (Krkonoše-Jizera Crystalline complex, Bohemian Massif): indicator of changes

F

in physico-chemical conditions in mineralizing system. J. Geosci. 60, 149–161.

O

Pourtier, E., Devidal, J.L., Gibert, F., 2010. Solubility measurements of synthetic

O

neodymium monazite as a function of temperature at 2 kbars, and aqueous

Acta 74(6), 1872–1891.

PR

neodymium speciation in equilibrium with monazite. Geochim. Cosmochim.

PR

New York and London, pp. 766.

E-

Povarennykh, A.S., 1972. Crystal Chemical Classification of Minerals. Plenum Press,

Rabbia, O.M., Hernández, L.B., French, D.H., King, R.W., Ayers, J.C., 2009. The El

AL

Teniente porphyry Cu–Mo deposit from a hydrothermal rutile perspective. Miner

R N

Deposita 44(8), 849–866.

Ren, Z., Zhou, T.F., Hollings, P., White, N.C., Wang, F.Y., Yuan, F., 2018. Trace

U

element geochemistry of molybdenite from the Shapinggou super-large porphyry

JO

Mo deposit, China. Ore Geol. Rev. 95, 1049–1065.

Richter, L., Diamond, L.W., Atanasova, P., Banks, D.A., Gutzmer, J., 2018. Hydrothermal formation of heavy rare earth element (hree)–xenotime deposits at 100 °C in a sedimentary basin. Geology 46(3), 263–266. Sasmaz, A., Yavuz, F., Sagiroglu, A., Akgul, B., 2005. Geochemical patterns of the Akdagmadeni (Yozgat， Central Turkey) fluorite deposits and implications.

JOURNAL PRE-PROOF

J.Asian Earth Sci. 24(4), 469–479. Seedorff, E., Dilles, J.H., Proffett, J.M., Einaudi, M.T., Zurcher, L., Stavast, W.J.A., Johnson,

D.A.,

Barton,

M.D.,

2005.

Gustafson,

Porphyry

deposits:

F

Characteristics and origin of hypogene features. Econ. Geol. 100th A.V. 251–298.

O

Seedorff, E., Einaudi, M.T., 2004a. Henderson porphyry molybdenum system,

O

Colorado: I. Sequence and abundance of hydrothermal mineral assemblages,

PR

flow paths of evolving fluids, and evolutionary style. Econ. Geol. 99, 3–37. Seedorff, E., Einaudi, M.T., 2004b. Henderson porphyry molybdenum system,

E-

Colorado: II. Decoupling of introduction and deposition of metals during

PR

geochemical evolution of hydrothermal fluids. Econ. Geol. 99, 39–72. Sengör, A.M.C., Natal’in, B.A., Burtman, V.S., 1993. Evolution of the Altaid tectonic

AL

collage and Palaeozoic crustal growth in Eurasia. Nature 364, 299–307.

R N

Shirey, S.B., Walker, R.J., 1998. The Re–Os isotope system in cosmochemistry and high temperature geochemistry. Annual Review of Earth and Planetary Sciences

U

26, 423–500.

R.H.,

Wilkinson,

J.J.,

O’Neill,

H.St.C.,

Berry,

A.J.,

2017.

JO

Sievwright,

Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts. Contrib. Miner. Petrol. 172(8), 62.

Sillitoe, R.H., 1972. A plate tectonic model for the origin of porphyry copper deposits. Econ. Geol. 67, 184–197. Sillitoe, R.H., 2010. Porphyry copper systems. Econ. Geol. 105, 3–41.

JOURNAL PRE-PROOF

Sinclair, D.W., Jonasson, I.R., Kirkham, R.V., Soregaroli, A.E., 2009. Rhenium and Other Platinum-group Metals in Porphyry Deposits. Open File 6181. Geological Survey of Canada, Ottawa, Canada.

F

Sinclair, W., 2007. Porphyry deposits. Mineral Deposits of Canada: A Synthesis of

O

Major Deposit-Types, District Metallogeny, the Evolution of Geological

PR

Deposits Division, Special Publication 5: 223–243.

O

Provinces, and Exploration Methods. Geological Association of Canada, Mineral

systems. Geology 13, 469–474.

