Keywords: Cu-Pb-Zn-bearing granitoids, W-bearing granites, Microgranular enclaves, Skarn, Magmatic-hydrothermal system, Zonation, Structural control, Permeability, Petrogenesis, Metallogenesis, Middle-Late Jurassic, Nanling

Granitoids and their related mineralization is always the highly focused topic for geologists all over the world. The Nanling Range in South China is one of the most famous metallogenic belts around the world, especially for its large-scale W-Sn mineralization.

Middle-Late Jurassic is the most important epoch for granitic magmatism and associated mineralization in this region. Although numerous studies have been carried out on the petrogenesis and metallogenesis of the Middle-Late Jurassic ore-bearing granitoids in the Nanling Range, there are still great controversies and problems remaining to be solved, especially on the Cu-Pb-Zn-bearing and W-bearing granitoids and their skarn mineralization. Four main scientific problems are proposed as follows: (1) What are the petrogenetic differences and links between the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range? (2) How do the skarn deposits structurally connect to the Middle-Late Jurassic ore-bearing granitoids in the Nanling Range? (3) What are the genetic links between different mineralization types and the formation mechanism of complex zonation in the Middle-Late Jurassic Cu-Pb-Zn skarn deposits in the Nanling Range? (4) What are the key factors controlling the occurrence of unusual magnesian skarn W mineralization during Late Jurassic in the Nanling Range? The Tongshanling-Weijia area in the western part of the Nanling Range is selected as the study area. The main research objects of this Ph.D. thesis are the Tongshanling Cu-Pb-Zn and Weijia W skarn deposits. The South China Block is a major continental component with a complex history of tectonic evolution in East Asia. It was constructed through a Neoproterozoic (1.0 -0.8 Ga) amalgamation of the Yangtze and Cathaysia Blocks. In Phanerozoic, the South China Block mainly experienced three tectonothermal events, i.e., the Early Paleozoic (460 -390 Ma) intracontinental orogeny, the Early Mesozoic (240 -200 Ma) intracontinental compressional deformation, and the Late Mesozoic (Jurassic to Cretaceous) palaeo-Pacific plate subduction. As a consequence, the corresponding multiple-aged (i.e., Neoproterozoic, Early Paleozoic, Triassic, Jurassic, and Cretaceous) granitoids and associated polymetallic mineral deposits are widely developed in South China. In the Nanling Range of South China, the most extensive Extended English abstract II Middle-Late Jurassic (165 -150 Ma) ore-bearing granitoids can be divided into W-bearing, Sn-bearing, Nb-Ta-bearing, and Cu-Pb-Zn-bearing granitoids. Skarn is one of the most important mineralization types for the Middle-Late Jurassic polymetallic mineral deposits especially the Cu-Pb-Zn and W deposits in the Nanling Range. The Tongshanling-Weijia area is situated in southern Hunan Province. The exposed strata in this area include Ordovician to Triassic systems except for the absence of Silurian system and Upper Permian to Lower Triassic series and are dominated by Devonian and Carboniferous systems. The Middle Devonian Qiziqiao Formation, the Upper Devonian Shetianqiao and Xikuangshan Formations, and the Shidengzi Member of the Upper Carboniferous Datang Stage are the main ore-bearing horizons in the Tongshanling-Weijia area. The structural framework of this area is south-north-to southwest-northeast-trending on the whole. The Tongshanling granodiorite and the Weijia granite are the dominant magmatic rocks in this area, which are genetically related to Cu-Pb-Zn and W mineralization, respectively. The Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit are distributed around the Tongshanling intrusion and constitute the Tongshanling Cu-Mo-Pb-Zn-Ag ore district. The Weijia W deposit is located 15 km to the northeast of the Tongshanling polymetallic ore district.

The Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range are distinctly different in mineralogy and geochemistry. The Cu-Pb-Zn-bearing granitoids are dominated by weakly fractionated metaluminous I-type amphibole-bearing granodiorites, which have higher CaO/(Na2O+K2O) ratios, light/heavy rare earth element (LREE/HREE) ratios, and δEu values, lower Rb/Sr ratios, and weak Ba, Sr, P, and Ti depletions. The W-bearing granites are mainly highly differentiated peraluminous S-type granites, which have lower CaO/(Na2O+K2O) ratios, LREE/HREE ratios, and δEu values, higher Rb/Sr ratios, and strong Ba, Sr, P, and Ti depletions. The Cu-Pb-Zn-bearing and W-bearing granitoids were formed predominantly between 155.2 Ma and 167.0 Ma (peak value: 160.6 Ma) and between 151.1 Ma and 161.8 Ma (peak value: 155.5 Ma), respectively.

There is a time gap of about 5 Ma between the two different types of ore-bearing granitoids.

Based on detailed geochronological and geochemical studies of both the Tongshanling Nov. 2018 X.D. HUANG III Cu-Pb-Zn-bearing and Weijia W-bearing granitoids and combined with a comparison between the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range, a genetic model of the two different types of ore-bearing granitoids has been proposed. The underplated basaltic magmas induced by the subduction of the palaeo-Pacific plate provided heat to firstly cause partial melting of the mafic amphibolitic basement in the lower crust, resulting in the formation of Cu-Pb-Zn mineralization related granodioritic magmas. With the development of basaltic magma underplating, the muscovite-rich metasedimentary basement in the upper-middle crust was then partially melted to generate W-bearing granitic magmas.

The non-simultaneous partial melting of one source followed by the other brought about a time gap of about 5 Ma between the Cu-Pb-Zn-bearing and W-bearing granitoids.

The microgranular enclaves in the Tongshanling granodiorite have dioritic compositions with a mineralogy dominated by plagioclase, amphibole, and biotite. Abundant residual materials, such as mafic mineral clots, inherited and metamorphic zircon, and Ca-rich core plagioclase, occur in the enclaves and are in favor of a restite origin. The amphibole-rich clots are considered as vestiges of residual pyroxene-rich precursors from the source. Three types of amphibole, i.e., magmatic, metamorphic, and magma reworked metamorphic amphibole, have been recognized in the granodiorite and its enclaves according to their different occurrences, textures, and compositions. The zonal amphibole-rich clots exhibit increasing Al and decreasing Si contents from interior amphibole to exterior amphibole and also from core to rim in amphibole grains, and the outer parts of enclave magmatic zircon have higher ThO2+UO2 contents and lower Zr/Hf ratios than the inner parts, showing the process of magma reworking of the restite enclaves. Based on the textural and compositional evidence, these microgranular enclaves are thought to be reworked restite enclaves. This is also supported by thermobarometric calculation. A model illustrating the formation process of reworked restite enclave has been proposed. Combined with previous experimental studies of partial melting, the Tongshanling granodiorite is deduced to be derived from dehydration melting of amphibolite in the mafic lower crust. The fertile amphibolitic source is beneficial to the formation of Cu-Pb-Zn-bearing granodiorites in the Nanling Range. Table 1- Table 8-1. F contents and some related parameters of different F-bearing minerals in the Weijia W deposit .... reaction, structural controls, etc.

Magma emplacement-induced structural control on skarn formation at the Tongshanling

Tables

The Nanling Range in South China is one of the most famous metallogenic belts around the world, especially for its large-scale W-Sn mineralization. A great number of granitoids and associated mineral deposits are widely developed in the Nanling Range (Fig. 1-1).

Although these granitoids and related ore deposits were formed in multiple periods, i.e., Early Paleozoic, Triassic, Jurassic, and Cretaceous (Fig. 1-1), Middle-Late Jurassic is the most important epoch for granitic magmatism and associated mineralization in this region [START_REF] Mao | [END_REF](Mao et al., , 2013a;;[START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Fu | Metallogenesis of W(Sn) deposits and their exploration in Nanling Range, China[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF]. Four dominant types of Middle-Late Jurassic ore-bearing granitoids in the Nanling Range, i.e., W-bearing (e.g., Yaogangxian, Dengfuxian, Weijia, Xihuashan, Dajishan, etc., Fig. 1-1), Sn-bearing (e.g., Huashan-Guposhan, Jiuyishan, Qitianling, Qianlishan, Hehuaping, etc.), Nb-Ta-bearing (e.g., Dajishan, Jianfengling, Laiziling, etc.), and Cu-Pb-Zn-bearing (e.g., Shuikoushan, Baoshan, Tongshanling, Dabaoshan, etc., Fig. 1-1) granitoids, have been recognized by previous studies [START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Fu | Metallogenesis of W(Sn) deposits and their exploration in Nanling Range, China[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF]. Although numerous studies have been carried out on the petrogenesis of these Middle-Late Jurassic ore-bearing granitoids (e.g., Wang et al., 2003a;[START_REF] Zhang | Study on the characteristics, origin and related metallogeny of granites in Dajishan and Piaotang, Southern Jiangxi Province[END_REF][START_REF] Li | [END_REF][START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Fu | Metallogenesis of W(Sn) deposits and their exploration in Nanling Range, China[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF][START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF][START_REF] Dong | Petrogenesis of the Yaogangxian granites and implications for W mineralization, Hunan Province[END_REF]Zhang, 2014;[START_REF] Zuo | Characterization of element geochemistry, LA-ICP-MS zircon U-Pb age, and Hf isotope of granodiorite in the Shuikoushan deposit, Changning, Hunan Province[END_REF][START_REF] Yang | Petrogenesis of the Mesozoic Shuikoushan peraluminous I-type granodioritic intrusion in Hunan Province, South China: Middle-lower crustal reworking in an extensional tectonic setting[END_REF]Zhao et al., 2016aZhao et al., , 2016b;;[START_REF] Wu | Highly fractionated granites: Recognition and research[END_REF]Zhang et al., 2017a), there are still great controversies remaining to be solved, especially on the origins of the Cu-Pb-Zn-bearing and W-bearing granitoids.

Based on the occurrence of dark microgranular enclaves and the interpretation of geochronological and geochemical data, it is generally considered that the Middle-Late Jurassic Cu-Pb-Zn-bearing granitoids in the Nanling Range, which are dominated by I-type amphibole-bearing granodiorites, were formed by mixing of crust-derived and mantle-derived magmas (Wang et al., 2003a;[START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF][START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF]Zhao et al., 2016b). However, these microgranular enclaves do not show any credible evidence, except for some Sr-Nd isotopes [START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF], supporting magma mixing and detailed petrographic and mineralogical studies of these microgranular enclaves are absent. It is noteworthy that the zircon Hf isotopic compositions of these microgranular enclaves are similar to those of their [START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF].

host granitoids, both of which show typical crust-derived features [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Xie | [END_REF][START_REF] Zuo | Characterization of element geochemistry, LA-ICP-MS zircon U-Pb age, and Hf isotope of granodiorite in the Shuikoushan deposit, Changning, Hunan Province[END_REF][START_REF] Yang | Petrogenesis of the Mesozoic Shuikoushan peraluminous I-type granodioritic intrusion in Hunan Province, South China: Middle-lower crustal reworking in an extensional tectonic setting[END_REF]Zhao et al., 2016b). [START_REF] Zuo | Characterization of element geochemistry, LA-ICP-MS zircon U-Pb age, and Hf isotope of granodiorite in the Shuikoushan deposit, Changning, Hunan Province[END_REF] and [START_REF] Yang | Petrogenesis of the Mesozoic Shuikoushan peraluminous I-type granodioritic intrusion in Hunan Province, South China: Middle-lower crustal reworking in an extensional tectonic setting[END_REF] proposed that the Shuikoushan granodiorite was derived from partial melting of the mafic lower crust. Thus, the petrogenesis of these Cu-Pb-Zn-bearing granitoids is still disputable and needs further investigations.

For the Late Jurassic W-bearing granites in the Nanling Range, it is widely accepted that they are dominated by highly fractionated S-type two-mica, muscovite, and biotite granites and were mainly derived from partial melting of crustal metasedimentary rocks [START_REF] Zhang | Study on the characteristics, origin and related metallogeny of granites in Dajishan and Piaotang, Southern Jiangxi Province[END_REF][START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Fu | Metallogenesis of W(Sn) deposits and their exploration in Nanling Range, China[END_REF][START_REF] Dong | Petrogenesis of the Yaogangxian granites and implications for W mineralization, Hunan Province[END_REF]Zhang, 2014;[START_REF] Jiang | Petrogenesis of the Late Jurassic peraluminous biotite granites and muscovite-bearing granites in SE China: geochronological, elemental and Sr-Nd-O-Hf isotopic constraints[END_REF].

However, some researchers thought that these W-bearing granites are highly fractionated I-type granites and were mainly derived from partial melting of crustal meta-igneous rocks [START_REF] Li | [END_REF][START_REF] Wu | Highly fractionated granites: Recognition and research[END_REF]Zhang et al., 2017a). [START_REF] Li | [END_REF] pointed out that the Jurassic amphibole-bearing granodiorite, biotite monzogranite, K-feldspar granite, and two-mica (muscovite) granite constitute a metaluminous to weakly peraluminous evolution series of I-type granites. It is reasonable that the highly fractionated properties of the W-bearing granites enhance the difficulty of distinguishing their source rocks [START_REF] Chappell | Aluminium saturation in I-and S-type granites and the characterization of fractionated haplogranites[END_REF][START_REF] Gao | Distinction between S-type and peraluminous I-type granites: Zircon versus whole-rock geochemistry[END_REF][START_REF] Wu | Highly fractionated granites: Recognition and research[END_REF]. Therefore, the petrogenesis of these W-bearing granites and the relationship between the W-bearing granites and the Cu-Pb-Zn-bearing granodiorites require further studies.

The Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids related mineral deposits in the Nanling Range are dominated by skarn, greisen, quartz vein, and carbonate replacement mineralization in which only skarn is of great importance to both of the Cu-Pb-Zn and W deposits [START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Mao | [END_REF]Mao et al., , 2013a;;[START_REF] Fu | Metallogenesis of W(Sn) deposits and their exploration in Nanling Range, China[END_REF]. A number of Middle-Late Jurassic Cu-Pb-Zn and W skarn deposits appear in the western part of the Nanling Range. Study on the genesis and ore-forming processes of these Cu-Pb-Zn and W skarn deposits is beneficial to understanding the differences between Cu-Pb-Zn and W skarn mineralization and the regional metallogenic regularities of Cu-Pb-Zn and W in the Nanling Range.

The Middle-Late Jurassic Cu-Pb-Zn skarn deposits in the Nanling Range, such as the Tongshanling, Baoshan, Shuikoushan, Dabaoshan, and Huangshaping deposits, commonly have the characteristic of association of different mineralization types which include skarn, carbonate replacement, sulfide-quartz vein, etc. [START_REF] Wang | Metallogenic model and prospecting potential in Dabaoshan molybdenum polymetallic ore deposit[END_REF][START_REF] Zhu | Sulfur and lead isotope constraints on ore formation of the Huangshaping W-Mo-Bi-Pb-Zn polymetallic ore deposit, Hunan Province, South China[END_REF][START_REF] Lu | Genesis of the Shuikoushan lead-zinc deposit, Changning City, Hunan Province[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF][START_REF] Bao | Characteristics of sulfur isotope geochemistry of Baoshan Cu-Mo-Pb-Zn-Ag polymetallic deposit, Hunan Province and its geological significance[END_REF][START_REF] Qu | Metallogenic chronology of the stratiform Cu orebody in the Dabaoshan Cu polymetallic deposit, northern Guangdong Province and its geological significance[END_REF][START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Dai | Ore-forming model of Dabaoshan poly-metal deposit in Guangdong Province[END_REF][START_REF] Huang | Precise zircon U-Pb and molybdenite Re-Os dating of the Shuikoushan granodiorite-related Pb-Zn mineralization, southern Hunan, South China[END_REF][START_REF] Xie | S, Pb, C and O isotopic characteristics and sources of metallogenic materials of Baoshan Pb-Zn deposit, southern Hunan province[END_REF]Ding et al., 2016a). In addition, complex zonation of metals and mineralization types may occur in an individual Cu-Pb-Zn skarn deposit or ore district. For instance, the Tongshanling Cu-Mo-Pb-Zn-Ag skarn ore district is constituted by three ore deposits, i.e., the Tongshanling Cu-Pb-Zn, Jiangyong Pb-Zn-Ag, and Yulong Mo deposits, distributing around the Tongshanling granodioritic intrusion [START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF]Zhao et al., 2016b). The Tongshanling Cu-Pb-Zn deposit shows a zonation of proximal skarn (endoskarn and exoskarn), distal skarn, and sulfide-quartz veins between them [START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF][START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]. The Jiangyong Pb-Zn-Ag deposit is composed of proximal skarn and distal carbonate replacement [START_REF] Yi | Geochemical characteristics of Antangling lead-zinc deposit in the Tongshanling orefield[END_REF][START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF]. The Yulong Mo deposit comprises only skarn [START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF]Zhao et al., 2016b). Although numerous geochronological and geochemical studies have been carried out on these Middle-Late Jurassic Cu-Pb-Zn skarn deposits (e.g., [START_REF] Lu | U-Pb and Re-Os isotope geochronology of Baoshan Cu-Mo polymetallic deposit in Hunan province[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF][START_REF] Qu | Metallogenic chronology of the stratiform Cu orebody in the Dabaoshan Cu polymetallic deposit, northern Guangdong Province and its geological significance[END_REF][START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Huang | Precise zircon U-Pb and molybdenite Re-Os dating of the Shuikoushan granodiorite-related Pb-Zn mineralization, southern Hunan, South China[END_REF], the links between different mineralization types and the genesis of complex zonation are still poorly understood.

Essentially, all economic W skarns are calcic throughout the world [START_REF] Kwak | W-Sn skarn deposits and related metamorphic skarns and granitoids[END_REF], such as the well-known Zhuxi (China), Xintianling (China), Shizhuyuan (China), Yaogangxian (China), CanTung (Canada), Pine Creek (USA), King Island (Australia), Salau (France), and Los Santos (Spain) deposits [START_REF] Meinert | World skarn deposits[END_REF][START_REF] Pan | Dating the giant Zhuxi W-Cu deposit (Taqian-Fuchun Ore Belt) in South China using molybdenite Re-Os and muscovite Ar-Ar system[END_REF]. Magnesian W skarns are uncommon and have been rarely reported [START_REF] Guy | Pétrologie et géochimie isotopique (S, C, O) des skarns à scheelite de Costabonne (Pyrénées orientales, France)[END_REF][START_REF] Casquet | El skarn de W-Sn del Carro del Diablo (Sistema Central Español)[END_REF][START_REF] Kwak | W-Sn skarn deposits and related metamorphic skarns and granitoids[END_REF][START_REF] Dubru | Distribution of scheelite in magnesian skarns at Traversella (Piemontese Alps, Italy) and Costabonne (Eastern Pyrenees, France): Nature of the associated magmatism and influence of fluid composition[END_REF][START_REF] Vander Auwera | Trace elements (REE) and isotopes (O, C, Sr) to characterize the metasomatic fluid sources: evidence from the skarn deposit (Fe, W, Cu) of Traversella (Ivrea, Italy)[END_REF]. However, the discovery of the Late Jurassic super-large Weijia W deposit (ca. 300,000 t WO3) in the Nanling Range that comprises predominant magnesian W skarn (ca. 240,000 t WO3) and subordinate calcic W skarn (ca. 60,000 t WO3) demonstrates and highlights the importance of magnesian skarn for W mineralization. Scientifically the Weija deposit presents a special case of W skarn deposit.

Such unusual economic mineralization is of great interest to economic geologists and provides an excellent opportunity for further understanding of W skarn mineralization. Since the concealed Weijia W deposit is still unmined, however, very few studies have been carried out on its metallogenesis and mineralization process, except for some publications of deposit geology and ore-bearing granite (e.g., Li et al., 2012a;[START_REF] Hu | Ore controlling factors and metallogenic regularity of concealed tungsten-fluorite deposits in Weijia of Hunan[END_REF]Zhao et al., 2016aZhao et al., , 2016b)). No genetic model has been proposed for this particular W skarn deposit so far and the key factors that control magnesian skarn W mineralization are still unknown.

Although numerous geochronological and geochemical studies have revealed that the Middle-Late Jurassic Cu-Pb-Zn and W skarn deposits in the Nanling Range are genetically associated with granitoids (e.g., [START_REF] Bi | Stable isotope geology of the Xintianling scheelite deposit[END_REF][START_REF] Li | Re-Os isotopic chronology of molybdenites in the Shizhuyuan polymetallic tungsten deposit, Southern Hunan[END_REF][START_REF] Liu | Isotope geochemistry of the Yejiwei deposit in the Shizhuyuan W-Sn ore field in Hunan Province[END_REF][START_REF] Lu | U-Pb and Re-Os isotope geochronology of Baoshan Cu-Mo polymetallic deposit in Hunan province[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF][START_REF] Ma | Re-Os isotopic chronology of molybdenites in Huangshaping lead-zinc deposit, southeast Hunan, and its geological implications[END_REF][START_REF] Yao | Re-Os isotope dating of molybdenites in the Huangshaping Pb-Zn-W-Mo polymetallic deposit, Hunan Province, South China and its geological significance[END_REF][START_REF] Lei | Petrogenetic and metallogenic age determination of the Huangshaping lead-zinc polymetallic deposit and its geological significance[END_REF][START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF][START_REF] Qu | Metallogenic chronology of the stratiform Cu orebody in the Dabaoshan Cu polymetallic deposit, northern Guangdong Province and its geological significance[END_REF][START_REF] Zhu | Characteristics of stable isotopes S, Pb, O, and H in the Yaogangxian tungsten deposits, Hunan Province[END_REF][START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Huang | Precise zircon U-Pb and molybdenite Re-Os dating of the Shuikoushan granodiorite-related Pb-Zn mineralization, southern Hunan, South China[END_REF][START_REF] Shuang | Fluid-inclusion geochemistry of the large-sized Xintianling tungsten deposit, Hunan Province, China[END_REF]Zhao et al., 2016aZhao et al., , 2016b)), the detailed structural connecting process between them is still unclear. Previous studies on skarn deposits mainly focused on metasomatism, zonation, skarn mineralogy, geochemistry, and petrogenesis [START_REF] Meinert | World skarn deposits[END_REF]. However, little attention has been paid to structural control (e.g., [START_REF] Love | The lithologic, stratigraphic, and structural setting of the giant Antamina copper-zinc skarn deposit, Ancash, Peru[END_REF]Li et al., 2014a;[START_REF] Ducoux | Synkinematic skarns and fluid drainage along detachments: The West Cycladic Detachment System on Serifos Island (Cyclades, Greece) and its related mineralization[END_REF], especially the magma emplacement related one, on skarn formation. Magma emplacement-induced structural control is crucial to understanding the process of skarnization and can provide important information for prospecting and exploration. In addition, the roles of some other key parameters affecting skarn formation, such as permeability, were also rarely considered.

The anisotropy of permeability in country rocks, which could be derived from magma emplacement-induced structures, may control the location and scale of skarnization to a certain extent. Thus, except for geochemical studies, studies on magma emplacement-induced structural control and permeability constraint are also of great importance and will be beneficial to further understanding the mechanism of skarn formation.

Scientific problems

Under on the research background mentioned above, four main scientific problems concerning the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids and associated skarn deposits in the Nanling Range are proposed as follows.

(1) What are the petrogenetic differences and links between the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range?

(2) How do the skarn deposits structurally connect to the Middle-Late Jurassic ore-bearing granitoids in the Nanling Range?

(3) What are the genetic links between different mineralization types and the formation mechanism of complex zonation in the Middle-Late Jurassic Cu-Pb-Zn skarn deposits in the Nanling Range?

(4) What are the key factors controlling the occurrence of unusual magnesian skarn W mineralization during Late Jurassic in the Nanling Range?

Topic selection and research contents 1.2.1. Topic selection

The Tongshanling-Weijia area in the western part of the Nanling Range is an ideal region for studying the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids and associated skarn deposits. In the Tongshanling-Weijia area, the Tongshanling granodiorite and Weijia granite are spatially adjacent with a distance of 15 km and are genetically associated with Cu-Pb-Zn and W skarn mineralization, respectively. These Cu-Pb-Zn-bearing and W-bearing granitoids and related skarn deposits were formed contemporaneously in Middle-Late Jurassic [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]Zhao et al., 2016aZhao et al., , 2016b)). As described above, the Tongshanling Cu-Mo-Pb-Zn-Ag skarn ore district exhibits a complex zonation of metals and different mineralization types and the Weijia W skarn deposit contains dominant magnesian W skarn and subordinate calcic W skarn.

Therefore, the Tongshanling-Weijia area is selected as the study area of this Ph.D. thesis. The Tongshanling and Weijia deposits, which act as a window of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids and related skarn deposits in the Nanling Range, are the main research objects of this Ph.D. thesis. Consequently, this Ph.D. thesis is entitled "Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids and their skarn mineralization in the Nanling Range, South China: the Tongshanling and Weijia deposits".

Research contents

This Ph.D. thesis mainly contains the following research contents.

(1) Petrogenesis of the Tongshanling Cu-Pb-Zn-bearing granodiorite and Weijia W-bearing granite. Comparison of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range.

(2) Petrogenesis and formation process of the microgranular enclaves in the Tongshanling granodiorite.

(3) Regional structural features in the Tongshanling-Weijia area. Local structural control on skarn formation at the Tongshanling Cu-Pb-Zn deposit induced by magma emplacement.

(4) Zonation and genesis of the Tongshanling Cu-Mo-Pb-Zn-Ag skarn ore district which includes the Tongshanling Cu-Pb-Zn, Jiangyong Pb-Zn-Ag, and Yulong Mo deposits.

(5) Ore-forming process of the Weijia W skarn deposit. Key factors controlling the unusual magnesian skarn W mineralization in the Weijia deposit.

Research methodology and technical route 1.3.1. Research methodology

This Ph.D. thesis was finished mainly through the following research methods.

(1) Field observation, sample collection, and sample processing: regional and local structural analyses, deposit geological study, mineral separation, thin section making, whole-rock powder preparation, etc.

(2) Structural study: deformation analysis, RSCM thermometry, and calcite EBSD mapping.

(3) Petrographic study: optical microscope and scanning electron microscope observations.

(4) Mineralogical study: SEM elemental mapping, EMP analysis of major elements, and LA-ICP-MS analysis of trace elements.

(5) Geochronological study: zircon, garnet, and titanite U-Pb and molybdenite Re-Os dating.

(6) Petrogeochemical study: whole-rock major elements, trace elements, and Sr-Nd isotopes and zircon Hf isotope.

(7) Ore deposit geochemical study: S and Pb isotopes of sulfide minerals and H-O isotopes of quartz.

Technical route

Petrogenesis of granitoids was studied by zircon U-Pb dating and Hf isotope and whole-rock geochemistry. Petrogenesis of microgranular enclaves was studied through petrography and mineralogy. Magma emplacement-induced structural control on skarn formation was studied by structural analysis, RSCM thermometry, and EBSD mapping.

Zonation and genesis of the Tongshanling polymetallic ore district were studied through molybdenite Re-Os and garnet and titanite U-Pb dating and S, Pb, H-O isotopes.

Metallogenesis of the Weijia W deposit and key factors controlling the unusual magnesian W skarn were studied by RSCM thermometry, whole-rock geochemistry, and mineralogy.

Workload and research achievements

Workload

The details of completed workload during my Ph.D. study are listed in Table 1-1.

Main findings and innovations

Main findings and innovations of this Ph.D. thesis are listed as follows.

(1) The Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range were derived from non-simultaneous partial melting of the mafic amphibolitic basement and the muscovite-rich metasedimentary basement, respectively.

(2) The microgranular enclaves of the Tongshanling granodiorite are reworked restite enclaves derived from partial melting of the mafic amphibolitic source.

(3) The exoskarn and sulfide-quartz veins in the Tongshanling Cu-Pb-Zn deposit are structurally controlled by the magma emplacement-induced wall-rock deformation.

(4) The different mineralization types and ore deposits in the Tongshanling polymetallic ore district are genetically linked together and are the productions of evolution and zonation of the same skarn system associated with the Tongshanling granodioritic intrusion.

(5) The key factors controlling the occurrence of unusual magnesian skarn W mineralization during Late Jurassic in the Nanling Range mainly include an enriched source, a fluorine-rich magma, a strong crystal fractionation, and a fluorine-rich hydrosaline melt. (To be continued on the next page) Chapter 2. Geological setting

South China

South China is world famous for the widespread multiple-aged granitoids and related polymetallic mineral deposits, especially the extremely abundant W-Sn deposits, and has attracted great interests of numerous geologists and scientific research institutes to carry out countless studies on its geodynamic evolution, magmatism, and mineralization [START_REF] Hsu | Tungsten deposits of southern Kiangsi, China[END_REF][START_REF] Hsu | Discovery of granites of the Caledonian age in southern Kiangsi[END_REF]Hsu et al., , 1963aHsu et al., , 1963b;;Institute of Geochemistry, CAS, 1979;[START_REF] Mo | Geology of granitoids in the Nanling Range[END_REF]Department of Geology, NJU, 1981;[START_REF] Xu | On the two genetic series of granites in southeastern China and their metallogenetic characteristics[END_REF][START_REF] Xu | On the genetic series of granites, as exemplified by the Mesozoic granites of South China[END_REF][START_REF][END_REF][START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF];

The Granitoid Research Group of the Nanling Project, MGMR, 1989;[START_REF] Hua | A preliminary discussion on the Mesozoic metallogenic explosion in East China[END_REF][START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF][START_REF] Shu | Late Mesozoic tectonism of southeast China[END_REF][START_REF] Wang | Petrogenesis of the Late Mesozoic granitic volcanic-intrusive complexes and crustal evolution in Southeastern China[END_REF][START_REF] Hua | Metallogenic systems related to Mesozoic and Cenozoic granitoids in South China[END_REF][START_REF] Hua | Three major metallogenic events in Mesozoic in South China[END_REF]Sun et al., 2005;Sun, 2006;Zhou et al., 2006a[START_REF] Zhou | Introduction to the special issue of Mesozoic W-Sn deposits in South China[END_REF]Li and Li, 2007;[START_REF] Li | [END_REF][START_REF] Li | Amalgamation between the Yangtze and Cathaysia Blocks in South China: Constraints from SHRIMP U-Pb zircon ages, geochemistry and Nd-Hf isotopes of the Shuangxiwu volcanic rocks[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of south China: Part 1, polyphase deformation in the Jiuling and Lianyunshan domains of the central Jiangnan Orogen[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of South China: Early Paleozoic sinistral and Triassic dextral transpression in the east Wuyishan and Chencai domains[END_REF]Li et al., , 2018a;;Wang et al., 2007a[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Wang et al., , 2017a;;[START_REF] Zaw | Nature, diversity of deposit types and metallogenic relations of South China[END_REF][START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF][START_REF] Mao | [END_REF][START_REF] Mao | [END_REF][START_REF] Mao | [END_REF]Mao et al., , 2011bMao et al., , 2013a;;[START_REF] Faure | Palaeozoic collision between the North and South China blocks, Triassic intracontinental tectonics, and the problem of the ultrahigh-pressure metamorphism[END_REF][START_REF] Faure | Intracontinental subduction: a possible mechanism for the Early Palaeozoic Orogen of SE China[END_REF]Faure et al., , 2016aFaure et al., , 2016b[START_REF] Faure | Tectonics and geodynamics of South China: An introductory note[END_REF][START_REF] Shu | Mesozoic tectonic evolution of the Southeast China Block: New insights from basin analysis[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF][START_REF] Wan | The tectonics of China: data, maps and evolution[END_REF][START_REF] Hu | Multiple Mesozoic mineralization events in South China-an introduction to the thematic issue[END_REF][START_REF] Shu | An analysis of principal features of tectonic evolution in South China Block[END_REF][START_REF] Zhao | Precambrian geology of China[END_REF]Pirajno, 2013;[START_REF] Zhang | Tectonics of South China Continent and its implications[END_REF][START_REF] Hu | Reviews and new metallogenic models of mineral deposits in South China: An introduction[END_REF][START_REF] Zhao | Genetic types, mineralization styles, and geodynamic settings of Mesozoic tungsten deposits in South China[END_REF]. As one of the main continental fragments disaggregated from the Gondwana supercontinent that assembled together with Siberia to construct the present Eurasia [START_REF] Metcalfe | Gondwana dispersion and Asian accretion: Tectonic and palaeogeographic evolution of eastern Tethys[END_REF], the South China Block is a major continental component with a complex history of tectonic evolution in East Asia [START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF][START_REF] Shu | Late Mesozoic tectonism of southeast China[END_REF]Li and Li, 2007;Wang et al., 2007a[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Wang et al., , 2017a;;[START_REF] Faure | Palaeozoic collision between the North and South China blocks, Triassic intracontinental tectonics, and the problem of the ultrahigh-pressure metamorphism[END_REF][START_REF] Faure | Intracontinental subduction: a possible mechanism for the Early Palaeozoic Orogen of SE China[END_REF]Faure et al., , 2016aFaure et al., , 2016b[START_REF] Faure | Tectonics and geodynamics of South China: An introductory note[END_REF][START_REF] Li | Amalgamation between the Yangtze and Cathaysia Blocks in South China: Constraints from SHRIMP U-Pb zircon ages, geochemistry and Nd-Hf isotopes of the Shuangxiwu volcanic rocks[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of south China: Part 1, polyphase deformation in the Jiuling and Lianyunshan domains of the central Jiangnan Orogen[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of South China: Early Paleozoic sinistral and Triassic dextral transpression in the east Wuyishan and Chencai domains[END_REF]Li et al., , 2018a;;[START_REF] Shu | Mesozoic tectonic evolution of the Southeast China Block: New insights from basin analysis[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF][START_REF] Wan | The tectonics of China: data, maps and evolution[END_REF][START_REF] Shu | An analysis of principal features of tectonic evolution in South China Block[END_REF][START_REF] Zhao | Precambrian geology of China[END_REF][START_REF] Zhang | Tectonics of South China Continent and its implications[END_REF]. The South China Block

Geodynamic evolution

It is generally accepted that the South China Block was constructed through a Neoproterozoic amalgamation of the Yangtze Block and the Cathaysia Block with the Jiangnan Orogen as the suture zone between them (Figs. 2-2 and 2-3a), although the precise time of the amalgamation is still controversial from 1.0 Ga to 0.8 Ga [START_REF] Li | Grenvillian continental collision in south China: New SHRIMP U-Pb zircon results and implications for the configuration of Rodinia[END_REF][START_REF] Li | Neoproterozoic granitoids in South China: crustal melting above a mantle plume at ca. 825 Ma?[END_REF](Li et al., , 2007b[START_REF] Li | Obduction-type granites within the NE Jiangxi Ophiolite: Implications for the final amalgamation between the Yangtze and Cathaysia Blocks[END_REF][START_REF] Li | Amalgamation between the Yangtze and Cathaysia Blocks in South China: Constraints from SHRIMP U-Pb zircon ages, geochemistry and Nd-Hf isotopes of the Shuangxiwu volcanic rocks[END_REF](Li et al., , 2014b;;Wang and Li, 2003;Shu et al., 2006a[START_REF] Shu | Geochronological and geochemical features of the Cathaysia block (South China): New evidence for the Neoproterozoic breakup of Rodinia[END_REF]Zhou et al., 2006b;Wang et al., 2007a;[START_REF] Cawood | Locating South China in Rodinia and Gondwana: A fragment of greater India lithosphere?[END_REF]Yao et al., 2014a). After the collision of the Yangtze Block and the Cathaysia Block, the South China Block experienced a regional-scale extension during Late Neoproterozoic which led to the formation of rift basins that contain a set of siliciclastic sediments coeval with bimodal volcanic rocks (800 -690 Ma; Fig. 2-3b) (Wang and Li, 2003;[START_REF] Shu | Geochronological and geochemical features of the Cathaysia block (South China): New evidence for the Neoproterozoic breakup of Rodinia[END_REF]Li et al., 2014b). Then the Cathaysia Block underwent a stable intraplate neritic-bathyal depositional stage from Sinian to Early Paleozoic (690 -460 Ma;

Fig. 2-3c) during which thick siliciclastic sediments were formed [START_REF] Shu | Early Paleozoic depositional environment and intraplate tectono-magmatism in the Cathaysia Block (South China): Evidence from stratigraphic, structural, geochemical and geochronological investigations[END_REF] without volcanic magmatism and any evidence for the input of mantle-derived materials.

In Phanerozoic, the South China Block mainly experienced three tectonothermal events, i.e., Early Paleozoic, Triassic, and Jurassic-Cretaceous events, which were generally referred to as "Caledonian or Kwangsian", "Indosinian", and "Yanshanian" movements by Chinese Early Mesozoic (cited from [START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF].

geologists, respectively (Ting, 1929;[START_REF] Hsu | Discovery of granites of the Caledonian age in southern Kiangsi[END_REF]Hsu et al., , 1963aHsu et al., , 1963b;;[START_REF] Ren | On the geotectonics of southern China[END_REF][START_REF] Hua | A preliminary discussion on the Mesozoic metallogenic explosion in East China[END_REF][START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF][START_REF] Hua | Metallogenic systems related to Mesozoic and Cenozoic granitoids in South China[END_REF][START_REF] Hua | Three major metallogenic events in Mesozoic in South China[END_REF]Wang et al., 2005aWang et al., , 2010Wang et al., , 2011a[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Zhou et al., 2006a;[START_REF] Chen | Ordovician graptolite-bearing strata in southern Jiangxi with a special reference to the Kwangsian Orogeny[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF]. The Early Paleozoic tectonic movement was commonly recognized according to the presence of a conspicuous unconformity between the Middle Devonian and Silurian strata, pervasive shortening deformation, and high-grade metamorphism [START_REF] Grabau | Stratigraphy of China, Part I, Paleozoic and Older[END_REF]Ting, 1929;[START_REF] Lin | Phanerozoic tectonics of south China block: New insights from the polyphase deformation in the Yunkai massif[END_REF][START_REF] Faure | Intracontinental subduction: a possible mechanism for the Early Palaeozoic Orogen of SE China[END_REF][START_REF] Charvet | Structural development of the Lower Paleozoic belt of South China: Genesis of an intracontinental orogen[END_REF][START_REF] Li | Magmatic and metamorphic events during the early Paleozoic Wuyi-Yunkai orogeny, southeastern South China: New age constraints and pressure-temperature conditions[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of south China: Part 1, polyphase deformation in the Jiuling and Lianyunshan domains of the central Jiangnan Orogen[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of South China: Early Paleozoic sinistral and Triassic dextral transpression in the east Wuyishan and Chencai domains[END_REF][START_REF] Charvet | The Neoproterozoic-Early Paleozoic tectonic evolution of the South China Block: An overview[END_REF][START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF]. It is now commonly interpreted as an intracontinental orogeny due to the lack of ophiolitic rocks, accretionary complexes, volcanic rocks with arc affinities, and the input of mantle-derived components in granitic magmatism [START_REF] Faure | Intracontinental subduction: a possible mechanism for the Early Palaeozoic Orogen of SE China[END_REF][START_REF] Charvet | Structural development of the Lower Paleozoic belt of South China: Genesis of an intracontinental orogen[END_REF][START_REF] Li | Magmatic and metamorphic events during the early Paleozoic Wuyi-Yunkai orogeny, southeastern South China: New age constraints and pressure-temperature conditions[END_REF][START_REF] Charvet | The Neoproterozoic-Early Paleozoic tectonic evolution of the South China Block: An overview[END_REF][START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF]. Three competing tectonic models have (Figs. 2-3d and 2-4c;[START_REF] Shu | Early Paleozoic depositional environment and intraplate tectono-magmatism in the Cathaysia Block (South China): Evidence from stratigraphic, structural, geochemical and geochronological investigations[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF]. This tectonic event was constrained in chronology by newly grown mica 40 Ar/ 39 Ar dating at 450 -390 Ma with contemporaneous anatectic granites dated at 460 -390 Ma [START_REF] Shu | Study of the 40 Ar/ 39 Ar isotopic age for the Early Paleozoic tectonothermal event in the Wuyishan region, South China[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF][START_REF] Charvet | Structural development of the Lower Paleozoic belt of South China: Genesis of an intracontinental orogen[END_REF][START_REF] Shu | An analysis of principal features of tectonic evolution in South China Block[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of south China: Part 1, polyphase deformation in the Jiuling and Lianyunshan domains of the central Jiangnan Orogen[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of South China: Early Paleozoic sinistral and Triassic dextral transpression in the east Wuyishan and Chencai domains[END_REF]. During Late Paleozoic from 390 Ma to 240 Ma, the South China Block underwent a stable intraplate carbonate depositional stage in a littoral-neritic environment resulting in the formation of a series of limestone, dolomite, and clastic rocks (Fig. 2-3e; Shu et al., 2006b[START_REF] Shu | Late Paleozoic-Early Mesozoic geological features of South China: Response to the Indosinian collision event in Southeast Asia[END_REF][START_REF] Shu | Mesozoic tectonic evolution of the Southeast China Block: New insights from basin analysis[END_REF].

