Apatite in granitoids related to polymetallic mineral deposits in southeastern Hunan Province, Shi–Hang zone, China: Implications for petrogenesis and metallogenesis

    Apatite in granitoids related to polymetallic mineral deposits in southeastern Hunan Province, Shi–Hang zone, China: implications for petrogenesis and metallogenesis Teng Ding, Dongsheng Ma, Jianjun Lu, Rongqing Zhang PII: DOI: Reference:

S0169-1368(15)00036-0 doi: 10.1016/j.oregeorev.2015.02.004 OREGEO 1441

To appear in:

Ore Geology Reviews

Received date: Revised date: Accepted date:

16 September 2014 3 February 2015 4 February 2015

Please cite this article as: Ding, Teng, Ma, Dongsheng, Lu, Jianjun, Zhang, Rongqing, Apatite in granitoids related to polymetallic mineral deposits in southeastern Hunan Province, Shi–Hang zone, China: implications for petrogenesis and metallogenesis, Ore Geology Reviews (2015), doi: 10.1016/j.oregeorev.2015.02.004

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ACCEPTED MANUSCRIPT Apatite in granitoids related to polymetallic mineral deposits in southeastern Hunan Province, Shi–Hang zone, China: implications

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Teng Ding, Dongsheng Ma*, Jianjun Lu, Rongqing Zhang

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for petrogenesis and metallogenesis

State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering,

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Nanjing University, Nanjing 210023, China

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Abstract The area of southeastern Hunan Province, China, located within the southwestern part of the Shi–Hang metallogenic zone, is characterized by abundant Cu–Pb–Zn, W, and Sn polymetallic ore deposits that are closely associated with coeval late Mesozoic granodiorite porphyries and biotite

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granites, respectively. Here, we present new major and trace element concentrations and 87Sr/86Sr ratios

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of apatites from six ore-bearing granitic rocks, as determined by electron microprobe, laser ablation–inductively coupled plasma–mass spectrometry, and thermal ionization mass spectrometer,

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which allow us to determine the main controls on the formation of these different types of mineralization and to explore how these controls are reflected in variations in apatite chemical and isotopic compositions. The apatite data indicate that granodiorite porphyry intrusions related to

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Cu–Pb–Zn mineralization are oxidized and formed as a result of slab dehydration, melting of the mantle wedge overlying a subducted slab, and the partial melting of crustal material. The release of abundant Cl- and H2O-rich fluids from the slab triggered mantle melting and the extraction of metals that were precipitated within the deposits. In comparison, granites related to W and Sn deposits are moderately oxidized to reduced, and were generated by the partial melting of crustal material with only limited input from mantle-derived magmas. Granites associated with the W and Sn mineralization formed in a intra-arc rifting-related tectonic environment. The fact that these numerous polymetallic ore deposits formed in the same area during two successive periods of mineralization, the first from 180 to 160 Ma and the second from 160 to 140 Ma, indicates that the tectonic environment of southeastern Hunan Province evolved from a continental arc associated with the subduction of the Paleo-Pacific Plate and the formation of Cu–Pb–Zn deposits to a later intra-arc rifting environment

ACCEPTED MANUSCRIPT associated with the formation of W and Sn deposits as a consequence of slab roll-back and mantle upwelling during the Late Jurassic. This study reveals that apatite compositions can be used as a proxy to reflect the differences between granitoids and their associated mineralization, and identify reginal

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metallogeny and tectonic evolution.

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Keywords: Polymetallic deposits, apatite, petrogensis and metallogenesis, tectonic evolution, southeastern Hunan Province.

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1. Introduction

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Apatite, Ca5(PO4)3(OH, F, Cl), is the most abundant accessory mineral within igneous rocks, primarily because it is stable in a wide variety of geological settings and over a range of different geological

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processes (Watson, 1980). A number of different elements can substitute into the structure of apatite,

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and this mineral can contain a number of trace elements by substitution in both anion and cation sites, including halogens (F, Cl), strontium (Sr), thorium (Th), and the rare earth elements (REEs). This

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means that apatite can be used as an indicator of planetary halogen compositions, and quantitative ion microprobe measurements of apatite from lunar basalts have shown that portions of the lunar mantle and/or crust are more volatile rich than previously thought (Boyce et al., 2010). Apatite has also been

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used to determine the characteristics of metamorphic fluids within the mantle. For example, O'Reilly and Griffen (2000) and Douce et al. (2011) classified apatite within Phanerozoic mantle material into “Apatite A” and “Apatite B” groups using halogen and other trace element abundances, with the former resulting from metasomatism by Cl-, CO2- and H2O-rich fluids, forming apatite with higher concentrations of Cl, CO2, Sr, and other trace elements compared with the latter (O'Reilly and Griffin, 2000; Douce et al., 2011). In addition, apatite can be used as a proxy to determine the petrogenetic evolution of granites, and significant amounts of research have been devoted to the use of apatite in granitic rocks to distinguish between S- and I-type granites (Sha and Chappell, 1999; Belousova et al., 2001; Chu et al., 2009). Other research has focused on using apatite 87Sr/86Sr ratios to approximate the initial 87Sr/86Sr ratio of the host rocks, primarily as Rb cannot easily substitute into the apatite lattice (Tsuboi and Suzuki, 2003; Tsuboi, 2005). Miles et al. (2014) also used the Mn contents of apatite to determine the oxidation state

ACCEPTED MANUSCRIPT of silicic magmas, yielding the following equation: logfO2 = − [0.0022 ± 0.0003]Mn – [9.75 ± 0.46], where Mn content is measured in ppm. However, with the exception of this research, little work has been undertaken on using the chemical composition of apatite within granitic rocks to determine the

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petrogenetic history of the intrusions and the association between granite magmatism and mineralization (Belousova et al., 2002; Cao et al., 2012).

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The geology of southeastern Hunan Province, within the southwestern Shi–Hang zone of southeastern China, is characterized by the occurrence of several polymetallic ore deposits, the majority of which formed during the late Mesozoic and are associated with coeval intrusive and

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volcanic rocks (Hua et al., 2007; Mao et al., 2007, 2013; Chen et al., 2008; Li et al., 2013a). Previous research suggests that the type of mineralization within granite-associated ore deposits is related to the

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source of the granitic magma, the oxidation state of granite, and the degree of fractional crystallization of the associated granite: Sn mineralization is usually linked with S-type granites that are reduced and

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have undergone fractional crystallization, Cu mineralization is usually associated with oxidized and

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intermediate I-type granites, and W mineralization has little correlation with the redox state of the affinity of the granite (Ishihara, 1977, 1981; Blevin and Chappell, 1992, 1995; Ballard et al., 2002).

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Because igneous rocks are the dominant source of metals and fluids within polymetallic skarn deposits (e.g., skarn Cu–Pb–Zn and W–Sn deposits; Meinert et al., 2005), research into mineralization-related granites is a necessary step to better understand the processes involved in the formation of these types

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of mineral deposits. Here, we present new chemical and isotopic analysis of apatite within granitic rocks from six polymetallic ore deposits, namely, granodiorite porphyries associated with skarn Cu–Pb–Zn deposits and biotite granites associated with skarn W and Sn deposits. These apatites were analyzed by electron microprobe, laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS), and thermal ionization mass spectrometer (TIMS), and the data obtained during this study allow us to answer the following questions: (1) Are the differences between these granitoids reflected by variations in apatite compositions? (2) How does the composition of apatite reflect the factors controlling the formation of the differing types of Cu–Pb–Zn, W, and Sn mineralization in the study area? and (3) Can apatite chemical compositions be used to identify changes in the regional metallogeny and provide information on the tectonic evolution of southeastern Hunan Province?