E-

Stein, H.J., Hannah, J.L., 1985. Movement and origin of ore fluids in Climax-type

PR

Stein, H.J., Markey, R.J., Morgan, J.W., Hannah, J.L., Schersten, A., 2001. The remarkable Re-Os chronometer in molybdenite: how and why it works. Terra

AL

Nova 13, 479–486.

R N

Š temprok, M., 1971. The iron-tungsten-sulfur system and its geological application. Miner. Deposita 6, 302–312.

U

Stuart, F.M., Burnard, P.G., Taylor, R.P., Turner, G., 1995. Resolving mantle and

JO

crustal contributions to ancient hydrothermal fluids: He–Ar isotopes in fluid inclusions from Dae Hwa W-Mo mineralisation, South Korea. Geochim. Cosmochim. Acta 59, 4663–4673.

Sun, S.S., McDonough, W.F., 1989. Chemical and isotopic systematics of oceanic basalt: implications for mantle composition and processes. Geological Society London Special Publication 42(1), 315–345.

JOURNAL PRE-PROOF

Sun, X.M., Zhang, Y., Xiong, D.X., Sun, W.D., Shi, G.Y., Zhai, W., Wang, S.W., 2009. Crust and mantle contributions to gold-forming process at the Daping deposit, Ailaoshan gold belt, Yunnan, China. Ore Geol. Rev. 36, 235–249.

F

Sun, Y., Liu, J.M., Zeng, Q.D., Chu, S.X., Zhou, L.L., Wu, G.B., Gao, Y.Y., Shen,

O

W.J., 2013. Geological characteristics and molybdenite Re-Os ages of the

O

Baituyingzi Mo-Cu field, eastern Inner Mongolia and their geological

PR

implications. Acta Petrol. Sin. 29(1), 241–254 (in Chinese with English abstract). Taylor, S.R., Mclennan, S.M., 1985. The Continental Crust: its composition and

E-

evolution. London: Blackwell, 57–72.

PR

Thomas, H.V., Large, R.R., Bull, S.W., Maslennikov, V., Berry, R.F., Fraser, R., Froud, S., Moye, R., 2011. Pyrite and pyrrhotite textures and composition in

AL

sediments, laminated quartz veins, and reefs at Bendigo Gold Mine, Australia:

R N

insights for ore genesis. Econ. Geol. 106, 1–31. Todorov, T., Staikov, M., 1985. Rhenium content in molybdenite from ore

U

mineralizations in Bulgaria. Geol. Balc. 15(6), 45–58.

JO

Turner, G., Burnard, P.B., Ford, J.L., Gilmour, J.D., Lyon, I.C., Stuart, F.M., 1993. Tracing fluid sources and interaction: discussion. Philos. Trans. Phys. Sci. Eng. 344, 127–140.

Turner, G., Stuart, F.M., 1992. Helium/heat ratios and deposition temperatures of sulphides from the ocean floor. Nature 357, 581–583 Ulrich, T., Günther, D., Heinrich, C.A., 2002. The evolution of a porphyry Cu–Au

JOURNAL PRE-PROOF

deposit, based on LA-ICP-MS analysis of fluid inclusions: Bajo de la Alumbrera, Argentina. Econ. Geol. 97, 1889–1920. Uzkut, I., 1974. Zur Geochemie de Molybdans. Gebruder Borntraeger, Berlin, pp. 226.

F

Van Baalen, M.R., 1993. Titanium mobility in metamorphic systems; a review. Chem.

O

Geol. 110(1–3), 233–249.

O

Voudouris, P., Melfos, V., Spry, P.G., Bindi, L., Moritz, R., Ortelli, M., Kartal, T.,

PR

2013. Extremely Re-rich molybdenite from porphyry Cu-Mo-Au prospects in Northeastern Greece: mode of occurrence, causes of enrichment, and

E-

implications for gold exploration. Minerals 3, 165–191.

PR

Wang, G.R., Wu, G., Xu, L.Q., Li, X.Z., Zhang, T., Quan, Z.X., Wu, H., Li, T.G., Liu, J., Chen, Y.C., 2017. Molybdenite Re-Os age, H-O-C-S-Pb isotopes, and fluid

AL

inclusion study of the Caosiyao porphyry Mo deposit in Inner Mongolia, China.