Triassic is the main period for the development of the South China tectonic framework (Faure et al., 2016a[START_REF] Faure | Tectonics and geodynamics of South China: An introductory note[END_REF]. The Triassic tectonic movement was initially recognized due to the Late Triassic (Norian) angular unconformity of conglomerate and sandstone overlaying folded and metamorphosed rocks in Vietnam of the Indochina Block [START_REF] Deprat | Étude des plissements et des zones d'écrasement de la Moyenne et de la Basse Rivière Noire[END_REF][START_REF] Deprat | Études géologiques sur la région septentrionale du Haut-Tonkin (feuilles de Pa Kha, Ha Giang, Ma-Li-Po, Yen Minh)[END_REF][START_REF] Fromaget | Sur la structure des Indosinides[END_REF][START_REF] Fromaget | L'Indochine française, sa structure géologique, ses roches, ses mines et leurs relations possibles avec la tectonique[END_REF]. In South China, the Triassic event is recorded as a regional Late Triassic unconformity, folding, thrusting, ductile shearing, metamorphism, and granitic magmatism (Wang et al., 2005a[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF][START_REF] Lin | Phanerozoic tectonics of south China block: New insights from the polyphase deformation in the Yunkai massif[END_REF][START_REF] Shu | Late Paleozoic-Early Mesozoic geological features of South China: Response to the Indosinian collision event in Southeast Asia[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF][START_REF] Zhang | NE-SW-trending Hepu-Hetai dextral shear zone in southern China: Penetration of the Yunkai Promontory of South China into Indochina[END_REF]Chu et al., 2012aChu et al., , 2012b;;Faure et al., 2016aFaure et al., , 2016b[START_REF] Faure | Tectonics and geodynamics of South China: An introductory note[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of south China: Part 1, polyphase deformation in the Jiuling and Lianyunshan domains of the central Jiangnan Orogen[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of South China: Early Paleozoic sinistral and Triassic dextral transpression in the east Wuyishan and Chencai domains[END_REF]). An

Alps-type collision model (Fig. 2-4d) was proposed by [START_REF] Hsü | Mesozoic overthrust tectonics in south China[END_REF][START_REF] Hsü | Tectonics of South China: Key to understanding West Pacific geology[END_REF] to explain the origin of this tectonic event based on interpreting the Banxi Group as a Mesozoic ophiolitic mélange. However, subsequent studies revealed that the Banxi Group is composed of a Neoproterozoic turbidite sequence [START_REF] Gu | Provenance and tectonic setting of the Proterozoic turbidites in Hunan, South China: Geochemical evidence[END_REF]Wang and Li, 2003;Wang et al., 2007a).

Although it is now widely accepted that the Triassic tectonic movement in the South China

Block is an intraplate deformation event [START_REF] Lin | Phanerozoic tectonics of south China block: New insights from the polyphase deformation in the Yunkai massif[END_REF][START_REF] Shu | Late Paleozoic-Early Mesozoic geological features of South China: Response to the Indosinian collision event in Southeast Asia[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF]Chu et al., 2012aChu et al., , 2012b;;[START_REF] Faure | The South China Block-Indochina collision: Where, when, and how?[END_REF], the geodynamic mechanism of this event is still disputed with the following models: (1) flat-slab subduction model of the palaeo-Pacific plate (Figs.

2-4e and 2-5a-d) proposed by Li and Li (2007), (2) intraplate oblique convergence of the Yangtze Block and the Cathaysia Block (Fig. 2-4f) proposed by Wang et al. (2005a), and (3) collision of the South China Block with the Indochina Block and/or the North China Block (Figs. 2-4g and 2-6a-b) [START_REF] Lepvrier | The Early Triassic Indosinian orogeny in Vietnam (Truong Son Belt and Kontum Massif); implications for the geodynamic evolution of Indochina[END_REF][START_REF] Faure | Palaeozoic collision between the North and South China blocks, Triassic intracontinental tectonics, and the problem of the ultrahigh-pressure metamorphism[END_REF][START_REF] Cai | A new model for the Indochina and South China collision during the Late Permian to the Middle Triassic[END_REF]; Wang et al., 2013;[START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF][START_REF] Li | New insights into Phanerozoic tectonics of south China: Part 1, polyphase deformation in the Jiuling and Lianyunshan domains of the central Jiangnan Orogen[END_REF]. [START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF] emphasized that the interaction between the South China Block and the surrounding blocks/plates provided the first-order driving force for the Triassic intracontinental deformation across the South China Block. The third tectonic model is becoming more and more popular than the former two, however, the influence of the palaeo-Pacific plate subduction during Triassic is still uncertain [START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF].

During Late Mesozoic (Jurassic-Cretaceous), the South China Block was dominated by an extensional tectonic regime, which is demonstrated by the occurrence of abundant granitoid rocks with an evident input of juvenile mantle-derived components, the wide distribution of extensional basins, the existence of extensional tectonomagmatic associations, the extensional information recorded by magma emplacement processes, and the absence of compressional deformation structures [START_REF] Shu | Late Mesozoic tectonism of southeast China[END_REF]Shu et al., 2006b[START_REF] Shu | Mesozoic tectonic evolution of the Southeast China Block: New insights from basin analysis[END_REF][START_REF] Shu | An analysis of principal features of tectonic evolution in South China Block[END_REF][START_REF] Wang | Late Mesozoic basin and range tectonics and related magmatism in Southeast China[END_REF][START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Wei et al., 2014aWei et al., , 2014b[START_REF] Wei | An early extensional event of the South China Block during the Late Mesozoic recorded by the emplacement of the Late Jurassic syntectonic Hengshan Composite Granitic Massif (Hunan, SE China)[END_REF]. [START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF] firstly proposed the model of palaeo-Pacific plate subduction with changing angles (Fig. 234567) to understand the origin of the large-scale Late Mesozoic granitic magmatism in Southeastern China. A combination of the palaeo-Pacific plate subduction induced back-arc extensional setting, asthenosphere upwelling, basaltic magmas underplating, and crustal anatexis is thought to be the key mechanism for the generation of these Late Mesozoic granitoid rocks [START_REF] Shu | Late Mesozoic tectonism of southeast China[END_REF]Zhou et al., 2006a). A transition of regional tectonic regime from the Tethysian domain to the palaeo-Pacific domain is suggested to occur in Early-Middle Jurassic [START_REF] Shu | Late Mesozoic tectonism of southeast China[END_REF]Zhou et al., 2006a;[START_REF] Shu | An analysis of principal features of tectonic evolution in South China Block[END_REF]. Li and Li (2007) interpreted the Late Mesozoic granitoid rocks as a result of postorogenic magmatism induced

2-6d

). However, the geophysical study on granite emplacement mechanism carried out by [START_REF] Liu | Incremental emplacement of the late Jurassic mid-crustal, lopolith-like Qitianling pluton, South China, revealed by AMS and Bouguer gravity data[END_REF] revealed that the Late Jurassic Qitianling pluton in South China was formed during a period of tectonic quiescence. Therefore, the Jurassic tectonic setting in South China remains a subject of controversy that need to be solved by further studies.

Multiple-aged granitoids and volcanic rocks

The outcrop area of the multiple-aged granitoids in the South China Block is about , 2006). In addition, the Jurassic and Cretaceous volcanic rocks have outcrop areas of 1,170 km 2 and 89,620 km 2 , respectively (Fig. 2-8; Zhou et al., 2006a).

These multiple-aged granitoids and volcanic rocks in the South China Block respectively have unique spatial distributions, chronological features, structural characteristics, mineralogical and geochemical compositions, and relations with tectonic events.

The Neoproterozoic granitoids mostly occur as peraluminous granite batholiths along the southeastern margin of the Yangtze Block in southern Anhui, northern Jiangxi, southern Hubei, and northern Guangxi Provinces (Fig. 2345678), such as the Xucun, Jiuling, Motianling, and Yuanbaoshan granites. They were partially deformed as gneissoid granites and coexist with a set of slightly earlier formed Neoproterozoic island-arc volcanic-sedimentary sequence [START_REF] Zhou | My thinking about granite geneses of South China[END_REF]Sun, 2006). These Neoproterozoic granites generally contain aluminum-rich minerals, such as cordierite, muscovite, tourmaline, and garnet, and are considered as S-type granites [START_REF] Li | Neoproterozoic granitoids in South China: crustal melting above a mantle plume at ca. 825 Ma?[END_REF][START_REF] Zhou | My thinking about granite geneses of South China[END_REF]. Some Neoproterozoic I-type granitoids also appear in 2006 andZhou et al., 2006a).

the South China Block, such as the Huangling complex in western Hubei Province (Fig. 2345678)

which is comprised of dominant Na-rich tonalite-trondhjemite-granodiorite association and minor K-rich calc-alkaline intrusions [START_REF] Li | Neoproterozoic granitoids in South China: crustal melting above a mantle plume at ca. 825 Ma?[END_REF]. The Neoproterozoic granitoids were mostly formed at ca. 830 Ma and were derived from partial melting of various crustal sources with different influences by juvenile mantle-derived components [START_REF] Li | Neoproterozoic granitoids in South China: crustal melting above a mantle plume at ca. 825 Ma?[END_REF][START_REF] Zhou | My thinking about granite geneses of South China[END_REF]Sun, 2006;Yao et al., 2014a;Zhang et al., 2016a;Wang et al., 2017a;[START_REF] Xiang | Neoproterozoic mineralization in a hydrothermal cassiterite-sulfide deposit at Jiumao, northern Guangxi, South China: Mineral-scale constraints on metal origins and ore-forming processes[END_REF]. [START_REF] Li | Neoproterozoic granitoids in South China: crustal melting above a mantle plume at ca. 825 Ma?[END_REF] introduced a model of mantle plume beneath South China to interpret the origin of these Neoproterozoic granitoids, however, it is now more accepted that the generation of these Neoproterozoic granitoids was related to the amalgamation of the Yangtze and Cathaysia Blocks and its post-orogenic extension [START_REF] Zhou | My thinking about granite geneses of South China[END_REF]Sun, 2006;Yao et al., 2014a;Wang et al., 2017a).

The Early Paleozoic granitoids are mainly distributed in the boundary areas between Jiangxi and Fujian, Jiangxi and Hunan, Hunan and Guangxi, and Guangxi and Guangdong Provinces (Fig. 2345678). However, Early Paleozoic volcanic rocks and associated mafic intrusions are poor in the South China Block interior [START_REF] Zhou | My thinking about granite geneses of South China[END_REF]Sun, 2006;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Zhang et al., 2017d). These Early Paleozoic granitoids can be divided into relatively earlier gneissoid granites and relatively later massive granitoids with respective peak ages of ca. 440 Ma and ca. 420 Ma (Sun, 2006;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF][START_REF] Shu | Early Paleozoic depositional environment and intraplate tectono-magmatism in the Cathaysia Block (South China): Evidence from stratigraphic, structural, geochemical and geochronological investigations[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF]. The gneissoid granites are less voluminous than the massive granitoids and generally contain muscovite, garnet, and tourmaline. The massive granitoids mostly occur as large-volume batholiths and laccoliths and are characterized by peraluminous biotite monzonitic granites, two-mica monzonitic granites, and muscovite-(garnet) granites [START_REF] Wu | Geological and geochemical characteristics and genesis of the Caledonian Wanyangshan granite in the Nanling Mountains, South China[END_REF][START_REF] Charvet | Structural development of the Lower Paleozoic belt of South China: Genesis of an intracontinental orogen[END_REF][START_REF] Li | Magmatic and metamorphic events during the early Paleozoic Wuyi-Yunkai orogeny, southeastern South China: New age constraints and pressure-temperature conditions[END_REF][START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]. There are also some biotite granodiorites and hornblende-bearing granites. For the petrogenesis of these Early Paleozoic granitoids, Sun ( 2006) pointed out that the gneissoid granites were formed through crustal partial melting by a combined compression, ductile deformation, and migmatization mechanism, whereas, the massive granitoids were formed by partial melting of dominant crustal materials with possible input of mantle-derived components under an extensional tectonic setting. [START_REF] Zhang | LA-ICPMS zircon U-Pb geochronology of late Early Paleozoic granites in eastern Hunan and western Jiangxi provinces, South China[END_REF][START_REF] Zhang | Geochronological and geochemical constraints on the petrogenesis of Middle Paleozoic (Kwangsian) massive granites in the eastern South China Block[END_REF] and Wang et al. (2011a) proposed that these Early Paleozoic granitoids probably originated from partial melting of Proterozoic metapelite and meta-igneous rocks with poor input of juvenile mantle-derived components. [START_REF] Li | Magmatic and metamorphic events during the early Paleozoic Wuyi-Yunkai orogeny, southeastern South China: New age constraints and pressure-temperature conditions[END_REF] and Wang et al. (2011a) interpreted their origin to be related to increased thermal weakening of the thickened continental crust during Early Paleozoic.

The Late Paleozoic magmatic rocks in the South China Block are dominated by the voluminous Emeishan basalts and related intrusions in Southwest China which were formed at ca. 260 Ma in Late Permian [START_REF] Xu | Petrologic and geochemical constraints on the petrogenesis of Permian-Triassic Emeishan flood basalts in southwestern China[END_REF][START_REF] Fan | Geochronology and geochemistry of Permian basalts in western Guangxi Province, Southwest China: Evidence for plume-lithosphere interaction[END_REF][START_REF] Zhou | Two magma series and associated ore deposit types in the Permian Emeishan large igneous province, SW China[END_REF]. However, the Late Paleozoic granitoids are rarely exposed and are dominantly distributed in southern Hainan Island. These Late Paleozoic granitoids in Hainan are characterized by calc-alkaline gneissoid granites which have ages of 267 -252 Ma, show the geochemical features of I-type granites, and are thought to be related to a continental arc setting [START_REF] Li | Initiation of the Indosinian orogeny in South China: evidence for a Permian magmatic arc on Hainan Island[END_REF][START_REF] Chen | Zircon LA-ICP-MS U-Pb dating of granitic gneisses from Wuzhishan area, Hainan, and geological significances[END_REF]. They are temporally similar to the gneissoid granodiorites in the Ailaoshan-Song Ma suture zone between the South China Block and the Indochina Block [START_REF] Lan | Geochemical and Sr-Nd isotopic characteristics of granitic rocks from northern Vietnam[END_REF][START_REF] Carter | Understanding Mesozoic accretion in Southeast Asia: Significance of Triassic thermotectonism (Indosinian orogeny) in Vietnam[END_REF][START_REF] Carter | Was the Indosinian orogeny a Triassic mountain building or a thermotectonic reactivation event?[END_REF].

The Triassic granitoids are mainly spread in southeastern Guangxi, Hunan, northern Guangdong, southern Jiangxi, and western Fujian Provinces (Fig. 2 Ma [START_REF] Wang | Petrogenesis of the Late Mesozoic granitic volcanic-intrusive complexes and crustal evolution in Southeastern China[END_REF][START_REF] Li | Zircon U-Pb age and its geological significance for Qiongzhong pluton in Qiongzhong area, Hainan Island[END_REF]Wang et al., 2005bWang et al., , 2007b[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Peng et al., 2006a;Zhou et al., 2006a;[START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF][START_REF] Zhang | Petrogenesis of the concealed Daqiling intrusion in Guangxi and its tectonic significance: Constraints from geochemistry, zircon U-Pb dating and Nd-Hf isotopic compositions[END_REF]. Except for the garnet-and cordierite-bearing granites in the Darongshan-Shiwandashan and northern Yunkai domains, most of these peraluminous massive granitoids are biotite monzonitic granites, two-mica monzonitic granites, and muscovite granites [START_REF] Zhou | Geochemistry of the granitoids in Mesozoic metamorphic belt of coastal Fujian Province[END_REF][START_REF] Wang | Petrogenesis of the Late Mesozoic granitic volcanic-intrusive complexes and crustal evolution in Southeastern China[END_REF]Zhou et al., 2006a;[START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF]. The Triassic granitoids contain both S-type and I-type granites and are dominated by S-type granites. It is generally accepted that these granitoids were derived from partial melting of crustal metamorphic basements without significant addition of juvenile mantle-derived components [START_REF] Ge | Mesozoic magmatism in Hainan Island (SE China) and its tectonic significance: geochronology, geochemistry and Sr-Nd isotope evidences[END_REF][START_REF] Deng | SHRIMP U-Pb zircon dating of the Darongshan-Shiwandashan granitoid belt in southeastern Guangxi, China[END_REF]Wang et al., 2007b). For the petrogenetic mechanism of these Triassic granitoids, Wang et al. (2002aWang et al. ( , 2007b) ) emphasized the importance of isostatic adjustment of the thickened continental crust, with heat supplied from in-situ radiogenic heating in the thickened continental crust, and subsequent heating by underplated basaltic magmas. Zhou et al. (2006a) interpreted the earlier gneissoid granites as syn-collisional granites and the later massive granitoids as late collisional granitoids.

The Jurassic granitoids occupy the largest exposure area of the whole multiple-aged granitoids in South China and are mostly distributed in Guangdong, Hunan, Jiangxi, and Fujian Provinces far away from the southeast coastline (Fig. 2345678). These Jurassic granitoids show a southwest-northeast trend of spatial distribution overall and exhibit a west-east extending trend in the Nanling Range made up of three distinguishable belts which are the northern Qitianling-Jiufeng belt, the middle Dadongshan-Guidong belt, and the southern Fogang-Xinfengjiang belt (Fig. 2-8;Sun, 2006;Zhou et al., 2006a;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]. These Jurassic granitoids were mainly formed from 165 Ma to 150 Ma and are composed of I-type, S-type, and A-type granitoids and minor syenites [START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF][START_REF] Hua | Metallogenic systems related to Mesozoic and Cenozoic granitoids in South China[END_REF][START_REF] Hua | Three major metallogenic events in Mesozoic in South China[END_REF]Sun et al., 2005;Sun, 2006;Zhou et al., 2006a;Li and Li, 2007;[START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF][START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Jiang | Characteristics and genesis of Mesozoic A-type granites and associated mineral deposits in the Southern Hunan and Northern Guangxi provinces along the Shi-Hang Belt, South China[END_REF][START_REF] Mao | [END_REF]Mao et al., , 2013a;;[START_REF] Zhu | Early Yanshanian NE trending Sn/W-bearing A-type granites in the western-middle part of the Nanling Mts region[END_REF][START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Huang et al., 2017a). Compared with the Jurassic granitoids, the Jurassic volcanic rocks are obviously less exposed and are mostly spread in southern Hunan, southern Jiangxi, northeastern Guangdong, and southwestern Fujian Provinces with a rough west-east trend.

They were dominantly formed in Early-Middle Jurassic from 195 Ma to 170 Ma and are mainly composed of bimodal magmatic assemblages of basalt and rhyolite with similar abundances (Zhou et al., 2006a;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF].

The Cretaceous granitoids occupy the second largest exposure area of the whole multiple-aged granitoids in South China and are mainly spread in the coastal Guangdong, Fujian, and Zhejiang Provinces with a southwest-northeast extending trend, and also in the Lower Yangtze northern Hunan, southern Hubei, and southern Anhui Provinces with a west-north-east trend of spatial distribution (Fig. 2345678). These Cretaceous granitoids were mainly formed from 135 Ma to 80 Ma with two peak ages of 125 Ma and 93 Ma and are composed of I-type, S-type, and A-type granitoids, and minor alkaline rocks [START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF][START_REF] Wang | Petrogenesis of the Late Mesozoic granitic volcanic-intrusive complexes and crustal evolution in Southeastern China[END_REF][START_REF] Hua | Metallogenic systems related to Mesozoic and Cenozoic granitoids in South China[END_REF][START_REF] Hua | Three major metallogenic events in Mesozoic in South China[END_REF]Sun, 2006;Zhou et al., 2006a;Li and Li, 2007;[START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF][START_REF] Mao | [END_REF]Mao et al., , 2013a;;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF][START_REF] Yan | Petrogenetic contrastive studies on the Mesozoic early stage ore-bearing and late stage ore-barren granites from the southern Anhui Province[END_REF]. Compared with the Cretaceous granitoids, the Cretaceous volcanic rocks are much more voluminous and are mainly distributed in the coastal Zhejiang, Fujian, and Guangdong Provinces constituting a northeast-trending volcanic zone (Fig. 2345678). They were mainly formed from 130 Ma to 85

Ma and are dominated by granitic volcanic-subvolcanic-intrusive assemblages with minor mafic rocks (Zhou et al., 2006a;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF].

The Early-Middle Jurassic volcanic rocks in the South China Block were interpreted as to genetically associated with crust-mantle interaction under a rift-like setting in response to the far-field effect induced by the palaeo-Pacific plate subduction (Zhou et al., 2006a(Zhou et al., , 2006c;;[START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF][START_REF] He | Petrogenesis and tectonic significance of a Mesozoic granite-syenite-gabbro association from inland South China[END_REF][START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]. Zhou et al. (2006a) proposed that the formation of these Early-Middle Jurassic volcanic rocks might mark the ending of the old

Tethysian tectonic regime and the beginning of the new palaeo-Pacific tectono-magmatic cycle. The explosive formation of the Late Mesozoic granitoids and the Cretaceous volcanic rocks is widely considered as a result of the palaeo-Pacific plate subduction, asthenosphere upwelling, basaltic magmas underplating, and crustal anatexis, and maybe also post-orogenic extension [START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF][START_REF] Shu | Late Mesozoic tectonism of southeast China[END_REF][START_REF] Wang | Petrogenesis of the Late Mesozoic granitic volcanic-intrusive complexes and crustal evolution in Southeastern China[END_REF]Zhou et al., 2006a;Li and Li, 2007;[START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF]Mao et al., 2013a;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF]Huang et al., 2017a;Li et al., 2018a). Compared with the Early Paleozoic and Triassic granitoids, the Late Mesozoic granitoids distinctly contain more juvenile mantle-derived components (Zhou et al., 2006a;[START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF].

Polymetallic mineralization

Numerous mineral deposits of W, Sn, rare metals, base metals, and precious metals have [START_REF] Hua | [END_REF][START_REF] Hua | Metallogenic systems related to Mesozoic and Cenozoic granitoids in South China[END_REF][START_REF] Hua | Three major metallogenic events in Mesozoic in South China[END_REF][START_REF] Mao | Large-scale tungsten-tin mineralization in the Nanling region, South China: Metallogenic ages and corresponding geodynamic processes[END_REF][START_REF] Mao | [END_REF][START_REF] Mao | [END_REF]Mao et al., , 2009b[START_REF] Mao | [END_REF]Mao et al., , 2011bMao et al., , 2013a;;[START_REF] Zaw | Nature, diversity of deposit types and metallogenic relations of South China[END_REF][START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF]Chen et al., , 2015a;;[START_REF] Ma | Metallogenetic characteristics of the important deposits in South China[END_REF][START_REF] Pei | South China great granite province and its metallogenic series of tungsten-tin poly-metallics[END_REF]Cheng et al., 2010;[START_REF] Hu | Multiple Mesozoic mineralization events in South China-an introduction to the thematic issue[END_REF][START_REF] Fu | Metallogenesis of W(Sn) deposits and their exploration in Nanling Range, China[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF]Pirajno, 2013;[START_REF] Sheng | Outline of metallogeny of tungsten deposits in China[END_REF][START_REF] Hu | Major scientific problems on low-temperature metallogenesis in South China[END_REF][START_REF] Hu | Reviews and new metallogenic models of mineral deposits in South China: An introduction[END_REF][START_REF] Zhao | Genetic types, mineralization styles, and geodynamic settings of Mesozoic tungsten deposits in South China[END_REF][START_REF] Zhou | Geological settings and metallogenesis of Qinzhou Bay-Hangzhou Bay orogenic juncture belt, South China[END_REF][START_REF] Zhou | Introduction to the special issue of Mesozoic W-Sn deposits in South China[END_REF]. The vast majority of these multiple-aged mineral deposits are temporally and spatially closely associated with the multiple-aged granitoids in the South China Block (Fig. 2-10;[START_REF] Hua | Metallogenic systems related to Mesozoic and Cenozoic granitoids in South China[END_REF][START_REF] Mao | Large-scale tungsten-tin mineralization in the Nanling region, South China: Metallogenic ages and corresponding geodynamic processes[END_REF][START_REF] Mao | [END_REF][START_REF] Mao | [END_REF]Mao et al., , 2009b[START_REF] Mao | [END_REF]Mao et al., , 2011bMao et al., , 2013a;;[START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Ma | Metallogenetic characteristics of the important deposits in South China[END_REF]Pei et al., 2008;[START_REF] Cheng | Geochronology framework of the W-Sn mineralization granites in western South China and their geological significance[END_REF][START_REF] Hu | Multiple Mesozoic mineralization events in South China-an introduction to the thematic issue[END_REF][START_REF] Fu | Metallogenesis of W(Sn) deposits and their exploration in Nanling Range, China[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF][START_REF] Hu | Major scientific problems on low-temperature metallogenesis in South China[END_REF][START_REF] Hu | Reviews and new metallogenic models of mineral deposits in South China: An introduction[END_REF][START_REF] Zhao | Genetic types, mineralization styles, and geodynamic settings of Mesozoic tungsten deposits in South China[END_REF][START_REF] Zhou | Geological settings and metallogenesis of Qinzhou Bay-Hangzhou Bay orogenic juncture belt, South China[END_REF][START_REF] Zhou | Introduction to the special issue of Mesozoic W-Sn deposits in South China[END_REF].

The Neoproterozoic mineralization has been discovered mainly in the Jiangnan Orogen between the Yangtze and Cathaysia Blocks so far. They are dominated by Sn and also some W deposits which are related to the Neoproterozoic granites in the Jiangnan Orogen, such as the Baotan Sn orefield associated with the Pingying granite (Zhang et al., 2016a;[START_REF] Chen | Zircon and cassiterite U-Pb ages, petrogeochemistry and metallogenesis of Sn deposits in the Sibao area, northern Guangxi: constraints on the neoproterozoic granitic magmatism and related Sn mineralization in the western Jiangnan Orogen, South China[END_REF], the Jiumao Sn deposit associated with the Yuanbaoshan granite (Yao et al., 2014a;[START_REF] Xiang | Neoproterozoic mineralization in a hydrothermal cassiterite-sulfide deposit at Jiumao, northern Guangxi, South China: Mineral-scale constraints on metal origins and ore-forming processes[END_REF], the Biaoshuiyan and Heiwanhe Sn-W deposits associated with the Fanjingshan granite [START_REF] Xia | The geochemical features and genesis of Heiwan River W-Sn deposit in Guizhou[END_REF][START_REF] Zhu | Geological character and ore-controlling factors of Biaoshuiyan tin (tungsten) deposit in Fanjing Mountain[END_REF]Wang et al., 2011b), the Nanjia and Wuya W deposits associated with the Motianling granite [START_REF] Pan | Basic geological characteristics and its genesis of Wuya scheelite deposit in Congjiang[END_REF]Liu et al., 2016aLiu et al., , 2016b)), and the Huashandong W deposit associated with the Jiuling granite [START_REF] Zhong | SHRIMP U-Pb zircon geochemistry of the Jiuling granitic complex batholith in Jiangxi Province[END_REF][START_REF] Liu | Carbonate replacement and sometimes sulfide-quartz vein are also important mineralization types in the skarn Cu-Pb-Zn deposits. For instance, the Tongshanling Cu-Pb-Zn deposit is composed of skarn Cu (Mo), skarn Cu-Pb-Zn, sulfide-quartz vein Cu-Pb-Zn, and carbonate replacement Pb-Zn orebodies[END_REF]. [START_REF] Chen | Zircon and cassiterite U-Pb ages, petrogeochemistry and metallogenesis of Sn deposits in the Sibao area, northern Guangxi: constraints on the neoproterozoic granitic magmatism and related Sn mineralization in the western Jiangnan Orogen, South China[END_REF] Ma, 420 ± 4 Ma, 424 ± 5 Ma) deposit by LA-ICP-MS coltan U-Pb dating [START_REF] Che | Multi-aged mineralization of niobium and tantalum in South China: Constrained by in situ columbite-tantalite U-Pb LA-ICP-MS dating[END_REF].

During Triassic, some Nb-Ta deposits were formed at ca. 240 Ma and more W-Sn, Nb-Ta, and also U, Pb-Zn, Mo deposits were formed at ca. 220 150 [START_REF] Ma | Metallogenetic characteristics of the important deposits in South China[END_REF]Chen et al., 2015b;[START_REF] Liu | Geochemical characteristics of REEs and trace elements and Sm-Nd dating of scheelite from the Zhuxi giant tungsten deposit in northeast Jiangxi[END_REF][START_REF] Pan | Dating the giant Zhuxi W-Cu deposit (Taqian-Fuchun Ore Belt) in South China using molybdenite Re-Os and muscovite Ar-Ar system[END_REF]Wang et al., 2017b;[START_REF] He | Genesis of Zhuxi copper-tungsten deposit in Jiangxi Province: Insights from mineralogy and chronology[END_REF] in northern Jiangxi Province have changed the distribution framework of tungsten resources in South China.

Nanling Range

The Nanling Range covers a total area of about 200,000 km 2 in the central-southern part of South China from 111° E to 117° E and from 23°20' N to 26°40' N and includes southern Hunan, southern Jiangxi, northern Guangdong, northeastern Guangxi, and western Fujian Provinces (Fig. 1-1; Shu et al., 2006b;[START_REF] Zhou | Petrogenesis of the Late Mesozoic granitoids and lithosphere dynamic evolution in the Nanling Range[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF]

Chapter 3. Geology of the Tongshanling-Weijia area

In geography, the Tongshanling-Weijia area is situated in southern Hunan Province about 120 km to the east of Guilin (Fig. 1-1) and at the boundary region among Daoxian, Jiangyong, and Jianghua Counties. In geology, it is located in the conjunction zone between the Yangtze and Cathaysia Blocks, in the western part of the Nanling Range metallogenic belt (Fig. 1-1), and also in the southwestern part of the Qinzhou-Hangzhou metallogenic belt. The Haiyangshan-Dupangling, Jiuyishan, and Huashan-Guposhan plutons are distributed to the west, east, and south of the Tongshanling-Weijia area, respectively.

Stratigraphy

In the Tongshanling-Weijia area, the exposed strata include Ordovician to Triassic Ceshui Member of shale with intercalated marl, and the ca. 146-m-thick Zimenqiao Member of limestone with intercalated dolomitic limestone (Fig. 3-2). The Upper Carboniferous strata, i.e., the Hutian Group, consists of dolostone with a thickness larger than 170 m (Fig. 3-2). The Lower Permian strata, i.e., the Qixia Formation, is made up of chert-bearing limestone with a thickness larger than 40 m (Fig. 3-2). The Upper Triassic strata overlay the Lower Permian and Carboniferous strata by an angular unconformity and are composed of conglomerate, marl, and shale with a thickness larger than 60 m (Fig. 3-2).

Structures

The structural framework of the Tongshanling-Weijia area is south-north-to southwest-northeast-trending on the whole (Fig. 3-1). The folds in this area comprise alternatively appeared anticlines and synclines which are cut through by faults (Fig. 3

Magmatism

The Tongshanling granodiorite porphyry and the Weijia granite porphyry are the main magmatic rocks in the Tongshanling-Weijia area (Fig. 3-1). The Tongshanling granodiorite porphyry was emplaced as stocks with a total exposure area of 12 km 2 (Fig. 3

Mineralization

The polymetallic mineralization in the Tongshanling-Weijia area contains Cu-Pb-Zn and W mineralization associated with the Tongshanling granodiorite porphyry and the Weijia granite porphyry, respectively (Fig. 3-1). The Tongshanling Cu-Pb-Zn deposit, Jiangyong

Pb-Zn-Ag deposit, and Yulong Mo deposit, which are distributed around the Tongshanling granodioritic intrusion, constitute the Tongshanling Cu-Mo-Pb-Zn-Ag ore district (Fig. 3-1).

The Tongshanling polymetallic ore district is one of the oldest mines in the Nanling Range.

The ore-bearing horizons of these mineral deposits are the Middle Devonian Qiziqiao Formation, the Upper Devonian Shetianqiao Formation and Xikuangshan Formation, and the Shidengzi Member of the Upper Carboniferous Datang Stage (Fig. 3-2). The mineralization types of these mineral deposits include skarn, sulfide-quartz vein, and carbonate replacement with the Tongshanling Cu-Pb-Zn deposit dominated by skarn and sulfide-quartz vein mineralization, the Jiangyong Pb-Zn-Ag deposit dominated by carbonate replacement mineralization, and the Yulong Mo deposit dominated by skarn mineralization (Fig. 3-2). The Weijia W deposit is a recently discovered super-large scheelite skarn deposit in the Nanling Range. It is distributed in the contact zone between the Weijia granite porphyry and wall rocks (Fig. 3-1) and is mainly composed of magnesian and calcic skarn W orebodies, which appear in the Middle Member (dolostone) and Upper Member (limestone) of the Qiziqiao Formation, respectively (Fig. 3-2). The Weijia scheelite skarn deposit is a special case that is characterized by large-scale magnesian skarn mineralization and is significantly different from the other scheelite skarn deposits in the Nanling Range and also around the world which are mostly dominated by calcic skarn mineralization.

Chapter 4. Different origins of the Cu-Pb-Zn-bearing and W-bearing granitoids

Introduction

The Nanling Range of South China is world famous for its widely developed multiple-aged granitic magmatism (Early Paleozoic, Triassic, Jurassic, and Cretaceous) and related polymetallic mineralization (W, Sn, Nb, Ta, Cu, Pb, Zn, etc.) (Fig. 1-1) and thus has been of interest to geologists for a long time. Relative to Early Paleozoic, Triassic, and Cretaceous granitoids, Jurassic granitoids and related mineral deposits are the most important in the Nanling Range [START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF]Mao et al., 2013a). According to the association of ore-forming elements, petrographic and geochemical characteristics, the Jurassic ore-bearing granitoids in the Nanling Range can be divided into four different types:

W-bearing, Sn-bearing, Nb-Ta-bearing, and Cu-Pb-Zn-bearing. The W-bearing granites are dominated by crust-derived S-type two-mica, muscovite, and biotite granites [START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF]. The Sn mineralization is mainly associated with aluminous A-type (A2-type) granites [START_REF] Jiang | Characteristics and genesis of Mesozoic A-type granites and associated mineral deposits in the Southern Hunan and Northern Guangxi provinces along the Shi-Hang Belt, South China[END_REF][START_REF] Zhu | Early Yanshanian NE trending Sn/W-bearing A-type granites in the western-middle part of the Nanling Mts region[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF]. The Nb-Ta-bearing granites are mostly highly fractionated albite granites [START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF]. The Cu-Pb-Zn mineralization is predominantly related to amphibole-bearing metaluminous calc-alkaline granodiorites (Wang et al., 2003a;[START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF]. Various kinds of granitoids have distinct diversities in terms of metallogenic specialization. A comparative study of different types of ore-bearing granitoids will not only improve the understanding of the mechanism that controls metallogenic specialization, but also has important implications for prospecting and exploration.

The Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range are obviously different in terms of their petrography and geochemistry. However, the mechanism that created these differences is still not well understood. Numerous studies have been conducted on these two types of ore-bearing granitoids. The W-bearing granites are considered to be products of the partial melting of an old metasedimentary basement [START_REF] Zhang | Study on the characteristics, origin and related metallogeny of granites in Dajishan and Piaotang, Southern Jiangxi Province[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF][START_REF] Dong | Petrogenesis of the Yaogangxian granites and implications for W mineralization, Hunan Province[END_REF]Zhang, 2014), however, the petrogenesis of the Cu-Pb-Zn-bearing granitoids is still controversial. Wang et al. (2003a) held an opinion that the diorites-granodiorites in southeastern Hunan Province mainly originated from basaltic rocks from depleted mantle and were contaminated by some old crustal materials. Another opinion proposed by [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF] based on the Tongshanling granodiorite is that this type of granitoid was produced by the mixing of dominant melts from the partial melting of metasedimentary basement and some mantle-derived basaltic magmas. [START_REF] Yang | Petrogenesis of the Mesozoic Shuikoushan peraluminous I-type granodioritic intrusion in Hunan Province, South China: Middle-lower crustal reworking in an extensional tectonic setting[END_REF] considered that the Shuikoushan granodiorite originated from amphibole-dehydration melting of mafic rocks in the middle-lower crust.

Petrography of granitoids

Tongshanling granodiorite porphyry

The Tongshanling granodiorite is porphyritic and has a medium-fine granitic texture (Fig.

4-1a-c

). Phenocrysts are generally 1 -5cm in size and locally some plagioclase megacrysts can be greater than 10 cm. Rock-forming minerals are dominated by plagioclase (45 vol.%), K-feldspar (22 vol.%), quartz (20 vol.%), biotite (10 vol.%), and amphibole (3 vol.%).

Accessory minerals include mainly apatite, zircon, titanite, allanite, rutile, sulfides, and Fe-Ti oxide minerals. The Fe-Ti oxide minerals are mainly magnetites. Plagioclases with An%

Dioritic dark enclaves

Dioritic dark enclaves are commonly observed in the Tongshanling granodiorite porphyry. They are mostly ellipsoidal and several to dozens of centimeters in size. There is no quenched boundary between the enclaves and their host rocks. The enclaves have a fine granular texture and occasionally contain plagioclase phenocryst, which generally has a reaction rim (Fig. 4-1d). The mineral assemblage of the enclaves is the same as the host granodiorite porphyry, but the abundance of mafic minerals in the enclaves can reach 50 vol%.

The ratios of amphibole to biotite in the enclaves are quite variable. In most cases amphiboles are more than biotites (Fig. 4-1e), except for a few enclaves in which mafic minerals are dominated by biotites (Fig. 4-1f). Amphibole-rich clots (Fig. 4-1g) are common in the dark enclaves. Plagioclases have a zonal texture, An% values of 22 -45, and mostly show sericitized calcium-rich cores. Apatites have a needle-like or elongated prismatic shape (Fig.

4-1h).

Tongshanling granite porphyry

The Tongshanling granite porphyry has a porphyritic texture (Fig. 4-1i) and phenocrysts are mainly 0.2 -3 mm sized plagioclase (35 vol%), K-feldspar (30 vol%), quartz (30 vol%), and biotite (5 vol%). The matrix exhibits a fine-granular to felsitic texture (Fig. 4-1i).

Accessory minerals include mainly zircon and apatite. An embayed resorption texture is common for quartz phenocrysts. Biotites are brown and generally contain apatite inclusions.

Weijia granite porphyry

The Weijia granite porphyry is light red or off-white in outcrops at the surface and has a porphyritic texture. Phenocrysts are 30 -50 vol% in content and are comprised of quartz, K-feldspar, albite, and minor biotite. The phenocryst granularity is 0.5 -5 mm except for a few phenocrysts larger than 1 cm. The matrix has a fine granular to felsitic texture (Fig. 4-1j and k) and contains a few muscovites. Quartz phenocrysts generally have a hexagonal bipyramidal shape and resorption texture (Fig. 4-1j). In the rim of some K-feldspar phenocrysts, microgranular quartz grains, with a grain size of 10 -100 μm, constitute a "Pearlitic margin" texture (Fig. 4-1k), and the size of these quartz grains increases from inside to outside. A micrographic texture (Fig. 4-1l) can be found in K-feldspars. Accessory minerals include zircon, thorite, xenotime, monazite (Fig. 4-2d-f), niobite, samarskite, fergusonite, scheelite, parisite, and ilmenite.

Sampling and analytical methods

The samples of the Tongshanling granodiorite porphyry and its dioritic dark enclaves, the Tongshanling and Weijia granite porphyries were collected from outcrops at the surface and in the adits of mines.

Zircons were extracted by standard density and magnetic separation techniques. Intact and transparent zircon grains were handpicked under a binocular microscope, then mounted in an epoxy resin disc and polished. Cathodoluminescence (CL) image was obtained using a JEOL JSM-6510 scanning electron microscope equipped with a Gatan Mini-CL detector at the Beijing GeoAnalysis Co. Ltd. Whole-rock trace and rare earth element (REE), Sr-Nd isotope, and zircon U-Pb and Hf isotope analyses were performed at the State Key Laboratory for Mineral Deposits Research, Nanjing University.