2. Geological background

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2.1 Tectonic setting Southeastern Hunan Province is located in the Cathaysia Block (Fig. 1a), which is thought to have

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amalgamated with the Yangtze Block during the ~970 Ma Jinning orogenic event (Li and McCulloch, 1996). The basement of the Cathaysia Block is dominated by Paleo- to Mesoproterozoic metamorphic

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rocks that are overlain by Neoproterozoic to Paleozoic continental and neritic marine sediments (Yuan et al., 1991; Wang et al., 2007; Jiang et al., 2009). The Cathaysia Block is characterized by the occurrence of intensive Mesozoic magmatism from the Jurassic to the Cretaceous, which formed a

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distinct igneous belt that becomes younger towards the coast (Zhou et al., 2006). This Mesozoic magmatism was also associated with the formation of numerous volcanic–intrusive complexes that are

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characterized by high Nd values and young Nd model ages (TDM). These igneous rocks are located in a long, narrow zone that extends from Hangzhou in Zhejiang Province to Shiwandashan in Guangxi

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Province and which is approximately parallel to NE–SW-trending grabens in this area. This zone has

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been named the “Shi–Hang zone” (Fig. 1a; Gilder et al., 1991), and it is filled with clastic sedimentary rocks that are interlayered by volcanic rocks, all of which are thought to have been deposited in a

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backarc extensional tectonic environment associated with subduction of the Paleo-Pacific Plate (Li et al., 2004; Zhou et al., 2006; Jiang et al., 2009). Southeastern Hunan Province, within the southwestern part of the Shi–Hang zone, contains

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numerous and large-scale polymetallic mineral deposits associated with coeval magmatism, including W and Sn deposits that have huge reserves (Fig. 1b; Jiang et al., 2006; Mao et al., 2011). These include the Shizhuyuan skarn W–Sn–Bi deposit, which is related to the Qianlishan biotite granite and is one of the largest W deposits in China, and the Furong Sn deposit, which is related to the Qitianling hornblende biotite granite and contains the third largest reserves of Sn within China. This area also contains the Baoshan and Tongshanling skarn Cu–Pb–Zn deposits, which are the major producers of Pb and Zn in Hunan Province. This important endowment means that this region has been the focus of a significant amount of geological and mineral exploration and research.

2.2 Ore deposits and related granitoids

2.2.1 Baoshan and Tongshanling Cu–Pb–Zn deposits

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The Baoshan (BS) polymetallic deposit contains a total reserve of 122.2 × 104 t of Cu, Pb, and Zn metal (unpublished data of Baoshan Mining Company), and is dominated by chalcopyrite, galena,

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sphalerite, and molybdenite. The deposit contains chalcopyrite and molybdenite disseminated within calcic skarn in contact with the granodiorite porphyry, whereas galena and sphalerite are located within

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distal carbonate-hosted stratiform and stratabound orebodies. A molybdenite Re–Os isochron age of 160 ± 2 Ma for this mineralization is within error of the U–Pb age of the granodiorite porphyry (158 ± 2 Ma; Lu et al., 2006), indicating that the mineralization within this deposit is associated with the

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granodiorite porphyry. The granodiorite porphyry is dominated by alkali feldspar (~35%), plagioclase (~30%), biotite (~15%), and quartz (~15%), with accessory apatite, zircon, rutile, and magnetite. This

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intrusion also contains mafic magmatic enclaves and this area also contains exposed porphyry and volcanic tuffs, with all three igneous units having consistent zircon U–Pb ages of 157.7 ± 1.1, 155.2 ±

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1.4 and 156.4 ± 1.4 Ma, respectively (Xie et al., 2013).

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The Tongshanling (TSL) polymetallic deposit has total reserves of 249.2 × 104 t contained Cu, Pb, and Zn metal (unpublished data of Tongshanling Mining Company). The deposit is dominated by

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chalcopyrite, galena, sphalerite, and molybdenite, with chalcopyrite-dominated copper mineralization being generally hosted by quartz veins and galena and sphalerite being hosted by stratiform and stratabound orebodies that are similar in form to those within the Baoshan deposit. The pluton in this

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area is a granodiorite porphyry with a zircon U–Pb age of 163.6 ± 2.1 Ma (Jiang et al., 2009), within the analytical error of a molybdenite Re–Os isochron age of 161.8 ± 1.7 Ma for mineralization in this area (Huang and Lu, 2014). The Tongshanling porphyritic granodiorite contains alkali feldspar (~35%), plagioclase (~25%), quartz (~25%), biotite (~10%), and minor amounts of amphibole, with accessory apatite, zircon, rutile, and magnetite.

2.2.2 Xitian and Xintianling W deposits

The Xitian (XT) deposit contains 32.5 × 10 4 t of W and Sn metal (Wu et al., 2011), and is associated with two kinds of granitic intrusions: a Late Triassic biotite monzonitic granite and a Late Jurassic two-mica monzonitic granite, which are associated with W-Sn and Sn mineralization, respectively (Fig. 1c). Tungsten-tin mineralization in this area is characterized by scheelite, cassiterite, pyrite, and

ACCEPTED MANUSCRIPT chalcopyrite, which are disseminated within a skarn along the contact of the Triassic biotite monzonitic granite that yields a zircon U–Pb age of 220.7 ± 0.1 Ma (Yao et al., 2013). However, tin mineralization in this area is also associated with greisen-vein-hosted cassiterite, molybdenite, pyrite, and chalcopyrite.

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Molybdenite and muscovite within Sn-mineralized greisen veins has yielded a Re–Os isochron age of

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150.0 ± 2.7 Ma (Liu et al., 2008a) and 40Ar–39Ar isochron ages of 156.5 ± 1.7 to 155.4 ± 1.7 Ma (Ma et

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al., 2008), respectively, which lie within the uncertainty of the zircon U–Pb age of the associated two-mica monzonitic granite (154.4 ± 0.7 Ma; Yao et al., 2013). Here, we focus on the Late Triassic biotite monzonitic granite that is associated with scheelite mineralization; this granite is medium- to

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fine-grained and contains alkali feldspar (~30%), plagioclase (~30%), quartz (~30%), and biotite (~8%), with accessory apatite, sphene, magnetite and zircon. Previous research has suggested that the Xitian

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biotite monzonitic granite is an A-type granite that formed within an extensional intraplate environment triggered by Triassic upwelling of asthenospheric material (Cai et al., 2013; Yao et al., 2013).

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The Xintianling (XTL) deposit is located to the northeastern part of the Qitianling composite granite,

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which has been subdivided into at least three successive stages of emplacement (Zhu et al., 2009). This deposit is a large-scale skarn scheelite deposit containing 32 × 104 t of W metal and minor amounts of

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Mo and Bi (Yuan et al., 2012). The mineralization in the Xintianling district is associated with an biotite monzonitic granite that has yielded zircon U–Pb ages ranging between 165 and 164 Ma (Zhang et al., 2011a). The mineralization in this area is dominated by scheelite in the proximal calcic skarn and

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lesser sulfides in the distal skarn and limestone. This scheelite mineralization yields a molybdenite Re–Os isochron age of 161.7 ± 9.3 Ma (Yuan et al., 2012), which is within analytical error of the age of the biotite monzonitic granite. This granite has a medium-grained texture and contains quartz (~35%), alkali feldspar (~34%), plagioclase (~23%), and biotite (~7%) with accessory magnetite, ilmenite, zircon, sphene, apatite, and allanite.

2.2.3 Furong and Hehuaping Sn deposits

The Furong (FR) deposit is hosted in the southwestern part of the Qitianling granite and formed in close temporal and spatial association with the second stage of magmatism (Fig. 1d; Zhu et al., 2009). This deposit contains more than 60 × 104 t of Sn metal (Wei et al., 2002), and the tin mineralization within the granite is associated with skarn and chlorite alteration of the hornblende biotite granite; the

ACCEPTED MANUSCRIPT mineralization is fault controlled (Jiang et al., 2006). Ore minerals of this deposit are cassiterite along with minor pyrite and molybdenite.

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Ar–39Ar dating of muscovite within greisen veins yielded

mineralization-related ages of 160.1 ± 0.9 to 156.1 ± 0.4 Ma (Mao et al., 2004), consistent with zircon

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U–Pb ages of the hornblende biotite granite (157.1 ± 1.2 to 155.5 ± 1.3 Ma; Zhao et al., 2006). The hornblende biotite granite has a coarse-grained texture and is mineralogically similar to the Xintianling

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granite.