R N

Ore Geol. Rev. 81, 728–744.

Wang, L.Q., Tang, J.X., Wang, D.H., Luo, M.C., Chen, W., Huang, F., 2012. Rare

U

earth element and trace element teatures of molybdenite in Bangpu Mo (Cu)

JO

deposit, Maizhokuanggar, Xizang (Tibet), and their constrains on the nature of the ore-forming fluid. Geol. Rev. 58(5), 887–892 (in Chinese with English abstract).

Williams, S.A., Cesbron, F.P., 1977. Rutile and apatite: useful prospecting guides for porphyry copper deposits. Mineral. Mag. 41, 288–292. Williams-Jones, A.E., Heinrich, C.A., 2005. Vapor transport of metals and the

JOURNAL PRE-PROOF

formation of magmatic-hydrothermal ore deposits. Econ.c Geol. 100th A.V. 1287–1312. Williams-Jones, A.E., Migdisov, A.A., Samson, I.M., 2012. Hydrothermal

F

mobilisation of the rare earth elements: A tale of "Ceria" and "Yttria". Elements

O

8(5), 355–360.

O

Williams-Jones, A.E., Samson, I.M., Olivo, G.R., 2000. The genesis of hydrothermal

PR

fluorite REE deposits in the Gallinas Mountains, New Mexico. Econ. Geol. 95(2), 327–341.

E-

Winderbaum, L., Ciobanu, C.L., Cook, N.J., Paul, M., Metcalfe, A., Gilbert, S., 2012.

Geosci. 44, 823–842.

PR

Multivariate analysis of a LA–ICP-MS trace element dataset for pyrite. Math.

AL

Windley, B.F., Alexeiev, D., Xiao, W., Kröner, A., Badarch, G., 2007. Tectonic

R N

models for accretion of the Central Asian Orogenic Belt. J. Geol. Soc. 164, 31– 47.

U

Wu, G., Li, X.Z., Xu, L.Q., Wang, G.R., Liu, J., Zhang, T., Quan, Z.X., Wu, H., Li,

JO

T.G., Zeng, Q.T., Chen, Y.C., 2017. Age, geochemistry, and Sr-Nd-Hf-Pb isotopes of the Caosiyao porphyry Mo deposit in Inner Mongolia, China. Ore Geol. Rev. 81, 706–727.

Wu, H., Wu, G., Tao, H., Wang, G.R., Li, T.G., Chen, J.Q., Yang, N.N., 2014. Molybdenite Re-Os dating and fluid inclusion study of Dasuji porphyry molybdenum deposit in Zhuozi County, central Inner Mongolia. Miner. Deposit

JOURNAL PRE-PROOF

33(6), 1251–1267 (in Chinese with English abstract). Wu, L.Y., Hu, R.Z., Peng, J.T., Bi, X.W., Jiang, G.H., Chen, H.W., Wang, Q.Y., Liu, Y.Y., 2011. He and Ar isotopic compositions and genetic implications for the

F

giant Shizhuyuan W–Sn–Bi–Mo deposit, Hunan Province, South China. Int.

O

Geol. Rev. 53, 677–690.

O

Xiao, W.J., Windley, B.F., Han, C.M., Liu, W., Wan, B., Zhang, J.E., Ao, S.J., Zhang,

PR

Z.Y., Song, D.F., 2018. Late Paleozoic to early Triassic multiple roll-back and oroclinal bending of the Mongolia collage in Central Asia. Earth-Sci. Rev. 186,

E-

94–128.

PR

Xiao, W.J., Windley, B.F., Hao, J., Zhai, M.G., 2003. Accretion leading to collision and the Permian Solonker suture, Inner Mongolia, China, termination of the

AL

Central Asian Orogenic Belt. Tectonics 22(6), 8-1–8-20.

R N

Xiong, Y., Wood, S., 2002. Experimental determination of the hydrothermal solubility of ReS2 and the Re–ReO2 buffer assemblage and transport of rhenium

U

under supercritical conditions. Geochem. Trans. 3, 1–10.