The U-Pb isotope of zircons was determined by an Agilent 7500a ICP-MS equipped with a New Wave UP213 laser sampler. Analysis was performed with a beam diameter of 25 μm, 5

Hz repetition rate, energy of 10-20 J/cm 2 , acquisition time of 60 s, and background measurement of 40 s. Zircon Lu-Hf isotope was analyzed using a Neptune Plus MC-ICP-MS attached to a New Wave UP193FX laser ablation system. Analysis was performed with a beam diameter of 35 μm, 10 Hz repetition rate, acquisition time of 60 s, and acquisition number of 200 times. The detailed analytical procedures and data processing methods followed [START_REF] Zhang | Petrogenesis of the concealed Daqiling intrusion in Guangxi and its tectonic significance: Constraints from geochemistry, zircon U-Pb dating and Nd-Hf isotopic compositions[END_REF].

Whole-rock powder was dissolved in Teflon vessel using a HF+HNO3 mixture for trace element, rare earth element and Sr-Nd isotope analyses. Trace and rare earth elements were determined by a Finnigan MAT Element II HR-ICP-MS. The analytical conditions and procedure followed [START_REF] Gao | Analysis of trace elements in rock samples using HR-ICPMS[END_REF]. The analytical precision for most elements was better than 5 %. A cation-exchange resin was used to separate and purify Sr and Nd using the method described by [START_REF] Pu | Separation method of Rb-Sr, Sm-Nd using DCTA and HIBA[END_REF]. The Sr and Nd isotopic ratios were determined by a Neptune Plus MC-ICP-MS. The parameters for mass fractionation correction and data processing were the same as those described by [START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF] and [START_REF] Zhang | Petrogenesis of the concealed Daqiling intrusion in Guangxi and its tectonic significance: Constraints from geochemistry, zircon U-Pb dating and Nd-Hf isotopic compositions[END_REF].

Whole-rock major element compositions were measured using a wet chemical method at Ma (Fig. 4-4d). Old inherited cores are common in magmatic zircons of the granitoids from this study area. Inherited cores usually have a rounded shape (Fig. 4-3) and their 206 Pb/ 238 U ages are concentrated in range of 800 -1200 Ma and 2350 -2500 Ma (Appendix 4-1).

Zircon Hf isotope

The analytical results of zircon Hf isotope are listed in Appendix 4-2. The Tongshanling granodiorite porphyry and its dioritic dark enclaves have consistent zircon εHf (t) values (-11.6 --6.3 and -9.3 --6.9, respectively) and Hf model ages (1.60 -1.94 Ga and 1.64 -1.79 Ga, respectively) (Fig. 4-5a-d). The Tongshanling granite porphyry has a larger variation of zircon εHf (t) and T C DM (Hf) values (-16.1 --0.2 and 1.22 -2.22 Ga, respectively) (Fig. 4-5e andf). The values of zircon εHf (t) and T C DM (Hf) of the Weijia granite porphyry change in range of -4.6 --1.7 and 1.31 -1.50 Ga (Fig. 4-5g and h), respectively. The 800 -1200 Ma inherited zircon cores mainly have εHf (t) values of -0.4 -+6.9 (mostly above +2. GDP: granodiorite porphyry; GP: granite porphyry.

Whole-rock major elements

The analytical results of whole-rock major element, trace and rare earth element and Sr-Nd isotopic compositions of granitoids from the Tongshanling-Weijia area are listed in Appendix 4-3 and the main geochemical features are shown in Table 4- [START_REF] Miller | Hot and cold granites? Implications of zircon saturation temperatures and preservation of inheritance[END_REF].

I-type granite field and the Tongshanling and Weijia granite porphyries are plotted in the S-type granite field.

Whole-rock trace and rare earth elements

The Tongshanling granodiorite porphyry has low Rb/Sr ratios, high Zr/Hf ratios, and weak Ba, Nb, P, and Ti depletions as shown in the spider diagram . Its REE patterns slope to the right, without obvious Eu negative anomalies (Fig. 4-7b). Compared with the granodiorite porphyry, the dioritic dark enclaves have a distinctly higher ΣREE abundance and more visible Sr and Eu depletions (Fig. 4-7c andd). The Tongshanling granite porphyry has similar Rb/Sr and Zr/Hf ratios to the Tongshanling granodiorite porphyry, and exhibits

Whole-rock Sr-Nd isotopes

The Tongshanling granodiorite porphyry and its dioritic dark enclaves have ( 87 Sr/ 86 Sr)i ratios of 0.708955 -0.710682 and 0.710023 -0.711200, εNd (t) values of -6.9 --4.2 and -6.7 --5.

Degree of fractionation

The Tongshanling granodiorite porphyry is an amphibole-bearing metaluminous calc-alkaline granitoid, and has low differentiation indexes and Rb/Sr ratios, high CaO/(Na2O+K2O) ratios and δEu values ( , with an evidently lower fractionation degree than the W-bearing Weijia granite porphyry.

Petrogenesis

The Tongshanling granodiorite porphyry has typical crust-derived Sr-Nd-Hf isotopic signatures (Table 4-1), indicating an origin from the partial melting of crustal materials. The existence of hornblende and hornblende-rich dioritic dark enclaves, low aluminum saturation indexes and ( 87 Sr/ 86 Sr)i ratios (Table 4- The dioritic dark enclaves have a zircon U-Pb age and Sr-Nd-Hf isotopic compositions that are consistent with the host granodiorite porphyry (4)(5), indicating they have the same source. The aggregated amphiboles in the dark enclaves and granodiorite porphyry (Fig. 4-1c and g) generally contain actinolitic cores (Al2O3: 2.5 -3.7 wt.%) and hornblende rims (Al2O3: 4.7 -8.9 wt.%). This phenomenon is common in calc-alkaline granodiorites and their dark enclaves, and was considered to be the result of a reaction between unmelted residual pyroxenes and melts based on studies of mineral chemistry, REE and isotopes [START_REF] Castro | Amphibole-rich polycrystalline clots in calc-alkaline granitic rocks and their enclaves[END_REF][START_REF] Sial | Amphibole-rich clots in calc-alkalic granitoids in the Borborema province, northeastern Brazil[END_REF]Stephens, 2001;[START_REF] Martin | Amphiboles in the igneous environment[END_REF]. Because the plagioclase crystallized from dioritic and granodioritic magmas is generally andesine to oligoclase, the calcium-rich cores (An% > 70) of plagioclase from the dark enclaves and granodiorite porphyry might be the residue from source going through partial melting. The reaction rim of plagioclase phenocrysts from the enclaves (Fig. 4-1d)

implies that these phenocrysts originated from the host magmas and that there is mass exchange between the enclaves and host magmas. CL images of magmatic zircons from the enclaves show the texture of dark rim and bright core . Relative to the bright core, the dark rim has higher Th and U concentrations (ThO2+UO2 contents of rim and core: 0.12 -0.32 wt.% and 0.04 -0.21 wt.%, respectively), and lower Zr/Hf ratios (rim: 74 -86, core: 86 -110), which are similar to those of the magmatic zircons from the host granodiorite porphyry (ThO2+UO2 contents: 0.01 -0.44 wt.%, Zr/Hf ratios: 68 -94), also indicating a mass exchange between the enclaves and host magmas. Therefore, it is very likely that the dioritic dark enclaves are reaction products of the restites from source after partial melting and granodioritic magmas. Nanling Range [START_REF] Dong | Petrogenesis of the Yaogangxian granites and implications for W mineralization, Hunan Province[END_REF]. Thus, both the Tongshanling and Weijia granite porphyries are S-type granite. They might be derived from the partial melting of metasedimentary rocks in the upper-middle crust. The Weijia granite porphyry went through a high degree of differentiation, whereas the Tongshanling granite porphyry is a weakly fractionated granite.

Sources of the Cu-Pb-Zn-bearing and W-bearing granitoids

The main features of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range are summarized in Table 4-2. The Cu-Pb-Zn-bearing granitoids were mainly formed at 155.2 -167.0 Ma, with a peak value of 160.6 Ma, and the W-bearing granites were predominantly formed at 151.1 -161.8 Ma, with a peak value of 155.5 . Overall, these two different types of ore-bearing granitoids were formed in the Middle-Late Jurassic, however, the W-bearing granites were formed about 5 Ma later than the Cu-Pb-Zn-bearing granitoids. The Cu-Pb-Zn-bearing granitoids are mostly metaluminous calc-alkaline amphibole-bearing granodiorites, with low degrees of fractionation [START_REF] Wang | Metallogenic model and prospecting potential in Dabaoshan molybdenum polymetallic ore deposit[END_REF][START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF][START_REF] Yang | Petrogenesis of the Mesozoic Shuikoushan peraluminous I-type granodioritic intrusion in Hunan Province, South China: Middle-lower crustal reworking in an extensional tectonic setting[END_REF]. The W-bearing granites are peraluminous alkaline granites and are highly differentiated [START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF]Dong et al., 2014) (Figs. 4-6, 4-7 and 4-9a).

The Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range have ( 87 Sr/ 86 Sr)i ratios of 0.708 -0.712 and > 0.712, εNd (t) values of -10 --2 (peak value: -7 --6) and -14 --7 (peak value: -10 --9), and zircon εHf (t) values of -13 --7

(peak value: -11 --10) and -14 --8 (peak value: -13 --12), respectively, indicating that they were both derived from the partial melting of continental crust.

The Middle-Late Jurassic Cu-Pb-Zn-bearing granitoids in the Nanling Range have the features of I-type granites. They are plotted in the I-type granite field of the ACF diagram (Fig.

4-6d

) and are plotted in the field of partial melts from metabasaltic to metatonalitic sources in the AMF-CMF diagram (Fig. 4-9c). These granitoids have high Mg/(Mg+Fe) ratios (Fig.

4-9b

). All these features show that they were derived from the partial melting of mafic rocks.

This type of ore-bearing granitoids has an average zircon saturation temperature of 750 °C (Table 4-2), which is distinctly lower than the formation temperature (840 -1139 °C) of the granulitic mafic xenoliths in the Daoxian basalt [START_REF] Kong | Petrology and chronology of granulite xenolith in Daoxian county, Hunan Province[END_REF][START_REF] Dai | Geochronology, geochemistry and Hf-Sr-Nd isotopic compositions of Huziyan mafic xenoliths, southern Hunan Province, South China: Petrogenesis and implications for lower crust evolution[END_REF],

indicating that the source of this type of granitoids is not a granulitic basement. According to the experimental study of [START_REF] Beard | Dehydration melting and water-saturated melting of basaltic and andesitic greenstones and amphibolites at 1, 3, and 6.9 kb[END_REF], dehydration melting of amphibolites would generate water-unsaturated weakly peraluminous to metaluminous granodioritic melts, with residual plagioclase and pyroxene, whereas partial melting in water-saturated conditions Mainly -10 --2 (peak value: -7 --6) Mainly -14 --7 (peak value: -10 --9)

Zircon ε Hf (t) value Mainly -13 --7 (peak value: -11 --

10)

Mainly -14 --8 (peak value: -13 --

12)

Notes: a The Cu-Pb-Zn-bearing granitoids include Shuikoushan, Baoshan, Huangshaping, Tongshanling, Dabaoshan intrusions, etc., the Huangshaping ore-bearing granites are mainly granite porphyry and quartz would produce Ca-rich, and Fe-, Mg-, Ti-, and K-poor and strongly peraluminous melts, with residual amphibole. The Middle-Late Jurassic Cu-Pb-Zn-bearing granitoids in the Nanling Range are Fe-, Mg-, and K-rich metaluminous granodiorites, therefore, they were in all probability derived from dehydration melting of amphibolites. The granulitic mafic xenoliths in the Daoxian basalt were formed under a pressure of 0.88 -1.24 GPa with a corresponding depth of 29 -41 km [START_REF] Dai | Geochronology, geochemistry and Hf-Sr-Nd isotopic compositions of Huziyan mafic xenoliths, southern Hunan Province, South China: Petrogenesis and implications for lower crust evolution[END_REF], suggesting that the lower limit of the depth of the amphibolitic basement is presumably 29 km. [START_REF] Yang | Petrogenesis of the Mesozoic Shuikoushan peraluminous I-type granodioritic intrusion in Hunan Province, South China: Middle-lower crustal reworking in an extensional tectonic setting[END_REF] Table 4-2). According to experimental studies, metagreywackes can be partially melted to produce granitic melts only when the temperature is higher than 800 °C [START_REF] Vielzeuf | Partial melting of metagreywackes. Part I. Fluid-absent experiments and phase relationship[END_REF][START_REF] Gardien | Experimental melting of biotite + plagioclase + quartz ± muscovite assemblages and implications for crustal melting[END_REF]. Under the temperature conditions of below 800 °C, muscovite is the only possible rock-forming mineral that can be greatly dehydrated [START_REF] Miller | Hot and cold granites? Implications of zircon saturation temperatures and preservation of inheritance[END_REF], and muscovite-rich metapelites can be partially melted to generate granitic magmas even when the temperature is lower than 750 °C (Thompson, 1982;[START_REF] Gardien | Experimental melting of biotite + plagioclase + quartz ± muscovite assemblages and implications for crustal melting[END_REF]. Thus, it can be considered that the source of the W-bearing granites is a muscovite-rich metasedimentary basement in the upper-middle crust.

The zircon Hf model ages of the W-bearing granites (1.50 -2.30 Ga, peak value: 1.95 Ga) indicate that the metasedimentary basement which as the W-bearing granite source was mainly formed in the Paleoproterozoic.

Genetic model of the Cu-Pb-Zn-bearing and W-bearing granitoids

The

Summary

The Tongshanling granodiorite porphyry and Weijia granite porphyry were formed at 160 -164 Ma and about 158 Ma, respectively. The statistics of the zircon U-Pb ages indicate that the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range were formed mainly at about 160 Ma and 155 Ma, respectively. There is a time gap of about 5

Ma between the formation of the two different types of ore-bearing granitoids.

The Middle-Late Jurassic Cu-Pb-Zn-bearing granitoids in the Nanling Range are dominated by metaluminous amphibole-bearing granodiorites, which have a low degree of fractionation and the features of I-type granites, whereas the Late Jurassic W-bearing granites are highly differentiated peraluminous S-type granites.

A comparison of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range revealed that the Cu-Pb-Zn-bearing granitoids were mainly derived from the partial melting of the mafic amphibolitic basement in the lower crust and that the W-bearing granites were predominantly derived from the partial melting of the muscovite-rich metasedimentary basement in the upper-middle crust. The time gap of about 5

Ma between the two different types of ore-bearing granitoids arose from the non-simultaneous partial melting of different granitoid sources.

Introduction

Microgranular enclaves in granitoids have long been studied, as they can provide significant information for the petrogenetic mechanism of their host granitoids. Various models have been proposed to explain the origin of microgranular enclaves, including magma mixing, restite after partial melting, accidental xenolith, and disrupted cumulate (autolith) [START_REF] Didier | Granites and Their Enclaves[END_REF][START_REF] Didier | Enclaves and Granite Petrology[END_REF], among which magma mixing [START_REF] Vernon | Microgranitoid enclaves in granites-globules of hybrid magma quenched in a plutonic environment[END_REF][START_REF] Dorais | Origin of mafic enclaves in the Dinkey Creek pluton, Central Sierra Nevada Batholith, California[END_REF][START_REF] Poli | Model for the origin and significance of microgranular enclaves in calc-alkaline granitoids[END_REF][START_REF] Blundy | Petrogenesis of mafic inclusions in granitoids of the Adamello Massif, Italy[END_REF][START_REF] Yang | Multiple sources for the origin of granites: Geochemical and Nd/Sr isotopic evidence from the Gudaoling granite and its mafic enclaves, northeast China[END_REF][START_REF] Yang | Tracing magma mixing in granite genesis: in situ U-Pb dating and Hf-isotope analysis of zircons[END_REF][START_REF] Barbarin | Mafic magmatic enclaves and mafic rocks associated with some granitoids of the central Sierra Nevada batholith, California: nature, origin, and relations with the hosts[END_REF][START_REF] Zhao | Hf isotopic composition of zircons from the Huashan-Guposhan intrusive complex and their mafic enclaves in northeastern Guangxi: Implication for petrogenesis[END_REF][START_REF] Cheng | Granite, gabbro and mafic microgranular enclaves in the Gejiu area, Yunnan Province, China: a case of two-stage mixing of crust-and mantle-derived magmas[END_REF][START_REF] Perugini | The mixing of magmas in plutonic and volcanic environments: Analogies and differences[END_REF][START_REF] Fu | Magma mixing in the Kalaqin core complex, northern North China Craton: Linking deep lithospheric destruction and shallow extension[END_REF]Zhang et al., 2016b) and restite [START_REF] White | Ultrametamorphism and granitoid genesis[END_REF][START_REF] Chappell | The importance of residual source material (restite) in granite petrogenesis[END_REF]Chen et al., 1989b[START_REF] Chen | Mafic inclusions from the Glenbog and Blue Gum granite suites, southeastern Australia[END_REF][START_REF] Chen | Mafic enclaves of some I-type granites of the Palaeozoic Lachlan Fold Belt, southeastern Australia[END_REF][START_REF] Chappell | Restite enclaves and the restite model[END_REF][START_REF] Chappell | Magma mixing and the production of compositional variation within granite suites: evidence from the granites of southeastern Australia[END_REF][START_REF] White | Application of the restite model to the Deddick granodiorite and its enclaves-a reinterpretation of the observations and data of Maas et al[END_REF][START_REF] Chappell | Origin of enclaves in S-type granites of the Lachlan Fold Belt[END_REF] were the most hotly debated hypotheses. In recent years, mixing of mafic and felsic magmas was the most popular petrogenetic interpretation for dark microgranular enclaves and their host granitoids which show juvenile and evolved isotopic signatures, respectively (e.g., [START_REF] Yang | Multiple sources for the origin of granites: Geochemical and Nd/Sr isotopic evidence from the Gudaoling granite and its mafic enclaves, northeast China[END_REF][START_REF] Yang | Tracing magma mixing in granite genesis: in situ U-Pb dating and Hf-isotope analysis of zircons[END_REF][START_REF] Zhao | Hf isotopic composition of zircons from the Huashan-Guposhan intrusive complex and their mafic enclaves in northeastern Guangxi: Implication for petrogenesis[END_REF][START_REF] Cheng | Granite, gabbro and mafic microgranular enclaves in the Gejiu area, Yunnan Province, China: a case of two-stage mixing of crust-and mantle-derived magmas[END_REF][START_REF] Fu | Magma mixing in the Kalaqin core complex, northern North China Craton: Linking deep lithospheric destruction and shallow extension[END_REF]. This interpretation was also frequently cited for those granitoids and enclaves with similar isotopic compositions (e.g., [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Liu | Origin of mafic microgranular enclaves (MMEs) and their host quartz monzonites from the Muchen pluton in Zhejiang Province, Southeast China: Implications for magma mixing and crust-mantle interaction[END_REF][START_REF] Luo | The Middle Triassic Meiwu batholith, West Qinling, Central China: implications for the evolution of compositional diversity in a composite batholith[END_REF]. However, it is noteworthy that magma mixing is primarily controlled by the viscosities of different end-members, and a low viscosity interval between mafic and felsic magmas favors their mixing [START_REF] Sato | Study of effect of magma pocket on mixing of two magmas with different viscosities and densities by analogue experiments[END_REF][START_REF] Perugini | The mixing of magmas in plutonic and volcanic environments: Analogies and differences[END_REF]Laumonier et al., 2014aLaumonier et al., , 2014b[START_REF] Laumonier | Experimental mixing of hydrous magmas[END_REF].

Under experimental conditions of 300 MPa and relatively slow strain rates (10 -5 -10 -3 s -1 ), the rheological threshold for mixing of basaltic and haplotonalitic magmas under water-absent and water-saturated conditions occurs at 1160 -1170 °C (Laumonier et al., 2014a) and around 1000 °C [START_REF] Laumonier | Experimental mixing of hydrous magmas[END_REF], respectively. It is inconceivable for most natural granitic magmas to keep such high temperatures to have a large-scale mixing with mafic magmas. [START_REF] Wu | Discussions on the petrogenesis of granites[END_REF] pointed out that the existence of magmatic enclaves is indicative of a limited magma mixing.

In the Nanling Range of South China, dark microgranular enclaves are commonly observed in the Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites, such as the Tongshanling [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF] and Baoshan [START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF] granodiorites. Previous studies interpreted these enclaves as a result of mantle-derived mafic magma and crust-derived felsic magma mixing [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF], and it was widely considered that the Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites have an origin of crust-mantle mixing (e.g., Wang et al., 2003a;[START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Li | The Mesozoic syntexis type granite-related Cu-Pb-Zn mineralization in South China[END_REF][START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF]Zhao et al., 2016b).

However, another hypothesis, partial melting of the mafic lower crust, has been proposed in recent years [START_REF] Yang | Petrogenesis of the Mesozoic Shuikoushan peraluminous I-type granodioritic intrusion in Hunan Province, South China: Middle-lower crustal reworking in an extensional tectonic setting[END_REF]Huang et al., 2017a), and gave rise to a reconsideration of the origin of the Cu-Pb-Zn-bearing granodiorites. The arguments for these two different interpretations were both primarily based on geochemistry and geochronology, but petrographic and mineralogical evidence was absent.

The Tongshanling intrusion, which is a typical Cu-Pb-Zn-bearing granodiorite containing microgranular enclaves and has been intensely studied in terms of geochronology and geochemistry, was chosen as the research target. In this study, detailed petrographic and mineralogical researches have been carried out on the Tongshanling granodiorite and its microgranular enclaves to better constrain the genesis of microgranular enclaves and provide petrogenetic implications for the Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites in the Nanling Range.

Tongshanling granodiorite and its microgranular enclaves

The Tongshanling intrusion as stock with a total exposure area of 12 km 2 (Fig. 3-1) has an approximately homogeneous composition of amphibole-bearing biotite granodiorite (Fig.

5-1a) and does not show obvious lithological zonation except for local variation of mineral

granularity. It has SiO2 contents of 63.7 -70.1 wt.% and is metaluminous (aluminum saturation index: 0.9 -1.0), high-K calc-alkaline and weakly fractionated [CaO/(Na2O+K2O): 0.3 -0.6;

Rb/Sr: 0.5 -1.3], and shows characteristics of I-type granites (Huang et al., 2017a). Three deposits, the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit, are distributed around this intrusion (Fig. 3-1). These deposits occur in the concealed contact zone between granodiorite and carbonate rocks, and its peripheral zone. By zircon U-Pb and molybdenite Re-Os dating, it was revealed that the Tongshanling granodiorite (164 -160

Ma; [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF]Zhao et al., 2016b;Huang et al., 2017a) and its surrounding deposits (162 -160 Ma; [START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]Zhao et al., 2016b) were formed contemporaneously.

Dark microgranular enclaves are commonly found scattered throughout the Tongshanling granodiorite. They occur as separate individuals, which are several to dozens of centimeters in size and generally have round to ellipsoid shapes (Fig. 5-1b). The contact of the enclaves with the host rock is gradational (Fig. 5-1b), and chilled margin and magmatic flow foliation are absent. Most enclaves are fine-grained and homogeneous, and some contain a few plagioclase phenocrysts (Fig. 5-1b). Previous zircon U-Pb geochronology showed that they were formed at 163 -160 Ma [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF]Huang et al., 2017a), which is identical to that of the host granodiorite. These enclaves mostly have dioritic compositions (53.4 -59.4 wt.% SiO2), and show similar Mg/(Mg+Fe) ratios (0.4 -0.5) and HREE-depleted REE patterns with the host rock, but higher ΣREE contents and larger negative Eu anomalies (Huang et al., 2017a).

Petrography

Tongshanling granodiorite

The Tongshanling granodiorite is medium-to coarse-grained, porphyritic (Fig.

5-1a),
and consists primarily of plagioclase (ca. 45 vol.%), K-feldspar (ca. 22 vol.%), quartz (ca. 20 vol.%), biotite (ca. 10 vol.%), and amphibole (ca. 3 vol.%). The phenocrysts are mainly 1 -5 cm sized, except for some local plagioclase megacrysts with a size up to 10 cm. Plagioclase is primarily euhedral to subhedral oligoclase to andesine with zonal texture, and occasionally includes a sericitized core which has an embayed margin and generally occupies less than 30 vol.% of the whole plagioclase (Fig. 5-2a). Amphibole is green colored and mostly occurs as euhedral (Fig. constitute millimetric polycrystalline amphibole-rich clots together with a few biotite and plagioclase (Fig. 5-1e). The aggregated amphibole is obviously finer grained (< 300 μm) than the isolated ones and is generally connected by a granoblastic triple-junction texture (Fig.

5-1f).

Biotite is brown and dominantly distributes in the matrix as euhedral to subhedral crystals. A few anhedral biotite crystals are distributed as interstitial along the boundary between the aggregated amphibole grains (Fig. 5-1f). Accessory minerals include zircon, apatite, titanite, allanite, rutile, sulfide, and Fe-Ti oxide minerals. The Fe-Ti oxide minerals are dominated by magnetite.

Microgranular enclaves

The fine-grained (Fig

Analytical methods

Major element analyses of plagioclase, amphibole, and biotite were carried out with a Chinese Geological Standard Glasses CGSG-1 and CGSG-2 were used as external standards to plot calibration curve. GSE-1G was analyzed for quantity control of the time-dependent calibration for sensitivity drift. The off-line data processing was performed using a program called ICPMSDataCal (Liu et al., 2008b).

Analytical results

Plagioclase

Representative microprobe analyses of plagioclase from the Tongshanling granodiorite and its microgranular enclaves are listed in Appendix 5-1. In the granodiorite, most plagioclase crystals show an anorthite range from An21 to An48 (Fig. 5-3). The plagioclase with a sericitized core has an anorthite content of An71 -An72 and An31 -An64 at the core and rim, respectively (Fig. 5-2a). In the enclaves, the plagioclase rims have an anorthite content of An22 -An45, similar to that of the core-free plagioclase in the host granodiorite, whereas, the sericitized cores show an anorthite range from An65 to An76 (Fig. 5-3). Thus, the enclave plagioclase shows a discontinuous compositional change from core to rim (Fig. 5-2b). The Ca-rich plagioclase cores of both the granodiorite and its enclaves are almost uniform in composition without obvious zonation (Fig. 5-2).

Amphibole

The different occurrences of amphibole (i.e., enclosed, isolated, and aggregated) in the Tongshanling granodiorite and its enclaves are all calcium amphibole, and show a large compositional variation, but have quite consistent Mg/(Mg+Fe) ratios (0.44 -0.58) (Fig. 5-4;

Appendix 5-2). In the classification of [START_REF] Hawthorne | IMA report: Nomenclature of the amphibole supergroup[END_REF], for the granodiorite, the enclosed and most isolated crystals plot in the pargasite field; some isolated ones plot in the magnesio-hornblende field; the core and rim of aggregated amphibole grains plot in the transition field from tremolite to magnesio-hornblende and in the magnesio-hornblende field, respectively (Fig. 5-4a). For the enclaves, the core and rim of clot interior amphibole grains plot in the tremolite and in the transition field from tremolite to magnesio-hornblende, respectively;

both the clot exterior amphibole and the isolated amphibole plot in the magnesio-hornblende field (Fig. 5-4a). Among all the different occurrences of amphibole, the enclosed amphibole in the granodiorite has the highest Al [1.55 -2.12 apfu (atoms per formula unit)] and lowest Si (6.25 -6.82 apfu) contents (Fig. 5-4b). Most isolated amphibole crystals in the granodiorite have Al contents of 1.34 -1.62 apfu and Si contents of 6.62 -6.88 apfu and a few have obviously lower

Al (1.04 -1.11 apfu) and higher Si (7.04 -7.12 apfu) contents (Fig. 5-4b). The aggregated amphibole of both the granodiorite and its enclaves shows distinctly lower Al and higher Si contents than the enclosed and dominant isolated amphibole in the granodiorite (Fig. 5-4b). The In the trace element binary diagrams (Fig. 5-6), it is clearly separated from the other occurrences of amphibole by lower contents of Rb, Sr, Cs, Ba, Zr, Hf, Nb, Ta, Th, U, ΣREE, Y, Zn, Pb, Sn, W, V, Sc, Ga, and In.

Biotite

Biotite crystals of the Tongshanling granodiorite and its microgranular enclaves have similar major element compositions (Appendix 5-4). Their Mg/(Mg+Fe) ratio varies in a show some differences in the trace element compositions (Appendix 5-3). The enclave biotite has lower Sr, Ba, ΣREE, Y, Zn, Pb, W, Sc, Co, Ni, Ga, and In contents, and higher Sn and V contents than that of the granodiorite (Figs. 5-8 and 5-9).

Zircon

Magmatic zircon of the granodiorite shows well-developed oscillatory zoning, and generally includes an inherited core (Fig. 5-10a). Their ThO2+UO2 contents and Zr/Hf ratios The restite model was mostly discussed and developed by the studies of granites and their enclaves in the Lachlan Fold Belt [START_REF] White | Ultrametamorphism and granitoid genesis[END_REF][START_REF] Chappell | The importance of residual source material (restite) in granite petrogenesis[END_REF]Chen et al., 1989b[START_REF] Chen | Mafic inclusions from the Glenbog and Blue Gum granite suites, southeastern Australia[END_REF][START_REF] Chen | Mafic enclaves of some I-type granites of the Palaeozoic Lachlan Fold Belt, southeastern Australia[END_REF][START_REF] Chappell | Restite enclaves and the restite model[END_REF][START_REF] Chappell | Magma mixing and the production of compositional variation within granite suites: evidence from the granites of southeastern Australia[END_REF][START_REF] White | Application of the restite model to the Deddick granodiorite and its enclaves-a reinterpretation of the observations and data of Maas et al[END_REF][START_REF] Chappell | Origin of enclaves in S-type granites of the Lachlan Fold Belt[END_REF]. Restite microgranular enclaves in calc-alkaline I-type granitoids generally have some diagnostic textural features as follows:

(1) remnants of refractory materials, such as Ca-rich plagioclase, inherited zircon, and possibly pyroxene produced by dehydration melting reactions;

(2) mafic mineral clots coexisted with Ca-rich plagioclase;

(3) residual metamorphic texture inherited from the source.

In the enclaves of the Tongshanling granodiorite, mafic mineral clots are widely scattered (Fig. 5-1h, j, and m). These clots are comprised of anhedral to subhedral crystals and do not exhibit the typical texture of serial crystallization as in magmatic rocks. The metamorphogenic granoblastic triple-junction texture in the interior of zonal amphibole-rich clots (Fig. 5-1l)

directly reflects the restite information from the metamorphic source [START_REF] Castro | Amphibole-rich polycrystalline clots in calc-alkaline granitic rocks and their enclaves[END_REF][START_REF] Sial | Amphibole-rich clots in calc-alkalic granitoids in the Borborema province, northeastern Brazil[END_REF]. The commonly occurred old zircon cores (Fig. 5-10c; Huang et al., 2017a) are also indicative of an inheritance from the crustal source. The chaotic internal texture of the dominant enclave zircon grains (Fig. 5-10d ande) is different from the magmatic oscillatory-zoned texture and is similar to the convoluted zoning and recrystallization texture of zircon formed by high-temperature metamorphism [START_REF] Hoskin | Metamorphic zircon formation by solid-state recrystallization of protolith igneous zircon[END_REF][START_REF] Corfu | Atlas of zircon textures[END_REF][START_REF] Wu | Genesis of zircon and its constraints on interpretation of U-Pb age[END_REF][START_REF] Harley | Zircon behaviour and the thermal histories of mountain chains[END_REF]. In all probability, this kind of zircon is metamorphic zircon maintained from the source after partial melting. With an irregular margin and almost uniform composition without zonation (Fig. 5-2b), the sericitized Ca-rich plagioclase cores are distinctly different from the fresh zonal magmatic plagioclase. The confined sericitization only in the core rather than in the rim (Fig. 5-2b) may indicate that the core plagioclase was an early existed phase which has been altered by magmatic fluids before the crystallization of rim plagioclase. Therefore, these plagioclase cores are thought to be of a restite origin. They are analogous to the residual plagioclase described by [START_REF] Chappell | The importance of residual source material (restite) in granite petrogenesis[END_REF]. The existence of these residual minerals implicates that the temperature of partial melting was insufficient to thoroughly melt the source materials. Thus, these microgranular enclaves are restite enclaves and show the same petrographic features as the restite enclaves of I-type granites in the Lachlan Fold Belt (e.g., [START_REF] Chen | Mafic inclusions from the Glenbog and Blue Gum granite suites, southeastern Australia[END_REF][START_REF] Chen | Mafic enclaves of some I-type granites of the Palaeozoic Lachlan Fold Belt, southeastern Australia[END_REF].

Vestiges of magma reworking

The textural vestiges of restite enclaves reworked by the host magma are evident in the microgranular enclaves. The plagioclase phenocrysts in the enclaves show identical features to the matrix plagioclase in the host granodiorite with a similar granularity and composition (An30 -An40, measured by optical microscope) and without Ca-rich cores (Fig. 5-1i). They were probably formed by transfer of accidental crystals from the host magma. [START_REF] White | Application of the restite model to the Deddick granodiorite and its enclaves-a reinterpretation of the observations and data of Maas et al[END_REF] emphasized that the restite enclaves could contain a melt phase which has been produced

during partial melting but is insufficient to disaggregate the enclave into the magma. The reaction rim of plagioclase phenocryst (Fig. 5-1i) could be formed by reaction of the accidental plagioclase with the initial melt in the enclaves. [START_REF] Vernon | Interpretation of microstructures of microgranitoid enclaves[END_REF] pointed out that poikilitic texture results from magmatic crystallization with relatively low nucleation rates and high growth rates. Thus, the poikilitic texture of K-feldspar (Fig. 5-1n) and quartz (Fig. 5-1o) in the enclaves in all probability reflects an input of late-stage silica-rich melt from the host magma.

There is a progressive change of texture and mineral proportion from the zonal amphibole-rich clot interior to exterior (Fig. 5-1j-l) and then to the amphibole-biotite clot (Fig. 5-1m), with gradually obscurer granoblastic triple-junction texture and elevated biotite content, showing a progressive reaction process of the restite with the accidental melt from the host magma. This accidental melt was also probably responsible for the formation of the magmatic rims of residual plagioclase (Fig. 5-2b) and zircon (Fig. 5-10c and f). The process of magma reworking is also reflected by the gradational contact between the enclaves and the host granodiorite (Fig.

5-1g).

Compositional evidence

Magmatic amphibole

Both natural amphibole [START_REF] Duan | In situ major and trace element analysis of amphiboles in quartz monzodiorite porphyry from the Tonglvshan Cu-Fe (Au) deposit, Hubei Province, China: insights into magma evolution and related mineralization[END_REF] and experimental studies [START_REF] Schmidt | Amphibole composition in tonalite as a function of pressure: an experimental calibration of the Al-in-hornblende barometer[END_REF][START_REF] Ernst | Experimental phase-equilibrium study of Al-and Ti-contents of calcic amphibole in MORB-A semiquantitative thermobarometer[END_REF] have revealed that, during magmatic crystallization with decreasing pressure and temperature, the early-crystallized amphibole is more Al-enriched and Si-depleted than the late-crystallized amphibole. The dominant idiomorphic isolated amphibole in the Tongshanling granodiorite shows normal magmatic growth zonation (Appendix 5-2) and was evidently formed by magmatic crystallization. With higher Al and lower Si contents than the isolated amphibole (Fig. 5-4b), the enclosed amphibole is also of magmatic origin but was crystalized earlier than the isolated one. In the plot of the generalized tschermakite vs. edenite components (Fig. 5-11), the magmatic amphibole is distributed away from the tremolite end-member and is obviously separated from the other occurrences of amphibole. Assuming that the whole-rock composition of the Tongshanling granodiorite is similar to the melt composition from which the magmatic amphibole was crystallized, the REE distributions of model magmatic amphibole calculated by partition coefficients in felsic (dacitic to rhyolitic) melts [START_REF] Arth | Behaviour of trace elements during magmatic processes-a summary of theoretical models and their applications[END_REF] are consistent with those of the isolated amphibole (Fig. 5-12), further demonstrating its magmatic origin.

Metamorphic amphibole

It is notable that, compared with the magmatic amphibole, the amphibole grains in the enclave zonal clots show a contrary compositional zonation and distinctly lower Al and higher Si contents (Fig. 5-4b; Appendix 5-2), indicating that they were not formed by magmatic crystallization. The clot interior amphibole has a granoblastic triple-junction texture (Fig. 5-1l)

and the grain core is compositionally close to the tremolite end-member (Fig. 5-11), thus the actinolitic core amphibole is considered to be of a metamorphic origin. A study of analogous amphibole-rich clots in granodiorite by [START_REF] Castro | Amphibole-rich polycrystalline clots in calc-alkaline granitic rocks and their enclaves[END_REF] argued that the actinolitic Model magmatic amphibole 1 and 2 are calculated by partition coefficients in felsic melts with rhyolitic and dacitic compositions [START_REF] Arth | Behaviour of trace elements during magmatic processes-a summary of theoretical models and their applications[END_REF], respectively, assuming that the whole-rock composition of the Tongshanling granodiorite is similar to the melt composition in which magmatic amphibole has been crystallized. Model residual clinopyroxene 1, 2, and 3 are calculated by partition coefficients in dacitic melt [START_REF] Arth | Behaviour of trace elements during magmatic processes-a summary of theoretical models and their applications[END_REF][START_REF] Fujimaki | Partition coefficients of Hf, Zr, and REE between phenocrysts and groundmasses[END_REF] in terms of 10% partial melting with a restite comprised of 30% clinopyroxene + 70% plagioclase (model 1), 50%

clinopyroxene + 50% plagioclase (model 2), and 45% clinopyroxene + 45% plagioclase + 10% amphibole (model 3), respectively, using the amphibolite of the regional metamorphic basement [START_REF] Li | Timing of the Cathaysia Block formation: Constraints from SHRIMP U-Pb zircon geochronology[END_REF] as the source rock. Model residual amphibole 3 is calculated by the restite model 3. The whole-rock REE compositions of the Tongshanling granodiorite and its microgranular enclaves are from Huang et al. (2017a). The REE concentrations of all model residual minerals and natural samples are normalized by chondrite [START_REF] Boynton | Cosmochemistry of the rare earth elements: meteorite studies[END_REF].

core amphibole is actually a pseudomorph after a primary pyroxene-rich precursor, which is expected to be relatively poor in Al and has been transformed into amphibole by a complex reaction. They supposed that this reaction may have occurred by hydrogenation of the primary pyroxene with a magnesio-hornblende armor [pyroxene + fluids (OH, etc.) → actinolite] or may also have occurred as a direct discontinuous reaction of the pyroxene with the melt (pyroxene + melt1 → hornblende + melt2). [START_REF] Martin | Amphiboles in the igneous environment[END_REF] considered that the former hypothesis is more dependable. The actinolitic core amphibole in the Tongshanling microgranular enclaves contains significantly lower REE contents than the magmatic amphibole (Fig. 5-5a and b). It is consistent with the hypothesis that the actinolitic core amphibole was transformed from primary residual pyroxene which has significantly lower REE partition coefficients than amphibole in felsic melt [START_REF] Arth | Behaviour of trace elements during magmatic processes-a summary of theoretical models and their applications[END_REF][START_REF] Fujimaki | Partition coefficients of Hf, Zr, and REE between phenocrysts and groundmasses[END_REF]. This is also responsible for the distinctly lower contents of the other incompatible elements in the actinolitic core amphibole (Fig. 5-6a-h). It is reasonable that the incompatible elements tend to concentrate in melt during partial melting and give rise to a depleted remnant. The obvious Eu negative anomalies and weak LREE depletions of the actinolitic core amphibole (Fig. 5-5b) indicate the coexistence of plagioclase in residual materials (Stephens, 2001). This has been further demonstrated by the occurrence of abundant residual Ca-rich plagioclase cores in the enclaves. As revealed by previous experimental studies, dehydration melting of amphibolite at crustal pressure and temperature usually produces a pyroxene-and plagioclase-rich restite in which the pyroxene is dominated by clinopyroxene [START_REF] Beard | Dehydration melting and water-saturated melting of basaltic and andesitic greenstones and amphibolites at 1, 3, and 6.9 kb[END_REF][START_REF] Wolf | Dehydration-melting of amphibolite at 10 kbar: the effects of temperature and time[END_REF][START_REF] Johannes | Petrogenesis and Experimental Petrology of Granitic Rocks[END_REF]. Using the amphibolite of the regional metamorphic basement [START_REF] Li | Timing of the Cathaysia Block formation: Constraints from SHRIMP U-Pb zircon geochronology[END_REF] as the source rock of the Tongshanling granodiorite, the REE distributions of model residual clinopyroxene calculated in terms of 10% partial melting with a model restite comprised of different proportions of clinopyroxene, plagioclase and amphibole are similar to the actinolitic core amphibole but with lower REE contents especially when residual amphibole occurs (Fig.