The Hehuaping (HHP) magnesian skarn type tin deposit contains 19.7 × 104 t of Sn metal (Mao et al., 2013), and the tin mineralizaion with cassiterite U–Pb isochron ages of 157.8 ± 4.1 to 154.8 ± 5.8 Ma

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is spatially associated with a biotite granite pluton that has zircon U–Pb ages of 157.1 ± 0.8 to 155.3 ± 1.2 Ma (Zhang et al., 2011b; Zhang et al., 2015). Geochemically and mineralogically, this biotite

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granite is similar to other granites related to Sn deposits in south China, which have affinities of A2-type granite (Zhang et al., 2011b; Yao et al., 2014). The Hehuaping granite is coarse grained and is

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dominated by alkali feldspar (~35%), quartz (~35%), plagioclase (~25%), and biotite (~5%), with

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accessory apatite, zircon, rutile, monazite, and thorite.

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2.3 Granitoid geochemical compositions

The whole-rock geochemical compositions of representative granitoids from the study area are given in

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Table 1. All of the mineralization-associated granitoids in this area contain >65 wt% SiO2 and with Na2O + K2O contents of 5.84 to 8.17 wt%, and are shoshonitic to high-K and calc-alkaline in composition (Fig. 2a). They have aluminous saturation index (ACNK) values of 0.7 to 1.11, suggestive of metaluminous to peraluminous granitoids (Fig. 2b), and formed under variable redox state conditions, with log(Fe2O3/FeO) vs FeO* (where FeO* = 0.9 × Fe2O3 + FeO) (Blevin, 2004) values for the Cu–Pb–Zn porphyries (Baoshan and Tongshanling deposits) being indicative of formation under moderately oxidized to strongly oxidized conditions, whereas the W and Sn granites formed under reduced to moderately oxidized conditions (Fig. 2c). The Bashan and Tongshanling porphyries are classified as volcanic-arc granites, whereas the W and Sn granites in the study area have within-plate affinities (Fig. 2d). The Xitian W-bearing granite formed in an intraplate rifting environment (Yao et al., 2013), whereas the other W- and Sn-bearing granites are considered to have formed in an intra-arc rifting environment (Jiang et al., 2006; Hua et al., 2007; Jiang et al., 2009).

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3. Sampling and analytical methods Six representative granitic rock samples were collected from Baoshan and Tongshanling skarn

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Cu–Pb–Zn deposits, the Xitian and Xintianling skarn W deposits, and the Furong and Hehuaping Sn deposits (detailed sampling locations see Fig. 1b-d). The samples are fresh except for those from the

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Xitian and Forong deposits, which are slightly altered, mainly due to chloritization. All of the apatites obtained from representative granitic rocks within southeastern Hunan Province are subhedral to euhedral and hexagonal, and are usually present as inclusions within biotite and matrix (Fig. 3),

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suggesting that these apatites crystallized during the early stages of magmatism and were not affected by later fractional crystallization. The above features suggest that these apatites may provide evidence

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of the original magma that eventually formed these granites.

The apatites analyzed during this study were concentrated using heavy liquid separation techniques

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before clear apatite grains were handpicked under a binocular microscope. Coarse-grained and euhedral

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apatites were mounted in an epoxy block before being polished for electron microprobe and LA–ICP–MS analysis. A further ~300 coarse-grained and euhedral apatites without visible inclusions

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were also separated for Sr isotopic analysis. Apatite major element compositions were determined by electron microprobe analysis using a JEOL JXA-8100M electron microprobe at Nanjing University, Nanjing, China, using an accelerating voltage

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of 15 kV, a probe current of 20 nA, and a peak counting time of 20 s. All of the data acquired during this study were corrected using standard ZAF correction procedures (Jurek and Hulinky, 1980). Apatite trace element compositions were determined by LA–ICP–MS at Northwest University, Xi’an, China, using a Geolass 200M laser and an Agilent 7500a ICP–MS instrument using helium (He) as the carrier gas. Glitter 4.0 software was used to determine elemental concentrations using a NIST-610 glass standard for external standardization and the Ca content of each grain determined by electron microprobe for internal standardization. The precision and accuracy of the analysis undertaken during this study are better than ± 10%, and more detailed descriptions of the techniques used are given in Liu et al. (2002). Apatite Sr isotopic compositions were determined using thermal ionization mass spectrometry and a Triton Ti instrument at Nanjing University, Nanjing, China. These analyses used ~300 clear and euhedral apatites separated from each sample analyzed during this study and used the approach

ACCEPTED MANUSCRIPT outlined in Pu et al. (2004). Measured 87Sr/86Sr ratios were adjusted to the NBS SRM 987 standard with 87

Sr/86Sr = 0.71025 ± 0.00013.

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4. Results

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There is little correlation between apatite major element concentrations, such as P, Ca, Mn, Fe, Si and halogens (Table 2; Fig. 4a). All of the apatites analyzed during this study are fluorapatites, although apatites from porphyritic intrusions associated with Cu–Pb–Zn deposits generally contain more Cl but

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less F than do apatites from granites associated with W and Sn mineralization, with apatites from the Tongshanling granodiorite porphyry generally containing >0.1 wt% Cl and apatites from the Baoshan

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granodiorite porphyry generally containing >0.2 wt% Cl, whereas the apatites associated with W- and Sn-bearing granites generally contain <0.1 wt% Cl. In contrast, apatites from Cu–Pb–Zn porphyries

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generally contain <3.5 wt% F, whereas apatites within W- and Sn-bearing granites generally

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contain >3.5 wt% F. In addition, apatites within Sn-bearing granites contain slightly higher F contents compared with apatites within W-bearing granites.

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There is no clear difference in the concentrations of U, Th, and Pb in the apatites analyzed during this study (Table 2), although Y and Sr concentrations negatively correlate within these apatites (Table 2; Fig. 4b). Apatites from Cu–Pb–Zn porphyries generally contain more Sr but less Y compared with

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apatites from W-bearing and Sn-bearing granites. For example, apatites from the Baoshan Cu–Pb–Zn granodiorite porphyry have Sr concentrations of 359–819 ppm and Y concentrations of 451–1143 ppm, apatites from the Xintianling W-bearing granite have Sr concentrations of 86–98 ppm and Y concentrations of 534–1915 ppm, and apatites from the Hehuaping Sn-bearing granite have Sr concentrations of 70–161 ppm and Y concentrations of 1551–3763 ppm. Apatites from Sn-bearing granites analyzed during this study have high total REE concentrations (6308–15,188 ppm), with REE concentrations in apatites within W-bearing granites being lower (2574–10,182 ppm), and apatites within Cu–Pb–Zn porphyries having the lowest total REE concentrations of those analyzed during this study (1897–6468 ppm). All of the apatites are preferentially enriched in light REEs (LREEs; La–Eu) compared to heavy REEs (HREEs; Gd–Lu), with LREE/HREE ratios for apatites within Sn-bearing granites, W-bearing granites, and Cu–Pb–Zn porphyries of 2.6–9.4, 3.7–11.8, and 3.7–12.6, respectively. In addition, apatites within intrusions

ACCEPTED MANUSCRIPT related to the different types of mineralization have distinctly different chondrite-normalized REE distribution patterns (Fig. 5), with apatites from Sn-bearing granites being strongly depleted in Eu (Figs 4d and 5), whereas apatites from W-bearing granites have HREE patterns that increase with increasing

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atomic weight. The REE distribution patterns of the apatites are generally similar to the patterns for the host granitic rocks, with some of the middle REE (MREE) enrichments present potentially relating to

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the differentiation of minerals that preferentially incorporate either LREEs (such as allanite) or HREEs (such as zircon; Hsieh et al., 2008).

Apatites within Cu–Pb–Zn porphyries generally have lower 87Sr/86Sr ratios than those within W- and 87

Sr/86Sr ratio values of 0.707859–0.710954, 0.712381–0.726216, and

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Sn-bearing granites, with

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0.716835, respectively (Table 2).