JO

Xu, L.L., Bi, X.W., Hu, R.Z., Tang, Y.Y., Jiang, G.H., Qi, Y.Q., 2014. Origin of the oreforming fluids of the Tongchang porphyry Cu-Mo deposit in the JinshajiangRed River alkaline igneous belt, SW China: constraints from He, Ar and S isotopes. J. Asian Earth Sci. 79, 884–894. Yaxley, G.M., Green, D.H., Kamenetsky, V., 1998. Carbonatite metasomatism in the southeastern Australian lithosphere. J. Petrol. 39(11–12), 1917–1930.

JOURNAL PRE-PROOF

Yu, X.Q., Chen, W., Li, W., 2008. Discovery and prospecting significace of Dasuji porphyry molybdenum deposit, Inner Mongolia. Geol. Pros. 44(2): 29–37 (in Chinese with English abstract).

F

Zeng, Q.D., Guo, W.K., He, H.Y., Zhou, L.L., Cheng, G.H., Su, F., Wang, Y.B.,

O

Wang, R.L., 2018. He, Ar, and S isotopic compositions and origin of giant

O

porphyry Mo deposits in the Lesser Xing’an Range–Zhangguangcai Range

PR

metallogenic belt, northeast China. J. Asian Earth Sci. 165(1), 285–240. Zeng, Q.D., Liu, J.M., Chu, S.X., Fu, G.L., Yu, W.B., Li, Z.M., Gao, Y.Y., Li, Y.J.,

E-

Sun, Y., Zhou, L.L., Duan, X.X., Zhang, S., Wang, Y.B., 2011. Mesozoic

PR

granitic magmatism and molybdenum ore-forming processes in the Xilamulun metallogenic belt. J. Jilin Univ. (Earth Sci. Ed.) 41(6), 1705–1725 (in Chinese

AL

with English abstract).

R N

Zeng, Q.D., Liu, J.M., Qin, K.Z., Fan, H.R., Chu, S.X., Wang, Y.B., Zhou, L.L., 2013. Types, characteristics, and time–space distribution of molybdenum deposits in

U

China: Int. Geol. Rev. 55(11), 1311–1358.

JO

Zeng, Q.D., Liu, J.M., Xiao, W.J., Chu, S.X., Wang, Y.B., Duan, X.X., Sun, Y., Zhou, L.L., 2012. Mineralizing types, geological characteristics and geodynamic background of Triassic molybdenum deposits in the northern and southern margins of North China Craton. Acta Petrol. Sin. 28(2), 357–371 (in Chinese with English abstract). Zeng, Q.D., Liu, J.M., Zhang, Z.L., Chen, W.J., Qin, F., Zhang, R.B., Yu, W.B.,

JOURNAL PRE-PROOF

Zhang, X.H., Zhai, M.G., 2009. Mineralizing types, geological characteristics and

geodynamic

background

of

molybdenum

deposits

in

Xilamulun

molybdenum polymetal metallogenic belt on northern margin of North China

F

Craton. Acta Petrol. Sin. 25(5), 1225–1238 (in Chinese with English abstract).

O

Zhai, D., Liu, J.J., Ripley, E.M., Wang, J.P., 2015. Geochronological and He-Ar-S

PR

northeastern China. Lithos 213, 338–352.

O

isotopic constraints on the origin of the Sandaowanzi gold-telluride deposit,

Zhang, S.H., Zhao, Y., Davis, G.A., Ye, H., Wu, F., 2014. Temporal and spatial

E-

variations of Mesozoic magmatism and deformation in the North China Craton:

131(0), 49–87.

PR

Implications for lithospheric thinning and decratonization. Earth-Sci. Rev.

AL

Zhang, T., Chen, Z.Y., Xu, L.Q., Chen, Z.H., 2009. The Re-Os isotopic dating of

R N

molybdenite from the Dasuji molybdunum deposit in Zhuozi County of Inner Mongolia and its geological significance. Rock Miner. Anal. 28(3), 279–282 (in

U

Chinese with English abstract).

JO

Zhang, Y., Ma, Y.B., Zhang, T., Zhang, Z.J., Ding, J.H., Li, C., 2019. Geochronology and geochemistry of the Dasuji Mo deposit in the northern margin of the North China Block: Implications for ore genesis and tectonic setting. Ore Geol. Rev. 104, 101–113. Zhao, G.C., Sun, M., Wilde, S.A., Li, S.Z., 2005. Late Archean to Paleoproterozoic evolution of the North China Craton: Key issues revisited. Precambr. Res. 136,

JOURNAL PRE-PROOF

177–202. Zheng, J., Yu, D., Wu, W., Yang, Z., Liu, Y., 2011. Typomorphic characteristics of arsenopyrite in the Bake Gold Deposit, eastern Guizhou Province. Geoscience

F

25(4), 750–758.