5-12

). However, the model residual amphibole contains distinctly higher REE contents than the actinolitic core amphibole (Fig. 5-12). Thus, the results of REE distribution modeling indicate that the actinolitic core amphibole was transformed from primary residual pyroxene by hydrogenation, during which the REE contents had increased due to its higher REE partition coefficients, rather than directly preserved as residual amphibole.

Magma reworked metamorphic amphibole

The increasing Al and decreasing Si contents from core to rim of the clot interior amphibole grains and also from interior to exterior of the whole zonal clot (Fig. 5-4b), with a trend from metamorphic amphibole to magmatic amphibole (Fig. 5-11), show the process of magma reworking of the restite enclaves. In consideration of the consistent REE patterns with the magmatic amphibole (Fig. 5-5a and b), the rim of clot interior amphibole grains may have been formed by reaction of the actinolitic amphibole with the host magma. [START_REF] Castro | Amphibole-rich polycrystalline clots in calc-alkaline granitic rocks and their enclaves[END_REF] and Stephens (2001) considered that this reaction was induced dominantly by diffusive exchange along the grain boundaries. With a similar compositional zonation to the clot interior amphibole but higher Al and lower Si contents (Fig. 5-4), the clot exterior amphibole was formed by a more intense magma reworking than the clot interior amphibole. The isolated enclave amphibole has magma reworked compositions (Fig. 5-11) and consistent REE patterns with the magmatic amphibole (Fig. 5-5a and c), suggesting that it is also magma reworked amphibole and is deduced to be transformed from isolated residual pyroxene. The high-Al and low-Si isolated amphibole may result from a more intense reworking by a late and evolved host melt than the low-Al and high-Si isolated amphibole.

Zircon and plagioclase

The composition zonation of enclave magmatic zircon (Fig. 5-10c) has recorded two different melts existed in the enclaves. Huang et al. (2017a) reported that both the inner parts and outer parts of enclave magmatic zircon have consistent U-Pb ages and Hf isotopic compositions with the magmatic zircon in the host granodiorite, indicating that they were sequentially crystallized from different melts with the same origin. The outer parts have higher ThO2+UO2 contents and lower Zr/Hf ratios than the inner parts, and are more similar to those of the magmatic zircon in the host granodiorite (Fig. 5-10b), suggesting that the outer magmatic zircon was crystallized from a late and more evolved host melt, whereas, the inner parts with lower ThO2+UO2 contents and higher Zr/Hf ratios (Fig. 5-10b) may be crystallized from the initial melt retained in restite. The magmatic rims of enclave plagioclase may have been crystallized from the initial melt or the evolved host melt. However, the consistent compositions of magmatic plagioclase in the enclaves and their host granodiorite (Fig. 5-3) and the discontinuous compositional change within the enclave plagioclase from core to rim (Fig.

5-2b

) indicate that the magmatic rim plagioclase in the enclaves was in all probability dominantly crystallized from the evolved host melt.

Biotite

The temperature of biotite dehydration melting is much lower than that of amphibole dehydration melting [START_REF] Johannes | Petrogenesis and Experimental Petrology of Granitic Rocks[END_REF]. Therefore, the enclave biotite should not be a residual phase when amphibole broke down. However, it has lower contents of ΣREE and some other incompatible elements such as Sr, Ba, Y, Zn, Pb, and W than the magmatic biotite in the host granodiorite (Figs. 5-8 and 5-9a-d), reflecting some residual information. The consistent major element compositions of biotite in the granodiorite and its enclaves (Fig. 567) indicate an intense reworking of the restite by the host magma.

Residual materials in the granodiorite

There are also some residual materials in the host granodiorite, such as the old zircon cores

Geochemical signatures

The Harker plots of the Tongshanling granodiorite and its microgranular enclaves show excellent linearities (Fig. 5678910111213). This phenomenon coincides with the restite model and was explained to be result from progressive separation of melt and restite [START_REF] White | Ultrametamorphism and granitoid genesis[END_REF][START_REF] Chappell | The importance of residual source material (restite) in granite petrogenesis[END_REF]. Previous studies showed that the microgranular enclaves have quite consistent evolved Sr-Nd and zircon Hf isotopic compositions with their host granodiorite, with both the enclaves and granodiorite having respective ( 87 Sr/ 86 Sr)i ratios of 0.710 -0.711 and 0.709 -0.711, Nd (t) values of -6.7 --5.0 and -6.9 --4.2, and zircon Hf (t) values of -11.5 --6.9 and -12.2 --6.9 [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF]Zhao et al., 2016b;Huang et al., 2017a). They are distinct from those mantle-derived enclaves which have more juvenile isotopic signatures than the host granitoids (e.g., [START_REF] Yang | Multiple sources for the origin of granites: Geochemical and Nd/Sr isotopic evidence from the Gudaoling granite and its mafic enclaves, northeast China[END_REF][START_REF] Yang | Tracing magma mixing in granite genesis: in situ U-Pb dating and Hf-isotope analysis of zircons[END_REF][START_REF] Zhao | Hf isotopic composition of zircons from the Huashan-Guposhan intrusive complex and their mafic enclaves in northeastern Guangxi: Implication for petrogenesis[END_REF][START_REF] Cheng | Granite, gabbro and mafic microgranular enclaves in the Gejiu area, Yunnan Province, China: a case of two-stage mixing of crust-and mantle-derived magmas[END_REF][START_REF] Fu | Magma mixing in the Kalaqin core complex, northern North China Craton: Linking deep lithospheric destruction and shallow extension[END_REF]. The almost contemporaneous mantle-derived mafic rocks adjacent to the Tongshanling et al., 2003b;[START_REF] Li | Jurassic intraplate magmatism in southern Hunan-eastern Guangxi: 40 Ar/ 39 Ar dating, geochemistry, Sr-Nd isotopes and implications for tectonic evolution of SE China[END_REF][START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF]. It was impossible to produce these enclaves with the same isotopic signatures as their host granodiorite by crust-mantle magma mixing. These isotopic features are suggestive of a crustal origin for the enclaves and preclude the possibility of mantle-derived mafic magmatic crystallization, which further support the interpretation of the enclaves as reworked restite.

Geothermobarometry

5.6.3.1. Temperature

Numerous mineral thermometers, include amphibole, plagioclase, and biotite, have been proposed to estimate the temperature conditions of magmatic process (e.g., [START_REF] Holland | Non-ideal interactions in calcic amphiboles and their bearing on amphibole-plagioclase thermometry[END_REF][START_REF] Henry | The Ti-saturation surface for low-to-medium pressure metapelitic biotites: Implications for geothermometry and Ti-substitution mechanisms[END_REF][START_REF] Putirka | Igneous thermometers and barometers based on plagioclase + liquid equilibria: Tests of some existing models and new calibrations[END_REF][START_REF] Putirka | Thermometers and barometers for volcanic systems[END_REF][START_REF] Putirka | Amphibole thermometers and barometers for igneous systems and some implications for eruption mechanisms of felsic magmas at arc volcanoes[END_REF][START_REF] Ridolfi | Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130 °C and 2.2 GPa[END_REF].

Various thermometers (Table 5- Although there are some differences between different calculation methods and some thermometers yielded overestimated [START_REF] Ridolfi | Stability and chemical equilibrium of amphibole in calc-alkaline magmas: an overview, new thermobarometric formulations and application to subduction-related volcanoes[END_REF][START_REF] Molina | Calcic amphibole thermobarometry in metamorphic and igneous rocks: New calibrations based on plagioclase/amphibole Al-Si partitioning and amphibole/liquid Mg partitioning[END_REF][START_REF] Putirka | Igneous thermometers and barometers based on plagioclase + liquid equilibria: Tests of some existing models and new calibrations[END_REF] Eq. 4a of [START_REF] Putirka | Amphibole thermometers and barometers for igneous systems and some implications for eruption mechanisms of felsic magmas at arc volcanoes[END_REF] and underestimated (Eq. 4b of Putirka, 2016) temperatures (Table 5-1), several general regularities are evident. The temperature recorded by magmatic amphibole decreases progressively from the enclosed ones through the inner and to the outer of isolated ones (Table 5-1; Fig. 5-14a andb). This is in accordance with their petrographic crystallization sequence. The actinolitic core amphibole and the Ca-rich core plagioclase record distinctly higher temperatures than the isolated magmatic amphibole and the magmatic rim plagioclase, respectively (Table 5-1). This is consistent with the restite origin of the actinolitic core amphibole and the Ca-rich core plagioclase. The magmatic rim plagioclase and biotite in the enclaves show consistent temperatures with those in the host granodiorite, respectively (Table 5-1; Fig. 5-14c), suggesting that during the process of magma reworking the enclave plagioclase and biotite were in equilibrium with the host melt. The high-Al and low-Si isolated amphibole and the rim of clot exterior amphibole grains in the enclaves have similar temperatures which are slightly lower than that of the isolated magmatic amphibole (Table 5-1;

Pressure

Al-in-hornblende barometer can provide an effective approach to estimate the magma emplacement depth of near-solidus granitic systems with highly restrictive conditions [START_REF] Schmidt | Amphibole composition in tonalite as a function of pressure: an experimental calibration of the Al-in-hornblende barometer[END_REF][START_REF] Anderson | The effects of temperature and f O2 on the Al-in-hornblende barometer[END_REF][START_REF] Ridolfi | Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130 °C and 2.2 GPa[END_REF]Mutch et al., 2016;[START_REF] Putirka | Amphibole thermometers and barometers for igneous systems and some implications for eruption mechanisms of felsic magmas at arc volcanoes[END_REF]. The Tongshanling granodiorite contains all the necessary equilibrium phases, The Tongshanling granodiorite belongs to low-temperature granites in terms of the relatively low zircon saturation temperature (Table 5-2) and the occurrence of inherited zircon [START_REF] Chappell | Lachlan Fold Belt granites revisited: high-and low-temperature granites and their implications[END_REF][START_REF] Miller | Hot and cold granites? Implications of zircon saturation temperatures and preservation of inheritance[END_REF]. The low-temperature and deep-emplaced granodioritic magma is indicative of a relatively high viscosity to a certain extent which is favorable for carrying some residual materials from the source. Different from volcanic rocks in which the anhydrous primary residual minerals, such as pyroxene, can be commonly preserved as phenocrysts, the deep-emplaced magma is beneficial to drive an intense reworking of the residual materials during slow cooling [START_REF] Chappell | The importance of residual source material (restite) in granite petrogenesis[END_REF]. Thus, the residual pyroxene might have been totally transformed into amphibole in such a deep-emplaced magma. This Nd (t) value -6.6 --5.9 -7.3 --5.0 -6.9 --4.2 -8.2 --6.8

Zircon Hf (t) value -10.8 --7.9 -12.0 --9.2 -12.2 --6.9 -11.8 --7.5

could account for the absence of residual pyroxene in the Tongshanling granodiorite and its microgranular enclaves.

The model for reworked restite enclave

Based on the nature of reworked restite enclaves with distinct textural and compositional features described above, the formation process of the microgranular enclaves in the Tongshanling granodiorite is deduced as follows (Fig. 5-15).

Stage 1: Formation of granodioritic melt and restite during partial melting. Partial melting of the mafic amphibolitic basement in the lower crust produced a metaluminous and high-K calc-alkaline granodioritic melt coexisted with a primary pyroxene-rich restite that mainly comprised of pyroxene, plagioclase, and also refractory accessory minerals, such as zircon. Most melt was extracted and constituted a granodioritic magma with a few residual materials. There were still a few initial melts maintained in the restite due to its high viscosity.

Stage 2: Preliminary reaction of the restite enclave with the initial melt. Some fragments of restite were carried by the ascending host magma. With the cooling of magma, the inner parts of magmatic zircon were firstly crystallized from the initial melt in the restite enclaves.

The pyroxene-rich precursors were transformed into actinolite by progressive hydrogenation from exterior to interior. Some small clots had a more intense reaction with the initial melt and formed magnesio-hornblende and a few biotite in the exteriors. The isolated residual pyroxene was also transformed into magnesio-hornblende with low Al and high Si contents.

Stage 3: Further reaction of the restite enclave with the evolved host melt. The composition of the host melt was gradually evolved with crystallization. Progressive input of the evolved host melt led to a further reaction of the restite enclaves with the melt. This resulted in the formation of the outer parts of magmatic zircon and the magmatic rims around residual Ca-rich plagioclase. The exteriors of most clots had been transformed into magnesio-hornblende. The small clots showed more Al-enriched and Si-depleted compositions of magnesio-hornblende and might have a higher biotite content than the large ones due to the more intense reaction with the melt. Some low-Al and high-Si isolated amphibole crystals were transformed into high-Al and low-Si ones.

Stage 4: Formation of the reworked restite enclave. With the reaction between the restite enclaves and the host magma, the zonal amphibole-rich clots had been formed. The small clots might have been transformed into non-zoning amphibole-rich clots or amphibole-biotite clots.

The input of late-stage silica-rich melt from the host magma led to the formation of the poikilitic texture of K-feldspar and quartz in the restite enclaves. After the granodioritic magma had been completely solidified, the reworked restite enclaves were survived as dark For the magma reworked amphibole, the deeper colored ones have a more intense reaction with the melt and higher Al contents than the paler colored ones.

microgranular enclaves in the host granodiorite.

Petrogenetic implications

Restite may provide an important indication for the source nature of the host granitoids since it is remnant of refractory material after partial melting of the source rocks. Because the Tongshanling microgranular enclaves are restite which has been partially modified by the host granodioritic magma, the primary restite should be more mafic than the dioritic compositions.

The pyroxene-rich precursors of the amphibole-rich clots, which have silica-poor compositions and mainly consist of pyroxene and Ca-rich plagioclase, may represent the primary restite from the source after partial melting. To produce such a composition of primary restite and a granodioritic magma showing I-type features, the source should have a relatively mafic composition, such as amphibolite (e.g., [START_REF] Chen | Mafic inclusions from the Glenbog and Blue Gum granite suites, southeastern Australia[END_REF][START_REF] Sial | Amphibole-rich clots in calc-alkalic granitoids in the Borborema province, northeastern Brazil[END_REF]Stephens, 2001).

Dehydration melting of amphibolite can generate metaluminous granodioritic melts with a pyroxene-rich restite at pressure lower than 10 kbar [START_REF] Beard | Dehydration melting and water-saturated melting of basaltic and andesitic greenstones and amphibolites at 1, 3, and 6.9 kb[END_REF][START_REF] Johannes | Petrogenesis and Experimental Petrology of Granitic Rocks[END_REF], whereas, water-saturated melting of amphibolite will produce strongly peraluminous melts with a restite dominated by amphibole [START_REF] Beard | Dehydration melting and water-saturated melting of basaltic and andesitic greenstones and amphibolites at 1, 3, and 6.9 kb[END_REF]. A pressure estimation of granulitic mafic xenoliths (8.8 -12.4 kbar; [START_REF] Dai | Geochronology, geochemistry and Hf-Sr-Nd isotopic compositions of Huziyan mafic xenoliths, southern Hunan Province, South China: Petrogenesis and implications for lower crust evolution[END_REF] in the Huziyan basalt (ca. 150 Ma), which occurs at 20 km north-northeast to the Tongshanling intrusion, suggests that the mafic amphibolitic basement should be located at a depth corresponding to a pressure lower than 8.8 kbar. Therefore, dehydration melting of amphibolite at pressure lower than 8.8 kbar was in all probability responsible for the origin of the metaluminous Tongshanling granodiorite. The zircon Hf model ages of the Tongshanling granodiorite and its microgranular enclaves (1.5 -2.1 Ga and 1.6 -2.0 Ga, respectively, both with a peak value of 1.75 Ga; [START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF]Zhao et al., 2016b;Huang et al., 2017a) indicate that the amphibolitic basement was mainly formed in Paleoproterozoic. The It is noteworthy that, the lower crust of South China, especially the mafic amphibolitic basement, has fertile ore-forming metals. For instance, the amphibolites of the Tianjinping Formation and the Mayuan Group have Cu contents of 57.7 ppm and 66.5 ppm, and Zn contents of 119 ppm and 118 ppm, respectively [START_REF] Li | Timing of the Cathaysia Block formation: Constraints from SHRIMP U-Pb zircon geochronology[END_REF], which are distinctly higher than those of the middle and upper crusts in South China [START_REF] Gao | Chemical composition of the continental crust as revealed by studies in East China[END_REF] and are also higher than those of the lower crust reported by [START_REF] Rudnick | Nature and composition of the continental crust: A lower crustal perspective[END_REF]. Such a fertile source is beneficial to the formation of Cu-Pb-Zn-bearing granodiorites in the Nanling Range.

The Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites in the Nanling Range have similar mineralogical and geochemical features (Table 5-2). They are generally hornblende-bearing, metaluminous and high-K calc-alkaline rocks with high Mg/(Mg+Fe) ratios and low evolutionary degrees, and show characteristics of I-type granites (Table 5-2).

They also have similar evolved Sr-Nd and zircon Hf isotopic compositions (Table 5-2). With regard to the previously proposed two different genetic models for these Cu-Pb-Zn-bearing granodiorites, i.e., crust-mantle mixing and partial melting of the mafic lower crust, our research stands by the latter and provides inspiration for the further study.

Chapter 6. Magma emplacement-induced structural control on skarn formation

Introduction

Skarn deposits, as one of the most important mineralization types for a lot of metals, have attracted a great interest of numerous geologists. Previous studies mainly focused on metasomatism, zonation, skarn mineralogy, geochemistry, and petrogenesis [START_REF] Meinert | World skarn deposits[END_REF]. However, little attention has been paid to structural control (e.g., [START_REF] Love | The lithologic, stratigraphic, and structural setting of the giant Antamina copper-zinc skarn deposit, Ancash, Peru[END_REF]Li et al., 2014a;[START_REF] Ducoux | Synkinematic skarns and fluid drainage along detachments: The West Cycladic Detachment System on Serifos Island (Cyclades, Greece) and its related mineralization[END_REF], especially the magma emplacement related one, on skarn formation. Magma emplacement-induced structural control is crucial to understanding the process of skarnization and can provide important information for prospecting and exploration. In South China, multiple-aged granitoids and polymetallic deposits are widely developed (Figs. 2-8-2-10, Zhou et al., 2006a;[START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF]Mao et al., 2013a). Although numerous geochronological and geochemical studies have revealed that most mineral deposits are genetically associated with granitoids (e.g., [START_REF] Yang | Skarn-type tungsten mineralization associated with the Caledonian (Silurian) Niutangjie granite, northern Guangxi, China[END_REF]Zhang et al., 2015a;Chen et al., 2016;Zhao et al., 2016b;[START_REF] Xiang | Neoproterozoic mineralization in a hydrothermal cassiterite-sulfide deposit at Jiumao, northern Guangxi, South China: Mineral-scale constraints on metal origins and ore-forming processes[END_REF], the detailed connecting process between them is still unclear. The magma-dynamic study of [START_REF] Liu | Incremental emplacement of the late Jurassic mid-crustal, lopolith-like Qitianling pluton, South China, revealed by AMS and Bouguer gravity data[END_REF] revealed that the emplacement of the Jurassic granitoids in South China was not driven by tectonic deformation.

Therefore, these granitoids are good cases for the study of local wall-rock deformation induced by volume force involved in the emplacement of granitoids. This study takes the Middle-Late Jurassic Tongshanling Cu-Pb-Zn deposit in southern Hunan Province of China (Fig. 6-1a) as an excellent example to decipher magma emplacement-induced structural control on skarn formation.

Regional structural analysis

The exposed strata in the Tongshanling area are dominated by Devonian and Carboniferous carbonate rocks (Fig. 6-1). These strata have been deformed and developed a lot of north-south to northeast-southwest striking folds and faults (Fig. 6-1). The folds are composed of alternatively appeared anticlines and synclines which are cut through by the faults (Fig. 6-1b and c). A vast majority of these faults show an east to southeast vergent thrusting or a sinistral strike-slip sense and several ones are normal faults (Fig. 6-1b-d).

During Middle-Late Jurassic, the Tongshanling granodioritic magmas intruded into the carbonate strata as stock (Fig. 6-1b and c) and then caused Cu-Pb-Zn mineralization.

Normal fault

Both the normal faults to the west and east of the Tongshanling intrusion strike consistently with the regional thrust faults and dip to west to northwest (Figs. 6-1b and 6-2).

The carbonate rocks adjacent to these normal faults do not show any deformation except for brittle fractures (Fig. 6-2). At a southern outcrop of the western normal fault, automorphic calcite accumulates along the fault plane as vein steeply cutting the bedding and broken by a later sinistral strike-slip movement (Fig. 6-2a-c). At a northern outcrop, the calcite mainly distributes in the footwall of the normal fault (Fig. 6-2d). For the eastern normal fault, two generations of calcite are recognized, with the late calcite being more coarse-grained, automorphic and pure, and having a lower hardness than the early one (Fig. 6-2e-l). Some wall-rock breccias are observed in the first-generation calcite from a southern outcrop (Fig.

6-2l

).

Contact zone

The carbonate rocks in the contact zone close to the Tongshanling intrusion have been strongly marbleized and deformed (Fig. 6-3). The recrystallized calcite crystals mostly have an elongated shape (Fig. 6-3c, e, andh). In the northeastern contact zone, the foliation dips to north to northeast, cuts the bedding with a steeper angle, and shows a sense of normal motion (Fig. 6-3a, b, andd). From proximal to distal, the intensity of marbleization and the density of foliation gradually decrease and finally to the undeformed carbonate strata (Fig. 6-3a). The southern contact zone exhibits distinctly stronger marbleization and deformation with a higher density of foliation than the northeastern contact zone (Fig. 6-3). In the southern contact zone, the bedding is invisible and the foliation is wrinkled near the intrusion (Fig. 6-3g). Notably, the foliation rotates around the southern boundary of the intrusion and is parallelized to the contact (Fig. 6-3f, i, and j). The dip angle of foliation in the southern contact zone is larger than that in the northeastern contact zone (Fig. 6-3).

Deposit geology

The Tongshanling Cu-Pb-Zn deposit occurs in the northeastern concealed contact zone between the granodiorite and carbonate rocks and its peripheral zone (Fig. 6-4). This deposit shows an obvious zonation with a proximal skarn, a distal skarn, and sulfide-quartz veins between them (Fig. 6-4). The proximal skarn is distributed in the granodiorite and in the limestone of the Middle Devonian Qiziqiao Formation and can be further divided into massive endoskarn extending along the border of granodiorite and peripheral vein exoskarn (Fig. 6-4). The sulfide-quartz veins mainly occur in the Qiziqiao limestone with minor in the Upper Devonian Shetianqiao limestone (Fig. 6-4). Differently, the distal skarn is stratiform and evidently controlled by the argillaceous limestone of the Upper Devonian Xikuangshan Formation (Fig. 6-4). The distal skarn is not the research object of this study and will not be

Endoskarn

With irregular shapes, the massive endoskarn dominantly consists of garnet and pyroxene with minor retrograde minerals, such as actinolite and epidote. It has a brown color and does not show a clear zonation (Fig. 6-5a). Sulfide ore bodies in the endoskarn are composed of chalcopyrite and pyrrhotite coexisting with abundant quartz and show a banded structure (Fig. 6-5a). The sulfide and quartz bands dip to north to northeast in general (Fig.

6-5a

).

Exoskarn

The exoskarn veins, with a width of dozens of centimeters, have a brownish green color on the whole (Figs. 6-5b-c and 6-6a). They cut across the bedding by a steeper angle and

Sulfide-quartz vein

The sulfide-quartz veins are a dozen to tens of centimeters in width (Fig. 6-7c andd).

They consistently dip to north to northeast and cut the bedding (Fig. 6-7c and d). Compared with the deformed marble close to exoskarn, the wall rocks of sulfide-quartz veins have not been strongly marbleized and deformed (Fig. 6-7c and d). Some outcrops show a sense of normal motion (Fig. 6-7d). Ore minerals are chalcopyrite, sphalerite, galena, pyrite, and arsenopyrite.

Sampling and analytical methods

Thirty-six carbonate samples from surface and underground outcrops and a drill core (ZK1001) to the north of the Tongshanling intrusion were collected for Raman spectroscopy of carbonaceous material (RSCM) analysis among which eight samples were further selected for electron backscatter diffraction (EBSD) mapping (sample locations shown in Figs. 6-1-6-5). Garnets in the endoskarn and exoskarn were sampled for compositional analysis by electron microprobe (EMP).

RSCM analysis was carried out by a Renishaw InVIA Reflex micro-spectrometer coupled to a DM2500 Leica microscope at Bureau de Recherches Géologiques et Minières (BRGM), Orléans, France. An argon laser with 0 = 514.5 nm was used as exciter. Instrument control and Raman measurements were performed by the Renishaw Wire 3.4 software. Before analysis, the spectrometer was calibrated using the 520.4 cm -1 line of silicon. To check within-sample structural heterogeneity, at least 10 spectra were recorded for each sample.

Each spectrum was acquired through 5 -10 accumulations and an acquisition time of 10 -20 s. The off-line data were processed using the program PeakFit v4.06 with a Voigt function. f, j). The temperatures obtained by the deformed marble in the contact zone range from 570 °C to 599 °C (Figs. 6-1b and 6-3a, f). A gradational transition of lithology from marble at the contact zone to limestone near the surface with progressively decreasing temperatures from 601 °C to 320 °C is revealed by the drill core ZK1001 (Fig. 678). In the Tongshanling Cu-Pb-Zn deposit, from proximal to distal, the metamorphosed carbonate rocks close to the endoskarn, exoskarn, sulfide-quartz veins, and distal skarn underwent temperatures of 618 -624 °C, 595 -619 °C, 500 -547 °C, and 461 -515 °C, respectively (Fig. 6-4).

EBSD mapping

EBSD analytical results of carbonate samples are shown in Figure 6-9. Near the regional normal faults, the calcite grains have no shape preferred orientation (SPO) and show a weak crystallographic preferred orientation (CPO) by the smaller grains but not by the larger grains (Fig. 6-9a and b). The elongated calcite and dolomite grains in the contact zone have an obvious SPO (Fig. 6-9c-g). They mostly show a CPO with their c-axis aligned with the long axis of the grains and clockwise oblique to the Z-axis of the sample frame (Fig. 6-9c-g). The fine-grained samples (Fig. 6-9c and f-g) have a more well-defined c-axis maximum than the coarse-grained samples (Fig. 6-9d and e). In the fine-grained samples, the c-axis maximum of the smaller grains is more confined than that of the larger grains (Fig. 6-9c and f-g). In the coarse-grained samples, the c-axes of the larger grains are roughly normal to the XZ plane (Fig. 6-9d and e). The calcite grains in a calcite (20 %)-dolomite (80 %) composite sample from the southern contact zone have distinctly more perpendicular c-axes to the XZ plane than the dolomite grains (Fig. 6-9f and g). With a strong SPO, the calcite adjacent to the exoskarn at underground gallery shows a consistent CPO (Fig. 6-9h) with the calcite in the northeastern contact zone at surface (Fig. 6-9c). The calcite near the peripheral sulfide-quartz veins does not have a SPO but shows a CPO by the smaller grains, whereas, not by the larger ones (Fig. 6-9i).

Garnet composition

Representative EMP analyses of garnet are listed in Appendix 6-2. Both the garnets in the endoskarn and exoskarn are grandite (Py+Al+Sp < 7.8 %) (Fig. 6-10). The composition of Mineral abbreviations: Ad = andradite, Al = almandine, Gr = grossularite, Py = pyrope, Sp = spessartine.

Discussion

The Early-Middle Triassic intracontinental deformation in the eastern South China Block has been generally recognized as a northwest-southeast compression associated with a series of northeast-southwest striking folds and thrust faults [START_REF] Wang | Phanerozoic tectonics of the South China Block: Key observations and controversies[END_REF][START_REF] Shu | Early Paleozoic and Early Mesozoic intraplate tectonic and magmatic events in the Cathaysia Block, South China[END_REF]. In the Tongshanling area, the Early-Middle Triassic intracontinental compression caused folding and thrusting of the Devonian and Carboniferous carbonate strata which were further intruded by the Middle-Late Jurassic granodioritic magmas (Fig. 6-1b andc). The regional west-to northwest-dipping normal faults (Figs. 6-1b and 6-2) should be formed under an extensional setting most probably induced by the Late Triassic to Early Jurassic decompression and/or the subduction of the Paleo-Pacific plate rather than the emplacement of the Tongshanling intrusion. The calcite distributed along or in the footwall of the normal faults (Fig. 6-2) may be generated by a later decompressive precipitation after an earlier pressure dissolution. At the eastern normal fault, the first-generation calcite is fine-grained with a higher hardness and contains some wall-rock breccias, whereas the second-generation calcite is automorphic, coarse-grained and pure (Fig. 6-2c and d), indicating a transition from a relatively compressive setting to a relatively extensional setting. This is in accordance with the regional tectonic evolution from Triassic compression to Jurassic extension.

The organization degree of carbonaceous material is not affected by retrogression, thus the RSCM thermometry records the peak metamorphic temperature [START_REF] Beyssac | Raman spectra of carbonaceous material in metasediments: a new geothermometer[END_REF].

Since the carbonate strata far away from the Tongshanling intrusion have not been influenced by magmatic heating and also have not been deformed by regional metamorphism, the temperature recorded by the strata (ca. 300 °C) may arise from burial metamorphism corresponding to a depth of ca. 10 km (calculated by a gradient of 30 °C/km). This is comparable to the emplacement depth of the Tongshanling granodiorite (ca. 10 km) calculated by Al-in-hornblende barometer [START_REF] Huang | Reworked restite enclave: Petrographic and mineralogical constraints from the Tongshanling intrusion, Nanling Range, South China[END_REF]. The slightly higher temperature of the fractured limestone could result from local heating during normal faulting.

Combining the results of RSCM thermometry and EBSD mapping with structural analysis, it is confidently concluded that the wall-rock metamorphism and deformation around the Tongshanling intrusion was induced by magma emplacement. The critical evidence is listed as follows:

(1) the wall-rock metamorphism and deformation are limited in the contact zone (Fig. 6-3); (2) the metamorphic temperature and the marbleization degree of wall rocks gradually decrease outward from the contact zone (Figs. 6-3 and 6-8);

(3) the foliation of deformed marble, which cuts the bedding and shows a sense of normal motion, keeps in parallel with the intrusion boundary and dips outward (Fig. 6-3); (4) the density of foliation gradually decreases outward from the contact zone (Fig. 6-3); (5) different from the undeformed calcite close to the regional normal faults, the calcite in the contact zone has much stronger SPO and CPO (Fig. 6789). Compared with the northeastern contact zone, the southern contact zone has a much stronger intensity of marbleization and deformation with steeper-dipping foliation (Fig. 6-3), indicating that the magma conduit of the Tongshanling intrusion should be located in the southern part.

Rheological behaviour of naturally and experimentally deformed carbonates and microstructural evolution of calcite and dolomite during deformation have been the topics of numerous studies (e.g., [START_REF] Pieri | Rheological and microstructural evolution of Carrara marble with high shear strain: results from high temperature torsion experiments[END_REF][START_REF] Barnhoorn | The role of recrystallisation on the deformation behaviour of calcite rocks: large strain torsion experiments on Carrara marble[END_REF][START_REF] Oesterling | Strain dependent variation of microstructure and texture in naturally deformed Carrara marble[END_REF][START_REF] Seaton | Recrystallization of high-pressure marble (Sivrihisar, Turkey)[END_REF][START_REF] Kushnir | The mechanical and microstructural behaviour of calcite-dolomite composites: An experimental investigation[END_REF][START_REF] Berger | Dolomite microstructures between 390° and 700 °C: Indications for deformation mechanisms and grain size evolution[END_REF]. Mineral composition, grain size, temperature, and strain greatly affect the deformation mechanism of carbonate minerals. The clockwisely oblique CPO of deformed calcite in the contact zone (Fig. 6-9c-g) is indicative of a high shear strain with subgrain rotation recrystallization and grain size reduction (as demonstrated by [START_REF] Pieri | Rheological and microstructural evolution of Carrara marble with high shear strain: results from high temperature torsion experiments[END_REF][START_REF] Barnhoorn | The role of recrystallisation on the deformation behaviour of calcite rocks: large strain torsion experiments on Carrara marble[END_REF][START_REF] Oesterling | Strain dependent variation of microstructure and texture in naturally deformed Carrara marble[END_REF]. The weaker CPO of the coarse-grained samples may result from post-deformational grain growth at elevated temperature (> 500 °C), possibly over a prolonged period of time. Although the experimental observation of [START_REF] Barnhoorn | Post-deformational annealing of calcite rocks[END_REF] revealed that post-deformational annealing does not produce a significant change of CPO in a short time (not exceed 24 hours), a natural case of [START_REF] Seaton | Recrystallization of high-pressure marble (Sivrihisar, Turkey)[END_REF] proved that long-term grain growth at high temperature can destroy pre-existing CPO. The deformation mechanism of calcite-dolomite composite is strongly controlled by strain partitioning between calcite and dolomite [START_REF] Kushnir | The mechanical and microstructural behaviour of calcite-dolomite composites: An experimental investigation[END_REF].

During high-temperature deformation, dolomite is generally stronger than calcite with a dominant deformation mechanism of dislocation creep, whereas calcite undergoes dislocation creep and dynamic recrystallization [START_REF] Kushnir | The mechanical and microstructural behaviour of calcite-dolomite composites: An experimental investigation[END_REF][START_REF] Berger | Dolomite microstructures between 390° and 700 °C: Indications for deformation mechanisms and grain size evolution[END_REF]. The dolomite in the calcite-dolomite composite sample from the southern contact zone was deformed mainly by c <a> and r slip systems (Fig. 6-9f), whereas the calcite was deformed dominantly by r <a> and f slip systems (Fig. 6-9g).

Previous molybdenite Re-Os dating revealed that the exoskarn and sulfide-quartz veins were formed contemporaneously with the emplacement of the Tongshanling intrusion [START_REF] Huang | Geological characteristics and Re-Os geochronology of Tongshanling polymetallic ore field, South Hunan, China[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]. In comparison with the endoskarn garnet, the compositional The permeability of crust exponentially decreases with depth [START_REF] Ingebritsen | Geological implications of a permeability-depth curve for the continental crust[END_REF][START_REF] Ingebritsen | The physical hydrogeology of ore deposits[END_REF]. Recrystallization of calcite during marbleization will further significantly decrease the permeability of carbonate rocks. With a depth of ca. 10 km, unfractured marble is almost impermeable (permeability could be lower than 10 -20 m 2 , unpublished experimental data). However, fracturing can dramatically increase the permeability of rocks [START_REF] Ingebritsen | The physical hydrogeology of ore deposits[END_REF][START_REF] Coelho | Permeability of sheeted dykes beneath oceanic ridges: Strain experiments coupled with 3D numerical modeling of the Troodos Ophiolite, Cyprus[END_REF]. Thus, the magma emplacement-induced wall-rock deformation was critically important for creating permeability to promote the infiltration of magmatic fluids along fractures and then structurally controlled the wall-rock skarnization. A schematic model illustrating the magma emplacement-induced structural control on skarn formation of the Tongshanling Cu-Pb-Zn deposit is shown in Figure 6-11.

This study provides a new viewpoint for understanding the connecting process between skarn systems and granitoids and enlightens further prospecting and exploration for mineral deposits related to granitoids, especially the deep-emplacement granitoids, in South China and also around the world. Magma emplacement-induced wall-rock fractures are ideal permeable zones and are beneficial to hydrothermal mineralization.

Summary

The regional normal faults in the Tongshanling area were formed under the tectonic change from Triassic compression to Jurassic extension earlier than the emplacement of the Tongshanling intrusion.

The emplacement of the Tongshanling intrusion started from the southern part and induced wall-rock marbleization and deformation in the contact zone.

The magma emplacement-induced wall-rock deformation significantly increased permeability to promote the infiltration of magmatic fluids along fractures and then structurally controlled the formation of exoskarn and sulfide-quartz veins.

Chapter 7. Zonation and genesis of the Tongshanling

Cu-Mo-Pb-Zn-Ag skarn system

Introduction

Association and zonation of various alteration and mineralization types are commonly observed in natural magmatic-hydrothermal systems, such as porphyry and skarn systems [START_REF] Meinert | World skarn deposits[END_REF][START_REF] Sillitoe | Porphyry copper systems[END_REF][START_REF] Soloviev | Geology, mineralization, and fluid inclusion characteristics of the Kensu W-Mo skarn and Mo-W-Cu-Au alkalic porphyry deposit, Tien Shan, Kyrgyzstan[END_REF][START_REF] Soloviev | Geology, mineralization, and fluid inclusion characteristics of the Kumbel oxidized W-Cu-Mo skarn and Au-W stockwork deposit in Kyrgyzstan, Tien Shan[END_REF][START_REF] Soloviev | Geology, mineralization, stable isotope geochemistry, and fluid inclusion characteristics of the Novogodnee-Monto oxidized Au-(Cu) skarn and porphyry deposit, Polar Ural, Russia[END_REF][START_REF] Catchpole | Timing of porphyry (Cu-Mo) and base metal (Zn-Pb-Ag-Cu) mineralisation in a magmatic-hydrothermal system-Morococha district, Peru[END_REF][START_REF] Pirajno | Intracontinental porphyry and porphyry-skarn mineral systems in Eastern China: Scrutiny of a special case "Made-in-China[END_REF][START_REF] Soloviev | Geology, mineralization, and fluid inclusion characteristics of the Skrytoe reduced-type W skarn and stockwork deposit, Sikhote-Alin, Russia[END_REF]. Comprehensive study on the relationship between these alteration and mineralization types through geology, geochronology, geochemistry, etc., will greatly promote the understanding of ore-forming process and is also beneficial to further prospecting and exploration. The Middle-Late Jurassic Cu-Pb-Zn deposits in the Nanling Range, South China, include the Shuikoushan, Baoshan, Tongshanling, and Huangshaping deposits in southeastern Hunan Province, and the Dabaoshan deposit in northern Guangdong Province (Fig. 1-1), are characterized by multiple mineralization types that are spatially associated and zoned [START_REF] Lu | Genesis of the Shuikoushan lead-zinc deposit, Changning City, Hunan Province[END_REF][START_REF] Qu | Metallogenic chronology of the stratiform Cu orebody in the Dabaoshan Cu polymetallic deposit, northern Guangdong Province and its geological significance[END_REF][START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Xie | S, Pb, C and O isotopic characteristics and sources of metallogenic materials of Baoshan Pb-Zn deposit, southern Hunan province[END_REF]Ding et al., 2016a). For instance, carbonate replacement and skarn are the predominant mineralization types of the Shuikoushan Pb-Zn-Au-Ag [START_REF] Lu | Genesis of the Shuikoushan lead-zinc deposit, Changning City, Hunan Province[END_REF][START_REF] Huang | Precise zircon U-Pb and molybdenite Re-Os dating of the Shuikoushan granodiorite-related Pb-Zn mineralization, southern Hunan, South China[END_REF], Baoshan Cu-Mo-Pb-Zn-Ag [START_REF] Lu | U-Pb and Re-Os isotope geochronology of Baoshan Cu-Mo polymetallic deposit in Hunan province[END_REF][START_REF] Xie | S, Pb, C and O isotopic characteristics and sources of metallogenic materials of Baoshan Pb-Zn deposit, southern Hunan province[END_REF],

Tongshanling Cu-Mo-Pb-Zn-Ag [START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]Zhao et al., 2016b), and

Huangshaping Pb-Zn-W-Mo [START_REF] Yao | Re-Os isotope dating of molybdenites in the Huangshaping Pb-Zn-W-Mo polymetallic deposit, Hunan Province, South China and its geological significance[END_REF]Ding et al., 2016a) deposits; sulfide-quartz veins are also important in the Tongshanling ore district [START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]Zhao et al., 2016b); the Dabaoshan deposit mainly consists of porphyry Mo (W), skarn Mo-W, and stratiform Cu-Pb-Zn orebodies (Wang et al., 2011c;[START_REF] Qu | Metallogenic chronology of the stratiform Cu orebody in the Dabaoshan Cu polymetallic deposit, northern Guangdong Province and its geological significance[END_REF][START_REF] Mao | Physical and chemical evolution of the Dabaoshan porphyry Mo deposit, South China: Insights from fluid inclusions, cathodoluminescence, and trace elements in quartz[END_REF].