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5. Discussion

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5.1 Redox state of granitic rocks

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Eu and Ce anomalies in apatite can be used as proxies for the redox state of a magma (Prowatke and Klemme, 2006; Chu et al., 2009; Cao et al., 2012; Miles et al., 2014), primarily because the REE3+ generally substitute for Ca2+ in apatite, which is hosted by both sevenfold and ninefold coordinated

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positions: REE3+ + Si4+ = Ca2+ + P5+ (Fleet and Pan, 1997; Sha and Chappell, 1999). Both Eu and Ce have two ionic valences: Eu3+/Eu2+ and Ce4+/Ce3+. The fact that Eu3+ has a more similar ionic radius (R) to Ca2+ than to Eu2+ within both of the positions in apatite and Ce4+ does not have any odd number coordination compared with Ce3+, which has both sevenfold and ninefold coordinated positions, means that Ce3+ has the same ionic radius in both sites as Ca2+ (Shannon, 1976). This means that apatite preferentially incorporates Eu3+ and Ce3+ rather than Eu2+ and Ce4+ (Cao et al., 2012). Low-oxygen-fugacity conditions will lead to high Eu2+/Eu3+ and Ce3+/Ce4+ ratios within a magma, leading to only limited substitution of Eu3+ but significant substitution of Ce3+ into apatite, generating a strong negative Eu anomaly and a positive Ce anomaly within the apatite. In comparison, high-oxygen-fugacity conditions will result in a melt with high Eu3+ but low Ce3+ concentrations and significant Eu3+ but limited Ce3+ substitution into apatite, thus generating moderate negative to even slightly positive Eu and slightly positive to negative Ce anomalies in apatite (Sha and Chappell, 1999;

ACCEPTED MANUSCRIPT Cao et al., 2012; MacDonald et al., 2013). Another explanation for the Eu anomaly in apatite is related to the competition between apatite and plagioclase within a magma. Crystallization of sufficient plagioclase prior to the crystallization of

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apatite will generate a Eu-depleted melt, meaning that later-crystallized apatites will have significantly negative Eu anomalies. However, any apatite crystallized before the onset of significant plagioclase

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crystallization would be free of negative Eu anomalies (Tollari et al., 2008). Equilibrium apatite REE compositions can also be approximately calculated using whole-rock REE concentrations (VanTongeren and Mathez, 2012). Previous research has indicated that magnetite-series (oxidized)

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granitoids have Fe2O3/FeO ratios of >0.5 whereas ilmenite-series (reduced) granitoids have ratios of <0.5 (Ishihara, 1977, 1981), providing us with an appropriate experimentally determined partition

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coefficient (Dap/melt REE ) of melts with Fe2O3/FeO = 6.0 for (moderately) oxidized granitoids (the Baoshan and Tongshanling porphyries and the Xitian and Xintianling granites), and apply an appropriate Dap/melt REE

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for melts with FeO/Fe2O3 = 12.2 for reduced melts, including the Furong and Hehuaping granites, with

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both Dap/melt values being taken from Fujimaki (1986). The calculated apatite REE distribution patterns REE are shown as heavy black lines in Fig. 5 and are generally consistent with analytically determined REE

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concentrations (Fig. 5), suggesting that apatite Eu anomalies are controlled by variations in oxygen fugacity. In addition, the anomalously high measured HREE concentrations in some apatites may be related to the low zircon abundances within the host granite or the fact that apatite within these granites

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crystallized before zircon. It should also be noted that the granitic rocks from different deposits have approximate ACNK values and percentage abundances of plagioclase as mentioned in section 2, which further confirms that plagioclase crystallization may not have significantly influenced apatite Eu anomalies. Granitic rocks associated with Cu–Pb–Zn mineralization generally form from oxidized magmas, whereas granites related to Sn deposits form from reduced magmas, and those associated with W deposits can form from either oxidized or reduced granitic magmas (Blevin and Chappell, 1992, 1995; Ballard et al., 2002; Meinert et al., 2005; Sun et al., 2013). These relationships are related to the fact that sulfur exists as SO42− in oxidized environments, which means that melts do not become saturated in chalcophile elements, resulting in primary magmas with high initial concentrations that do not precipitate sulfides during magma migration and differntiation (Sun et al., 2004; Nadeau et al., 2010). A high-oxygen-fugacity condition is crucial for the formation of chalcophile element mineralization, and

ACCEPTED MANUSCRIPT this factor explains the absence of porphyry Cu deposits from intraplate environments that are not associated with slab subduction (Sun et al., 2004, 2013). Reduced granitic melts can contain more SnO2 than do oxidized melts (Bhalla et al., 2005), with high-oxygen-fugacity conditions enabling Sn4+ to

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substitute for Ti4+ and Fe3+ within titanite and magnetite (Farges et al., 2006). This means that Sn is strongly concentrated in the later aqueous-dominated stages of fractionation of a reduced magma,

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leading to the potential formation of Sn deposits, whereas oxidized magmas will precipitate Sn within minerals in the granite, meaning that any late-segregated aqueous fluids would be Sn depleted (Wang et al., 2013). The behavior of W under different redox conditions is still unclear, with W being present in

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basaltic melts as W4+ (Ertel et al., 1996) but as W6+ in granitic melts (O'Neill et al., 2008). Experimental research suggests that more than 1000 ppm of WO3 is required to saturate granitic melts,

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meaning that these melts are unsaturated in W-bearing minerals even in highly evolved granites (Stemprok, 1990; Che et al., 2013). This suggests that W deposits are related to late-stage hydrothermal

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processes involving NaCl–HCl–H2O system fluids that can transport W as tungstates, enabling WO3

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concentrations in these fluids to reach thousands of ppm (Wood and Samson, 2000). The oxygen fugacity of a magma can reflect both the source of the magma and the tectonic

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environment of magma generation, with oxidized magmas (I-type granite) generally being associated with mantle material or slab melting and S-type magmas being associated with partial melting of the crust (Ishihara, 1977, 1981; Blevin and Chappell, 1992, 1995; Bryant et al., 2007). Moreover, apatite

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within I-type granites generally has higher Eu values (Eu = 2EuN/(SmN + GdN); Ce = 2CeN/(LaN + PrN) than apatite within S-type granites (Sha and Chappell, 1999; Chu et al., 2009). Apatites within the Baoshan and Tongshanling porphyries associated with Cu–Pb–Zn deposits have the highest Eu values (0.20–0.65) and lowest Ce values (1.04–1.12; Fig. 6) of any of the apatites analyzed during this study, suggesting that they formed from oxidized magmas that typically incorporate mantle-derived material. Abundant basaltic mafic magmatic enclaves are present in the porphyritic intrusions associated with these deposits, providing more evidence of mantle-derived input (Jiang et al., 2009; Xie et al., 2013). Apatites from the Xitian and Xintianling granites have moderate Eu (0.16–0.44) and Ce (1.10–1.16) values (Fig. 6), suggesting that these W granites formed from magmas under moderate-oxygen-fugacity conditions and containing less mantle-derived and more crust-derived material compared with Cu–Pb–Zn deposits. These W granites also contain basaltic mafic magmatic enclaves (Zhu et al., 2009; Yao et al., 2013). Apatites within the Furong and Hehuaping granites associated with Sn deposits have

ACCEPTED MANUSCRIPT the lowest Eu (0.02–0.09) and highest Ce (1.07–1.16) values (Fig. 6), suggesting that these granites formed from reduced magmas that are usually generated by the partial melting of crustal material with

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limited mantle input (Zhu et al., 2009; Yao et al., 2014).

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5.2 Sr isotopic compositions

Rb is highly incompatible in apatite and has a partition coefficient Dap-met of 0.0013 between apatite and Rb granitic melt (Prowatke and Klemme, 2006), meaning that very little Rb can enter apatite lattice

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(concentrations of Rb in apatite usually less than 1 ppm; Creaser and Gray, 1992). This means that the Sr/86Sr ratio of apatite is not significantly affected by Rb decay and can be used to approximate the

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initial Sr isotopic composition of the host granitic rock, or, at least, the upper limit of the initial Sr/86Sr (ISr) ratio (Tsuboi and Suzuki, 2003; Tsuboi, 2005).