O

Zong, K.Q., Klemd, R., Yuan, Y., He, Z.Y., Guo, J.L., Shi, X.L., Liu, Y.S., Hu, Z.C.,

O

Zhang, Z.M., 2017. The assembly of Rodinia: The correlation of early

PR

Neoproterozoic (ca. 900 Ma) high-grade metamorphism and continental arc formation in the southern Beishan Orogen, southern Central Asian Orogenic Belt

JO

U

R N

AL

PR

E-

(CAOB). Precambr. Res. 290, 32–48.

JOURNAL PRE-PROOF

Table 1. Detailed information of all samples in this study. Sample location

Sample description

Minerals*

Method

CC-54

Open pit: 1295m

Granite

Py

Trace elements

DSJ-35

Drill hole ZK105: 280m

Granite

Rut

Trace elements

DSJ-22

Drill hole ZK111: 370m

Vein 1.1: Qtz + Kfs

Mag, Rut, Mo

Trace elements

DSJ-77

Drill hole ZK1313: 615m

Vein 1.1: Qtz + Kfs

Py

Trace elements

CC-40

Open pit: 1295m

Vein 2.1: Qtz ± Mo

Mag, Rut, Mo

Trace elements

CC-25

Open pit: 1295m

Vein 2.2: Qtz + Mo stockwork

Mo

CC-28

Open pit: 1295m

Vein 2.3: Qtz + Mo ± Fl

Mo

CC-53

Open pit: 1295m

Granite, Vein 2.3: Qtz + Mo ± Fl

Mo, Mag

Trace elements

DSJ-27

Drill hole ZK111: 220m

Granite, Vein 2.3: Qtz + Mo ± Fl

Mag, Rut, Mo

Trace elements

DSJ-19

Drill hole ZK111: 180m

Vein 2.4: Qtz + Mo + Py

Rut, Mo, Py

Trace elements,

CC-21

Open pit: 1295m

Vein 2.4: Qtz + Mo + Py

Mo, Py

Trace elements

DSJ-109

Drill hole ZK1319: 310m

Vein 3.1: Qtz + Pb + Zn + Py

Py

Trace elements

CC-36

Open pit: 1295m

Granite, Vein 3.2: Qtz + Py+Car+Fl

Py

Trace elements

DSJ-39

Drill hole ZK115: 125m

Vein 3.2: Car + Qtz + Py

Py

Trace elements

F

Sample

Trace elements

O

O

PR

E-

Trace elements

JO

U

R N

AL

PR

*Minerals represent the kinds of mineral for analysis. Mag=magmatite, Rut=rutile, Mo=molybdenite, Py=pyrite.

JOURNAL PRE-PROOF

Table 2. Summary of magnetite and rutile chemistry from different samples Mag. (in Gra.)

Mag. (in veins)

Rut. (in Gra.)

Rut. (in veins)

Al (ppm)