However, the relationship between these different mineralization types was rarely considered in previous studies. Whether they are genetically linked or not is still ambiguous.

The Tongshanling polymetallic ore district is located in the western part of the Nanling

Range metallogenic belt about 120 km to the east of Guilin and in the suture zone between the Yangtze Block and Cathaysia Block (Fig. 1 granodiorite and these surrounding deposits (Wang et al., 2003a;[START_REF] Yi | Geochemical characteristics of Antangling lead-zinc deposit in the Tongshanling orefield[END_REF][START_REF] Wei | Geochemical characteristics and zircon SHRIMP U-Pb dating of the Tongshanling granite in Hunan province, South China[END_REF][START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF][START_REF] Quan | Petrogenesis of granodiorites in Tongshanling deposit of Hunan Province: Constraints from petrogeochemistry, zircon U-Pb chronology and Hf isotope[END_REF][START_REF] Cai | The origin of ore-forming material in the Tongshanling Cu-polymetallic ore field in Hunan Province: Constraints from S-Pb-C isotopes[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]Zhao et al., 2016b;Huang et al., 2017a;[START_REF] Wang | Another remarkable feature of these skarn deposits is the association of different ore-forming elements. For instance, the Huangshaping deposit is dominated by skarn W-Mo and carbonate replacement Pb-Zn mineralization[END_REF], the relationships of the three deposits and different mineralization types are still unknown.

In this study, new geochronological data of garnet and titanite U-Pb and molybdenite

Re-Os ages and geochemical data of S, Pb, and H-O isotopic compositions are presented based on detailed geological information and paragenetic sequences to constrain the genetic links and ore-forming processes of the different deposits and mineralization types in the Tongshanling Cu-Mo-Pb-Zn-Ag ore district.

Deposit geology

Tongshanling Cu-Pb-Zn deposit

The Tongshanling Cu-Pb-Zn deposit occurs in the northeastern concealed contact zone between the Tongshanling granodiorite and country rocks, and its peripheral zone (Figs. 3-1, (Fig. 7-5a). Sparse disseminated sphalerite and pyrite grains occasionally appear in the chalcopyrite. There is no galena in the endoskarn ores.

Proximal exoskarn

The proximal exoskarn mostly occurs as veins with a width of dozens of centimeters in the upper member of the Qiziqiao Formation (Fig. 7-4b). These exoskarn veins commonly exhibit a well-developed outward zonation from garnet-pyroxene through wollastonite (Fig.

7-6c

) to marble and contain late quartz in the center (Fig. 7-4b). They are green-colored on the whole (Fig. 7-4b) and the pyroxene/garnet ratio is distinctly higher than that of the endoskarn. Ore minerals are chalcopyrite, sphalerite, galena, pyrrhotite, and pyrite (Figs. 7-5b and 7-6d). The (sphalerite + galena)/chalcopyrite and pyrite/pyrrhotite ratios of the exoskarn ores are remarkably higher than those of the endoskarn ores.

Distal skarn

Different form the proximal skarn, the distal skarn is evidently controlled by the argillaceous limestone of the Xikuangshan Formation and has stratiform shapes with thicknesses of several meters (Figs. 7-2 and 7-4c). Some residual protolith pieces of argillaceous limestone are observed in the distal skarn (Fig. 7-4d). The distal skarn does not

show an obvious zonation. The roof and floor of the distal skarn are generally silicified limestone (Fig. 7-4c) which is widely and continuously spread in the lower member of the (2) Proximal exoskarn ore (Ccp + Sp + Gn + Po + Py + skarn minerals + Qz + Cal) (Figs.

7-5b and 7-6c-d);

(3) Distal skarn ore (Ccp + Sp + Gn ± Po + Py ± Apy + skarn minerals + Qz + Cal) (Figs.

7-5c-d and 7-6e-f);

(4) Cu-dominant sulfide-quartz vein ore (Ccp ± Sp ± Gn + Py + Apy + Qz) (Figs. 7-5e and 7-6g);

(5) Cu-Pb-Zn sulfide-quartz vein ore (Ccp + Sp + Gn + Py + Qz) (Figs. 7-5f and 7-6h);

(6) Pb-Zn sulfide-quartz vein ore (Sp + Gn + Py + Apy + Qz) (Fig. 7-5g);

(7) Carbonate replacement Pb-Zn sulfide vein ore (Sp + Gn + Py + Apy + Cal) (Fig. 7-5h).

Paragenesis

The paragenetic sequence of the Tongshanling Cu-Pb-Zn deposit (Fig. 7-7) is comprised

Jiangyong Pb-Zn-Ag deposit

The Jiangyong Pb-Zn-Ag deposit occurs in the northwestern concealed contact zone between the Tongshanling granodiorite and country rocks, and its peripheral zone (Figs.

Yulong Mo deposit

The performed by a 32-m ablating spot at 5 Hz with an energy density of 5 J/cm 2 for 45 s after measuring the gas blank for 20 s. Zircon 91500 [START_REF] Wiedenbeck | Three natural zircon standards for U-Th-Pb, Lu-Hf, trace element and REE analyses[END_REF] was used as the external standard and garnet QC04 and OH-1 [START_REF] Deng | Dating magmatic and hydrothermal processes using andradite-rich garnet U-Pb geochronometry[END_REF][START_REF] Seman | U-Pb geochronology of grossular-andradite garnet[END_REF] were used to monitor the process of garnet U-Pb dating. The matrix effect of garnet U-Pb dating has been proved to be minor [START_REF] Mezger | U-Pb systematics of garnet: dating the growth of garnet in the late Archean Pikwitonei granulite domain at Cauchon and Natawahunan Lakes, Manitoba, Canada[END_REF][START_REF] Deng | Dating magmatic and hydrothermal processes using andradite-rich garnet U-Pb geochronometry[END_REF][START_REF] Seman | U-Pb geochronology of grossular-andradite garnet[END_REF]. The off-line data processing was performed using a program called ICPMSDataCal (Liu et al., 2008b). Common lead was corrected by the 207 Pb method (Stern, 1997;[START_REF] Frost | Sphene (titanite): phase relations and role as a geochronometer[END_REF][START_REF] Aleinikoff | U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: an integrated SEM, EMPA, TIMS, and SHRIMP study[END_REF] and the 207 Pb-corrected 206 Pb/ 238 U ages were used to calculate the weighted average age.

Re-Os dating of molybdenite was carried out by a Thermo Electron TJA X-series ICP-MS in the Re-Os laboratory of the National Research Center of Geoanalysis, Chinese Academy of Geological Sciences, Beijing. The analyzed molybdenite was fine-grained (< 0.1 mm) in order to prevent decoupling of Re and 187 Os within large grains. Firstly, molybdenite was digested by HNO3-HCl solution in a Carius tube followed by heating for 10 hours at 230 °C with a stainless-steel jacket. Then, the Re was separated through solvent extraction and cation-exchange resin chromatography. The detailed analytical procedures were described by [START_REF] Shirey | Carius tube digestion for low-blank rhenium-osmium analysis[END_REF], [START_REF] Mao | Re-Os isotopic dating of molybdenites in the Xiaoliugou W (Mo) deposit in the northern Qilian mountains and its geological significance[END_REF][START_REF] Du | Preparation and certification of Re-Os dating reference materials: molybdenites HLP and JDC[END_REF]. Analytical blanks for Re and Os were 4.3 pg and 0.09 pg, respectively. Model ages were calculated by the following equation: t=[ln(1+ 187 Os/ 187 Re)]/ , in which is the 187 Re decay constant of 1.666×10 -11 /year [START_REF] Smoliar | Re-Os ages of group IIA, IIIA, IVA and IVB iron meteorites[END_REF]. The model age of the GBW04435 (JDC) molybdenite standard measured in this study is 141.0 ± 1.9 Ma and is consistent with the certified value of 139.6 ± 3.8 Ma [START_REF] Du | Preparation and certification of Re-Os dating reference materials: molybdenites HLP and JDC[END_REF].

U-Pb dating of titanite was performed by an Agilent 7700× ICP-MS coupled to an Excite 193 nm Photon Machines laser ablation system at Nanjing FocuMS Technology Co. Ltd., China. Each analysis was conducted with a 40-m ablating spot at 6 Hz with an energy density of 6.7 J/cm 2 for 45 s after measuring the gas blank for 15 s. Titanite BLR-1 [START_REF] Aleinikoff | Ages and origins of rocks of Killingworth dome, South-Central Connecticut: Implications for the tectonic evolution of southern New England[END_REF][START_REF] Mazdab | Characterization of flux-grown trace-element-doped titanite using the high-mass-resolution ion microprobe (SHRIMP-RG)[END_REF] was used as the external standard and Ontario titanite [START_REF] Corfu | Multistage zircon and titanite growth and inheritance in Archean gneiss complex, Winnipeg River Subprovince, Ontario[END_REF] was used to monitor the process of U-Pb dating. NIST SRM 610 was used as the reference material to calibrate the U, Th, and Pb concentrations of titanite by using 43 Ca as the internal calibration. The off-line data processing was performed using a program called ICPMSDataCal (Liu et al., 2008b). Common lead was corrected by the 207 Pb method (Stern, 1997;[START_REF] Frost | Sphene (titanite): phase relations and role as a geochronometer[END_REF][START_REF] Aleinikoff | U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: an integrated SEM, EMPA, TIMS, and SHRIMP study[END_REF]

Results

Garnet U-Pb dating

The

Molybdenite Re-Os dating

The Re-Os dating results of molybdenites from the Tongshanling Cu-Pb-Zn deposit and

Titanite U-Pb dating

The titanite used for U-Pb dating occurs as pseudomorphic crystals replacing biotite or coexists with sulfide minerals as an interstitial texture in the altered granodiorite (Fig. 7-12a).

This kind of titanite is evidently hydrothermal titanite formed by hydrothermal alteration of the granodiorite and is different from the automorphic and isolated magmatic titanite. The δ 34 S values of the sulfide minerals from the Tongshanling Cu-Pb-Zn deposit range from 0.2 ‰ to 5.0 ‰ and show variations of 1.9 -3.6 ‰, 2.5 -4.4 ‰, 1.9 -4.6 ‰, 0.2 -4.5 ‰, and 1.9 -5.0 ‰ for the proximal endoskarn, proximal exoskarn, sulfide-quartz vein, distal skarn, and carbonate replacement mineralization types, respectively (Fig. 7-13). One pyrrhotite sample from the altered granodiorite has a δ 34 S value of 3.9 ‰ (Fig. 7-13). In the proximal endoskarn ores, the δ 34 S values of molybdenite, chalcopyrite, and pyrrhotite are 3.2 -3.6 ‰, 2.2 -2.4 ‰, and 1.9 -2.1 ‰, respectively (Fig. 7-13). The chalcopyrite, sphalerite, and galena in the proximal exoskarn ores have respective δ 34 S values of 3.4 -4.4 ‰, 2.8 -3.9 ‰, and 2.5 -2.8 ‰ (Fig. 7-13). In the sulfide-quartz veins, chalcopyrite, sphalerite, and galena show respective δ 34 S values of 2.7 -4.6 ‰, 2.9 -4.5 ‰, and 1.9 -3.1 ‰ (Fig. 7-13). The molybdenite, chalcopyrite, sphalerite, and galena in the distal skarn ores have δ 34 S values of 4.5 ‰, 3.1 -3.6 ‰, 3.0 -3.4 ‰, and 0.2 -1.8 ‰, respectively (Fig. 7-13). In the carbonate replacement ores, the δ 34 S values of sphalerite and galena are 4.7 -5.0 ‰ and 1.9 -2.2 ‰, respectively (Fig. 7-13).

The δ 34 S values of the sulfide minerals from the Jiangyong Pb-Zn-Ag deposit vary from 0.2 ‰ to 3.3 ‰ and show ranges of 1.2 -2.6 ‰ and 0.2 -3.3 ‰ for the skarn and carbonate replacement mineralization types, respectively (Fig. 7-13). Two pyrrhotite samples from the altered granodiorite have δ 34 S values of 2.0 ‰ and 2.5 ‰ (Fig. 7-13). In the skarn ores, one sphalerite and three pyrrhotite samples show respective δ 34 S values of 2.6 ‰ and 1.2 -2.2 ‰ (Fig. 7-13). The sphalerite, pyrite, and galena in the carbonate replacement ores have δ 34 S values of 2.4 -3.3 ‰, 1.8 -2.6 ‰, and 0.2 -1.1 ‰, respectively (Fig. 7-13). The δ 34 S values of twelve molybdenite and one pyrrhotite samples from the skarn ores of the Yulong Mo deposit are 4.9 -6.3 ‰ and -0.3 ‰, respectively (Fig. 78910111213).

The sulfur isotopic fractionations and calculated temperatures of sulfide mineral pairs from the Tongshanling Cu-Pb-Zn deposit and Jiangyong Pb-Zn-Ag deposit are listed in Table 7-1. The δ 34 S values of sulfide minerals in isotopic equilibrium should be arranged in the sequence of δ 34 SMol > δ 34 Spy > δ 34 SSp = δ 34 SPo > δ 34 SCcp > δ 34 SGn [START_REF] Ohmoto | Isotopes of sulfur and carbon[END_REF].

According to the Δ 34 S values of sulfide mineral pairs, it is evidently concluded that the pyrrhotite-chalcopyrite in the proximal endoskarn ores and the sphalerite-chalcopyrite in the proximal exoskarn, sulfide-quartz vein, and distal skarn ores of the Tongshanling Cu-Pb-Zn deposit and the sphalerite-pyrrhotite in the skarn ores and the pyrite-sphalerite in the carbonate replacement ores of the Jiangyong Pb-Zn-Ag deposit were not formed in isotopic equilibrium (Table 7-1). Considering the positive Δ 34 SSp-Gn values (Table 7-1) and the close coexistence of sphalerite and galena, they were possibly formed in isotopic equilibrium. The calculate temperatures of the sphalerite-galena pairs reveal that the carbonate replacement ore-forming processes in the Tongshanling Cu-Pb-Zn deposit and Jiangyong Pb-Zn-Ag deposit have similar temperatures which are distinctly lower than those of the skarn and sulfide-quartz vein mineralization (Table 7-1).

Pb isotope

The analytical results of the Pb isotopic compositions of sulfide minerals are listed in

H-O isotopes

The analytical results of H-O isotopic compositions of the quartz from the Tongshanling

Discussion

Timing of mineralization

As a routine and effective method to directly constrain the metallogenic ages, molybdenite Re-Os dating has been widely used in the geochronological studies of ore-forming process (e.g., [START_REF] Stein | Origin of granite in the light of experimental studies in the system NaAlSi 3 O 8 -KAlSi 3 O 8 -SiO 2 -H 2 O[END_REF]Stein et al., , 2001;;[START_REF] Mao | Re-Os isotopic dating of molybdenites in the Xiaoliugou W (Mo) deposit in the northern Qilian mountains and its geological significance[END_REF]Mao et al., , 2008bMao et al., , 2013c;;[START_REF] Stein | Dating and tracing the history of ore formation[END_REF][START_REF] Catchpole | Timing of porphyry (Cu-Mo) and base metal (Zn-Pb-Ag-Cu) mineralisation in a magmatic-hydrothermal system-Morococha district, Peru[END_REF][START_REF] Sillitoe | Two ages of copper mineralization in the Mwombezhi Dome, northwestern Zambia: Metallogenic implications for the Central African Copperbelt[END_REF]. Several molybdenite Re-Os ages of the Tongshanling polymetallic ore district have been reported by previous studies. Except for the molybdenite Re-Os ages, two Sm-Nd isochron ages of 155 ± 8 Ma and Tongshanling Cu-Pb-Zn deposit, respectively, were achieved by previous studies [START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF][START_REF] Wang | Another remarkable feature of these skarn deposits is the association of different ore-forming elements. For instance, the Huangshaping deposit is dominated by skarn W-Mo and carbonate replacement Pb-Zn mineralization[END_REF]. These geochronological results are quite dispersed relative to the molybdenite Re-Os ages. In order to determine the time interval between skarn formation and sulfide mineralization, LA-ICP-MS U-Pb dating of the garnet from the proximal exoskarn of the Tongshanling Cu-Pb-Zn deposit was carried out in this study and yields a concordia age of 162.0 ± 3.7 Ma with a consistent weighted average 206 Pb/ 238 U age of 162.4 ± 4.2 Ma (Fig.

7-10

). These results are in accordance to the molybdenite Re-Os ages and reveal that there is no obvious time interval between skarn formation and sulfide mineralization.

The LA-ICP-MS U-Pb dating of the hydrothermal titanite in the altered granodiorite from the Tongshanling Cu-Pb-Zn deposit yields lower intercept ages of 155.5 ± 3.1 Ma and 155.6 ± 3.1 Ma in the Wetherill and Tera-Wasserburg U-Pb concordia diagrams, respectively (Fig. 7-12), with a consistent weighted average 206 Pb/ 238 U age of 154.4 ± 1.9 Ma (Fig. 7-12b).

These titanite U-Pb ages are about 5 Ma younger than the molybdenite Re-Os and garnet U-Pb ages and may reflect a slightly later hydrothermal event after the dominant skarn and sulfide-quartz vein mineralization. However, the nature and role of the later hydrothermal event are still unknown and need to be further studied. A possibility is that the later hydrothermal event was genetically related to the later carbonate replacement mineralization in the Tongshanling polymetallic ore district.

For the Jiangyong Pb-Zn-Ag deposit, up to date, there is no available mineral found for geochronological study of metallogenesis. Zhao et al. (2016b) obtained two zircon U-Pb ages of 160.7 ± 0.5 Ma and 160.5±0.9 Ma for the ore-bearing Tongshanling granodiorite sampled from the underground galleries in the Jiangyong Pb-Zn-Ag deposit. It is dependable to conjecture that the Jiangyong Pb-Zn-Ag deposit was formed temporally consistent with or slightly later than the Tongshanling granodiorite.

In a word, the three ore deposits in the Tongshanling polymetallic ore district were almost contemporaneously formed at 160 -162 Ma which is consistent with the zircon U-Pb age of the Tongshanling granodiorite (160 -164 Ma, Jiang et al., 2009;Zhao et al., 2016b;Huang et al., 2017a). Except for the carbonate replacement mineralization which is still not well constrained by geochronology, there are no evident time intervals between the different mineralization types in the Tongshanling ore district.

Sources of ore-forming materials

The sulfide minerals of the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit show a narrow variation of δ 34 S values from -0.3 ‰ to 6.3 ‰ (Fig. 7-13). Such S isotopic compositions are consistent with those of the sulfides derived from high-temperature magmas but are distinctly different from those of the sulfides precipitated from sea water and also the sulfides transformed from sulfate by organic reduction (Fig. 78910111213141516). Therefore, the sulfur for sulfide mineralization in the Tongshanling polymetallic ore district is magmatic sulfur originated from the Tongshanling granodioritic intrusion, whereas, the carbonate wall rocks almost do not make a contribution of sulfur to the metallogenesis.

The Pb isotopic compositions of the sulfide minerals from the three ore deposits are similar on the whole and are identical to those of the Tongshanling granodiorite (Fig. two different source-rock components (e.g., [START_REF] Anderson | Lead isotope evolution of mineral deposits in the Proterozoic Throssell Group, Western Australia[END_REF][START_REF] Schneider | Carbonate-hosted zinc-lead deposits in the Lower Cambrian of Hunan, South China: a radiogenic (Pb, Sr) isotope study[END_REF][START_REF] Cunha | Lead isotope constraints on the genesis of Pb-Zn deposits in the Neoproterozoic Vazante Group, Minas Gerais, Brazil[END_REF][START_REF] Zeng | Multiple isotope composition (S, Pb, H, O, He, and Ar) and genetic implications for gold deposits in the Jiapigou gold belt, Northeast China[END_REF]. The mixing of a lower crust-derived magma with relatively low U/Pb and Th/Pb ratios and an upper crust-derived component with relatively high U/Pb and Th/Pb ratios may be the genesis of the Pb isotopic linear trends revealed by the sulfide minerals from the Tongshanling ore district.

It is noteworthy that, the mafic amphibolitic lower crust in South China has fertile Cu and Zn contents but a barren Pb content. For instance, the exposed amphibolites in the Tianjinping Formation and the Mayuan Group which are the lower-crust basement of the Cathaysia Block have Cu contents of 57.7 ppm and 66.5 ppm, Zn contents of 119 ppm and 118 ppm, and Pb contents of 7.39 ppm and 8.46 ppm, respectively [START_REF] Li | Timing of the Cathaysia Block formation: Constraints from SHRIMP U-Pb zircon geochronology[END_REF]. Their Cu and Zn contents are distinctly higher than those of the upper crust (Cu: 29 ppm, Zn: 63 ppm) in Southeast China [START_REF] Gao | Chemical composition of the continental crust as revealed by studies in East China[END_REF] and are also higher than those of the lower crust (Cu: 26 ppm, Zn: 78 ppm) reported by [START_REF] Rudnick | Nature and composition of the continental crust: A lower crustal perspective[END_REF]. However, their Pb contents are distinctly lower than that of the upper crust (17 ppm) in Southeast China [START_REF] Gao | Chemical composition of the continental crust as revealed by studies in East China[END_REF].

Taylor and McLennan (1995) also reported a distinctly lower Pb content of the lower crust (4 ppm) than that of the upper crust (20 ppm). Therefore, the Cu and Zn of the Tongshanling ore district were most probably released from the mafic amphibolitic lower crust by partial melting, whereas, the Pb was extracted from the upper crust by the ascending granodioritic magma.

Nature of ore-forming fluids

The

Genetic links between different mineralization types and ore deposits

The Tongshanling Cu-Pb-Zn deposit exhibits a well-developed outward zonation from the proximal endoskarn (Fig. 7-4a) through the proximal exoskarn (Fig. 7-4b) to the sulfide-quartz veins (Fig. 7-4g) and then to the distal skarn (Fig. 7-4c) with an extending distance of several hundred meters (Fig. 7-2). Besides, a few late Pb-Zn sulfide-quartz veins (Fig. 7-4h) and carbonate replacement Pb-Zn sulfide veins (Fig. 7-4i) occur in the granodiorite and proximal wall rocks, respectively. Previous studies argued that the distal skarn mineralization was caused by hydrothermal overprint and reworking of a pre-enriched syndepositional source bed and belongs to stratabound mineralization during which the strata have made a significant contribution of ore-forming materials [START_REF] Long | Genetic characteristics and material sources of poly metallic deposit in Tongshanling[END_REF][START_REF] Chen | An investigation into the genesis of the Tongshanling "interformational skarn type" polymetallic deposit[END_REF][START_REF] Deng | The geological characteristics and genesis of Tongshanling polymetallic deposits, Hunan[END_REF]. However, the sulfide minerals from the distal skarn ores do not show any to the sulfide-quartz veins in the peripheral limestone (Fig. 7-4g), the sulfide-quartz veins are considered as later productions of the evolved skarn system relative to the earlier skarn. Then, the carbonate replacement Pb-Zn sulfide veins were formed with lower temperatures than the sulfide-quartz veins (Table 7- Cu-Pb-Zn deposits may be indicative of an extraction of Pb from the upper crust by the ascending lower crust-derived magmas as discuss before.

Notably, the molybdenite Re-Os ages revealed that the Cu-Pb-Zn deposits were formed mainly from 153.8 Ma to 166.0 Ma with a peak value of 159.9 Ma, whereas, the W deposits were formed mainly from 146.9 Ma to 160.0 Ma with a peak value of 154.5 Ma (Fig. 7

-17).

There is a time gap of about 5 Ma between the two different types of mineral deposits. This is highly consistent with the time gap of about 5 Ma between the Cu-Pb-Zn-bearing and W-bearing granitoids (Huang et al., 2017a) and further supports the petrogenetic model of non-simultaneous partial melting illustrating the origins of the Cu-Pb-Zn-bearing and W-bearing granitoids (Huang et al., 2017a). The molybdenite Re-Os ages of the Cu-Pb-Zn and W deposits are consistent with the zircon U-Pb ages of the Cu-Pb-Zn-bearing and W-bearing granitoids (Huang et al., 2017a), respectively, indicating that the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range are genetically associated with the contemporaneous ore-bearing granitoids.

The molybdenites from the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range have Re contents of 16.3 -1841 ppm and 0.003 -14.6 ppm, respectively (Fig.

7-18

). Such distinctly different molybdenite Re contents are indicative of different sources of ore-forming materials for the Cu-Pb-Zn and W deposits. [START_REF] Mao | Re-Os isotopic dating of molybdenites in the Xiaoliugou W (Mo) deposit in the northern Qilian mountains and its geological significance[END_REF] proposed that the Re contents of molybdenite progressively decrease from a mantle source (n × 10 -4 ) through a crust-mantle mixing source (n × 10 -5 ) to a crustal source (n × 10 -6 ). The low Re contents of the molybdenites from the W deposits are consistent with their upper-middle crust-derived ore-bearing granites and ore-forming materials. The high Re contents of the molybdenites from the Cu-Pb-Zn deposits are widely considered as an indicator of crust-mantle mixing-derived ore-forming materials (e.g., [START_REF] Lu | U-Pb and Re-Os isotope geochronology of Baoshan Cu-Mo polymetallic deposit in Hunan province[END_REF][START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF]Wang et al., 2011d;[START_REF] Huang | Precise zircon U-Pb and molybdenite Re-Os dating of the Shuikoushan granodiorite-related Pb-Zn mineralization, southern Hunan, South China[END_REF]. However, Stein et al. (2001) pointed that melting of mafic rocks may also be expected to produce high Re contents in associated molybdenites. Therefore, the high molybdenite Re contents of the Cu-Pb-Zn deposits can be well explained by the origin of the Cu-Pb-Zn-bearing granitoids, i.e., partial melting of the mafic amphibolitic lower crust, and the crust-mantle mixing source is not necessary. The progressively decreasing molybdenite Re contents from the earlier Cu-Pb-Zn deposits to the later W deposits (Fig. 7-18) reflect the non-simultaneous formation of the Cu-Pb-Zn-bearing and W-bearing granitoids by progressive partial melting from the mafic amphibolitic lower crust to the muscovite-rich metasedimentary upper-middle crust.

Summary

The Tongshanling Cu-Pb-Zn deposit shows a well-developed outward zonation from proximal endoskarn through proximal exoskarn to sulfide-quartz veins and then to distal skarn, additionally with a few late Pb-Zn sulfide-quartz veins and carbonate replacement Pb-Zn sulfide veins distributed in the proximal part. S, Pb, and H-O isotopic studies reveal that the ore-forming materials and fluids of the Tongshanling polymetallic ore district were derived from the Tongshanling intrusion. The Cu and Zn were most probably released from the mafic amphibolitic lower crust by partial melting, whereas, the Pb was extracted from the upper crust by the ascending granodioritic magma.

Based on the geological, geochronological, and isotopic geochemical studies, it is concluded that the different mineralization types and ore deposits in the Tongshanling ore district are genetically linked together and are the productions of evolution and zonation of the same skarn system associated with the Tongshanling granodioritic intrusion.

A comparison of the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range further supports the petrogenetic model of non-simultaneous partial melting illustrating the origins of the Cu-Pb-Zn-bearing and W-bearing granitoids.

Chapter 8. Ore-forming process of the Weijia scheelite skarn deposit

Introduction

About one-half of the world's tungsten resources are present as scheelite in skarn deposits [START_REF] Werner | International strategic mineral issues summary report-Tungsten[END_REF]. Essentially, all economic W skarns are calcic throughout the world [START_REF] Kwak | W-Sn skarn deposits and related metamorphic skarns and granitoids[END_REF], such as the well-known MacTung (Canada), CanTung (Canada), Pine Creek (USA), King Island (Australia), Sangdong (South Korea), Nui Phao (Vietnam), Uludağ (Turkey), Salau (France), Los Santos (Spain), Xintianling (China), Shizhuyuan (China), and Yaogangxian (China) deposits (see details in the Appendix of [START_REF] Meinert | World skarn deposits[END_REF]. Especially, the recently discovered giant Zhuxi W-Cu deposit (2.86 Mt WO3, Wang et al., 2017b) in northeastern Jiangxi Province of South China is also dominated by calcic skarn mineralization [START_REF] Pan | Dating the giant Zhuxi W-Cu deposit (Taqian-Fuchun Ore Belt) in South China using molybdenite Re-Os and muscovite Ar-Ar system[END_REF]. In contrast, magnesian W skarns are uncommon and have been rarely reported. For instance, the Costabonne W deposit (France) [START_REF] Guy | Pétrologie et géochimie isotopique (S, C, O) des skarns à scheelite de Costabonne (Pyrénées orientales, France)[END_REF][START_REF] Kwak | W-Sn skarn deposits and related metamorphic skarns and granitoids[END_REF][START_REF] Dubru | Distribution of scheelite in magnesian skarns at Traversella (Piemontese Alps, Italy) and Costabonne (Eastern Pyrenees, France): Nature of the associated magmatism and influence of fluid composition[END_REF], Carro del Diablo W-Sn deposit (Spain) [START_REF] Casquet | El skarn de W-Sn del Carro del Diablo (Sistema Central Español)[END_REF], and

Traversella Fe-W-Cu deposit (Italy) [START_REF] Dubru | Distribution of scheelite in magnesian skarns at Traversella (Piemontese Alps, Italy) and Costabonne (Eastern Pyrenees, France): Nature of the associated magmatism and influence of fluid composition[END_REF][START_REF] Vander Auwera | Trace elements (REE) and isotopes (O, C, Sr) to characterize the metasomatic fluid sources: evidence from the skarn deposit (Fe, W, Cu) of Traversella (Ivrea, Italy)[END_REF] are

several exceptional examples of magnesian W skarns. These latter are characterized by small-scale mineralization and are of less economic importance. Although dolomitic rocks are favorable hosts for some Fe, Sn, and Au skarns, general observations revealed that they tend to inhibit the development of W skarns [START_REF] Zharikov | Skarns[END_REF][START_REF] Einaudi | Skarn deposits[END_REF][START_REF] Kwak | W-Sn skarn deposits and related metamorphic skarns and granitoids[END_REF][START_REF] Ray | Skarns and skarn deposits in the Canadian Cordillera[END_REF][START_REF] Ray | A review of skarns in the Canadian Cordillera[END_REF][START_REF] Meinert | World skarn deposits[END_REF].

The discovery of the super-large Weijia scheelite skarn deposit in South China that comprises predominant magnesian W skarn and subordinate calcic W skarn demonstrates and highlights the importance of magnesian skarn for W mineralization. The Weijia W deposit has a total WO3 resource of ca. 300,000 t estimated by a cut-off grade of 0.12 wt.%, in which ca.

240,000 t are from the magnesian skarn with an average grade of ca. 0.18 wt.% and the rest ca.

60,000 t from the calcic skarn with an average grade of ca. 0.24 wt.% (No. 1 General Brigade of Hunan Geological and Mining Bureau for Nonferrous Metals, unpub. report, 2014; No. 418

Geological Team of Bureau of Geology and Mineral Exploration and Development of Hunan

Province, unpub. report, 2016). Since the concealed Weijia W deposit is still unmined, however, very few studies have been carried out on its metallogenesis and mineralization process, except for some publications of deposit geology and ore-bearing granite (e.g., Li et al., 2012a;[START_REF] Hu | Ore controlling factors and metallogenic regularity of concealed tungsten-fluorite deposits in Weijia of Hunan[END_REF]Zhao et al., 2016aZhao et al., , 2016b;;Huang et al., 2017a). Scientifically the Weija deposit presents a special case of scheelite skarn deposit. Such unusual economic mineralization is of great interest to economic geologists and provides an excellent opportunity for further understanding of W mineralization. Two main particularities have been evocated in preceding publications. First, it is genetically related to a highly fractionated porphyritic granite with petrographic features similar to those of the subvolcanic granites (Huang et al., 2017a). Such an association differs from most other W skarn deposits that are commonly related to deep-emplaced and coarse-grained granitoids [START_REF] Einaudi | Skarn deposits[END_REF][START_REF] Newberry | Scheelite skarn granitoids: An evaluation of the roles of magmatic source and process[END_REF][START_REF] Kwak | W-Sn skarn deposits and related metamorphic skarns and granitoids[END_REF][START_REF] Ray | An overview of skarn deposits[END_REF][START_REF] Meinert | World skarn deposits[END_REF].

Second, fluorite is abundant and is a potential economic resource of the Weijia W deposit [START_REF] Hu | Ore controlling factors and metallogenic regularity of concealed tungsten-fluorite deposits in Weijia of Hunan[END_REF]. However, no genetic model has been proposed for this particular deposit.

In this study, based on detailed observations of surface outcrops and numerous drill cores, systematic petrographic study, Raman spectroscopy of carbonaceous material (RSCM) thermometry, whole-rock geochemical analysis of altered granite, and mineralogical analyses of micas, skarn minerals, and scheelite are carried out to constrain the process of magmatic to hydrothermal evolution and magnesian and calcic skarnization and mineralization of the Weijia W deposit. Some key processes that control tungsten mineralization are then discussed based on these results and previous studies. Finally, a comprehensive genetic model of the Weijia W deposit is proposed.

Deposit geology

Stratigraphy

In the Weijia W deposit, the exposed strata are mainly Middle-Upper Devonian carbonate rocks that include the Middle Devonian Qiziqiao and Upper Devonian Shetianqiao and Xikuangshan Formations, some of which are covered by Quaternary sediments (Fig. 8-1). report, 2016).

Weijia granite

The Weijia granite was emplaced along the bedding (Fig. 8-2) and occurs as scattered bosses, ductoliths, apophyses, and dikes, with a total exposure area of ca. 1.3 km 2 (Fig. 8-1).

A rough estimation shows that the total volume of the Weijia granite not exceeds 1 km 3 . With a light red to off-white color, the fresh granite shows a typical porphyritic texture . The porphyritic Weijia granite contains 30 -50 vol.% of phenocrysts mostly with a and 8-4a-f). With a hexagonal bipyramidal shape, the quartz phenocrysts frequently exhibit an embayment texture (Fig. 8-4b). Micrographic texture is common in K-feldspar (Fig. 8-4c).

In the rim of some K-feldspar phenocrysts, microgranular quartz (10 -100 m), with a gradually increased grain size outward, constitutes a "pearlitic border" texture (Fig. 8-4d).

Biotite crystals mainly occur as phenocrysts, a large proportion of which are bleached (Fig.

8-4e

) in comparison to the fresh ones (Fig. 8-4a). White mica is distributed as interstitial crystals in the matrix (Fig. 8-4f) or coexists with fluorite as millimeter-sized bubble-like aggregates (Fig. 8-4g). Accessory minerals include fluorite, scheelite, zircon, thorite, xenotime, monazite (Fig. 8-4h and i), niobite, samarskite, fergusonite, parisite, ilmenite, etc.

The granite close to skarn orebodies has been widely altered and sometimes mineralized (Fig. 8-2) and is generally green-colored (Fig. 8-3b). The altered granite close to the magnesian skarn commonly shows a much stronger degree of alteration than that close to the calcic skarn. Serpentine, phlogopite, dolomite, and calcite are widespread in the altered granite near the magnesian skarn (Fig. 8-5). Serpentine usually cuts the granite as veinlets (Fig. 8-5a) or brecciates and replaces the phenocrysts (Fig. 8-5b). Phlogopite generally replaces the K-feldspar phenocrysts with a relict (Fig. 8-5c) or pseudomorph (Fig. 8-5d)

texture or occurs as alteration mineral colts in the matrix that are frequently constituted by a core of dolomite or calcite with/without fluorite and a rim of phlogopite (Fig. 8-5e and f).

Stockwork veins

It is interesting to note that the apex of the Weijia granite has been mined for kaolin.

Numerous stockwork veins and a few aplite veins are distributed at the apex of the Weijia granite. These stockwork veins are mostly northeast-southwest to north-south striking and steeply dip to northwest to west with some to southeast (Fig. 8-6). Three generations of stockwork veins have been distinguished according to their petrographic features. They are successivelly the first-generation K-feldspar-quartz pegmatite veins (Fig. 8 White mica commonly appears in the stockwork veins (Fig. 8-8a-c). The white mica in the K-feldspar-quartz pegmatite veins and (K-feldspar)-quartz veins or veinlets generally occurs as independent crystals and has a relatively large grain size of hundreds of microns (Fig. 8-8a and b), whereas, the white mica in the stockwork quartz veinlets is aggregated and is distinctly smaller with a grain size of several microns to dozens of microns (Fig. 8-8c). The biotite crystals in the granite with stockwork veins are widely bleached with the formation of abundant Fe-Ti oxides (Fig. 8-8d). White mica also appears in the matrix of granite with stockwork veins (Fig. 8-8e) and the bleached zone near stockwork veins (Fig. 8-8f).

Magnesian skarn

The magnesian skarn is distributed along the contact zone between the Weijia granite and dolostone (Fig. 8-2). With thicknesses of 85 -182 m, the magnesian skarn orebodies mostly occur as stratiform within the dolostone of the middle member of the Qiziqiao Formation and have a consistent strike-dip with the host strata (Fig. 8-2). They are buried at the depths below the surface of 200 -900 m (Fig. 8-2). The magnesian skarn generally occurs as green-colored stockwork veinlets in the fissures of dolostone with a millimeter-scale outward zonation from magnesian skarn through bleached marble to unaltered dolostone (Fig. 8-3c andd). This

8-10c).

The paragenetic sequence of the magnesian skarn is shown in Figure 8-11. In the pre-ore stage, some prograde minerals, i.e., garnet and pyroxene, were formed firstly followed by the formation of a few chondrodite, fluoborite, magnetite, and scheelite. Fluorite also began to precipitate. The syn-ore stage was dominated by the formation of abundant serpentine, phlogopite, fluorite, scheelite, calcite, and dolomite, some talc, chlorite, and sellaite, and a few later marialite, plagioclase, K-feldspar, and quartz. In the post-ore stage, carbonate minerals, fluorite, and quartz were still continually formed with the disseminated precipitation of some sulfide minerals, such as pyrite, arsenopyrite, chalcopyrite, sphalerite, and galena.

Calcic skarn

The calcic skarn is distributed along the contact zone between the Weijia granite and limestone (Fig. 8-2). With thicknesses of 14 -46 m, the calcic skarn orebodies mostly occur as massive or stratiform within the limestone of the upper member of the Qiziqiao Formation (Fig. 8-2). They have a buried depth shallower than 300 m and are partially exposed on the surface (Fig. 8-2). Surficial weathering of the calcic skarn led to the formation of a secondary weathering orebody with a WO3 resource of ca. 8,000 t and an enriched average grade of ca.

0.35 wt.% (No. 1 General Brigade of Hunan Geological and Mining Bureau for Nonferrous Metals, unpub. report, 2014). This weathering orebody is horizontally extended over the calcic skarn orebodies with a thickness of 3 -40 m (Fig. 8-2). It is composed of Quaternary sediments in which the content of residues increases with depth (Fig. 8-3f).

Wollastonite, garnet, and pyroxene are the predominant calcic skarn minerals (Fig. 8-3gj). At the reaction front of calcic skarn, marble was formed along the fluid pathways in limestone and overprinted by wollastonite and followed by garnet (Fig. 8-3g). Three generations of garnet have been distinguished in the calcic skarn, which are chronologically green-brown to yellow-brown disseminated or aggregated garnet, yellow-brown to red-brown vein-like garnet, and red-brown to dark brown vein-like or interstitial garnet (Fig. 8-3h-j).

The first-generation garnet is commonly zoned with some pyroxene inclusions inside and has been partially replaced by later minerals . By contrast, the second-generation vein-like garnet does not show a zonal texture and cuts earlier pyroxene (Fig. 8-12b). The third-generation interstitial garnet has a well-developed zonal texture with the remaining interstice filled by calcite (Fig. 8-12c). The pyroxene can be divided into an early generation of light green disseminated pyroxene (Fig. 8-3h) and a late generation of dark green pyroxene dominated by veinlets (Fig. 8-3h-j) and sometimes aggregated masses (Fig. 8-3i). The wollastonite contains an early generation that coexists with garnet and pyroxene and shows an intergrowth texture with fluorite and a late generation that occurs as veinlets cutting the earlier garnet, pyroxene, wollastonite, and fluorite (Fig. 8-12d ande). The matrix of the calcic skarn frequently exhibits a complex intergrowth texture of skarn minerals, calcite, fluorite, and quartz (Fig. 8-12f). Some columnar vesuvianite crystals with a zonal texture appear in the calcic skarn (Fig. 8-12g). The calcic skarn is cross-cut by (K-feldspar)-quartz veins or veinlets which are commonly enveloped by the late pyroxene (Fig. 8-3h-j). Fluorite veinlets were formed later and cut across the quartz veinlets (Fig. 8-3j). Late K-feldspar and quartz may coexist with fluorite (Fig. 8-12h). Scheelite is distributed in the calcic skarn as disseminated grains (Fig. 8-12b and h). The paragenetic sequence of the calcic skarn is shown in Figure 8-13. In the pre-ore stage, abundant prograde minerals, i.e., garnet, pyroxene, and wollastonite, were formed firstly followed by the formation of a few magnetite, vesuvianite, and scheelite. Fluorite also began to precipitate. The skarn minerals were still continually formed in the syn-ore stage.