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The Paleoproterozoic metasedimentary basement of the Cathaysia Block has ISr values of

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0.734708–0.758610 at 160 Ma and 0.726156–0.745626 at 220 Ma (Yuan et al., 1991; Jiang et al., 2009). Basalts within the same block have ISr values of 0.703560–0.705377 at 160 Ma and

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0.703403–0.706115 at 220 Ma (Li et al., 2004). The 87Sr/86Sr compositions of apatite samples from five deposits (excluding the Hehuaping deposit, as insufficient apatites were obtained from these samples) were determined during this study, the results of which are summarized in Table 2. Inferred

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Sr/86Sr

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ratio of apatite within Hehuaping deposit is also provided in this table and illustrated in Fig. 7 determined by ISr value of host granite (Zhang, 2014). Apatites within Cu–Pb–Zn porphyries (Baoshan and Tongshanling) have lower 87Sr/86Sr ratios (0.707859–0.710954) that are closer to the ISr values of basalts (Fig. 7) and are consistent with the whole-rock ISr values of these samples (0.706175–0.711777, see Table 1; Jiang et al., 2009; Xie et al., 2013), indicating that these granites formed from magmas that contained significant amounts of mantle-derived material. There are insufficient data to separate the 87

Sr/86Sr ratios of apatites from W- and Sn-bearing granites, but apatites from both types of granite have

high 87Sr/86Sr ratios (0.712381–0.726216). Unfortunately, the whole-rock ISr values are not available for comparison only except the Xintianling W deposit and Furong Sn deposit whose host rock ISr values (0.710837–0.713153) are approximate to the apatite

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Sr/86Sr ratios (0.712381–0.716835) without

surprise (see Table 1; Zhao et al., 2012a; Zhang, 2014). The 87Sr/86Sr ratios of apatites within W- and Sn-bearing granites are closer to the ISr values of Paleoproterozoic metasediments than to the basalts in

ACCEPTED MANUSCRIPT this area (Fig. 7), suggesting that these granites formed from magmas generated by the partial melting of crustal material, with only minimal contributions from mantle-derived material (Jiang et al., 2006; Yuan et al., 2012; Yao et al., 2013, 2014). This is consistent with the oxidization state of the magma

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determined by the apatite Eu and Ce anomalies, as discussed above.

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5.3 Sources of metasomatic fluids

All of the apatites from southeastern Hunan Province are fluorapatites, primarily because F is more

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compatible in silicate melts rather than in fluids during fractional crystallization (Webster, 1990). Apatites within Cu–Pb–Zn porphyries have high Cl and low F concentrations compared with apatites

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within W- and Sn-bearing granites, which contain only trace amounts of Cl but high concentrations of F (Fig. 8). The F and Cl contents of apatites of granitoids associated with the Dexing porphyry Cu

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deposit in the northeastern part of the Shi–Hang zone (Yao et al., 2007a) are similar to those within

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intrusions related to Cu–Pb–Zn deposits in southeastern Hunan Province, but have even higher Cl concentrations. The more active chemistry of Cl means that it is a more sensitive proxy than F and can

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therefore be used to derive more geological information. Previous research suggests Cl has a partition coefficient Dap/met of ~0.8 in basaltic melts (Mathez and Webster, 2005) but a Dap/met of 1.0–4.5 in Cl Cl granitic melts (Webster et al., 2009). Cl is highly compatible in apatite within a Cl-saturated melt,

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although if the melt is H2O-saturated then Cl is more compatible in aqueous fluids than in silicate melts. This means that Cl concentrations do not significantly decrease during fractional crystallization, meaning that evolved granites may have similar or increased Cl concentrations compared to the initial magma (Brehler and Fuge, 1974; Sha and Chappell, 1999; Sun et al., 2007). Therefore, apatite Cl concentrations reflect the initial Cl contents of the primary magma (Boyce et al., 2010), in turn indicating that the F and Cl concentrations of apatites from intrusions within southeastern Hunan Province retain the halogen compositions of the original magma. The concentration of Cl varies in different parts of the mantle but is not significantly influenced by Cl recycling (Lassiter et al., 2002). Experiments on mantle-derived melt inclusions (Lassiter et al., 2002) and on submarine volcanic glasses (Stroncik and Haase, 2004) suggest that the mantle generally contains low concentrations of Cl (usually <0.1 wt%). This means that the high concentrations of Cl within apatites from the Cu–Pb–Zn porphyries of the southeastern Hunan Province (Shi–Hang zone)

ACCEPTED MANUSCRIPT cannot be the result of the addition of mantle-derived material. However, these high Cl concentrations are also unlikely to have been derived from the partial melting of crustal material, primarily as sedimentary material would lose more Cl than F during weathering, as the former is highly compatible

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in aqueous fluids, leading to a process that concentrates F in the residue but depletes Cl (Brehler and Fuge, 1974; Blevin and Chappell, 1992). This is the reason that all of the apatites within S-type granites

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from the Lachlan Fold Belt in Australia contain <0.2 wt% Cl (mainly <0.1 wt%) (Sha and Chappell, 1999). Therefore, the Cu–Pb–Zn porphyries within southeastern Hunan Province must have sourced Cl from some other fluids, most probably by the melting of mantle wedge material as a result of the

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addition of fluids derived from a subducting slab, a process that releases mainly Cl-rich brines (Hedenqulst and Lowenstern, 1994; Lassiter et al., 2002). This fluid was most likely seawater, which

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was incorporated into the primitive mantle by hydrothermal recycling and/or slab subduction and was released by serpentine dehydration (Sumino et al., 2010; Kendrick et al., 2011; Kawamotoa et al., 2013;

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Reynard, 2013), suggesting that the Cu–Pb–Zn porphyries in the study area received a large amount of

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slab-derived fluids that were not conducive to the formation of W- and Sn-bearing granites. It is unclear whether Cl and F can influence the behavior of W and Sn in magmas. For example,

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experimental research by Keppler and Wyllie (1991) and Bai and Koster van Groos (1999) indicated that the presence of both Cl and F may mean that melts retain W and Sn rather than these elements being preferentially transferred to aqueous fluids, although Bhalla et al. (2005) suggested that Cl can

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increase the solubility of Sn in melts, and Wood and Samson (2000) proposed that the behavior of W is not affected by either F or Cl in a hydrothermal environment. In contrast, the chalcophile elements, such as Cu, Pb, Zn, Ag, and Au, are more sensitive to the presence of Cl than to the presence of F, meaning that the solubility of these elements can significantly increase with any increase in Cl content (Keppler and Wyllie, 1991; Bai and Koster van Groos, 1999; Hezarkhani et al., 1999; Archibald et al., 2001). Cl is highly incompatible and preferentially partitions into the liquid phase during slab dehydration (Stroncik and Haase, 2004; Sun et al., 2007), and Cl-enriched fluids are essential for the transportation of metals (Keppler and Wyllie, 1991; Bai and Koster van Groos, 1999), meaning that Cl is essential for magmas to be able to form Cu–Pb–Zn deposits. The F and Cl contents of apatites in granitic rocks from southeastern Hunan Province provide evidence of a slab-subduction environment and the addition of mantle materials during the formation of the magmas that generated the Cu–Pb–Zn porphyries in this area. The presence of a subducted plate is

ACCEPTED MANUSCRIPT generally accepted and has been named the Paleo-Pacific plate (Li et al., 2004; Zhou et al., 2006; Jiang et al., 2009; Mao et al., 2013). The slab-released fluids caused the melting of mantle wedge material, generating a high-oxygen-fugacity environment for the formation of the resulting fluids and magmas,

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which enhanced the extraction and transportation of the metals that ultimately formed the Cu–Pb–Zn deposits in this area. The partial melting of the lower crust with only a limited addition of material from

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the mantle formed the W- and Sn-bearing granites and associated mineralization in an intra-arc rifting environment, generating apatites with low Cl contents because both crustal melts and unmetasomatised mantle material contain only trace amounts of Cl and because the early weathering of crustal material

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also mobilizes Cl, while F is retained in the residue (Brehler and Fuge, 1974; Blevin and Chappell, 1992). Here, the Xitian W-bearing biotite monzonitic granite formed at ~220 Ma in an intraplate rifting

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environment (Yao et al., 2013). The other W- and Sn-bearing granites formed at ~160 Ma in an intra-arc rifting environment, associated with subduction of the Paleo-Pacific plate (Hua et al., 2007;

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Mao et al., 2007; Zhang et al., 2011a, b). In fact, it has long been suggested that granites which

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originate from extension in continental arc or intraplate settings are likely to have similar geochemical

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compositions (Eby, 1992; Whalen et al., 1996).