589-2068

818-1655

1524-11957

479-3709

Ca

362-1458

686-1341

126-903

8-326

Ti

1143-4598

2730-2930

V

996-3092

958-1639

568-941

364-3774

Cr

456-1700

49-2045

37-57

1-240

Mn

462-1419

661-1355

701-31415

Co

25-37

6-52

0.11-0.16

Ni

24-117

7-45

0.49-1.23

0.3-2.1

Cu

0.1-1.9

0.06-3

2.0-3.5

1.6-11.6

Zn

108-367

186-853

18-69

5-112

Ga

3-24

4-38

5.7-19.9

4-15

Ge

7-16

7-20

1.7-3.5

1.1-3.1

Se

6-19

7-10

1.2-3.3

0.3-16

Y

0.7-18

5-19

17-288

0.1-60

Zr

12-102

5-166

161-637

282-1055

Nb

517-2673

820-1708

78295-134619

76753-142025

Mo

7-41

0.2-16.7

1-39

3-78

Ag

0.01-0.3

0.01-0.07

2.3-4.9

2.8-5.6

Cd

0.01-0.2

0.028-0.031

0.09-0.5

0.2-0.8

Cs

0.01-0.5

0.03-0.6

0.2-1.3

0.001-0.8

La

1-28

0.5-18

28-54

20-78

3-40

0.06-35

52-163

0.3-176

0.1-2.7

0.4-3.3

1.3-3.0

0.002-13

0.2-10

1-10

4-15

0.02-30

Pr

56-13614

O

0.1-0.9

O

PR

E-

PR

R N

Nd

AL

Ce

F

Sample*

0.02-2

0.04-1.5

1-9

0.01-4

Eu

0.004-0.6

0.04-0.3

0.1-1

0.001-0.2

Gd

0.03-3

0.3-1

1-14

0.01-5

Tb

0.01-0.4

0.002-0.3

0.4-4

0.003-1

Dy

0.07-3

0.2-3

3-33

0.001-10

Ho

0.02-0.9

0.08-0.9

0.6-9

0.002-3

Er

0.07-2

0.17-4

2-37

0.01-12

Tm

0.01-0.5

0.05-0.9

0.5-8

0.004-3

Yb

0.09-3

0.36-5

5-77

0.06-25

Lu

0.02-1.3

0.05-1.2

1-13

0.01-4.4

Hf

0.06-2.2

0.05-2.3

17-75

31-126

Ta

2-38

4-57

8851-11114

4280-11322

W

123-534

5-282

1088-14456

577-8778

Pb

78-200

0.02-687

8-122

0.01-100

Th

0.08-7.6

0.1-16

6-32

0.03-19

JO

U

Sm

*Magnetite in granite were selected from samples O-CC-53 and O-DSJ-27; magnetite in veins from O-DSJ-22 and

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

O-CC-40; rutile in granite from O-DSJ-35; rutile in veins from O-DSJ-22, O-CC-40, O-DSJ-27, and O-DSJ-18.

JOURNAL PRE-PROOF

Table 3. Summary of molybdenite chemistry from different samples Vein 1.1

Vein 2.1

Vein 2.2

Vein 2.3

Vein 2.4

Li (ppm)