Besides the skarn minerals, the syn-ore stage was dominated by the formation of abundant fluorite, scheelite, and calcite and a few serpentine, phlogopite, and chlorite followed by a few later plagioclase, K-feldspar, zeolite, and quartz. In the post-ore stage, calcite, fluorite, and quartz were still continually formed with the disseminated precipitation of some sulfide minerals, such as pyrite, pyrrhotite, arsenopyrite, chalcopyrite, sphalerite, and galena.

Relationship between WO 3 and CaF 2 grades

Both the magnesian and calcic skarn scheelite ores contain abundant fluorite (mostly 5 -20 wt.%), and their WO3 grades show an obvious positive correlation with fluorite contents . The wall rocks (dolostone) near the magnesian skarn orebodies also

Sampling and analytical methods

Representative samples of the fresh and altered Weijia granite, stockwork veins at the apex of granite, and magnesian and calcic skarns and their adjacent carbonate wall rocks were collected from drill cores (numbered by ZK) and surface outcrops (numbered by WJ). They were firstly prepared as polished thin sections for petrographic studies under optical microscope and scanning electron microscope (SEM), and then for mineral composition analyses by SEM, electron microprobe (EMP), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Eleven polished thin sections of carbonate rocks close to the magnesian (six samples) and calcic (five samples) skarns were selected for RSCM thermometry. Twelve samples of altered granite spatially close to the magnesian (eight samples) and calcic (four samples) skarn orebodies were crushed to 200 mesh for whole-rock analyses of major and trace elements.

RSCM analysis was carried out by a Renishaw InVIA Reflex micro-spectrometer coupled to a DM2500 Leica microscope at Bureau de Recherches Géologiques et Minières (BRGM), Orléans, France. An argon laser with 0 = 514.5 nm was used as exciter. Instrument control and Raman measurements were performed by the Renishaw Wire 3.4 software. Before analysis, the spectrometer was calibrated using the 520.4 cm -1 line of silicon. To check within-sample structural heterogeneity, at least 10 spectra were recorded for each sample. Major element analyses of micas and skarn minerals were carried out with a CAMECA SX50 EMP at ISTO, France. The analytical conditions included an accelerating voltage of 15 kV, a beam current of 10 nA with diameter of 1 m, and counting times of 10 s for all elements and 5 s for background. The collected data were corrected by the ZAF procedures.

Calibration was performed using natural minerals and synthetic compounds.

Trace elements of garnet and scheelite were analyzed by an Agilent 7700× ICP-MS coupled to an Excite 193 nm Photon Machines laser ablation system at Nanjing FocuMS Technology Co. Ltd., China. Each analysis was carried out by a 50-m ablating spot at 8 Hz with energy of 4.5 mJ (transmittance 50%) for 40 s after measuring the gas blank for 15 s.

NIST SRM 610 was used as the external standard for quantitative calibration of the time-dependent drift of sensitivity and mass discrimination. The off-line data processing was performed using a program called ICPMSDataCal (Liu et al., 2008b).

Results

RSCM thermometry

The Raman spectrum of carbonaceous material comprises a first-order region of 1100 -1800 cm -1 and a second-order region of 2300 -3500 cm -1 (Tuinstra and Koenig, 1970;Nemanich and Solin, 1979). All measurements were performed in the first-order domain. In the first-order region, the graphite (G) band occurs around 1580 cm -1 and corresponds to in-plane vibration of aromatic carbons in the graphitic structure (Tuinstra and Koenig, 1970;Lespade et al., 1984;Wopenka and Pasteris, 1993). The defect bands D1 and D2 occur around 1350 cm -1 and 1620 cm -1 , respectively, corresponding to physical and chemical defects in the aromatic skeleton of carbonaceous material (Wopenka and Pasteris, 1993;Ferrari and Robertson, 2000). [START_REF] Beyssac | Raman spectra of carbonaceous material in metasediments: a new geothermometer[END_REF] defined the parameters R1 and R2 ratios, which are D1/G peak intensity (i.e., peak height) ratio and D1/(G + D1 + D2) peak area ratio, respectively, to evaluate the disorder degree of carbonaceous material. A negative linear correlation of the R2 ratio with the peak temperature of metamorphism in the range of 330 -640 °C was established by [START_REF] Beyssac | Raman spectra of carbonaceous material in metasediments: a new geothermometer[END_REF], i.e., T (°C) = -445 × R2 + 641. The RSCM thermometer was extended towards low temperatures of 200 -330 °C by [START_REF] Lahfid | Evolution of the Raman spectrum of carbonaceous material in low-grade metasediments of the Glarus Alps (Switzerland)[END_REF].

The Raman spectra of carbonaceous material in the carbonate rocks close to the magnesian and calcic skarns are shown in Figure 8-16. Some parameters of the Raman spectra, include the position and full width at half maximum (FWHM) of the G band, the R1 and R2 ratios, and the calculated temperature, are listed in Appendix 8-1. Compared with the Raman spectra of carbonaceous material in the carbonate rocks near the calcic skarn, the Raman spectra of carbonaceous material in the carbonate rocks near the magnesian skarn show higher R1 and R2 ratios, indicating higher degrees of disorder and corresponding to lower peak metamorphic temperatures (Appendix 8-1 and Fig. 8910111213141516). The Raman spectra of carbonaceous material in the carbonate rocks close to the magnesian and calcic skarns have respective R1 ratios of 0.44 -0.59 and 0.13 -0.20, respective R2 ratios of 0.33 -0.38 and 0.15 -0.20, and respective calculated temperatures of 470 -496 °C and 554 -576 °C (Appendix 8-1 and Fig.

8-16

). The RSCM thermometry reveals that the wall-rock metamorphic temperature of the magnesian skarn was about 80 °C lower than that of the calcic skarn.

Altered granite

The fresh Weijia granite is predominantly composed of quartz, K-feldspar, and albite, containing high SiO2 (73.86 -76.73 wt.%), Al2O3 (13.06 -14.27 wt.%), K2O (4.84 -6.78 wt.%), and Na2O (3.01 -3.72 wt.%) contents and low CaO (0.12 -0.88 wt.%), MgO (0.01 -0.17 wt.%), FeOTotal (0.12 -0.54 wt.%), and MnO (0.00 -0.01 wt.%) contents (Huang et al., 2017a). EDS elemental mapping of the altered granite close to the magnesian skarn shows that obvious Ca, Mg, Fe, and Mn gains happened during the hydrothermal alteration of granite (Fig. 8-17), corresponding to the formation of serpentine, phlogopite, dolomite, and calcite in the altered granite (Fig. 8-5). The matrix of the altered granite exhibits an evident Na loss (Fig. wt.%) than the fresh granite . In contrast, the altered granite close to the calcic skarn shows an obviously lower degree of mass transfer and has intermediate compositions between the fresh granite and the altered granite close to the magnesian skarn .

The CaO, MgO, FeOTotal, MnO, LOI, and Na2O contents of the altered granite close to the calcic skarn are 0.18 -1.26 wt.%, 0.04 -0.19 wt.%, 0.21 -0.73 wt.%, 0.00 -0.02 wt.%, 1.70 -2.02 wt.%, and 1.59 -3.19 wt.%, respectively (Fig. 8-19a-d). There are no strong Si, Ti, Al, and K (Fig. 8-19b) gains or losses during the hydrothermal alteration of granite.

For trace elements, the altered granite close to the magnesian skarn has distinctly higher LILE (large ion lithophile elements) such as Rb (412 -619 ppm) and Ba (66 -195 ppm) contents than the fresh granite (Rb: 260 -356 ppm, Ba: 7 -43 ppm, Huang et al., 2017a) (Fig. 8-19e). The altered granite close to the calcic skarn contains intermediate LILE contents (Rb:

309 -409 ppm, Ba: 25 -38 ppm) between the fresh granite and the altered granite close to the magnesian skarn . In contrast, the HFSE (high field strength elements) such as Th,

= {[Ce N /(La 2/3 N × Nd 1/3 N ) × Pr N /(La 1/3 N × Nd 2/3 N )] 0.5 × [Tb N /(Gd 2/3 N ×
Ho 1/3 N ) × Dy N /(Gd 1/3 N × Ho 2/3 N )] 0.5 } 0.5 , it quantifies the degree of the tetrad effect [START_REF] Irber | The lanthanide tetrad effect and its correlation with K/Rb, Eu/Eu*, Sr/Eu, Y/Ho, and Zr/Hf of evolving peraluminous granite suites[END_REF]. The data of fresh granite are from Huang et al. (2017a).

U, Nb, Ta, Zr, and Hf are more stable than the LILE and do not show strong gains or losses during the hydrothermal alteration of granite (Fig. 8-20a). Notably, the altered granite shows higher REE especially HREE contents and a stronger REE tetrad effect than the fresh granite . The altered granite close to the magnesian skarn has higher ΣREE Compared with the fresh biotite, the bleached biotite in the granite without stockwork veins has distinctly lower K2O contents of 0.32 -7.42 wt.% (Fig. 8-24) and TiO2 contents of 0.00 -2.23 wt.% and higher Al2O3 contents of 15.62 -25.44 wt.%, plotting in the lepidomelane and siderophyllite fields (Fig. 8-23a). To be exact, the bleached biotite is not true mica and is transforming into clay minerals.

In addition to the large variation of the K2O contents of the fresh and bleached biotite, the F contents of the fresh and bleached biotite also show a large variation (Fig. 8-24). The fresh and bleached biotite in the granite without stockwork veins and the bleached biotite in the granite with stockwork veins have progressively decreasing F contents of 1.93 -5.54 wt.% with a peak value of 2.9 wt.%, 0.03 -1.54 wt.% with a peak value of 0.5 wt.%, and 0.00 -1.65 wt.% with a peak value of 0.1 wt.% .

White mica

Representative EMP analytical results and crystallochemical calculations of the white mica in the Weijia granite and its stockwork veins are listed in Appendix 8-4. The white mica in the matrix of granite without stockwork veins contains SiO2 contents of 43.00 -51.00 wt.%, TiO2 contents of 0.00 -0.69 wt.%, Al2O3 contents of 28.81 -33.75 wt.%, FeO contents of 1.02 -7.37 wt.%, MnO contents of 0.00 -0.32 wt.%, MgO contents of 0.02 -0.37 wt.%, CaO contents of 0.00 -0.31 wt.%, Na2O contents of 0.02 -0.38 wt.%, and K2O contents of 6.89 -10.78 wt.% (Fig. 8-24) and plots dominantly in the muscovite field with some in the Li muscovite, Li phengite, and phengite fields (Fig. 8-23b). This kind of white mica mostly has F contents of 0.09 -1.54 wt.% with a peak value of 0.5 wt.% and some has F contents of 2.54 -4.63 wt.% with peak values of 3.1 wt.% and 4.3 wt.% .

Compared with the white mica in the matrix of granite without stockwork veins, the white mica coexisting with fluorite as aggregates in the granite without stockwork veins shows distinctly higher Al2O3 contents of 33.76 -37.69 wt.% and lower FeO contents of 0.00 -1.87 wt.% and F contents of 0.00 -1.62 wt.% with a peak value of 0.3 wt.% (Figs. 8-24 and 8-25d), all plotting in the muscovite field (Fig. 8-23b).

The white mica in the matrix of granite with stockwork veins can be divided into two , respectively. This kind of white mica shows F contents of 0.00 -4.51 wt.% with a peak value of 1.1 wt.% and plots in the muscovite, phengite, Li muscovite, and Li phengite fields (Fig. 8-23b).

EDS elemental mapping reveals that the white mica in the K-feldspar-quartz pegmatite veins has a zonal texture with the core showing higher Fe, F, and K contents and lower Al contents than the rim (Fig. 8 EDS elemental mapping reveals that the white mica in the (K-feldspar)-quartz veins or veinlets also has a zonal texture with the core showing higher Fe, F, and K contents and lower Al contents than the rim (Fig. 8-27). EMP analyses show that the core contains SiO2 contents of 44.62 -47.84 wt.%, TiO2 contents of 0.00 -0.28 wt.%, Al2O3 contents of 25.47 -33.33 wt.%, FeO contents of 1.67 -10.61 wt.%, MnO contents of 0.00 -0.66 wt.%, MgO contents of 0.00 -0.28 wt.%, CaO contents of 0.00 -0.34 wt.%, Na2O contents of 0.00 -0.53 wt.%, K2O contents of 9.57 -10.75 wt.% (Fig. 8-24), and F contents of 2.71 -8.12 wt.% with a peak value of 6.3 wt.% (Figs. 8-24 and 8-25h), plotting in the lepidolite, zinnwaldite, Li phengite, and Li muscovite fields (Fig. 8-23b). Whereas, the rim contains distinctly higher Al2O3 contents of 32.10 -35.12 wt.% and lower FeO contents of 0.43 -2.67 wt.%, K2O contents of 7.29 -10.35 wt.% (Fig. 8-24), and F contents of 0.00 -2.34 wt.% with a peak value of 0.3 wt.% , plotting predominantly in the muscovite and Li muscovite fields (Fig. 8-23b). The SiO2, TiO2, Al2O3, FeO, MnO, MgO, CaO, Na2O, and K2O contents of the white mica in the stockwork veinlets are 45.92 -51.56 wt.%, 0.00 -0.18 wt.%, 29.08 -33.70 wt.%, 0.61 -2.09 wt.%, 0.00 -0.22 wt.%, 0.06 -0.60 wt.%, 0.05 -0.42 wt.%, 0.03 -0.16 wt.%, and 7.55 -9.60 wt.% (Fig. 8-24), respectively. This kind of white mica shows extremely low F contents of 0.00 -0.69 wt.% with a peak value of 0.1 wt.% and is all plotted in the muscovite field (Fig. 8-23b).

Serpentine

EDS elemental mapping reveals that, during the process of magnesian skarnization, -2.57 wt.% with a peak value of 0.1 wt.% (Fig. 8-25j) and higher Al2O3 contents of 0.79 -6.83 wt.% and FeO contents of 3.67 -8.12 wt.%.

Phlogopite

BSE imaging (Fig. 8-10e) and EDS elemental mapping (Fig. 8-28j-aa) reveal that the late-formed phlogopite has higher Fe and lower Mg contents than the early-formed phlogopite. In the individual zoned phlogopite crystals, the later rim parts also show higher Fe and lower Mg contents than the earlier core parts (Fig. 8

Garnet

Representative EMP analytical results and crystallochemical calculations of the garnet in the magnesian and calcic skarns of the Weijia W deposit are listed in Appendix 8-7. The garnet in the magnesian skarn is grandite (Py+Al+Sp: 0.7 -13.8 mol.%, mostly 8.0 -13.8 mol.%) (Fig. 8-30a). It has SiO2 contents of 34.48 -37.81 wt.%, TiO2 contents of 0.00 -0.19 wt.%, Al2O3 contents of 14.68 -20.37 wt.%, FeO contents of 2.11 -9.33 wt.%, MnO contents of 0.22 -3.96 wt.%, MgO contents of 0.05 -3.13 wt.%, CaO contents of 30.39 -36.29 wt.%, Na2O contents of 0.00 -0.24 wt.%, and K2O contents of 0.00 -0.08 wt.%, showing a compositional variation between Gr67.4Ad21.7 and Gr86.3Ad8.6 (Fig. 8-30a). Uncommonly, the garnet in the magnesian skarn contains very high F contents of 0.51 -4.83 wt.% with a peak value of 3.2 wt.% (Fig. 8-25l).

EDS elemental mapping reveals that the first-generation garnet in the calcic skarn exhibits a well-developed compositional zonation with the later rim parts having higher Fe and lower Al contents than the earlier core parts (Fig. 8-31a-f) or an oscillatory compositional zoning of Al and Fe (Fig. 8-31g-r). However, the second-generation vein-like garnet in the All the three generations of garnets in the calcic skarn are grandite (Py+Al+Sp: 0.8 -9.3 mol.%) (Fig. 8-30b). The first-generation garnet has SiO2 contents of 34.19 -36.87 wt.%, TiO2 contents of 0.00 -0.28 wt.%, Al2O3 contents of 0.06 -6.91 wt.%, FeO contents of 20.15 -29.38 wt.%, MnO contents of 0.02 -1.89 wt.%, MgO contents of 0.00 -0.54 wt.%, CaO contents of 31.24 -34.38 wt.%, Na2O contents of 0.00 -0.06 wt.%, and K2O contents of 0.00 -0.10 wt.%, showing a compositional variation between Gr0.3Ad94.6 and Gr32.4Ad62.5 (Fig.

8-30b).

The second-generation garnet has SiO2 contents of 35.57 -37.56 wt.%, TiO2 contents of 0.00 -0.21 wt.%, Al2O3 contents of 5.17 -13.57 wt.%, FeO contents of 12.31 -21.57 wt.%, MnO contents of 0.07 -1.40 wt.%, MgO contents of 0.01 -0.36 wt.%, CaO contents of 31.99 -35.10 wt.%, Na2O contents of 0.00 -0.05 wt.%, and K2O contents of 0.00 -0.08 wt.%, showing a compositional variation between Gr25.0Ad73.8 and Gr59.4Ad35.2 (Fig. 8-30b).

The third-generation garnet has SiO2 contents of 36.36 -38.13 wt.%, TiO2 contents of 0.00 -0.11 wt.%, Al2O3 contents of 10.69 -19.78 wt.%, FeO contents of 7.14 -15.64 wt.%, MnO contents of 0.57 -2.29 wt.%, MgO contents of 0.00 -0.17 wt.%, CaO contents of 31.41

-35.01 wt.%, Na2O contents of 0.00 -0.03 wt.%, and K2O contents of 0.00 -0.06 wt.%, showing a compositional variation between Gr49.7Ad47.0 and Gr73.7Ad22.7 (Fig. 8-30b).

Although the Fe and Al contents gradually increase and decrease with time, respectively, in the individual generations (i.e., first generation and third generation) of garnets (Figs.

8-31a-f and 8-33), overall, the Fe and Al contents progressively decrease and increase, respectively, from the first-generation garnet through the second-generation garnet to the third-generation garnet (Fig. 8-30b). Compared with the garnet in the magnesian skarn, the three generations of garnets in the calcic skarn contain distinctly lower F contents of 0.00 -2.37 wt.% with a peak value of 0.1 wt.% (Fig. 8-25m). The garnet in the magnesian skarn and the third-generation garnet in the calcic skarn contain distinctly lower Ti and V contents than the first-generation and second-generation garnets in the calcic skarn (Fig. 8-35c). The HFSE (Zr, Hf, Th, and U) contents of the third-generation garnet in the calcic skarn are distinctly lower than those of the garnet in the magnesian skarn and the first-generation and second-generation garnets in the calcic skarn (Fig. 8-35d ande). The garnet in the magnesian skarn has distinctly lower W contents than the garnet in the calcic skarn (Fig. 8-35f). Among the three generations of garnets in the calcic skarn, the second-generation garnet contains the lowest W contents (Fig. 8-35f).

Pyroxene

Representative EMP analytical results and crystallochemical calculations of the pyroxene in the magnesian and calcic skarns of the Weijia W deposit are listed in Appendix 8-9. The pyroxene in the magnesian skarn is salite (Jo: 0.1 -1.6 mol.%) (Fig. 8-36a). Its SiO2, TiO2, Al2O3, FeO, MnO, MgO, CaO, Na2O, and K2O contents are 52.84 -55.58 wt.%, 0.00 -0.06 wt.%, 0.14 -0.92 wt.%, 0.88 -2.67 wt.%, 0.05 -0.50 wt.%, 17.13 -19.94 wt.%, 24.14 -26.16 wt.%, 0.00 -0.09 wt.%, and 0.00 -0.08 wt.%, respectively, showing a compositional variation between Di98.4Hd0.0 and Di99.9Hd0.0 (Fig. 8-36a). Both the early and late generations of pyroxenes in the calcic skarn are salite and the late-generation pyroxene contains slightly higher contents of johannsenite components (3.3 -10.2 mol.%) than the early-generation pyroxene (0.2 -5.2 mol.%) (Fig. 8-36b). The early-generation and late-generation pyroxenes show compositions close to the diopside and hedenbergite end members, respectively (Fig. 8-36b).

The early-generation pyroxene has SiO2 contents of 48.91 -54.97 wt.%, TiO2 contents of 0.00 -0.12 wt.%, Al2O3 contents of 0. showing a compositional variation between Di0.0Hd94.6 and Di32.3Hd63.4 (Fig. 8-36b).

Wollastonite

Representative EMP analytical results and crystallochemical calculations of the wollastonite in the calcic skarn of the Weijia W deposit are listed in Appendix 8-10. The early-generation wollastonite has SiO2 contents of 47.82 -49.37 wt.%, TiO2 contents of 0.00 -0.03 wt.%, Al2O3 contents of 0.00 -0.02 wt.%, FeO contents of 0.00 -0.07 wt.%, MnO contents of 0.01 -0.16 wt.%, CaO contents of 45.53 -47.05 wt.%, Na2O contents of 0.01 -0.05 wt.%, and K2O contents of 0.00 -0.03 wt.%. Compared with the early-generation wollastonite, the late-generation wollastonite contains distinctly higher FeO contents of 0.20 -1.49 wt.% and MnO contents of 0.24 -1.31 wt.% (Fig. 8-37).

Vesuvianite

Representative EMP analytical results and crystallochemical calculations of the vesuvianite in the calcic skarn of the Weijia W deposit are listed in Appendix 8-11. The vesuvianite has SiO2 contents of 33.45 -36.55 wt.%, TiO2 contents of 0.00 -0.14 wt.%, Na2O contents of 0.00 -0.08 wt.%, and K2O contents of 0.00 -0.07 wt.%. Notably, the vesuvianite contains high F contents of 1.04 -4.03 wt.% with peak values of 1.9 wt.% and 2.9 wt.% (Fig. 8-25n).

Scheelite

Representative Compared with the scheelite in the magnesian and calcic skarns, the scheelite in the stockwork quartz veinlets contains higher Na, K, Al, Sc, Fe, Ti, V, Mn, Ga, Ge, Sb, Zr, Hf, Nb, Ta, Th, U, REE, and Y contents and lower Mo contents (Fig. 8-39). The scheelite in the magnesian skarn shows distinctly higher Mg contents than the scheelite in the calcic skarn and stockwork quartz veinlets (Fig. 8-39d). Whether for the magnesian skarn or the calcic skarn, the early-generation scheelite has higher Na, Mg, Sc, Ga, Ge, Nb, Ta, REE, and Y contents and lower Mo contents than the late-generation scheelite (Fig. 8-39). Besides, for the magnesian skarn, the early-generation scheelite contains higher Cs, Sb, Zr, and Hf contents than the late-generation scheelite (Fig. 8-39j-l); for the calcic skarn, the early-generation scheelite contains higher Th and U contents and lower Ba contents than the late-generation scheelite (Fig. 8-39j and n).

Estimation of fluorine activity

The fluorine contents of the biotite in the Weijia granite, the white mica in the Weijia granite and its stockwork veins, the serpentine, phlogopite, and garnet in the magnesian skarn, (2005). The bleached biotite in the granite without stockwork veins yields HF concentrations of 10 -2.93 -10 -1.35 mole/dm 3 with a peak value of 10 -1.75 mole/dm 3 (calculated by a constant (To be continued on the next page)

temperature of 550 °C ). The bleached biotite in the granite with stockwork veins yields HF concentrations of 10 -2.91 -10 -1.49 mole/dm 3 with a peak value of 10 -1.95 mole/dm 3 (using a constant temperature of 500 °C ). Using the phlogopite fluorimeter, the HF concentrations calculated by the phlogopite in the magnesian skarn are 10 -3.03 -10 -1.45 mole/dm 3 with a peak value of 10 -2.75 mole/dm 3 (using a constant temperature of 450 °C ). Therefore, a progressive decreasing trend of HF concentration (fluorine activity) from 10 -1.00 mole/dm 3 through 10 -1.75 mole/dm 3 to 10 -1.95 mole/dm 3 and then to 10 -2.75 mole/dm 3 is revealed by the fresh and bleached biotite and phlogopite.

Discussion

Fluorine promoting magmatic fractionation and tungsten enrichment

The fresh biotite in the Weijia granite has high F contents (Figs. 8-24 and 8-25a), shows low IV (F) and IV (F/Cl) numbers , and yields high HF concentrations (10 - 1.5 -10 -0.7 mole/dm 3 ) by the biotite fluorimetry [START_REF] Aksyuk | Estimation of fluorine concentrations in fluids of mineralized skarn systems[END_REF], indicating that the Weijia granite was formed by crystallization of a F-rich magma. The HF concentration of the Weijia granitic magma is consistent with those of the other rare metal leucogranites and Li-F granites and pegmatites worldwide (10 -1.5 -10 -1 mole/dm 3 , [START_REF] Aksyuk | Estimation of fluorine concentrations in fluids of mineralized skarn systems[END_REF] and is significantly higher than those of the granitoids related to W-skarns in the western Cordillera (10 -2.8 -10 -1.8 mole/dm 3 , [START_REF] Aksyuk | Estimation of fluorine concentrations in fluids of mineralized skarn systems[END_REF] and also those of the porphyry Cu deposits (Fig. 8-42, Aksyuk, 2000).

The existence of abundant fluorine can dramatically reduce the viscosity and the minimum liquidus temperature of granitic melts by the formation of aluminofluoride (A1F 3- 6 ) complex anions that weaken the framework of aluminosilicate complexes [START_REF] Manning | The probable occurrence of interstitial Al in hydrous, F-bearing and F-free aluminosilicate melts[END_REF][START_REF] Manning | The effect of fluorine on liquidus phase relationships in the system Qz-Ab-Or with excess water at 1kb[END_REF]. The minimum liquidus temperature of granitic melts at 1 kbar changes progressively from 730 °C (Tuttle and Bowen, 1958) for the F-free system to 630 °C for the system with 4 wt.% added fluorine [START_REF] Manning | The effect of fluorine on liquidus phase relationships in the system Qz-Ab-Or with excess water at 1kb[END_REF]. As a consequence, the low viscosity and minimum liquidus temperature will lead to the formation of highly fractionated granites by protracting the process of crystallization differentiation. Such prolonged crystal fractionation will then result in the enrichment of the incompatible tungsten in the residual granitic melts especially at relatively low magmatic temperatures [START_REF] Audétat | Magmatic-hydrothermal evolution in a fractionating granite: A microchemical study of the Sn-W-F-mineralized Mole Granite (Australia)[END_REF][START_REF] Linnen | Granite-related rare-element deposits and experimental constraints on Ta-Nb-W-Sn-Zr-Hf mineralization[END_REF], even though the tungsten solubility in granitic melts is nearly independent of the fluorine content [START_REF] Linnen | Granite-related rare-element deposits and experimental constraints on Ta-Nb-W-Sn-Zr-Hf mineralization[END_REF][START_REF] Che | Tungsten solubility in evolved granitic melt: An evaluation of magmatic wolframite[END_REF]. Huang et al. (2017a) carried out detailed geochemical study of the Weijia granite and pointed out that it is a highly fractionated peraluminous S-type granite. It has high SiO2 contents and shows low CaO/(Na2O+K2O) and high Rb/Sr ratios, low δEu values, and strong Ba, Sr, P, and Ti depletions (Huang et al., 2017a). The Ti-in-biotite thermometry of the fresh biotite in the Weijia granite yields a low temperature of 569 -659 °C with a peak value of 635 °C . The RSCM thermometry of the carbonate rocks close to the magnesian and calcic skarns reveals that the peak metamorphic temperature of the wall rocks does not exceed 576 °C (Fig.

8-16

). All these thermometric results indicate a low magmatic temperature of the Weijia granite. The highly fractionated and low-temperature features of the Weijia granite are genetically related to the high fluorine activity.

The porphyritic texture with a felsitic to fine-grained matrix in the Weijia granite (Figs.

8-3a and 8-4a), the embayment texture of the hexagonal bipyramidal quartz phenocrysts (Fig. 8-4b), the micrographic texture in K-feldspar (Fig. 8-4c), and the distinctive "pearlitic border" texture of some K-feldspar phenocrysts (Fig. 8-4d) seem to suggest a shallow emplacement depth. [START_REF] Zhou | An understanding of the origin of the Tonglu Early Cretaceous volcanic-intrusive rocks[END_REF] reported the similar "pearlitic border" texture of the porphyroclastic K-feldspar in the Tonglu rhyodacite in Southeastern China and interpreted it as a result of boundary layer effect caused by compositional disequilibrium during a rapid crystallization process. However, the small grain size of matrix in porphyritic granites can also simply result from the crystallization under water-saturated conditions and is not necessarily produced by pressure quenching [START_REF] Whitney | The origin of granites: The role and source of water in the evolution of granitic magmas[END_REF][START_REF] Audétat | Magmatic-hydrothermal evolution in a fractionating granite: A microchemical study of the Sn-W-F-mineralized Mole Granite (Australia)[END_REF]. The embayment texture of quartz phenocrysts could be formed by a primary growth in F-rich magmas and is not necessarily to be the result of resorption in shallow environments [START_REF] Audétat | Magmatic-hydrothermal evolution in a fractionating granite: A microchemical study of the Sn-W-F-mineralized Mole Granite (Australia)[END_REF]. Notably, the Al-in-hornblende geobarometry of the contemporaneous Tongshanling granodiorite which is located 15 km to the southwest of the Weijia granite and emplaced in the same Middle-Upper Devonian carbonate strata (i.e., the Qiziqiao, Shetianqiao, and Xikuangshan Formations) yields a deep emplacement depth of ca. 10 km [START_REF] Huang | Reworked restite enclave: Petrographic and mineralogical constraints from the Tongshanling intrusion, Nanling Range, South China[END_REF]. Thus, the Weijia porphyritic granite should not be formed in a subvolcanic environment and its felsitic to fine-grained matrix was crystallized from the highly fractionated F-rich and water-saturated melts.

In summary, the high fluorine activity of granitic melts results in a low magmatic viscosity to enable the prolonged crystal fractionation and tungsten enrichment of the granitic magma to a relatively low temperature, finally with the porphyritic Weijia granite formed under a water-saturated condition.

Magmatic to hydrothermal evolution

The Weijia granite and its later stockwork veins from K-feldspar-quartz pegmatite veins (Fig. 8-7a) through (K-feldspar)-quartz veins (Fig. 8-7b) or veinlets to stockwork quartz veinlets (Fig. 8-7c) reflect a process of magmatic to hydrothermal evolution. Especially, the white mica in the K-feldspar-quartz pegmatite veins and (K-feldspar)-quartz veins or veinlets shows a zonal texture with F-rich cores and F-poor rims, whereas, the white mica in the stockwork quartz veinlets has F-poor compositions without zonation (8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27). Such an evolution trend from early F-rich compositions to late F-poor compositions of white mica (Fig. 89101112131415161718192021222324) is indicative of the magmatic to hydrothermal evolution, because fluorine prefers to partition in melt and its fluid-melt partition coefficient (D F fluid/melt ) is small even the melt contains a high fluorine concentration (e.g., D F fluid/melt = 0.4 at 3 wt.% F in the melt) [START_REF] London | Melt-vapor solubilities and elemental partitioning in peraluminous granite-pegmatite systems: experimental results with Macusani glass at 200 MPa[END_REF][START_REF] Webster | Partitioning of F and Cl between magmatic hydrothermal fluids and highly evolved granitic magmas[END_REF][START_REF] Carroll | Solubilities of sulfur, noble gases, nitrogen, chlorine, and fluorine in magmas[END_REF]. The occurrence of two groups of white mica in the matrix of granite with respective higher and lower F contents (Figs. 8-24 and 8-25c and e) also reflects the evolution process from the earlier magmatic stage with a higher fluorine activity to the later hydrothermal stage with a lower fluorine activity (Fig. 8-40d andf). Thus, the F-poor white mica coexisting with fluorite as aggregates in the granite is hydrothermal mica .

Abundant fluorite and the other F-rich minerals occur in the magnesian and calcic skarns, whereas, the Weijia granite contains almost no fluorine, only with minor preserved in the micas, indicating that the majority of fluorine in the granitic magma has been transported into the wall rocks. Considering the small D F fluid/melt value, it is speculated that the fluorine was probably dominantly transported by F-rich concentrated hydrosaline melts rather than by dilute hydrothermal fluids. Such hydrosaline melts could be generated by silicate-hydrosaline liquid immiscibility which has been demonstrated by natural and experimental studies [START_REF] Veksler | Experimental evidence of three coexisting immiscible fluids in synthetic granitic pegmatite[END_REF][START_REF] Badanina | Magmatic evolution of Li-F, rare metal granites: a case study of melt inclusions in the Khangilay complex, Eastern Transbaikalia (Russia)[END_REF][START_REF] Veksler | Element enrichment and fractionation by magmatic aqueous fluids: Experimental constraints on fluid-melt immiscibility and element partitioning[END_REF]. The enrichment of non-silicate anions, such as F -, Cl -, CO 2- 3 , and BO 3- 3 , is critical to the generation of the liquid immiscibility [START_REF] Veksler | Element enrichment and fractionation by magmatic aqueous fluids: Experimental constraints on fluid-melt immiscibility and element partitioning[END_REF]. [START_REF] Veksler | Element enrichment and fractionation by magmatic aqueous fluids: Experimental constraints on fluid-melt immiscibility and element partitioning[END_REF] pointed out that the hydrosaline melts are likely to have Na, Li, and alkaline earths enriched and K and heavier rare alkalis depleted compositions. Using homogenized melt inclusions, [START_REF] Badanina | Magmatic evolution of Li-F, rare metal granites: a case study of melt inclusions in the Khangilay complex, Eastern Transbaikalia (Russia)[END_REF] revealed the immiscibility between a Na-F-rich hydrosaline melt and a K-rich aluminosilicate melt in the most evolved units of the Orlovka granite complex. Between the silicate and hydrosaline melts, tungsten partitions strongly into the depolymerized hydrosaline liquids [START_REF] Gramenitskiy | The nature of W-specialised granites in the light of experimental data[END_REF], indicating the hydrosaline melts could be an important agent for tungsten enrichment and transportation from magma [START_REF] Veksler | Element enrichment and fractionation by magmatic aqueous fluids: Experimental constraints on fluid-melt immiscibility and element partitioning[END_REF].

Since the fluorine in the granitic magma has been mostly extracted into the immiscible hydrosaline melts, the later exsolved hydrothermal fluids from the residual aluminosilicate melts have a distinctly lower fluorine activity. Overprint of the later hydrothermal stage on the earlier magmatic stage led to the formation of the F-poor micas in the Weijia granite and its stockwork veins . This hydrothermal overprint is particularly evident in the bleached biotite of the granite which is transforming into clay minerals , in the zonal white micas of the stockwork veins , and in the peripheral bleached zone of the stockwork veins where biotite and F-rich white mica are absent . The occurrence of abundant kaolin at the apex of the Weijia granite, which is similar to that of the Beauvoir granite in the French Massif Central, may be genetically related to greisenization during the hydrothermal alteration [START_REF] Cuney | The Beauvoir topaz-lepidolite albite granite (Massif Central, France): the disseminated magmatic Sn-Li-Ta-Nb-Be mineralization[END_REF]. Hydrothermal alteration of the marginal granite close to carbonate rocks resulted in the gains of Ca, Mg, Fe, and Mn from wall rocks and the loss of Na into fluids (Fig. 8-19a, c, andd). The released Na from the granite could be important for the transportation of tungsten in the hydrothermal fluids as NaHWO 0 4 and NaWO - 4 [START_REF] Wood | The hydrothermal geochemistry of tungsten in granitoid environments: I. Relative solubilities of ferberite and scheelite as a function of T, P, pH, and m NaCl[END_REF]. This may also be implicated by the formation of late Na-bearing aluminosilicate minerals in the magnesian and calcic skarns, such as the marialite, zeolite, and plagioclase (8)(9)(10)(11)(12)(13). To a certain extent, the different alteration degrees of the granites close to the magnesian and calcic skarns are corresponding to the different mineralization scales of the magnesian and calcic skarns, respectively.

To sum up, during the magmatic to hydrothermal evolution of the Weijia granite, F-rich hydrosaline melts were firstly separated from magma by liquid immiscibility followed by the exsolution of F-poor hydrothermal fluids. Both of the F-rich hydrosaline melts and F-poor hydrothermal fluids could be the agents for tungsten transportation from magma.

Magnesian and calcic skarn formation

The differential formation of the magnesian and calcic skarns respectively in the middle-member dolostone and upper-member limestone of the Qiziqiao Formation is dominantly controlled by the different lithologies of the host carbonate strata (Fig. 8-2).

RSCM thermometry reveals that the magnesian skarn was formed under a distinctly lower temperature than the calcic skarn (Fig. 8910111213141516). This is consistent with the contrary mineral associations of the magnesian and calcic skarns which are dominated by retrograde minerals (serpentine and phlogopite) and prograde minerals (garnet, pyroxene, and wollastonite), respectively . Except for the serpentine and phlogopite, some other Mg-rich minerals, such as the sellaite, fluoborite, and chondrodite, occur in the magnesian skarn but are absent in the calcic skarn . Compared with the garnet in the calcic skarn, the garnet in the magnesian skarn contains higher Mg contents (Appendix 8-7 and Fig. 8-33). The pyroxene in the magnesian skarn is almost pure diopside (Fig. 8-36). All these features of the magnesian skarn are genetically related to the high Mg activity during skarn formation. Different from the calcic skarnization during which a high Ca activity is expected, the magnesian skarnization should be developed with a relatively low Ca activity and a high Mg activity which will result in a relatively high F activity. Because Ca can easily combine with F to form fluorite and decrease the F activity, whereas, it seems more difficult for Mg to combine with F to form sellaite. This is demonstrated by the occurrence of abundant fluorite but minor sellaite in the magnesian skarn . The relatively low temperature and high fluorine activity during magnesian skarnization are not favorable for the development of anhydrous prograde skarn minerals, such as forsterite and spinel, and lead to the formation of the special F-rich garnet (Fig. 8-25l). By contrast, the garnet formed with relatively high temperature and low fluorine activity during calcic skarnization has normal F-poor compositions (Fig. 8-25m).

Both of the serpentine and phlogopite in the magnesian skarn show decreasing Mg and increasing Fe contents from early to late ( Appendices 8-5 and8-6 andFigs. 8-28j-aa and8-29).

In addition, the serpentine shows a decreasing trend of F contents with time (Appendix 8-5).

These compositional variations indicate a coupled decreasing of F and Mg activities during magnesian skarn formation. F may have played an important role in releasing Mg from dolostone to form the magnesian skarn minerals. For the calcic skarn, the progressive changes of garnet compositions from andradite to grossularite (Fig. 8-33b) and pyroxene compositions from diopside to hedenbergite (Fig. 8-36b) indicate a decreasing trend of oxygen fugacity during skarn formation. This is also demonstrated by the evolution of negative Eu anomalies of the garnet REE patterns (Fig. 8-34b-d). The distinctly higher FeO and MnO contents of the late-generation wollastonite than those of the early-generation wollastonite (Fig. 8-37) implies a stronger contribution of components from wall rocks during the late stage of calcic skarn formation.

Calcium as the precipitant of fluorine and tungsten

The strong positive correlations between the WO3 and CaF2 grades of both the magnesian and calcic skarn ores seem to indicate a genetical link between tungsten and fluorine. However, previous experimental studies demonstrated that the tungsten solubilities in both silicate melts and aqueous fluids are almost independent of fluorine content [START_REF] Manning | The behaviour of tungsten in granitic melt-vapour systems[END_REF][START_REF] Keppler | Partitioning of Cu, Sn, Mo, W, U and Th between melt and aqueous fluid in the systems haplogranite-H 2 O-HCl and haplogranite-H 2 O-HF[END_REF][START_REF] Linnen | Granite-related rare-element deposits and experimental constraints on Ta-Nb-W-Sn-Zr-Hf mineralization[END_REF][START_REF] Che | Tungsten solubility in evolved granitic melt: An evaluation of magmatic wolframite[END_REF]. Thus, the positive correlation between the WO3 and CaF2 grades is not derived from a direct link between tungsten and fluorine. Instead, calcium, which is the shared precipitant for fluorine and tungsten to form fluorite and scheelite, respectively, could be the critical factor to induce the positive correlation between the WO3 and CaF2 grades in the skarn ores.