5.4 Regional metallogeny and tectonic evolution

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The melting of mantle wedge material triggered by slab-derived fluids preferentially concentrates Sr compared with Th, leading to the formation of granitic rocks with increasing Sr/Th ratios (Turner and Foden, 2001; Labanieh et al., 2012). In comparison, La/Sm ratios are not significantly influenced by either partial melting or fractional crystallization but instead are controlled by the amount of melting of subducted marine sediments, where increasing amounts of sedimentary melting causes an increase in the range of La/Sm ratios, although this melting also increases Th concentrations, resulting in stable Sr/Th ratios (Turner and Foden, 2001; Labanieh et al., 2012). This indicates that the melting of sediments overlying the subducting plate will cause Sr/Th ratios to remain stable but will increase the range of La/Sm ratios in the resulting magmas, whereas the addition of slab-released fluids will stabilize La/Sm ratios but increase the range of Sr/Th ratios within the resulting magmas. These two processes can be identified in binary plots of Sr/Th vs. La/Sm (Fig. 9). It is currently unclear whether the ratios of these elements in host rocks can be inherited by apatite.

ACCEPTED MANUSCRIPT In granitic melts, Sr can enter apatite by substituting for Ca, whereas Th and REEs are generally incorporated into apatite by other substitutions, such as: Th4+ + 2Si4+ = Ca2+ + 2P5+; REE3+ + Si4+ = Ca2+ + P5+; REE3+ + Na+ = 2Ca2+ (Sha and Chappell, 1999; MacDonald et al., 2013). These elements

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are compatible in apatite and have high partition coefficients with the exception of Th (Dap-liq = ~2.43, Sr Dap-liq = ~0.5, Dap-liq = ~4.85, Dap-liq = ~6.22; Prowatke and Klemme, 2006), suggesting that the Th La Sm

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concentrations of these elements in apatite reflect at least in part the concentrations in the host rock (Chu et al., 2009), with apatite La/Sm ratios being around 0.77 of the La/Sm ratio of the host rock, whereas apatite Sr/Th ratios are 4.86 times larger than the ratio of the host rock, although the

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consistency of these values means that they will not significantly change the trends within Sr/Th vs. La/Sm binary diagrams.

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The Cu–Pb–Zn porphyry deposits in southeastern Hunan Province, such as the Baoshan and Tongshanling deposits, are clearly related to slab dehydration, whereas the W- and Sn-bearing granites

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provide no indication of any relationship with slab dehydration or sediment melting (Fig. 9). Here, we

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compare our data to apatites from Carboniferous skarn Pb–Zn (AK-3) and scheelite (Zh-2 and Ash-1) deposits of the Central Asian Orogenic Belt (Cao et al., 2012). Apatites associated with the same type

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of mineralization in both areas are compositionally similar in terms of halogens and Eu and Ce anomalies (Cao et al., 2012). The apatites of Cu–Pb–Zn deposits of the Central Asian Orogenic Belt define a slab dehydration trend that is similar to that of apatites from Cu–Pb–Zn deposits in

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southeastern Hunan Province, meaning that both of these deposits formed in a similar fashion (Heinhorst et al., 2000; Xiao et al., 2009). However, apatites from W deposits within the Central Asian Orogenic Belt also provide evidence of sediment melting, a feature that is missing from apatites from southeastern Hunan Province (Fig. 9), suggesting that the former incorporated additional melts derived from marine sediments (Heinhorst et al., 2000; Xiao et al., 2009). These marine sediments are not present in southeastern Hunan Province because this area was affected by roll-back of the Paleo-Pacific Plate at ~155 Ma, forming an intra-arc rifting environment that was free of marine sediments and that was the site of formation of the Xintianling W deposit and the Furong and Hehuaping Sn deposits (Li et al., 2004; Zhou et al., 2006; Jiang et al., 2009). In addition, the formation of an intraplate extensional environment was triggered by the upwelling of asthenosphere, and this helped to produce the Xitian W deposit at ~220 Ma (Cai et al., 2013; Yao et al., 2013). Southeastern Hunan Province is characterized by numerous composite granite bodies, such as the

ACCEPTED MANUSCRIPT Dengfuxian, Xitian, and Wangxianling–Hehuaping granites. These granites formed during both the Indosinian and Yanshanian, but later granites in this area are more likely to be associated with mineralization (Mao et al., 2013). This region provides a natural laboratory for research into tectonism

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(Li et al., 2004, 2007; Mao et al., 2007; Jiang et al., 2009; Xie et al., 2013), and the formation of the late Mesozoic Cu–Pb–Zn, W, and Sn deposits in this area is often characterized by the early formation

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of Cu–Pb–Zn mineralization (Fig. 10A; Table 3). Combining the apatite geochemistry discussed here with previously obtained geochronological data indicates that the subducting Paleo-Pacific Plate reached the Shi–Hang zone at about 180–160 Ma, causing melting of mantle wedge material as a result

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of the addition of slab-derived fluids. These magmas also incorporated lower-crustal melts and ascended to form the oxidized, Cl-rich and lower-ISr Cu–Pb–Zn porphyries (Fig. 10B). The W- and

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Sn-bearing granites are Cl depleted, formed under medium to low oxygen-fugacities and have relatively high ISr values, indicating that they formed from magmas generated by the partial melting of

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metasedimentary material in an intra-arc extensional environment. This melting was triggered by slab

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6. Conclusions

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roll-back and the upwelling of asthenospheric material at around 160–150 Ma (Fig. 10C).

The chemical composition of apatite is a useful proxy for the petrogenetic and metallogenic history of

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magmas for the following reasons. (1) Apatite Eu and Ce anomalies provide evidence of the redox state of the magmas that formed the host granitic rocks, with Eu enrichment and Ce depletion being indicative of oxidized magma, and Eu depletion and Ce enrichment being indicative of reduced magma. (2) Apatite 87Sr/86Sr ratios reflect the Sr isotopic composition of the host granitic rocks. (3) Apatite F and Cl concentrations can reflect the enrichment or depletion of halogens within the host granitoids, with apatite associated with slab dehydration containing more Cl and less F whereas apatites related to magmas formed by partial melting of the crust contain less Cl and more F. Apatite major and trace element compositions indicate that the porphyries associated with Cu–Pb–Zn mineralization within southeastern Hunan Province formed in high-oxygen-fugacity conditions, and these apatites have low 87Sr/86Sr ratios, high Cl and low F contents, stable La/Sm ratios, and a wide range of Sr/Th ratios, suggesting that they formed from magmas containing significant amounts of mantle material that interacted with Cl- and H2O-rich slab-derived fluids. In comparison,

ACCEPTED MANUSCRIPT the W- and Sn-bearing granites formed under medium- to low-oxygen-fugacity conditions and contain apatites with high 87Sr/86Sr ratios, relatively high F and low Cl contents, and stable La/Sm and Sr/Th ratios, providing no evidence of interaction with slab-derived material and suggesting that they formed

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from magmas generated by the partial melting of metasediments in a rifting environment. Combining the apatite geochemistry presented here with geochronological data for these intrusions indicates that

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the tectonic regime of the area of southeastern Hunan Province transformed during the Late Jurassic from an early continental arc (associated with the formation of Cu–Pb–Zn deposits) related to the subduction of the Paleo-Pacific Plate to a later intra-arc rifting environment (associated with the

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formation of W and Sn deposits) that was triggered by slab roll-back and mantle upwelling.

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Acknowledgements

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We are grateful to Dr. Elena Belousova and an anonymous reviewer and Dr. Franco Pirajno

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(Editor-in-Chief) for their thoughtful reviews and constructive comments. This work was financially supported by the National Basic Research Program of China (Grant No. 2012CB416705), and the Key

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ACCEPTED MANUSCRIPT Table Captions Table 1. Major and trace element compositions and initial

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Sr/86Sr ratios of representative granitic rocks

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associated with Cu–Pb–Zn, W, and Sn deposits in southeastern Hunan Province, southeastern China.

Table 2. Average major and trace element compositions and 87Sr/86Sr ratios of apatites from representative granitic

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rocks associated with Cu–Pb–Zn, W, and Sn deposits in southeastern Hunan Province, southeastern China.

Table 3. Timing of formation of late Mesozoic Cu–Pb–Zn, W, and Sn deposits near the Shi–Hang zone of

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southeastern China.