0.04-0.3

0.01-0.9

1-62

0.02-1

0.03-1

Be

0.003-0.03

0.01-0.5

0.01-5

0.001-0.02

0.01-1

Sc

0.02-0.07

0.02-0.2

0.08-0.2

0.01-0.05

0.3-2

Ti

33-41

40-56

34-68

30-40

8-40

V

1.0-1.5

2.0-2.4

1-4

1-4

10-75

Cr

2-7

4-9

0.5-1.5

0.4-7

Mn

0.1-0.7

2-16

1-6

0.04-7

Fe

0.0003-0.6

0.05-0.09

0.03-0.2

0.004-0.03

0.1-1.2

Co

0.03-0.5

0.3-0.6

0.4-0.9

0.01-0.3

8-23

Ni

0.03-0.3

0.1-0.3

0.6-1.4

0.1-1

0.6-24

Cu

1.6-2.8

1-4

4-10

0.4-9

12-77

Zn

0.2-0.5

0.3-10

1-9

0.1-8

1-122

Ga

0.01-0.1

0.01-6

0.01-19

0.003-0.4

0.03-0.8

Ge

0.2-0.4

0.05-0.4

0.1-0.7

0.003-0.2

0.02-0.8

Se

15-23

14-17

9-16

5-30

3-11

Y

0.02-0.06

0.001-0.03

0.02-0.1

0.001-0.3

0.8-18

Zr

0.01-0.08

0.01-0.08

0.2-2

0.01-1

0.4-3

Nb

0.18-0.45

0.1-0.7

0.1-0.4

0.01-1

2-30

Ag

0.7-2.3

1.2-2.5

1.2-3.3

1-18

22-92

Cd

27-34

31-37

15-28

29-40

7-36

Sn

0.09-0.3

0.03-0.5

0.08-3

0.02-0.4

0.02-0.4

Cs

O

O

PR

E-

PR

1.1-60

2-10

0.01-0.2

0.06-1.5

0.27-0.44

0.02-4

0.01-1.3

0.1-0.3

0.02-0.5

0.1-2

0.001-0.4

0.03-0.5

1.3-2.6

0.3-1

0.1-3

0.04-1

3-35

2.6-5.3

0.2-1.3

0.4-5

0.08-3

9-47

Pr

0.12-0.22

0.01-0.14

0.04-0.4

0.01-0.3

0.9-4

Nd

0.11-0.69

0.02-0.17

0.1-1

0.04-0.8

3-16

Sm

0.01-0.2

0.01-0.03

0.02-0.2

0.01-0.2

0.6-3

Eu

0.001-0.008

0.0004-0.002

0.002-0.007

0.001-0.008

0.05-0.4

Gd

0.06-0.12

0.006-0.03

0.02-0.1

0.01-0.2

0.3-1.4

Tb

0.02-0.06

0.001-0.005

0.003-0.02

0.004-0.01

0.03-0.2

Dy

0.17-0.35

0.01-0.02

0.01-0.05

0.01-0.04

0.2-1

Ho

0.05-0.1

0.001-0.003

0.221-0.01

0.001-0.01

0.02-0.2

Er

0.01-0.28

0.002-0.01

0.003-0.02

0.001-0.03

0.05-0.4

Tm

0.001-0.06

0.0013-0.0015

0.0006-0.002

0.001-0.004

0.005-0.24

Yb

0.09-0.2

0.005-0.008

0.004-0.014

0.003-0.02

0.04-0.4

Lu

0.01-0.1

0.0016-0.002

0.0005-0.002

0.0005-0.002

0.005-0.05

Hf

0.007-0.009

0.004-0.03

0.02-0.09

0.003-0.08

0.03-0.1

Ta

0.02-0.03

0.03-0.09

0.002-0.03

0.002-0.02

0.002-0.1

W

11-17

2-20

6-33

1-47

25-138

U

Ce

JO

R N

La

AL

Sb

F

Sample*

JOURNAL PRE-PROOF Re

1-5

6-24

2-7

1-29

0.06-0.15

Bi

0.3-1.4

0.1-4.2

7-19

0.03-29

19-108

Table 3. (continued) Sample*

Vein 1.1

Vein 2.1

Vein 2.2

Vein 2.3

Vein 2.4

Pb

17-64

30-264

72-206

11-220

84-315

Th

0.002-0.005

0.001-0.02

0.01-0.9

0.001-1

8-21

F

*Molybdenite in vein 1.1 were selected from sample S-DSJ-22; those in vein 2.1 from S-CC-40; those in vein 2.2 from S-CC-25; those in vein 2.3 from S-CC-53-01, S-DSJ-27, and S-CC-28; those in vein 2.4 from S-DSJ-18 and

JO

U

R N

AL

PR

E-

PR

O

O

S-CC-21.

JOURNAL PRE-PROOF

Granite

Vein 1.1

Vein 2.4

Vein 3.1

Vein 3.2

Li (ppm)