It is noteworthy that the wall rocks (dolostone) close to the magnesian skarn orebodies contain significantly higher fluorite contents than those (limestone) close to the calcic skarn orebodies . This difference results from the higher calcium activity in the limestone than that in the dolostone which catches the fluorine in a relatively limited zone and prevents the outward escape of fluorine. To a certain extent, the high CaF2 but low WO3 grades of the dolostone close to the magnesian skarn are indicative of the independent relationship between tungsten and fluorine. During the process of skarn formation, the fluorine activity gradually decreases along with the precipitation of fluorite and the other F-bearing minerals. [START_REF] Lecumberri-Sanchez | Fluid-rock interaction is decisive for the formation of tungsten deposits[END_REF] emphasized that fluid-rock interaction is decisive for the formation of tungsten deposits and the precipitation of the main tungsten minerals scheelite (CaWO4) and wolframite [(Fe, Mn)WO4] thus depends on the availability of Ca, Fe, or Mn. Wang et al., (2017e) demonstrated that the released Ca by plagioclase breakdown controlled the scheelite mineralization in the Dongyuan and Zhuxiling porphyritic granodiorites, southern Anhui Province, China. A model of Fe-Mn and Ca released from biotite and apatite respectively by alteration to form wolframite and scheelite in granodiorite was proposed by Zhang et al., (2018a) to explain the genesis of the giant Dahutang W deposit in northwestern Jiangxi Province, China. In the skarn deposits, such as the Weijia W deposit, scheelite is predominantly hosted by skarn in the carbonate wall rocks. Therefore, it is evident that the key factor controlling the occurrences of scheelite orebodies in granitoids or wall rocks is calcium activity. The higher WO3 grades of the calcic skarn orebodies than those of the magnesian skarn ore bodies in the Weijia W deposit are controlled by the higher calcium activity during skarnization in limestone than that during skarnization in dolostone. This is also indicated by the distinctly lower Mg contents of the scheelite in the calcic skarn than those of the scheelite in the magnesian skarn (Fig. 8-39d).

Ore-forming process

Scheelite is a common mineral in various hydrothermal deposits and has been widely used as an indicator to trace ore-forming process (e.g., Li et al., 2018b;Zhang et al., 2018b;Zhao et al., 2018). The REE patterns of the scheelite from the Weijia W deposit can be divided into two different types on the whole, with one type of flat to slightly rightward sloping REE patterns with strong negative Eu anomalies and the other type of steeper rightward sloping REE patterns almost without Eu anomalies . These two different types of scheelite REE patterns are indicative of two generations of ore-forming liquids.

The scheelite in the stockwork quartz veinlets (Fig. 8-38a) and the early-generation scheelites in the magnesian and calcic skarns (Fig. 8-38b andd) were formed by the early-generation ore-forming liquids. Their REE patterns are similar to those of the Weijia granite but with distinctly higher REE contents (Fig. 8-38a, b, andd), indicating large REE partition coefficients between the liquids and granitic melts. The early-generation ore-forming liquids are in all probability the F-rich hydrosaline melts which have enriched incompatible elements and were earlier separated from magma by liquid immiscibility [START_REF] Veksler | Element enrichment and fractionation by magmatic aqueous fluids: Experimental constraints on fluid-melt immiscibility and element partitioning[END_REF]. The similar REE patterns of the early-formed scheelites with the granite result from an inheritance from the magma.

The late-generation scheelites in the magnesian and calcic skarns (Fig. 8-38c andd) were formed by the late-generation ore-forming liquids. They have distinctly lower REE contents than the Weijia granite (Fig. 8-38c andd), indicating small REE partition coefficients between the liquids and granitic melts. Thus, the late-generation ore-forming liquids are the F-poor hydrothermal fluids which have relatively depleted incompatible elements and were later separated from magma by exsolution. The enrichment of LREE and the disappearance of negative Eu anomalies of the late-formed scheelites may result from the hydrothermal alteration of feldspars which are characterized by LREE enrichment and positive Eu anomalies.

Therefore, both of the earlier separated F-rich hydrosaline melts and the later exsolved F-poor hydrothermal fluids have transported tungsten from the magma into the wall rocks for subsequent skarn mineralization.

Metallogenic model

Except for the processes of magmatic fractionation, magmatic to hydrothermal evolution, magnesian and calcic skarnization, and ore formation discussed above, the magma origin is another key process that controls tungsten mineralization. Romer andKroner (2015, 2016) emphasized that protolith enrichment, sedimentary and tectonic accumulation of enriched source rocks, and heat input from the mantle are prerequisite steps for the generation of W enriched melts. The existence of an enriched source in the Nanling Range is widely accepted due to the occurrences of abundant large-scale W deposits. The subduction of the palaeo-Pacific plate in South China during Late Mesozoic induced asthenosphere upwelling and basaltic magma underplating to promote partial melting of the enriched source and then generate W-bearing melts [START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF]Zhou et al., 2006a;Huang et al., 2017a).

Different source rocks may produce different types of ore-bearing melts. For instance, the partial melting of the lower-crust mafic amphibolitic rocks and the middle-upper-crust metasedimentary rocks in the Nanling Range during Middle-Late Jurassic produced W-bearing and Cu-Pb-Zn-bearing granitoids, respectively (Huang et al., 2017a). Notably, the S-type Weijia granite, the A-type Hehuaping granite, and the I-type Tongshanling granodiorite in the Nanling Range which were emplaced in the same Qiziqiao Formation at the same time during Middle-Late Jurassic but are genetically related to W, Sn, and Cu-Pb-Zn skarn mineralization, respectively (Yao et al., 2014b;Huang et al., 2017a). Thus, the nature of the enriched source is also a key factor controlling tungsten mineralization.

Based on the deposit geological, RSCM thermometric, whole-rock geochemical, and mineralogical studies and the discussion above, the comprehensive genetic model of the Weijia W deposit is summarized as follows. During Late Jurassic, with the subduction of the palaeo-Pacific plate, the underplated basaltic magmas heated and partially melted the enriched source in the Nanling Range to produce fluorine and tungsten enriched melts. The prolonged crystal fractionation of the fluorine-rich low-viscosity granitic magma to a relatively low temperature resulted in a strong enrichment of tungsten in the residual melts. During the magmatic to hydrothermal evolution, the earlier separated F-rich hydrosaline melts and the later exsolved F-poor hydrothermal fluids transported tungsten from the magma into the wall rocks. With the development of magnesian and calcic skarns, fluorine and tungsten were precipitated by calcium to form fluorite and scheelite, respectively. Fluorine was also involved in the formation of the other F-bearing minerals, such as serpentine and phlogopite. The relatively low temperature and high fluorine activity during magnesian skarnization prevented the development of anhydrous prograde skarn minerals, such as forsterite and spinel. The higher calcium activity during skarnization in limestone than that in dolostone resulted in the higher WO3 grades of calcic skarn than those of magnesian skarn.

Summary

The Weijia scheelite skarn deposit comprises dominant magnesian skarn and subordinate calcic skarn with abundant fluorite and is genetically related to a highly fractionated porphyritic granite with a felsitic to fine-grained matrix. The magnesian skarn generally occurs as stockwork veinlets in dolostone with a mineralogy dominated by serpentine and phlogopite. Wollastonite, garnet, and pyroxene are the main calcic skarn minerals. Scheelite is mostly distributed in the magnesian and calcic skarns as disseminated grains.

Biotite fluorimetry indicates that the Weijia granite was crystallized from a F-rich magma. The high fluorine activity of granitic melts results in a low magmatic viscosity to enable the prolonged crystal fractionation and tungsten enrichment of the granitic magma to a relatively low temperature, finally with the porphyritic Weijia granite formed under a water-saturated condition.

During the magmatic to hydrothermal evolution, F-rich hydrosaline melts were firstly separated from magma by liquid immiscibility followed by the exsolution of F-poor hydrothermal fluids. Both of the F-rich hydrosaline melts and F-poor hydrothermal fluids have transported tungsten from the magma into the wall rocks for subsequent skarn mineralization.

RSCM thermometry indicates a distinctly lower temperature of magnesian skarnization than calcic skarnization. The relatively low temperature and high fluorine activity during magnesian skarnization are not favorable for the development of anhydrous prograde skarn minerals, such as forsterite and spinel, and lead to the formation of the special F-rich garnet.

As the shared precipitant of fluorine and tungsten, calcium could be the critical factor to induce the positive correlation between the WO3 and CaF2 grades of skarn ores. The higher WO3 grades of the calcic skarn than those of the magnesian skarn are controlled by the higher calcium activity during skarnization in limestone than that in dolostone.

The key factors controlling the occurrence of unusual magnesian skarn W mineralization during Late Jurassic in the Nanling Range mainly include an enriched source, a fluorine-rich magma, a strong crystal fractionation, and a fluorine-rich hydrosaline melt.

Chapter 9. Conclusions and perspectives

Conclusions

Main conclusions of this Ph.D. thesis are summarized as follows.

(1) The Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range are dominated by weakly fractionated metaluminous I-type amphibole-bearing granodiorites and highly differentiated peraluminous S-type granites, respectively. They were mainly derived from non-simultaneous partial melting of the mafic amphibolitic basement in the lower crust and the muscovite-rich metasedimentary basement in the upper-middle crust, respectively. The compositional divergence between different sources accounted for the metallogenic specializations of ore-bearing granitoids and the non-simultaneous partial melting of one source followed by the other brought about a time gap of about 5 Ma between the Cu-Pb-Zn-bearing and W-bearing granitoids.

(2) Dark microgranular enclaves are commonly observed in the Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites in the Nanling Range. The microgranular enclaves in the Tongshanling granodiorite which contain abundant residual materials, such as mafic mineral clots, inherited and metamorphic zircon, and Ca-rich core plagioclase, are thought to be reworked restite enclaves formed by reaction of the restite with the host magma. The amphibole-rich clots are vestiges of residual pyroxene-rich precursors from the source. Consequently, the Tongshanling granodiorite was derived from dehydration melting of amphibolite in the mafic lower crust. The fertile amphibolitic source is beneficial to the formation of Cu-Pb-Zn-bearing granodiorites in the Nanling Range.

(3) In the Tongshanling area, the regional normal faults were in all probability formed during the Late Triassic to Early Jurassic decompression and are not related to the emplacement of the Middle-Late Jurassic Tongshanling granodiorite. Based on structural analysis, RSCM thermometry, and EBSD mapping, it is concluded that the emplacement of the Tongshanling granodiorite started from the southern part and induced wall-rock strong marbleization and deformation in the contact zone. The magma emplacement-induced wall-rock deformation significantly increased the permeability of wall rocks to promote the infiltration of magmatic fluids along fractures and then structurally controlled the formation of exoskarn and sulfide-quartz veins.

(4) Geochronological studies reveal that the three ore deposits in the Tongshanling polymetallic ore district were almost contemporaneously formed at 160 -162 Ma, consistent with the Tongshanling granodiorite (160 -164 Ma). S, Pb, and H-O isotopic studies indicate that the ore-forming materials and fluids of the Tongshanling ore district were derived from the Tongshanling intrusion. The Cu and Zn were most probably released from the mafic amphibolitic lower crust by partial melting, whereas, the Pb was extracted from the upper crust by the ascending granodioritic magma. The different mineralization types and ore deposits in the Tongshanling ore district are genetically linked together and are the productions of evolution and zonation of the same skarn system associated with the Tongshanling granodioritic intrusion.

(5) The Weijia granite was crystallized from a F-rich low-viscosity magma which had experienced a prolonged crystal fractionation and tungsten enrichment. The separation of F-rich hydrosaline melts by liquid immiscibility during the magmatic to hydrothermal evolution is important for tungsten transportation from the magma into the wall rocks.

The relatively low temperature and high fluorine activity during magnesian skarnization are not favorable for the development of anhydrous prograde skarn minerals. As the shared precipitant of fluorine and tungsten, calcium could be the critical factor to induce the positive correlation between the WO3 and CaF2 grades of skarn ores. The higher WO3 grades of the calcic skarn than those of the magnesian skarn are controlled by the higher calcium activity during skarnization in limestone than that in dolostone.

Perspectives

Although a lot of new findings and conclusions are achieved through this Ph.D. thesis, some parts need to be further improved, such as the structural study of mineral deposits, and some other studies are still insufficient, such as the metallogenic age of the Jiangyong Pb-Zn-Ag deposit, the geochemical compositions of ore-forming fluids, and the detailed physicochemical evolution during mineralization. In addition, the model of reworked restite enclaves should be further tested by the microgranular enclaves of the other Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites in the Nanling Range. A comparison between the microgranular enclaves of the Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites and Sn-bearing A2-type granites in the Nanling Range is necessary for understanding the origins of different ore-bearing granitoids.

For further research of the multiple-aged granitoids and associated polymetallic mineral deposits in South China, besides the common geochronological, geochemical, and mineralogical studies, more attentions should be paid to structural controls on mineralization which are crucial to understanding the ore-forming process and can provide important information for prospecting and exploration. Many newly developed methods, such as the Raman spectroscopy of carbonaceous material thermometry [START_REF] Beyssac | Raman spectra of carbonaceous material in metasediments: a new geothermometer[END_REF][START_REF] Lahfid | Evolution of the Raman spectrum of carbonaceous material in low-grade metasediments of the Glarus Alps (Switzerland)[END_REF], paleo-fluid flow orientation and velocity estimation [START_REF] Sizaret | Estimating the local paleo-fluid flow velocity: New textural method and application to metasomatism[END_REF][START_REF] Launay | Deciphering fluid flow at the magmatic-hydrothermal transition: A case study from the world-class Panasqueira W-Sn-(Cu) ore deposit (Portugal)[END_REF], permeability experimentation [START_REF] Coelho | Permeability of sheeted dykes beneath oceanic ridges: Strain experiments coupled with 3D numerical modeling of the Troodos Ophiolite, Cyprus[END_REF], and numerical modeling [START_REF] Eldursi | Numerical investigation of transient hydrothermal processes around intrusions: Heat-transfer and fluid-circulation controlled mineralization patterns[END_REF][START_REF] Ingebritsen | The physical hydrogeology of ore deposits[END_REF], should be introduced and applied to the further studies of metallogenesis in South China. Mutch, E.J.F., Blundy, J.D., Tattitch, B.C., Cooper, F.J., Brooker, R.A., 2016. An experimental study of amphibole stability in low-pressure granitic magmas and a revised Al-in-hornblende geobarometer.

Contributions to Mineralogy and Petrology 171, 85. + 641 [START_REF] Beyssac | Raman spectra of carbonaceous material in metasediments: a new geothermometer[END_REF] for samples with temperatures of 200 -320 °C and 330 -650 °C, respectively. Notes: a D 2 q: The Middle Devonian Qiziqiao Formation. b Raman shift center of the graphite band. c Full width at half maximum of the graphite band. d R1 = D1 / G height ratio. e R2 = D1 / (G + D1 + D2) area ratio. f T (°C) = -445 × R2 + 641 [START_REF] Beyssac | Raman spectra of carbonaceous material in metasediments: a new geothermometer[END_REF]. Notes: ZK802-6, ZK803-29, ZK1001-2, ZK1001-3, ZK1001-5, ZK1001-6, ZK1001-7, and ZK1001-9 were sampled from altered granite spatially close to the magnesian skarn orebodies; WJ29, WJ35, ZK706-1, and ZK706-2 were sampled from altered granite spatially close to the calcic skarn orebodies. a δEu = 2Eu N /(Sm N + Gd

N ). b TE 1,3 = {[Ce N /(La 2/3 N × Nd 1/3 N ) × Pr N /(La 1/3 N × Nd 2/3 N )] 0.5 × [Tb N /(Gd 2/3 N × Ho 1/3 N ) × Dy N /(Gd 1/3
N × Ho 2/3 N )] 0.5 } 0.5 , it quantifies the degree of the tetrad effect [START_REF] Irber | The lanthanide tetrad effect and its correlation with K/Rb, Eu/Eu*, Sr/Eu, Y/Ho, and Zr/Hf of evolving peraluminous granite suites[END_REF]. The Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range were mainly derived from non-simultaneous partial melting of the mafic amphibolitic rocks in the lower crust and the muscovite-rich metasedimentary rocks in the upper-middle crust, respectively. The fertile sources in the Nanling Range are beneficial to the formation of Cu-Pb-Zn and W deposits during Middle-Late Jurassic.

The lower-crust origin of the Cu-Pb-Zn-bearing granodiorites is further demonstrated by the dioritic microgranular enclaves in the Tongshanling granodiorite which are reworked restite enclaves derived from partial melting of the mafic amphibolitic source. The Cu and Zn associated with these intrusions were most probably released from the mafic amphibolitic lower crust by partial melting, whereas, Pb was extracted from the upper crust by ascending granodioritic magmas. The emplacement of these orebearing granitoid magmas may have a structural connection with the subsequent polymetallic mineralization in some way. For instance, the exoskarn and sulfide-quartz veins in the Tongshanling Cu-Pb-Zn deposit are evidently controlled by magma emplacement-induced wall-rock deformation. The different mineralization types and ore deposits in the Tongshanling Cu-Mo-Pb-Zn-Ag ore district are genetically linked together in the same skarn system as the productions of evolution and zonation. The Weijia granite was crystallized from a F-rich and water-saturated magma. The key factors controlling the occurrence of unusual magnesian skarn W mineralization during Late Jurassic in the Nanling Range mainly include a W enriched metasedimentary source, a fluorine-rich magma, a strong crystal fractionation, and a fluorine-rich hydrosaline melt.

Keywords: Cu-Pb-Zn-bearing granitoids; W-bearing granites; Microgranular enclaves; Skarn; Structural control; Petrogenesis; Metallogenesis; Middle-Late Jurassic; Nanling Range Les granitoïdes associés aux skarn à Cu-Pb-Zn et au W, dérivent, respectivement, de la fusion partielle de roches mafiques à amphiboles dans la croute inférieure et de roches métas-édimentaires riches en muscovite dans la croute moyenne-supérieure. Ces sources fertiles mobilisées pour la formation de ces plutons a permis la formation de gisements à Cu-Pb-Zn, et W au cours du Jurassique moyen. L'origine dans la croûte moyenne de la granodiorite de Tongshanling, associée aux minéralisations à Cu-Pb-Zn, a été montrée par l'étude des enclaves microgranulaires dioritiques qui sont des restites remaniées issues de la fusion partielle des amphibolites de la croûte inférieure. Le Cu et le Zn associées à ces plutons sont probablement issus de la croûte inférieure et ces métaux ont probablement étés remobilisés au cours de la fusion partielle. Le Pb issue de la croute supérieur a été collecté lors de l'ascension du magma qui a donné la granodiorite. Lors de leur mise en place ces granitoïdes ont exprimé leur potentiel minéralisateur. L'étude structural montre que la géométrie des corps minéralisés et en lien avec la déformation induite par la mise en place des plutons. Les différentes expressions de la minéralisation dans le district à Cu-

Figures

  Figures

Figure 1

 1 Figure 1-1. Distribution of multiple-aged granitoids and related mineral deposits in the Nanling Range of South China ....................................................................................................................................................

Figure 2

 2 Figure 2-1. Structural map showing the tectonic location and main tectonic elements of the South China Block Figure 2-2. Sketch map showing the tectonic location of South China. Simplified geological map of South China illustrating the distributions of main Phanerozoic structures and igneous rocks ................................

Figure 2

 2 Figure 2-3. Schematic model illustrating the geodynamic evolution of South China from Neoproterozoic to Early Mesozoic ............................................................................................................................................

Figure 2

 2 Figure 2-4. Schematic models illustrating the geodynamic mechanism of the Early Paleozoic and Triassic tectonic events in the South China Block ...........................................................................................

Figure 2

 2 Figure 2-5. Paleogeographic evolution of the South China Block from Permian to Jurassic, the flat-slab subduction model of the palaeo-Pacific plate, and postorogenic magmatism induced by slab foundering and retreating ...................................................................................................................

Figure 2

 2 Figure 2-6. Schematic model illustrating the driving mechanisms for the geodynamic evolution of the South China Block during Mesozoic ............................................................................................................

Figure 2

 2 Figure 2-7. Schematic model illustrating the palaeo-Pacific plate subduction with changing angles in Southeastern China during Late Mesozoic .........................................................................................

Figure 2

 2 Figure 2-8. Distribution of multiple-aged granitoids and volcanic rocks in South China .....................................

Figure 2

 2 Figure 2-9. Distribution of the Mesozoic mineral deposits in East China.............................................................

Figure 2 -

 2 Figure 2-10. Summary of the geodynamic evolution, granitic magmatism, and related mineralization in South China ................................................................................................................................................

Figure 3

 3 Figure 3-1. Geological map of the Tongshanling-Weijia area in southern Hunan Province .................................

Figure 3

 3 Figure 3-2. Stratigraphic column of the Tongshanling-Weijia area .......................................................................

Figure 4

 4 Figure 4-1. Petrographic photomicrographs of granitoids from the Tongshanling-Weijia area ............................

Figure 4

 4 Figure 4-2. Backscattered electron images of accessory minerals in the Tongshanling granodiorite porphyry and Weijia granite porphyry ......................................................................................................................

Figure 4

 4 Figure 4-3. Zircon cathodoluminescence images of granitoids from the Tongshanling-Weijia area ....................

Figure 4

 4 Figure 4-4. Zircon 206 Pb/ 238 U-207 Pb/ 235 U concordia diagrams of granitoids from the Tongshanling-Weijia area ..

Figure 4

 4 Figure 4-5. Histograms for zircon ε Hf (t) and T C DM (Hf) (Ga) values of granitoids from the Tongshanling-Weijia area .....................................................................................................................................................

Figure 4

 4 Figure 4-6. Major element diagrams of granitoids from the Tongshanling-Weijia area ........................................

Figure 4

 4 Figure 4-7. Primitive mantle-normalized spider diagrams and chondrite-normalized REE patterns of granitoids from the Tongshanling-Weijia area .....................................................................................................

Figure 4

 4 Figure 4-8. Sr-Nd isotopic compositions of granitoids from the Tongshanling-Weijia area .................................

Figure 4

 4 Figure 4-9. CaO/(Na 2 O+K 2 O)-Rb/Sr diagram, Mg/(Mg+Fe)-SiO 2 (wt.%) diagram, AMF-CMF diagram, and Rb (ppm)-(Y+Nb) (ppm) diagram of granitoids from the Tongshanling-Weijia area .............................

Figure 4 -

 4 Figure 4-11. Genetic model of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range ..................................................................................................................................

Figure 5

 5 Figure 5-1. Petrographic photographs of the Tongshanling granodiorite and its microgranular enclaves ............

Figure 5

 5 Figure 5-2. Compositional zonation of plagioclase with a Ca-rich core from the Tongshanling granodiorite and its microgranular enclaves ..................................................................................................................

Figure 5

 5 Figure 5-3. Composition of plagioclase from the Tongshanling granodiorite and its microgranular enclaves .....

Figure 5

 5 Figure 5-4. Mineral chemistry of amphibole from the Tongshanling granodiorite and its microgranular enclaves ............................................................................................................................................................

Figure 5

 5 Figure 5-5. Chondrite-normalized REE patterns of amphibole from the Tongshanling granodiorite and its microgranular enclaves .......................................................................................................................

Figure 5

 5 Figure 5-6. Trace element binary diagrams of amphibole from the Tongshanling granodiorite and its microgranular enclaves .......................................................................................................................

Figure 5

 5 Figure 5-7. Classification diagram of biotite from the Tongshanling granodiorite and its microgranular enclaves ............................................................................................................................................................

Figure 5

 5 Figure 5-8. Chondrite-normalized REE patterns of biotite from the Tongshanling granodiorite and its microgranular enclaves .......................................................................................................................

Figure 5

 5 Figure 5-9. Trace element binary diagrams of biotite from the Tongshanling granodiorite and its microgranular enclaves ..............................................................................................................................................

Figure 5 -

 5 Figure 5-10. Texture and mineral chemistry of zircon from the Tongshanling granodiorite and its microgranular enclaves ............................................................................................................................................

Figure 5 -

 5 Figure 5-11. Plot of the generalized tschermakite [( T Al-A Na-A K-2 A Ca) (apfu)] vs. edenite [( A Na+ A K+ A Ca) (apfu)] components for amphibole from the Tongshanling granodiorite and its microgranular enclaves ............................................................................................................................................

Figure 5 -

 5 Figure 5-12. REE distribution modelling of magmatic amphibole and residual clinopyroxene and amphibole ...

Figure 5 -

 5 Figure 5-13. Harker plots for FeO Total , MgO, CaO, and K 2 O of the Tongshanling granodiorite and its microgranular enclaves showing excellent linearities ......................................................................

Figure 5 -

 5 Figure 5-14. Physicochemical conditions estimated by mineral chemical compositions of amphibole and biotite from the Tongshanling granodiorite and its microgranular enclaves ................................................

Figure 5 -

 5 Figure 5-15. Schematic model illustrating the formation process of reworked restite enclave .............................

Figure 6

 6 Figure 6-1. Simplified geological map of the Tongshanling area showing the sample locations for Raman spectroscopy of carbonaceous material analysis and electron backscatter diffraction mapping.........

Figure 6

 6 Figure 6-2. Field observations of normal faults in the Tongshanling area ..........................................................

Figure 6

 6 Figure 6-3. Cross sections of the northeastern and southern contact zones from the Tongshanling intrusion to country rocks. ...................................................................................................................................

Figure 6

 6 Figure 6-4. Cross section of the Tongshanling Cu-Pb-Zn deposit .......................................................................

Figure 6

 6 Figure 6-5. Photographs of massive endoskarn, vein exoskarn, and deformed country rocks in the Tongshanling Cu-Pb-Zn deposit .............................................................................................................................

Figure 6

 6 Figure 6-6. Panoramic views of exoskarn in the Tongshanling Cu-Pb-Zn deposit showing skarn zonation and

Figure 6

 6 Figure 6-7. Photographs of vein-like quartz in the center of exoskarn or cutting through it and sulfide-quartz veins in the peripheral strata in the Tongshanling Cu-Pb-Zn deposit ...............................................

Figure 6

 6 Figure 6-8. Raman spectra of carbonaceous material in carbonate rocks from the Tongshanling Cu-Pb-Zn deposit and its adjacent area and temperatures calculated by the Raman spectroscopy of carbonaceous material thermometry .......................................................................................................................

Figure 6

 6 Figure 6-9. Crystallographic preferred orientation of calcite (dolomite) from the Tongshanling Cu-Pb-Zn deposit and its adjacent area determined by electron backscatter diffraction mapping.................................

Figure 6 -

 6 Figure 6-10. Compositions of garnets from the endoskarn and exoskarn of the Tongshanling Cu-Pb-Zn deposit ........................................................................................................................................................

Figure 6 -

 6 Figure 6-11. Schematic model illustrating the magma emplacement-induced structural control on skarn formation at the Tongshanling Cu-Pb-Zn deposit ............................................................................

Figure 7

 7 Figure 7-1. Geological maps of the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit .........................................................................................................................................

Figure 7

 7 Figure 7-2. Cross sections of the Tongshanling Cu-Pb-Zn deposit ......................................................................

Figure 7

 7 Figure 7-3. Cross sections of the Jiangyong Pb-Zn-Ag deposit and Yulong Mo deposit .....................................

Figure 7

 7 Figure 7-4. Outcrop-scale photos of different mineralization types of the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit .....................................................................

Figure 7

 7 Figure 7-5. Specimen-scale photos of different ore types of the Tongshanling Cu-Pb-Zn deposit .....................

Figure 7

 7 Figure 7-6. Petrographic photomicrographs of different mineralization and ore types of the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit .......................................

Figure 7

 7 Figure 7-7. Paragenetic sequence of the Tongshanling Cu-Pb-Zn deposit ..........................................................

Figure 7

 7 Figure 7-8. Paragenetic sequence of the Jiangyong Pb-Zn-Ag deposit ...............................................................

Figure 7

 7 Figure 7-9. Paragenetic sequence of the Yulong Mo deposit ..............................................................................

Figure 7 -

 7 Figure 7-10. Wetherill U-Pb concordia plots and weighted average 206 Pb/ 238 U age of garnet in the proximal exoskarn from the Tongshanling Cu-Pb-Zn deposit .......................................................................

Figure 7 -

 7 Figure 7-11. Re-Os isochrons and weighted average model ages of molybdenites from the Tongshanling Cu-Pb-Zn deposit and Yulong Mo deposit .....................................................................................

Figure 7 -

 7 Figure 7-12. Wetherill and Tera-Wasserburg U-Pb concordia plots and weighted average 206 Pb/ 238 U age of hydrothermal titanite in the altered granodiorite from the Tongshanling Cu-Pb-Zn deposit ..........

Figure 7 -

 7 Figure 7-13. S isotopic compositions of sulfide minerals from the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit ....................................................................................

Figure 7 -

 7 Figure 7-14. Pb isotopic compositions of sulfide minerals from the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit ....................................................................................

Figure 7 -

 7 Figure 7-15. H-O isotopic compositions of the fluids hosted by quartz from the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit ...................................................................

Figure 7 -

 7 Figure 7-16. S isotopic compositions of sulfide minerals from the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range ........................................................................................................

Figure 7 -

 7 Figure 7-17. Molybdenite Re-Os ages of the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range ..............................................................................................................................................

Figure 7 -

 7 Figure 7-18. Re contents of molybdenites from the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range ................................................................................................................................

Figure 8 - 1 .

 81 Figure 8-1. Geological map of the Weijia W deposit ..........................................................................................

Figure 8

 8 Figure 8-2. Cross section of the Weijia W deposit ..............................................................................................

Figure 8 - 3 .

 83 Figure 8-3. Petrographic photographs of the Weijia W deposit at hand-specimen scale .....................................

Figure 8

 8 Figure 8-4. Petrographic photomicrographs and backscattered electron images of the Weijia granite ...............

Figure 8

 8 Figure 8-5. Petrographic photomicrographs and backscattered electron images of the altered Weijia granite near the magnesian skarn .........................................................................................................................

Figure 8

 8 Figure 8-6. Equal-area lower hemisphere stereonet projection and density distribution of the poles of the stockwork veins at the apex of the Weijia granite ............................................................................

Figure 8 - 7 .

 87 Figure 8-7. Petrographic photographs of the stockwork veins at the apex of the Weijia granite at hand-specimen scale ..................................................................................................................................................

Figure 8 - 8 .

 88 Figure 8-8. Petrographic photomicrographs of micas in the stockwork veins and their adjacent zone at the apex of the Weijia granite .........................................................................................................................

Figure 8

 8 Figure 8-9. Stockwork magnesian skarn veinlets hosted by the dolostone enriched with carbonaceous materials in the Weijia W deposit .....................................................................................................................

Figure 8 -

 8 Figure 8-10. Petrographic photomicrographs and backscattered electron images of the magnesian skarn in the Weijia W deposit ............................................................................................................................

Figure 8 -

 8 Figure 8-11. Paragenetic sequence of the magnesian skarn in the Weijia W deposit ..........................................

Figure 8 -

 8 Figure 8-12. Backscattered electron images of the calcic skarn in the Weijia W deposit ...................................

Figure 8 -

 8 Figure 8-13. Paragenetic sequence of the calcic skarn in the Weijia W deposit ..................................................

Figure 8 -

 8 Figure 8-14. Variations of WO 3 and CaF 2 grades in representative drill cores of the magnesian and calcic skarns in the Weijia W deposit ...................................................................................................................

Figure 8 -

 8 Figure 8-15. Binary plot of CaF 2 and WO 3 grades in representative drill cores of the magnesian and calcic skarns in the Weijia W deposit ...................................................................................................................

Figure 8 -

 8 Figure 8-16. Raman spectra of carbonaceous material in carbonate rocks close to the magnesian and calcic skarns in the Weijia W deposit and temperatures calculated by the Raman spectroscopy of carbonaceous material thermometry ...............................................................................................

Figure 8 -

 8 Figure 8-17. Energy dispersive spectrometry elemental mapping of the altered Weijia granite close to the magnesian skarn .............................................................................................................................

Figure 8 -

 8 Figure 8-18. Energy dispersive spectrometry elemental mapping of the matrix of the altered Weijia granite close to the magnesian skarn ...................................................................................................................

Figure 8 -

 8 Figure 8-19. Binary plots of some major compositions, trace elements, and calculated parameters of the fresh and altered Weijia granite ......................................................................................................................

Figure 8 -

 8 Figure 8-20. Primitive mantle-normalized spider diagrams and chondrite-normalized REE patterns of the fresh and altered Weijia granite ...............................................................................................................

Figure 8 -

 8 Figure 8-21. Energy dispersive spectrometry elemental mapping of fresh biotite in the Weijia granite .............

Figure 8 -

 8 Figure 8-22. Energy dispersive spectrometry elemental mapping of bleached biotite in the Weijia granite .......

Figure 8 -

 8 Figure 8-23. (Fe Total +Mn+Ti-VI Al) (apfu)-(Mg-Li) (apfu) classification diagram of micas from the Weijia W deposit ............................................................................................................................................

Figure 8 -

 8 Figure 8-24. K 2 O and F contents of micas from the Weijia W deposit ...............................................................

Figure 8 -

 8 Figure 8-25. Histograms for F contents of different F-bearing minerals in the Weijia W deposit ......................

Figure 8 -

 8 Figure 8-26. Energy dispersive spectrometry elemental mapping of white mica in the K-feldspar-quartz pegmatite veins at the apex of the Weijia granite ...........................................................................

Figure 8 -

 8 Figure 8-27. Energy dispersive spectrometry elemental mapping of white mica in the (K-feldspar)-quartz veinlet at the apex of the Weijia granite .....................................................................................................

Figure 8 -

 8 Figure 8-28. Energy dispersive spectrometry elemental mapping of the magnesian skarn veinlets in the Weijia W deposit ............................................................................................................................................

Figure 8 -

 8 Figure 8-29. Energy dispersive spectrometry elemental mapping of phlogopite in the magnesian skarn of the Weijia W deposit ............................................................................................................................

Figure 8 -

 8 Figure 8-30. Compositions of garnets from the magnesian and calcic skarns in the Weijia W deposit ..............

Figure 8 -

 8 Figure 8-31. Energy dispersive spectrometry elemental mapping of the first-generation garnet in the calcic skarn of the Weijia W deposit ..................................................................................................................

Figure 8 -

 8 Figure 8-32. Energy dispersive spectrometry elemental mapping of the second-generation garnet in the calcic skarn of the Weijia W deposit .........................................................................................................

Figure 8 -

 8 Figure 8-33. Energy dispersive spectrometry elemental mapping of the third-generation garnet in the calcic skarn of the Weijia W deposit ..................................................................................................................

Figure 8 -

 8 Figure 8-34. Chondrite-normalized REE patterns of garnets from the magnesian and calcic skarns in the Weijia W deposit ........................................................................................................................................

Figure 8 -

 8 Figure 8-35. Trace element binary diagrams of garnets from the magnesian and calcic skarns in the Weijia W deposit ............................................................................................................................................

Figure 8 -

 8 Figure 8-36. Compositions of pyroxenes from the magnesian and calcic skarns in the Weijia W deposit .........

Figure 8 -

 8 Figure 8-37. Binary plot of FeO (wt.%) vs. MnO (wt.%) contents of wollastonite in the calcic skarn of the Weijia W deposit ........................................................................................................................................

Figure 8 -

 8 Figure 8-38. Chondrite-normalized REE patterns of scheelites from the stockwork quartz veinlets of granite and the magnesian and calcic skarns in the Weijia W deposit ...............................................................

Figure 8 -

 8 Figure 8-39. Trace element binary diagrams of scheelites from the stockwork quartz veinlets of granite and the magnesian and calcic skarns in the Weijia W deposit.....................................................................

Figure 8 -

 8 Figure 8-40. Histograms for F intercept value [IV (F)] of micas in the Weijia W deposit ..................................

Figure 8 -

 8 Figure 8-41. Histograms for F/Cl intercept value [IV (F/Cl)] of biotite and phlogopite in the Weijia W deposit Figure 8-42. F intercept value [IV (F)] vs. F/Cl intercept value [IV (F/Cl)] diagram for biotite and phlogopite in the Weijia W deposit .......................................................................................................................

  1. List of completed workload during my Ph.D. study ............................................................................Table 2-1. Main features of the Middle-Late Jurassic ore-bearing granitoids in the Nanling Range .................... Table 4-1. Main geochemical features of granitoids from the Tongshanling-Weijia area .................................... Table 4-2. Main features of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the NanlingRange ................................................................................................................................................... Geothermometry based on mineral chemical compositions of amphibole, plagioclase, and biotite from the Tongshanling granodiorite and its microgranular enclaves ............................................................ Table 5-2. Main features of the major Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites in the Nanling Range, South China ............................................................................................................................. Table 7-1. Sulfur isotopic fractionations and calculated temperatures of sulfide mineral pairs from the Tongshanling Cu-Pb-Zn deposit and Jiangyong Pb-Zn-Ag deposit ...................................................

Figure 1 - 1 .

 11 Figure 1-1. Distribution of multiple-aged granitoids and related mineral deposits in the Nanling Range of South China (modified after[START_REF] Chen | W-Sn-Nb-Ta-bearing granites in the Nanling Range and their relationship to metallogengesis[END_REF][START_REF] Chen | Multiple-aged granitoids and related tungsten-tin mineralization in the Nanling Range, South China[END_REF].

  is generally considered to link with the North China Block through the Qinling-Dabie-Sulu orogen to the north, connect with the Indochina Block by the Jinshajiang-Ailaoshan-Song Ma suture zone to the southwest, joint with the Songpan-Gantze Block through the Longmenshan fault to the northwest, and is bounded by the Pacific plate to the east (Fig.2-1). Faure et al.(2016a) proposed a hypothetic Triassic suture to the east of Hainan Island as the southern offshore of the South China Block (Fig.2-1).

Figure 2 - 1 .

 21 Figure 2-1. Structural map showing the tectonic location and main tectonic elements of the South China Block (cited from Faure et al., 2017).

Figure 2

 2 Figure 2-2. (a) Sketch map showing the tectonic location of South China. (b) Simplified geological map of South China illustrating the distributions of main Phanerozoic structures and igneous rocks (cited from Li et al., 2017).

Figure 2 - 3 .

 23 Figure 2-3. Schematic model illustrating the geodynamic evolution of South China from Neoproterozoic to

  Figure 2-4. Schematic models illustrating the geodynamic mechanism of the (a-c) Early Paleozoic and (d-g) Triassic tectonic events in the South China Block (cited from Li et al., 2017).

  2010), and (3) combined northwestward underthrusting of an inferred East China Sea Block and southeastward underthrusting of the Yangtze Block both beneath the Cathaysia Block

Figure 2 - 5 .

 25 Figure 2-5. Paleogeographic evolution of the South China Block from Permian to Jurassic, the flat-slab subduction model of the palaeo-Pacific plate, and postorogenic magmatism induced by slab foundering and retreating (cited from Li and Li, 2007).

Figure 2 - 6 .

 26 Figure 2-6. Schematic model illustrating the driving mechanisms for the geodynamic evolution of the South China Block during Mesozoic (cited from Wang et al., 2013).

Figure 2 - 7 .

 27 Figure 2-7. Schematic model illustrating the palaeo-Pacific plate subduction with changing angles in Southeastern China during Late Mesozoic (cited from[START_REF] Zhou | Origin of Late Mesozoic igneous rocks in Southeastern China: implications for lithosphere subduction and underplating of mafic magmas[END_REF].

Figure 2 - 8 .

 28 Figure 2-8. Distribution of multiple-aged granitoids and volcanic rocks in South China (modified after Sun,

  -8). However, Triassic volcanic rocks are almost absent in the South China Block. Two series of Triassic granitoids have been recognized as follows: (1) minor gneissoid granites dominantly along the Yunkai domain at the southern margin of the South China Block with ages of 250 -242 Ma; (2)voluminous peraluminous massive granitoids with two peak ages of ca. 240Ma and ca. 220

  been discovered in the South China Block, which are characterized by multiple-aged (Neoproterozoic, Early Paleozoic, Triassic, Jurassic, and Cretaceous) mineralization and are dominated by Mesozoic especially Late Mesozoic mineralization (Figs. 2-9 and 2-10; Hua

Figure 2 - 9 .