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Figure Captions

Fig. 1. (a) Sketch map showing the distribution of Mesozoic intrusive and volcanic rocks in southern China

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(modified after Zhou et al., 2006); (b) simplified geological map of southeastern Hunan Province showing the

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location of samples analyzed during this study; (c)-(d) distribution of granites within Xitian and Furong deposits,

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including the location of studied samples (adapted from Yao et al., 2013 and Zhu et al., 2009, respectively).

Fig. 2. Diagrams showing variations in the composition of representative granitic rocks from southeastern Hunan Province. (a) K2O vs. SiO2; (b) ANK vs. ACNK diagram, [ANK = molar Al2O3/(Na2O + K2O); ACNK = molar

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Al2O3/(CaO + Na2O + K2O];(c) redox classification diagram (after Blevin, 2004); (d) Ta vs. Yb tectonic discrimination diagram (after Pearce et al., 1984). Data sources are as follows: Baoshan: Xie et al. (2013); Tongshanling: Xudong Huang, unpublished data; Xitian: Yao et al. (2013); Xintianling: Zhang, 2014; Furong: Zhao et al. (2012a); Hehuaping: Yao et al. (2014).

Fig. 3. Back-scattered electron images showing examples of typical mineral assemblages and the occurrence of apatite in representative granitic rocks associated with Cu–Pb–Zn, W, and Sn mineralization within southeastern Hunan Province of southeastern China. Ap: apatite; Bt: biotite; Qtz: quartz; Pl: plagioclase; Gdp: granodiorite porphyry. BS: Baoshan Cu–Pb–Zn deposit; TSL: Tongshanling Cu–Pb–Zn deposit; XT: Xitian W deposit; XTL: Xintianling W deposit; FR: Furong Sn deposit; HHP: Hehuaping Sn deposit.

Fig. 4. Variation diagrams for minor and REE concentrations within apatites from different mineral deposits in

ACCEPTED MANUSCRIPT southeastern Hunan Province: (a) Cl vs. F; (b) Sr vs. Y; (c) Sr vs. Ce; (d) Ce anomaly values vs. Eu anomaly values. Eu = 2EuN/(SmN + GdN);Ce = 2CeN/(LaN + PrN). MME: mafic magmatic enclave; Gdp:

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granodiorite porphyry.

Fig. 5. Chondrite-normalized REE diagrams for apatites (colored symbols with colored lines) and their granitic

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host rocks (colored symbols with dashed lines) associated with Sn, Cu–Pb–Zn, and W mineralization in southeastern Hunan Province; heavy black lines indicate calculated apatite REE abundances based on host-rock

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REE concentrations. Chondrite-normalized values are from Sun and McDonough (1989). Symbols as in Fig. 4.

Fig. 7.

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Fig. 6. Ce anomalies vs. Eu anomalies for apatites from different mineral deposits in southeastern Hunan Province.

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Sr/86Sr values of apatites from different mineral deposits in southeastern Hunan Province; the

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compositions of the Ningyuan–Daoxian basalts are from Li et al. (2004) and the compositions of Paleoproterozoic

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metasediments are from Yuan et al. (1991); the 87Sr/86Sr ratio of apatite within Hehuaping Sn deposit is inferred

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from ISr value of host granite from Zhang, 2014.

Fig. 8. Cl vs. F contents of apatites from the Shi–Hang zone; the diamond area indicates the compositional range

AC

of apatites from the Dexing porphyry copper deposit using data sourced from Yao et al. (2007).

Fig. 9. Sr/Th vs. La/Sm for apatites from southeastern Hunan Province; left- and right-hand shaded areas indicate the compositions of apatites from Cu–Pb–Zn and W deposits within the Central Asia Orogenic Belt, respectively, using data from Cao et al. (2012).

Fig. 10. (A) Location of major Cu–Pb–Zn, W, and Sn deposits in the area around the Shi–Hang zone; (B) and (C) model showing the tectonic evolution of southeastern Hunan Province area during the Jurassic.

AC

CE P

TE

D

MA

NU

SC R

IP

T

ACCEPTED MANUSCRIPT

Fig. 1

D

MA

NU

SC R

IP

T

ACCEPTED MANUSCRIPT

AC

CE P

TE

Fig. 2

AC

CE P

TE

D

MA

NU

SC R

IP

T

ACCEPTED MANUSCRIPT

Fig. 3

MA

NU

SC R

IP

T

ACCEPTED MANUSCRIPT

AC

CE P

TE

D

Fig. 4

Fig. 5

MA

NU

SC R

IP

T

ACCEPTED MANUSCRIPT

AC

CE P

TE

D

Fig. 6

Fig. 7

MA

NU

SC R

IP

T

ACCEPTED MANUSCRIPT

AC

CE P

TE

D

Fig. 8

Fig. 9

NU

SC R

IP

T

ACCEPTED MANUSCRIPT

AC

CE P

TE

D

MA

Fig. 10

ACCEPTED MANUSCRIPT

Fe2O3

FeO

MnO

MgO

CaO

Na2O

K2O

P2O5

LOI

Total

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

BS MME

56.38

0.6

13.48

1.76

2.92

0.24

3.3

5.76

1.07

6.38

0.32

7.63

99.8

BS Tuff

65.53

0.49

14.42

1.53

2.45

0.07

1.27

4.53

2.79

3.67

0.24

3.09

100.07

BS Gdp

65.11

0.42

13.98

1.5

1.68

0.1

1.81

3

1.32

4.52

0.18

5.88

99.53

TSL

66.39

0.48

15.56

1.22

2.27

0.08

1.51

3.31

2.93

3.89

1.79

99.62

XT

73.21

0.33

13.47

0.25

1.53

0.08

0.69

1.54

IP

0.18

3.1

4.67

0.14

0.97

99.13

XTL

74.81

0.22

13.63

0.78

0.83

0.04

0.43

1.86

2.68

4.22

0.07

0.92

99.49

FR

71.95

0.4

13.79

0.99

1.45

0.04

0.42

1.66

2.9

5.27

0.13

0.72

99.72

HHP

73.28

0.28

12.94

0.62

1.68

0.04

0.24

1.69

2.78

4.22

0.09

1.97

99.81

Sr

Y

La

Ce

Pr

Nd

Sm

Eu

Gd

Tb

Dy

Ho

Er

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

BS MME

549

20.2

53

104

11.8

46.1

5.94

1.4

5.5

0.71

3.42

0.69

2.14

BS Tuff

488

15.5

50.1

93.7

10.1

37.6

5.95

1.57

4.95

0.66

3.08

0.56

1.57

BS Gdp

195

19.5

43.9

82.7

8.83

32.8

5.25

1.08

4.66

0.66

3.37

0.65

1.97

TSL

300

20

19.2

36.9

5.26

19.1

4.01

1.18

3.69

0.6

3.52

0.69

2.08

XT

177

18.1

56.4

108.2

11.9

40.7

6

0.95

4.68

0.59

3.34

0.62

1.95

XTL

145

8.5

30.2

53.1

5.1

17.2

2.38

0.53

1.87

0.27

1.3

0.27

0.88

FR

138

29.7

58

92.3

10.6

35.9

6.58

1.04

5.82

0.8

5.25

1.15

3.4

HHP

83.4

60.4

94.7

201

23.2

87.6

17.2

0.66

14.8

2.53

13.5

2.49

7.11

Deposit

Tm

Yb

Lu

(ppm)

(ppm)

(ppm)

0.34

BS Tuff

0.23

BS Gdp

0.32

TSL

0.32

XT

0.32

FR HHP

NU

Pb

Th

U

(ppm)

(ppm)

(ppm)

ACNK

Na2O+K2O

87

86

Initial Sr/ Sr

(wt%)

2.1

0.3

14.3

14.4

4.21

0.7

7.45

0.706175-0.706263

1.37

0.2

25.1

13.2

2.33

0.86

6.46

0.710746-0.710948

1.98

0.3

22.8

18.7

5.99

1.11

5.84

0.709506-0.711777

2.19

0.34

17.8

14.7

7.53

1.04

6.82

0.710058-0.710511

2.36

0.4

64.4

48.5

20.4

1.04

7.77

-

0.17

1.08

0.19

26.5

35.4

12.5

1.1

6.9

0.712091

0.51

3.31

0.53

30.53

38

13.2

1.02

8.17

0.710837-0.713153

1.1

6.08

0.85

25.9

60.4

16.5

1.06

7

0.712705

AC

BS MME

XTL

TE

Deposit

T

Al2O3

SC R

TiO2

CE P

Deposit

D

SiO2

MA

Table 1

BS and TSL: Baoshan and Tongshanling Cu–Pb–Zn deposit, average composition of similar granitoids from Jiang et al. (2009), Xie et al. (2013) and Xudong Huang (unpublished data); MME: mafic magmatic enclave; Gdp: granodiorite porphyry; XT: Xitian W deposit, data for host granite from Yao et al. (2013); XTL, HHP, and FR: Xintianling W deposit, Hehuaping and Furong Sn deposit, respectively, data for host granites from Zhang, 2014 and Zhao et al., 2012a.