0.03-0.3

0.01-0.1

0.001-0.09

0.01-0.2

0.001-0.1

Be

0.001-0.9

0.011-0.016

0.003-0.05

0.009-0.02

0.001-0.02

Sc

0.003-0.04

0.006-0.2

0.001-0.5

0.005-0.1

0.0003-0.05

Ti

13-54

12-14

5-16

13-17

13-17

V

0.03-0.1

0.005-0.07

0.006-0.3

0.04-0.2

0.005-0.07

Cr

0.2-1.6

0.3-0.9

0.2-1.3

0.6-2

Mn

0.4-9

0.4-0.9

0.1-5

0.1-1.4

Co

121-1637

552-1111

101-1007

123-1174

0.2-155

Ni

97-1544

50-131

7-290

13-248

0.05-23

Cu

1-47

0.01-0.08

0.02-15

0.6-3

0.005-0.1

Zn

0.1-2

0.3-1.4

0.02-1.2

1-3

0.04-0.6

Ga

0.01-0.5

0.001-0.09

0.001-0.1

0.006-0.2

0.0001-0.02

Ge

7.8-9.7

7.3-8.1

3.0-8.3

7.8-8.8

7.0-9.5

Se

2.8-8.1

0.9-7.9

0.3-14

0.2-13

1.6-12

Y

0.002-0.09

0.001-0.003

0.001-0.01

0.003-0.02

0.0001-0.0015

Zr

0.001-0.04

0.004-0.008

0.001-0.01

0.006-0.03

0.001-0.4

Nb

0.004-0.02

0.002-0.003

0.01-0.2

0.007-0.06

0.001-0.07

Mo

3-22

0.9-4

0.4-8

0.0002

0.0007-0.005

Ag

0.003-0.05

0.003-0.01

0.003-0.1

1-14

0.005-0.02

Cd

0.04-3

0.01-0.08

0.003-0.06

0.04-0.1

0.01-0.2

Sn

0.05-0.4

0.07-0.6

0.006-0.2

0.1-0.3

0.003-0.3

Cs

O

PR

E-

PR

0.1-2 0.2-1

0.01-0.8

0.01-0.02

0.003-2

0.008-0.03

0.001-0.03

0.03-0.2

0.06-0.1

0.001-0.1

0.05-0.2

0.01-0.2

0.2-5

0.05-0.09

0.005-2

0.0001-0.2

0.008-0.08

R N

La

AL

Sb

F

Sample*

O

Table 4. Summary of pyrite chemistry from different samples

0.5-11

0.1-0.4

0.03-1

0.002-0.1

0.01-0.2

Pr

0.001-0.6

0.01

0.001-0.04

0.05

0.001-0.007

Nd

0.02-3

-

0.0004-0.1

0.0002-0.009

0.006-0.02

Sm

0.01-0.7

0.006-0.03

0.003-0.04

0.01-0.06

0.001-0.05

Eu

0.006-0.09

0.005

0.0004-0.009

0.004-0.006

0.001-0.005

Gd

0.01-0.7

0.005-0.01

0.002-0.01

0.01-0.04

0.002-0.02

Tb

0.004-0.1

0.001

0.0004-0.004

0.002-0.003

0.001-0.002

Dy

0.002-0.8

-

0.001-0.02

0.005-0.02

0.003-0.008

Ho

0.002-0.1

0.002

0.0005-0.004

0.001-0.003

0.0009-0.002

Er

0.003-0.3

-

0.002-0.01

0.03

0.002-0.006

Tm

0.01-0.05

0.0001-0.002

0.001-0.002

0.002

0.0006-0.002

Yb

0.04-0.25

0.007

0.004-0.01

0.02

0.004-0.01

Lu

0.005-0.04

0.001-0.002

0.001-0.002

0.001-0.002

0.0006-0.0009

Hf

0.005-0.03

0.006-0.009

0.0005-0.03

0.01-0.02

0.003-0.009

Ta

0.002-0.008

0.001-0.002

0.0006-0.03

0.02

0.001-0.002

W

0.007-0.1

0.004-0.02

0.002-0.8

0.01-0.04

0.004-0.01

JO

U

Ce

JOURNAL PRE-PROOF

Table 4. (continued) Sample*

Granite

Vein 1.1

Vein 2.4

Vein 3.1

Vein 3.2

Re

0.001-0.2

0.001-0.02

0.002-0.02

0.003-0.03

0.005-0.02

Au

0.006-0.4

0.01-0.03

0.002-0.09

0.001-0.02

0.003-0.02

Pb

13-75

0.04-0.2

0.002-0.3

34-163

0.002-0.07

Th

0.001-0.02

0.002-0.003

0.001-0.03

0.001-0.008

0.0002-0.003

F

*Pyrite in granite were selected from sample S-CC-36 and S-CC-54; those in vein 1.1 from S-DSJ-77; those in vein 2.4 from S-DSJ-18 and S-CC-21; those in vein 3.1 from S-DSJ-109; those in vein 3.2 from S-DSJ-39 and S-

JO

U

R N

AL

PR

E-

PR

O

O

CC-36.

JOURNAL PRE-PROOF

Highlights 1. The Dasuji deposit records four metallogenic stages associated with nine different types of vein.

F

2. The magnetite within the hydrothermal veins was derived from the ore-related

O

granites.

JO

U

R N

AL

PR

E-

PR

O

3. The Pb, Zn, and Cu initially began to be precipitated during the end of Stage 2.

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF

JO

U

R N

AL

PR

E-

PR

O

O

F

JOURNAL PRE-PROOF