ACCEPTED MANUSCRIPT

FeO

MnO

Cl

F

Sr

Th

U

Pb

Y

La

Ce

Number

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(wt%)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

Baoshan (Cu–Pb–Zn) MME

13BS-08

42.39

53.91

0.21

0.11

0.14

0.47

2.97

1.36

393

48.6

24.2

5.2

892

726

1984

Baoshan (Cu–Pb–Zn) Tuff

13BS-17

43.03

54.09

0.14

0.10

0.12

0.34

Baoshan (Cu–Pb–Zn) Gdp

13BS-02

42.57

54.11

0.26

0.11

0.12

0.44

2.70

1.21

609

11.4

5.82

3.98

592

307

853

3.07

1.39

420

50

24.7

5.19

899

777

2099

Tongshanling (Cu–Pb–Zn)

TSL-05

42.86

54.10

0.16

0.12

0.12

0.19

2.94

1.28

296

24.4

22.5

5.85

783

553

1482

Xitian (W)

XT-JS-03

42.08

54.75

0.26

0.05

0.15

0.05

3.98

1.69

315

40.9

10.7

17.8

1220

1231

3343

Xintianling (W)

11XTL-60

42.16

54.62

0.27

0.06

0.16

0.07

3.64

1.55

90.5

38

19

5.2

1432

623

1711

Furong (Sn)

BLS11

42.48

54.00

0.43

0.07

0.07

0.06

3.87

1.64

76.9

75.1

24.9

8.55

2103

1615

4345

Hehuaping (Sn)

12802-08

42.51

53.89

0.21

0.16

0.12

0.03

3.99

1.69

104

15.2

6.44

6.78

2304

1440

3794

Sample

Pr

Nd

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

Number

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

Baoshan (Cu–Pb–Zn) MME Baoshan (Cu–Pb–Zn) Tuff

13BS-08

268

1298

304

30.9

251

34.4

177

32.1

77.7

9.67

58.3

13BS-17

126

672

189

33.7

186

25.7

131

23

51.8

5.92

33

Baoshan (Cu–Pb–Zn) Gdp

13BS-02

277

1321

301

33.4

248

33.8

174

31.9

77.9

9.74

Tongshanling (Cu–Pb–Zn)

TSL-05

199

948

212

18.5

170

23.9

131

25.4

67

Xitian (W)

XT-JS-03

439

2017

380

32.3

276

36.6

197

38.4

Xintianling (W)

11XTL-60

218

1012

245

16.9

236

35.3

204

Furong (Sn)

BLS11

547

2349

484

9.14

407

61

Hehuaping (Sn)

12802-08

506

2467

628

5.30

601

90

TE D

CE P

Deposit

IP

SiO2

CR

CaO

F,Cl = –O

US

P2O5

MA N

Sample

AC

Deposit

T

Table 2

Sr/86Sr

2σ

7.27

0.707859

7

4.01

0.710954

7

60

7.61

0.708939

12

9.53

65.4

8.90

0.709345

15

102

15.0

111

16.2

0.726216

13

42.7

119

17.6

132

22.9

0.712381

12

340

67.3

179

24.2

157

19.9

0.716835

7

475

84.0

189

22.2

127

14.8

0.712705*

-

*Inferred 87Sr/86Sr ratio of apatite determined by ISr value of host granite from Zhang, 2014. Abbreviations as in Table 1.

87

ACCEPTED MANUSCRIPT Table 3 Number

Name

Deposit

Analytical

type

mineral

Method

Age (Ma ± 2σ)

Reference

Mao and Wang (2000)

Cu–Pb–Zn Dexing

Cu–Au–Mo

Molybdenite

Re–Os

173

2

Yinshan

Cu–Au

Sericite

Ar–Ar

178.2 ± 1.4

3

Tongcun

Cu–Mo

Molybdenite

Re–Os

162.2 ± 1.3

Zhang et al. (2013)

4

Cunqian

Cu–Pb–Zn

Zircon

U–Pb

169.3 ± 1.1

Wang et al. (2012)

5

Yongping

Cu–Mo

Molybdenite

Re–Os

156.7 ± 2.8

Li et al. (2013b)

6

Tongshanling

Cu–Pb–Zn

Molybdenite

Re–Os

161.8 ± 1.7

Huang and Lu (2014)

7

Baoshan

Cu–Pb–Zn

Molybdenite

Re–Os

160 ± 2

Lu et al. (2006)

8

Shuikoushan

Cu–Pb–Zn

Zircon

U–Pb

163 ± 2

Ma et al. (2006)

9

Dabaoshan

Cu–Mo–W

Molybdenite

Re–Os

167 ± 2.5

Li et al. (2012)

10

Yuanzhuding

Cu–Mo

Molybdenite

Re–Os

155 ± 5

Chen et al. (2012)

11

Lenshuikeng

Cu–Pb–Zn

Zircon

U–Pb

162 ± 2

Zuo et al. (2010)

12

Yinkeng

Cu–Pb–Zn

Zircon

U–Pb

160 ± 1

Zhao et al. (2012b)

13

Yingqian

Cu–Pb–Zn

Zircon

U–Pb

172.2 ± 3

Guo et al. (2010)

14

Hehuaping

Sn–Pb–Zn

Zircon

U–Pb

157.1 ± 0.8

Zhang et al. (2011b)

15

Xianghualing

Sn–Pb–Zn

Muscovite

Ar–Ar

154.4 ± 1.1

Yuan et al. (2007)

16

Furong

Sn

17

Taoxiwo

18

Shizhuyuan

19

Xintianling

20

IP

SC R

NU

MA

Li et al. (2006)

Hornblende

Ar–Ar

154.7 ± 1.1

Peng et al. (2007)

Sn

Muscovite

Ar–Ar

154.8 ± 0.6

Peng et al. (2007)

W–Sn

Molybdenite

Re–Os

151 ± 3.5

Mao et al. (2004)

W–Mo

Phlogopite

Ar–Ar

157.06 ± 0.2

Mao et al. (2004)

Huangshaping

W–Mo

Molybdenite

Re–Os

154.8 ± 1.9

Yao et al. (2007b)

21

Yaogangxian

W

Muscovite

Ar–Ar

155.1 ± 1.1

Peng et al. (2006)

22

Da’ao

W–Sn

Molybdenite

Re–Os

151.4 ± 2.4

Fu et al. (2007)

23

Xiangdong

W–Nb–Ta

Molybdenite

Re–Os

150.5 ± 5.2

Cai et al. (2012)

Hukeng

W

Molybdenite

Re–Os

150.2 ± 2.2

Liu et al. (2008b)

Piaotang

W–Sn

Muscovite

Ar–Ar

152 ± 1.9

Zhang et al. (2009)

Xiongjiashan

W–Mo

Molybdenite

Re–Os

152 ± 20

Meng et al. (2007)

25 26

AC

24

CE P

TE

D

W–Sn

T

1

42

SC R

IP

T

ACCEPTED MANUSCRIPT

AC

CE P

TE

D

MA

NU

Graphical abstract

43

ACCEPTED MANUSCRIPT Highlights (1) Confirm the differences between granitoids can be reflected by variations in apatite compositions. (2) The composition of apatite reflect the factors controlling the different types of mineralization.

AC

CE P

TE

D

MA

NU

SC R

IP

T

(3) Apatite can be the proxy to identify regional metallogeny and tectonic evolution.

44