 29 Figure 2-9. Distribution of the Mesozoic mineral deposits in East China (Southeast China and Northeast China) (cited from Mao et al., 2011a).

Figure 2 - 10 .

 210 Figure 2-10. Summary of the geodynamic evolution, granitic magmatism, and related mineralization in South China.

  published a cassiterite U-Pb age of 829 ± 19 Ma by LA-ICP-MS analysis for the Menggongshan Sn deposit in the Baotan Sn orefield. Xiang et al. (2018) obtained two metallogenic ages of 831 ± 11 Ma and 828 ± 12 Ma for the Jiumao Sn deposit by LA-ICP-MS cassiterite U-Pb dating. Liu et al. (2015) constrained the formation time of the Huashandong W deposit at 805 ± 5 Ma by molybdenite Re-Os dating. The Early Paleozoic mineral deposits in South China discovered until now are mainly W (Sn) and also some Nb-Ta deposits and are temporally and spatially related to the later (ca. 420 Ma) Early Paleozoic granites (Fig. 2-10). The Yuechengling granitic complex in northern Guangxi Province is a typical case of the Early Paleozoic W-bearing granites. Yang et al. (2014) published a zircon U-Pb age of 421.8 ± 2.4 Ma and a scheelite Sm-Nd age of 421 ± 24 Ma for the Niutangjie W deposit at the southern margin of the Yuechengling granite. Chen et al. (2016) identified an Early Paleozoic W mineralization event in the Dushiling W deposit at the northeastern margin of the Yuechengling granite by zircon U-Pb dating (422.9 ± 2.1 Ma, 423.2 ± 2.4 Ma, 420.9 ± 2.3 Ma, 421.5 ± 2.5 Ma), scheelite Sm-Nd dating (417 ± 35 Ma), and titanite U-Pb dating (424 ± 13Ma, 425 ± 12 Ma). The Penggongmiao granitic batholith in southern Hunan Province was previously also regarded as an Early Paleozoic W-bearing granite. A dozen of scheelite-quartz veins have been detected at the southern contact zone between the Penggongmiao granite and country rocks in the Zhangjialong W deposit.

  systems except for the absence of Silurian system and Upper Permian to Lower Triassic series and are dominated by. The Upper Ordovician strata mainly occur in the northwestern part of the Tongshanling-Weijia area (Fig.3-1) with a thickness larger than 782 m and are composed of low-grade metasandstone with interbedded slate (Fig.3-2). The Lower Devonian strata overlay the Upper Ordovician strata by an angular unconformity and comprise conglomerate, pebbled sandstone, quartz sandstone, and siltstone with a thickness of ca. 120 m (Fig.3-2). The Middle Devonian series contains the lower Tiaomajian Formation and the upper Qiziqiao Formation with thicknesses of ca. 530 m and ca. 1080 m, respectively (Figs.3-1 and 3-2). The Tiaomajian Formation is constituted by a ca. 390-m-thick Lower Member of siltstone and silty shale with intercalated quartz sandstone and shale and a ca. 140-m-thick Upper Member of siltstone and quartz sandstone with intercalated shale and mudstone (Fig.3-2). The Qiziqiao Formation consists of a ca. 340-m-thick Lower Member of limestone, carbonaceous limestone, and marly limestone, a ca. 390-m-thick Middle Member of dolostone with intercalated dolomitic limestone, and a ca. 350-m-thick Upper Member of limestone with intercalated marly limestone (Fig.3-2). The Upper Devonian series contains the lower Shetianqiao Formation and the upper Xikuangshan Formation with thicknesses of.

Figure 3 - 1 .

 31 Figure 3-1. Geological map of the Tongshanling-Weijia area in southern Hunan Province (modified after Regional Geological Survey Team of Hunan Geology Bureau, 1975a, 1975b). 1: Tongshanling Cu-Pb-Zn deposit; 2: Jiangyong Pb-Zn-Ag deposit; 3: Yulong Mo deposit; 4: Weijia W deposit.

Figure 3 - 2 .

 32 Figure3-2. Stratigraphic column of the Tongshanling-Weijia area (according to Regional Geological Survey Team of Hunan GeologyBureau, 1975aBureau, , 1975b)).

  -1). A vast majority of the faults are thrust and strike-slip faults and several ones are normal faults. The folded and metamorphosed Ordovician strata and the angular unconformity between the Lower Devonian and Upper Ordovician strata record the Early Paleozoic intracontinental orogen in the South China Block. The Devonian and Carboniferous strata have been folded and faulted through the Triassic intracontinental compressive deformation in South China which also led to the angular unconformity of the Upper Triassic strata overlaying the folded Lower Permian and Carboniferous strata. The south-north-to southwest-northeast-trending structural framework in the Tongshanling-Weijia area was established dominantly by the Triassic tectonic event. During Middle-Late Jurassic, the Tongshanling and Weijia granitoids intruded into the folded and faulted Devonian and Carboniferous carbonate strata as stocks, dikes, apophyses, etc. (Fig. 3-1).

Figure 4 - 1 .

 41 Figure 4-1. Petrographic photomicrographs of granitoids from the Tongshanling-Weijia area. (a-c) Tongshanling granodiorite porphyry; (d-h) Dioritic dark enclaves; (i) Tongshanling granite porphyry; (j-l) Weijia granite porphyry. (a) "Pearlitic margin" texture of` K-feldspar phenocryst, the size of microgranular quartz grains is 200 -500 μm, crossed-polarized light. (b) Single-grained amphibole with short prismatic apatite inclusions, plane-polarized light. (c) Amphibole-rich clot, plane-polarized light. (d) Reaction rim of plagioclase phenocryst, crossed-polarized light. (e) Amphibole as the predominant dark mineral, plane-polarized light. (f) Biotite as the predominant dark mineral, plane-polarized light. (g) Amphibole-rich clot, plane-polarized light. (h) Needle-like or elongated prismatic apatites, plane-polarized light. (i) Porphyritic texture, the matrix has a felsitic texture, crossed-polarized light. (j) Hexagonal bipyramidal quartz phenocryst with resorption texture, crossed-polarized

Figure 4 - 2 .

 42 Figure 4-2. Backscattered electron (BSE) images of accessory minerals in the Tongshanling granodiorite porphyry and Weijia granite porphyry. (a-c) Tongshanling granodiorite porphyry; (d-f) Weijia granite porphyry. (a) Intergrowth of magnetite and allanite. (b) Magnetite and apatite inclusions in allanite. (c) Pyrite inclusions of magnetite in biotite. (d) Intergrowth of zircon, thorite, and monazite. (e) Intergrowth of zircon, thorite, and xenotime. (f) Intergrowth of monazite and xenotime. Mineral abbreviations: Mag = magnetite, Aln = allanite, Ap = apatite, Py = pyrite, Bt = biotite, Zrn = zircon, Thr = thorite, Mnz = monazite, Xtm = xenotime.

Figure 4 - 3 .

 43 Figure 4-3. Zircon CL images of granitoids from the Tongshanling-Weijia area. GDP: granodiorite porphyry; GP: granite porphyry. The smaller and larger circles represent the analytical spots of U-Pb and Hf isotope, respectively, and the numbers are U-Pb age and ε Hf (t) value.

  3) and T C DM (Hf) values of 1.18 -1.55 Ga. The 2350 -2500 Ma inherited zircon cores have εHf (t) values of +5.9 -+8.7 and T C DM (Hf) values of 2.44 -2.53 Ga.

Figure 4 - 4 .

 44 Figure 4-4. Zircon 206 Pb/ 238 U-207 Pb/ 235 U concordia diagrams of granitoids from the Tongshanling-Weijia area.

  1. In the TAS diagram (Fig.4-6a), the Tongshanling granodiorite porphyry samples are plotted in the granodiorite field, the dark enclaves mainly in the monzodiorite to diorite fields, and the Tongshanling and Weijia granite porphyries in the granite field. The Tongshanling granodiorite porphyry and its dioritic dark enclaves are metaluminous calc-alkaline rocks and the Tongshanling and Weijia granite porphyries are peraluminous alkaline granites (Fig.4-6b and c). In the ACF diagram (Fig.4-6d), the Tongshanling granodiorite porphyry and its dark enclaves are plotted in the

Figure 4 - 5 .

 45 Figure 4-5. Histograms for zircon ε Hf (t) and T C DM (Hf) (Ga) values of granitoids from the Tongshanling-Weijia area. The zircon Hf isotopic data of the Middle-Late Jurassic Cu-Pb-Zn-bearing granitoids in the Nanling Range (CGNR) are from Xie et al. (2013), Zuo et al. (2014), Zhao et al. (2016b), and unpublished data from our research group; the zircon Hf isotopic data of the Late Jurassic W-bearing granites in the Nanling Range (WGNR) are from Chen et al. (2013).

Figure 4 - 6 .

 46 Figure 4-6. Major element diagrams of granitoids from the Tongshanling-Weijia area. (a) TAS [(Na 2 O+K 2 O) (wt.%)-SiO 2 (wt.%)] classification diagram, after Middlemost (1994). (b) SiO 2 (wt.%)-A.R. diagram, after Wright (1969). (c) ANK-ACNK diagram. (d) ACF diagram, after Hine et al. (1978). GDP: granodiorite porphyry;GP: granite porphyry. The whole-rock geochemical data of the Middle-Late Jurassic Cu-Pb-Zn-bearing granitoids in the Nanling Range (CGNR) are fromWang et al. (2003a),[START_REF] Jiang | Middle to late Jurassic felsic and mafic magmatism in southern Hunan province, southeast China: Implications for a continental arc to rifting[END_REF],[START_REF] Xie | Origin of granodiorite porphyry and mafic microgranular enclave in the Baoshan Pb-Zn polymetallic deposit, southern Hunan Province: Zircon U-Pb chronological, geochemical and Sr-Nd-Hf isotopic constraints[END_REF]), Zuo et al. (2014),Zhao et al. (2016b), and unpublished data from our research group; the whole-rock geochemical data of the Late Jurassic W-bearing granites in the Nanling Range (WGNR) are from[START_REF] Zhang | Study on the characteristics, origin and related metallogeny of granites in Dajishan and Piaotang, Southern Jiangxi Province[END_REF], Zhang (2014),Zhao et al. (2016b), and unpublished data from our research group.

Figure 4 - 7 .

 47 Figure 4-7. Primitive mantle-normalized (Sun and Mcdonough, 1989) spider diagrams and chondrite-normalized (Boynton, 1984) REE patterns of granitoids from the Tongshanling-Weijia area. The legends and data sources of the Middle-Late Jurassic Cu-Pb-Zn-bearing (CGNR) and W-bearing (WGNR) granitoids in the Nanling Range are the same as Figure 4-6.

Figure 4 - 8 .

 48 Figure 4-8. Sr-Nd isotopic compositions of granitoids from the Tongshanling-Weijia area. (a) ε Nd (t)-( 87 Sr/ 86 Sr) i diagram, the Sr-Nd isotopic compositions of the Precambrian metasedimentary basement of the Nanling Range (MSBNR) are from Zhu et al. (2008) and Xie et al. (2013), the Ninyuan alkaline basalt and Daoxian high-Mg basalt are from Li et al. (2004) and Jiang et al. (2009), and the Huilongxu lamprophyre are from Wang et al. (2003b). (b) ε Nd (t)-t (Ma) diagram, the Nd isotopic evolution region of the Precambrian metasedimentary basement of the Nanling Range are from Sun et al. (2005). The legends and data sources of the Middle-Late Jurassic Cu-Pb-Zn-bearing (CGNR) and W-bearing (WGNR) granitoids in the Nanling Range are the same as Figure 4-6.

  1), rightward sloping REE patterns, and weak depletions of Ba, Sr, P, Ti, and Eu (Fig. 4-7a and b) exhibit the characteristics of I-type granite, and in the ACF diagram (Fig. 4-6d) the Tongshanling granodiorite porphyry is plotted in the I-type granite field. The high Mg/(Mg+Fe) ratios (0.42 -0.48) indicate a mafic source. In the AMF-CMF diagram (Fig. 4-9c), the Tongshanling granodiorite porphyry is plotted in the field of partial melts from metabasaltic to metatonalitic sources. All these features suggest that the Tongshanling granodiorite porphyry might be derived from the partial melting of the basaltic to tonalitic mafic lower crust.

Figure 4 - 9 .

 49 Figure 4-9. (a) CaO/(Na 2 O+K 2 O)-Rb/Sr diagram. (b) Mg/(Mg+Fe)-SiO 2 (wt.%) diagram. (c) AMF-CMF diagram, after Altherr et al. (2000), AMF = molar Al 2 O 3 /(MgO+FeO Total ), CMF = molar CaO/(MgO+FeO Total ). (d) Rb (ppm)-(Y+Nb) (ppm) diagram, after Pearce et al. (1984) and Förster et al. (1997), Syn-COLG: syn-collision granites; VAG: volcanic arc granites; WPG: within plate granites; ORG: ocean ridge granites. The legends and data sources of the Middle-Late Jurassic Cu-Pb-Zn-bearing (CGNR) and W-bearing (WGNR) granitoids in the Nanling Range are the same as Figure 4-6.

  Both the Tongshanling and Weijia granite porphyries were formed slightly later than the Tongshanling granodiorite porphyry (Fig.4-4c and d), and have similar Nd and zircon Hf isotopic compositions with crust-derived signatures (Table4-1 and Figs. 4-5 and 4-8). These granite porphyries are peraluminous alkaline granites and are plotted in the S-type granite field of the ACF diagram (Fig.4-6d). In the AMF-CMF diagram (Fig.4-9c), the Tongshanling granite porphyry is plotted in the field of partial melts from metagreywackes. The Weijia granite porphyry does not fall into the diagram due to its high degree of fractionation (AMF: 11.88 -69.08, CMF: 0.23 -3.14). Its low Mg/(Mg+Fe) ratios (0.04 -0.32) indicate that it might be product of the partial melting of metasedimentary rocks. Its spider diagram and REE patterns are similar to those of the typical S-type W-bearing Yaogangxian granite in the

  porphyry. b The W-bearing granites include Yaogangxian, Xintianling, Dengfuxian, Weijia, Xihuashan, Muziyuan, Piaotang, Dajishan intrusions, etc. The detailed data sources are shown in Appendix 4-4 and the captions of Figures 4-5 and 4-6.

Figure 4 -

 4 Figure 4-10. Zircon U-Pb ages of the Middle-Late Jurassic Cu-Pb-Zn-bearing (CGNR) and W-bearing (WGNR) granitoids in the Nanling Range. The data sources are shown in Appendix 4-4.

  estimated the depth of the amphibolitic source of the Shuikoushan granodiorite in Hunan Province and obtained an upper limit of 25 km. Therefore, it is speculated that as the source of the Cu-Pb-Zn-bearing granitoids, the depth of the amphibolitic basement in the lower crust is 25 -29 km. The zircon Hf model ages of the Cu-Pb-Zn-bearing granitoids (1.50 -2.20 Ga, peak value: 1.85 Ga) indicate that the amphibolitic basement was mainly formed in the Paleoproterozoic. SHRIMP zircon U-Pb dating of the amphibolite from the Mayuan Group, which is the basement of the Cathaysia Block, yielded a Paleoproterozoic age of 1766 ± 19 Ma (Li, 1997), confirming that there is Paleoproterozoic amphibolitic basement in the Nanling Range. The Late Jurassic W-bearing granites in the Nanling Range are plotted in the S-type granite field of the ACF diagram (Fig. 4-6d) and in the Precambrian metasedimentary basement of the Nanling Range in the Sr-Nd isotope diagram (Fig. 4-8), and they have low Mg/(Mg+Fe) ratios (Fig. 4-9b), indicating that they originated from the partial melting of metasedimentary rocks. In the AMF-CMF diagram (Fig. 4-9c), the W-bearing granites are mainly plotted in the field of partial melts from metagreywackes. They have an average zircon saturation temperature of 735 °C (

  Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range are plotted in the post-collision extension field of the Rb-(Y+Nb) tectonic discrimination diagram (Fig. 4-9d), indicating that they were formed in an extensional tectonic setting. The palaeo-Pacific plate subduction model was proposed by Zhou and Li (2000) and Zhou et al. (2006a) to explain the geodynamical mechanism of the Late Mesozoic large-scale granitic magmatism in South China. The extensional tectonic setting caused by the palaeo-Pacific plate subduction induced asthenosphere upwelling and basaltic magma underplating. Deep continental crust was partially melted by heating of the underplated basaltic magmas to generate granitic magmas. On the basis of the study of the petrogenesis and source signatures of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range, we proposed a genetic model for the two different types of ore-bearing granitoids (Fig. 4-11). By extensional decompression and heating of the underplated basaltic magmas, the mafic amphibolitic basement in the lower crust was first partially melted to produce Cu-Pb-Zn mineralization related granodioritic magmas. With further basaltic magma underplating, the W-bearing granitic magmas were generated by the partial melting of the muscovite-rich metasedimentary basement in the upper-middle crust. The time gap of about 5 Ma between the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range was caused by the non-simultaneous partial melting of different granitoid sources.

Figure 4 - 11 .

 411 Figure 4-11. Genetic model of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range. MC: magma chamber; MSB: metasedimentary basement; MAB: mafic amphibolitic basement; MGB: mafic granulitic basement.

Figure 5 - 1 .

 51 Figure 5-1. Petrographic photographs of the Tongshanling granodiorite and its microgranular enclaves. (a) Medium-to coarse-grained and porphyritic texture of the amphibole-bearing biotite granodiorite at specimen scale. (b) An ellipsoidal dark enclave in the granodiorite, which contains a few plagioclase phenocrysts, shows a gradational contact with the host, and does not have a chilled margin with magmatic flow foliation. (c) Idiomorphic and isolated amphibole in the granodiorite, plane-polarized light. (d) Enclosed amphibole in the

  Figure 5-2. Compositional zonation of plagioclase with a Ca-rich core (analysis was performed on the unaltered part) from the Tongshanling granodiorite and its microgranular enclaves.

  . 5-1g) dioritic dark enclaves have the same minerals, even accessory minerals, as their host granodiorite but in different proportions. They generally have a plagioclase content of 50 -60 vol.%, and 30 -50 vol.% of mafic minerals (Fig.5-1g and h), with a few K-feldspar and quartz. The mafic minerals of most enclaves are dominated by amphibole (Fig.5-1h), with the exception of some dominated by biotite. At the contact between the enclaves and their host rock, the mineral granularity and proportion of mafic minerals change gradually rather than sharply (Fig.5-1g). Plagioclase is mainly subhedral to anhedral and sometimes euhedral crystals which mostly consist of a sericitized core with an irregular margin and a fresh rim with zonal texture (Fig.5-2b). The sericitized core accounts for at least 60 vol.% of the whole plagioclase (Fig.5-2b). Notably, the quantity of core-bearing plagioclase and the proportion of sericitized core in the enclaves are much more than those in the host granodiorite. The plagioclase phenocrysts with a reaction rim and no sericitized cores (Fig.5-1i) appear occasionally. Biotite is brown and occurs primarily as anhedral to subhedral crystals. Compared with the host granodiorite, the majority of amphibole in the enclaves occurs as aggregated rather than isolated crystals (Fig.5-1h). The ratio of the aggregated and isolated amphibole contents is about 5:1. The aggregated amphibole, which mainly constitutes amphibole-rich clots together with a few biotite, is anhedral and has a similar grain size (< 300 μm) with the most other enclave minerals (Fig.5-1h and j). The isolated amphibole is mostly anhedral to subhedral (Fig.5-1h) and never appears as idiomorphic as that in the host granodiorite (Fig.5-1c). Nearly half of the amphibole-rich clots are several millimeters sized and are zoned with a pale-green to colorless interior and a deep-green colored exterior (Fig.5-1j); the another half is smaller in size and does not show a color zonation (Fig.5-1h). Although not always, the interior amphibole grains in the zonal clots also show a zonal feature, with the core being paler colored than the rim (Fig.5-1k). However, the clot exterior amphibole grains do not show a color zonation. A granoblastic triple-junction texture can be commonly observed in the clot interior where only amphibole appears but no interstitial biotite does (Fig.5-1l), whereas the clot exterior shows an anhedral granular texture of dominant amphibole and a few biotite crystals (Fig.5-1j). The biotite in the clot exterior occupies no more than 5 vol.% of the clot. Besides the amphibole-rich clots, some rarely-occurred mafic mineral clots are composed of amphibole and abundant biotite with an intergrowth texture, and do not have zonal feature and granoblastic triple-junction texture (Fig.5-1m). In these amphibole-biotite clots, the content of biotite is about 40 -50 vol.%. A few large-grained K-feldspar and quartz have a poikilitic texture and include the fine-grained amphibole, biotite, and plagioclase (Fig.5-1n and o).

CAMECA

  SX50 electron microprobe (EMP) at Institut des Sciences de la Terre d'Orléans (ISTO), France. Zircon was analyzed by a JEOL JXA-8100M EMP at the State Key Laboratory for Mineral Deposits Research (LAMD), Nanjing University (NJU), China. The analytical conditions included an accelerating voltage of 15 kV, a beam current of 10 nA (CAMECA, ISTO) or 20 nA (JEOL, LAMD, NJU) with beam diameter of 1 μm, and counting times of 10 s for all elements and 5 s for background. The collected data were corrected by the ZAF procedures. Calibration was performed using natural minerals and synthetic compounds. Trace element contents of amphibole and biotite were determined by an Agilent 7700× inductively coupled plasma mass spectrometry coupled to an Excite 193 nm Photon Machines laser ablation system (LA-ICP-MS) at Nanjing FocuMS Technology Co. Ltd. Each analysis was performed by a 25 -50-μm ablating spot at 5 -8 Hz with energy of 5 -5.5 mJ (transmittance 80%) for 40 s after measuring the gas blank for 15 s. USGS standard reference materials BIR-1G, BHVO-2G, and BCR-2G, NIST standard reference material 610, and

Figure 5 - 3 .

 53 Figure 5-3. Composition of plagioclase from the Tongshanling granodiorite and its microgranular enclaves.

Figure 5 - 4 .

 54 Figure 5-4. Mineral chemistry of amphibole from the Tongshanling granodiorite and its microgranular enclaves. (a) Classification diagram of amphibole [General formula: A 0-1 B 2 C 5 T 8 O 22 (OH, F, Cl) 2 , after Hawthorne et al., 2012], when Mg/(Mg+Fe 2+ ) < 0.9, the tremolite field represents an actinolitic composition (according to Leake et al., 1997). (b) Si (apfu)-Al Total (apfu) diagram. MI: mineral inclusion; II: inner of isolated amphibole; OI: outer of isolated amphibole; CA: core of aggregated amphibole grains; RA: rim of aggregated amphibole grains; I: isolated amphibole; CCI: core of clot interior amphibole grains; RCI: rim of clot interior amphibole grains; CCE: core of clot exterior amphibole grains; RCE: rim of clot exterior amphibole grains.

  core of aggregated amphibole grains in the granodiorite has lower Al contents (0.63 -0.81 apfu) and higher Si contents (7.33 -7.49 apfu) than the rim (Al: 0.90 -1.59 apfu; Si: 6.71 -7.31 apfu) (Fig.5-4b). Particularly, the core of clot interior amphibole grains in the enclaves shows actinolitic compositions [Mg/(Mg+Fe 2+ ) < 0.9; Fig.5-4a; Appendix 5-2] with the lowest Al (0.31 -0.52 apfu) and highest Si (7.49 -7.72 apfu) contents and the rim has higher Al (0.82 -1.28 apfu) and lower Si (7.01 -7.35 apfu) contents than the core (Fig.5-4b). Notably, although the clot exterior amphibole grains do not show a color zonation, they have zoned compositions, with the core having lower Al contents (0.81 -1.05 apfu) and higher Si contents (7.16 -7.30 apfu) than the rim (Al: 1.25 -1.30 apfu; Si: 6.88 -6.97 apfu) (Fig.5-4b). At clot scale, the exterior of zonal amphibole-rich clots shows more Al-enriched and Si-depleted amphibole compositions than those of the interior (Fig.5-4b). The isolated amphibole in the enclaves can be divided into two different groups with low-Al, high-Si and high-Al, low-Si compositions, respectively (Fig.5-4).Trace element compositions of amphibole are listed in Appendix 5-3. The isolated amphibole in the granodiorite has flat REE patterns with weak LREE depletions and obvious Eu negative anomalies (Fig.5-5a). The ΣREE contents are 307 -764 ppm and the mean Eu [ Eu = 2EuN/(SmN + GdN)] value is 0.05. The rim of clot interior amphibole grains and the isolated amphibole in the enclaves, with ΣREE contents of 485 -525 ppm and 317 -549 ppm, respectively, have the similar REE patterns and mean Eu value (0.06) (Fig.5-5b and c) to the isolated amphibole in the granodiorite. In contrast, although the core of clot interior amphibole grains in the enclaves also shows flat REE patterns with weak LREE depletions, it has distinctly lower ΣREE contents (99 -146 ppm) and a slightly higher mean Eu value (0.09) (Fig.5-5b).

Figure 5 - 5 .

 55 Figure 5-5. Chondrite-normalized (Boynton, 1984) REE patterns of amphibole from the Tongshanling granodiorite and its microgranular enclaves.

Figure 5 - 7 .

 57 Figure 5-7. Classification diagram of biotite (after Tischendorf et al., 1997) from the Tongshanling granodiorite and its microgranular enclaves.

Figure 5 - 8 .

 58 Figure 5-8. Chondrite-normalized (Boynton, 1984) REE patterns of biotite from the Tongshanling granodiorite and its microgranular enclaves.

Figure 5 - 9 .

 59 Figure 5-9. Trace element binary diagrams of biotite from the Tongshanling granodiorite and its microgranular enclaves. Legends are the same as Figures 5-7 and 5-8.

Figure 5 - 10 .

 510 Figure 5-10. Texture and mineral chemistry of zircon from the Tongshanling granodiorite and its microgranular enclaves. (a) CL image of a magmatic zircon with an inherited core from the granodiorite. (b) Zr/Hf-ThO 2 +UO 2 (wt.%) diagram of magmatic zircon from the granodiorite and its enclaves. (c) CL image showing the compositional zonation of a magmatic zircon with an inherited core from the enclaves. (d and e) Chaotic internal textures of metamorphic zircon in the enclaves. (f) Metamorphic zircon with a magmatic rim in the enclaves.

Figure 5 -

 5 Figure 5-11. Plot of the generalized tschermakite [( T Al-A Na-A K-2 A Ca) (apfu)] vs. edenite [( A Na+ A K+ A Ca) (apfu)] components for amphibole from the Tongshanling granodiorite and its microgranular enclaves (after Schumacher, 2007). Legends are the same as Figure 5-4.

Figure 5 -

 5 Figure 5-12. REE distribution modelling of magmatic amphibole and residual clinopyroxene and amphibole.

(

  , the Ca-rich plagioclase cores (Fig.5-2a), and the rarely-occurred amphibole-rich clots (Fig.5-1e). These residual materials can be directly inherited from the source after partial melting or can be derived from disaggregation of the restite enclaves reworked by the host magma. The amphibole-rich clots also have a metamorphic triple-junction texture (Fig.5-1f) and mainly consist of granoblastic amphibole with an actinolitic core surrounded by a magnesio-hornblende rim (Fig.5-4a), which are similar to those in the enclaves. In the amphibole-rich clots, the amphibole rim has distinctly higher Al and lower Si contents than the core (Fig.5-4b), showing a magma reworked signature. The low-Al and high-Si magma reworked isolated amphibole) may be derived from the disaggregation of amphibole-rich clots or transformed from isolated residual pyroxene just as in the enclaves.

Figure 5 -

 5 Figure 5-13. Harker plots for (a) FeO Total , (b) MgO, (c) CaO, and (d) K 2 O of the Tongshanling granodiorite and its microgranular enclaves showing excellent linearities. The data are from Huang et al. (2017a).

  1) were applied for temperature calculation to test the interpretation for enclave origin. Most magma reworked amphibole crystals, except for the intensely reworked high-Al and low-Si isolated amphibole and the rim of clot exterior amphibole grains in the enclaves, were not used for calculation due to their dis tinct compositional disequilibrium (low Al and high Si contents) with the host melt which would inevitably lead to an underestimation of temperature. The detailed results are listed in Table5-1.

Fig. 5 -

 5 Fig. 5-14a and b), indicating that the intensely reworked enclave amphibole was nearly in equilibrium with the host melt. However, they show notably lower temperatures than the early enclosed magmatic amphibole (Table 5-1; Fig. 5-14a and b), reflecting that an evolved host melt was responsible for the reworking of restite enclaves. The prediction of SiO2 in coexisting

  i.e., hornblende + biotite + plagioclase + orthoclase + quartz + titanite + Fe-Ti oxide + melt + fluid. Based on the calibration proposed by[START_REF] Anderson | The effects of temperature and f O2 on the Al-in-hornblende barometer[END_REF], the rim compositions of magmatic isolated amphibole [Mg/(Mg+Fe) > 0.35] in the granodiorite give a pressure of 2.6 -3.4 (3.0 ± 0.4) kbar (calculated with T = 750 °C) (Fig.5-14d), corresponding to a deep emplacement depth of 8.6 -11.2 km (3.3 km/kbar) with an average value of ca. 10 km. This result is consistent with those calculated by the calibration ofMutch et al. (2016) and the Equation 7a of[START_REF] Putirka | Amphibole thermometers and barometers for igneous systems and some implications for eruption mechanisms of felsic magmas at arc volcanoes[END_REF] on the whole, which are 2.7 -3.6 kbar and 2.5 -3.3 kbar, respectively.

Figure 5 -

 5 Figure 5-15. Schematic model illustrating the formation process of reworked restite enclave (see detailed description in the text). In the right diagram, the center and the surrounding parts show the evolutionary processes of the restite enclave and the host granodioritic magma, respectively. To better explain this model, the melt content in the enclave (spots in the center part of the right diagram) and the zircon size have been magnified.

  occurrence of the Tianjinping amphibolite(1766 ± 19 Ma;[START_REF] Li | Timing of the Cathaysia Block formation: Constraints from SHRIMP U-Pb zircon geochronology[END_REF] from the basement of the Cathaysia Block confirms the existence of the Paleoproterozoic amphibolitic basement in the Nanling Range.

Figure 6 - 1 .

 61 Figure 6-1. Simplified geological map of the Tongshanling area (modified after Regional Geological Survey Team of Hunan Geology Bureau, 1975a, 1975b) showing the sample locations for Raman spectroscopy of carbonaceous material (RSCM) analysis and electron backscatter diffraction (EBSD) mapping. The results of RSCM thermometry are presented as mean value ± standard deviation (°C) in Figure 6-1b and d, the same in the following figures.

Figure 6 - 2 .

 62 Figure 6-2. Field observations of normal faults (outcrop locations shown in Fig. 6-1b) in the Tongshanling area.

Figure 6 - 3 .

 63 Figure 6-3. Cross sections (section lines shown in Fig. 6-1b) of the (a-e) northeastern and (f-j) southern contact zones from the Tongshanling intrusion to country rocks.

Figure 6 - 4 .

 64 Figure 6-4. Cross section (section line shown in Fig. 6-1b) of the Tongshanling Cu-Pb-Zn deposit (modified after No. 206 Exploring Team of Hunan Metallurgical and Exploring Company, unpub. report, 1975).

Figure 6 - 5 .

 65 Figure 6-5. Photographs of (a) massive endoskarn, (b and c) vein exoskarn, and (d) deformed country rocks in the Tongshanling Cu-Pb-Zn deposit. Mineral abbreviations: Ccp = chalcopyrite, Grt = garnet, Po = pyrrhotite, Px = pyroxene, Qz = quartz, Wo = wollastonite.

Figure 6 - 6 .

 66 Figure 6-6. Panoramic views of exoskarn in the Tongshanling Cu-Pb-Zn deposit showing skarn zonation and evolution. Mineral abbreviations are the same as Figure 6-5.

  uniformly dip to north to northeast. Some parts of the exoskarn veins are parallel to the bedding and construct a steplike profile with the steeper parts. The country rocks have been strongly marbleized and deformed (Fig.6-5b-d).These exoskarn veins commonly exhibit a well-developed outward zonation from garnet-pyroxene through wollastonite to marble. Different from the deformed marble which consists of elongated calcite crystals, the marble envelope of the exoskarn comprises undeformed granular calcite crystals (Fig.6-5d). Three generations of garnets are distinguished. They are chronologically green-brown disseminated garnet in the wollastonite skarn, brown garnet coexisting with pyroxene, and red-brown vein-like garnet cutting the garnet-pyroxene skarn (Fig.6-6). Ore minerals are chalcopyrite, sphalerite, galena, pyrrhotite, and pyrite. Vein-like barren quartz occurs in the center of exoskarn (Fig.6-7a) or cuts through it (Fig.6-7b). A few sulfide-quartz veinlets appear at the distal end of exoskarn veins (Fig.6-6b).

Figure 6 - 7 .

 67 Figure 6-7. Photographs of vein-like quartz (a) in the center of exoskarn or (b) cutting through it and (c and d) sulfide-quartz veins in the peripheral strata in the Tongshanling Cu-Pb-Zn deposit. Mineral abbreviations are the same as Figure 6-5.

  Figure 6-8. Raman spectra of carbonaceous material in carbonate rocks from the Tongshanling Cu-Pb-Zn deposit and its adjacent area and temperatures calculated by the RSCM thermometry.

Figure 6 - 9 .

 69 Figure 6-9. Crystallographic preferred orientation (CPO) of calcite (dolomite) from the Tongshanling Cu-Pb-Zn deposit and its adjacent area determined by EBSD mapping. All pole figures are equal-area lower hemisphere projections based on one point per grain. D and N are the size and number of grains, respectively. (a and b)

Figure 6 -

 6 Figure 6-10. Compositions of garnets from the endoskarn and exoskarn of the Tongshanling Cu-Pb-Zn deposit.

  evolution of the three generations of exoskarn garnet indicates a progressive increase of magmatic components during the formation of the exoskarn and implies a genetical link between the exoskarn and the Tongshanling granodiorite. The exoskarn and sulfide-quartz veins strike and dip consistently with the foliation in the contact zone and cut the bedding. Both the results of RSCM thermometry and EBSD mapping of deformed marble adjacent to the exoskarn veins are comparable to those of deformed marble in the contact zone at surface. The peripheral sulfide-quartz veins are actually late-stage productions during the evolution of skarn system (Figs. 6-6b and 6-7a-b) and their wall rocks were marbleized under a lower temperature (Fig.6-8) and were deformed with a weaker CPO but no SPO (Fig.6-9i). Therefore, the exoskarn and sulfide-quartz veins are evidently controlled by the magma emplacement-induced wall-rock deformation. The undeformed marble envelope of the exoskarn (Fig.6-5d) may be formed by chemical recrystallization of the deformed marble during metasomatism and is suggestive of a post-deformational skarnization. The sulfide and quartz bands of the endoskarn (Fig.6-5a), with the same strike-dip as the exoskarn and sulfide-quartz veins, also reflect some information of the magma emplacement-induced structural control.

Figure 6 -

 6 Figure 6-11. Schematic model illustrating the magma emplacement-induced structural control on skarn formation at the Tongshanling Cu-Pb-Zn deposit.

Figure 7 - 1 .

 71 Figure 7-1. Geological maps of the (a) Tongshanling Cu-Pb-Zn deposit (modified after No. 206 Exploring Team of Hunan Metallurgical and Exploring Company, unpub. report, 1975), (b) Jiangyong Pb-Zn-Ag deposit (modified after No. 409 Geological Team of Bureau of Geology and Mineral Exploration and Development of Hunan Province, unpub. report, 2008), and (c) Yulong Mo deposit (modified after Institute of Geological Survey of South Hunan, unpub. report, 2012).

Figure 7 - 2 .

 72 Figure 7-2. Cross sections (section lines shown in Fig. 7-1) of the Tongshanling Cu-Pb-Zn deposit (modified after No. 206 Exploring Team of Hunan Metallurgical and Exploring Company, unpub. report, 1975).

Figure 7 - 3 .

 73 Figure 7-3. Cross sections (section lines shown in Fig. 7-1) of the (a) Jiangyong Pb-Zn-Ag deposit (modified after No. 409 Geological Team of Bureau of Geology and Mineral Exploration and Development of Hunan Province, unpub. report, 2008) and (b) Yulong Mo deposit (modified after Institute of Geological Survey of South Hunan, unpub. report, 2012).

Figure 7 - 4 .

 74 Figure 7-4. Outcrop-scale photos of different mineralization types of the (a-i) Tongshanling Cu-Pb-Zn deposit, (j-m) Jiangyong Pb-Zn-Ag deposit, and (n and o) Yulong Mo deposit. (a) Chalcopyrite + pyrrhotite mineralization accompanied by quartz in the massive proximal endoskarn. (b) Proximal exoskarn vein with an outward zonation from garnet-pyroxene through wollastonite to marble and late quartz in the center. (c) Exhausted stratiform distal skarn orebody with roof and floor of silicified limestone. (d) Residual argillaceous

Figure 7 - 5 .

 75 Figure 7-5. Specimen-scale photos of different ore types of the Tongshanling Cu-Pb-Zn deposit. (a) Proximal endoskarn ore. (b) Proximal exoskarn ore. (c and d) Distal skarn ore. (e) Cu-dominant sulfide-quartz vein ore. (f) Cu-Pb-Zn sulfide-quartz vein ore. (g) Pb-Zn sulfide-quartz vein ore. (h) Carbonate replacement Pb-Zn sulfide vein ore. Mineral abbreviations: Apy = arsenopyrite, Cal = calcite, Ccp = chalcopyrite, Gn = galena, Grt = garnet, Po = pyrrhotite, Px = pyroxene, Py = pyrite, Qz = quartz, Sp = sphalerite, Wo = wollastonite.

Figure 7 - 6 .

 76 Figure 7-6. Petrographic photomicrographs of different mineralization and ore types of the (a-h) Tongshanling Cu-Pb-Zn deposit, (i-l) Jiangyong Pb-Zn-Ag deposit, and (m-o) Yulong Mo deposit. (a) Coarse-grained garnet and pyroxene in the proximal endoskarn. (b) Chalcopyrite and pyrrhotite in the proximal endoskarn ore. (c) Coarse-grained pyroxene and wollastonite in the proximal exoskarn. (d) Chalcopyrite, sphalerite, galena, pyrrhotite, native bismuth, and actinolite in the proximal exoskarn ore. (e) Fine-grained garnet and pyroxene in

  of a prograde stage and a retrograde stage. Anhydrous skarn minerals wollastonite, garnet, and pyroxene were firstly formed in the prograde stage followed by a few scheelite and molybdenite. In the early retrograde stage, some hydrous skarn minerals, such as actinolite, vesuvianite, and epidote, replaced the anhydrous skarn by retrograde alteration. Sericite and chlorite were then formed by hydrothermal alteration of the granodiorite. Hydrothermal quartz, calcite, and sulfide minerals began to precipitate. The formation sequence of sulfide minerals started from pyrrhotite and pyrite through chalcopyrite to sphalerite and then to galena overall. The content of pyrite progressively increased with time. A little native bismuth was simultaneously precipitated with galena. With the occurrence of abundant quartz, the proximal Cu-dominant sulfide-quartz veins were formed and followed by the distal Cu-Pb-Zn sulfide-quartz veins and then the late Pb-Zn sulfide-quartz veins. Some Pb-Bi sulfides were contemporaneously precipitated with galena in the sulfide-quartz veins. The carbonate replacement Pb-Zn sulfide veins were formed at the latest.

Figure 7 - 7 .

 77 Figure 7-7. Paragenetic sequence of the Tongshanling Cu-Pb-Zn deposit.

  3-1, 7-1b, and 7-3a). It is characterized by carbonate replacement mineralization in the Shidengzi limestone of the Upper Carboniferous Datang. Although skarn mineralization is developed in the contact zone, it is not of great economic importance. The ore minerals of the skarn orebodies are dominated by pyrrhotite and pyrite with minor chalcopyrite (Fig.7-6i) and sphalerite. The carbonate replacement sulfide orebodies are distributed within the range of 350 m in distance from the contact zone.They generally show vein-like (Fig.7-4k), lentiform, and sackform geometries and mostly have a banded structure (Fig.7-4k-m). Sphalerite, galena, pyrite, pyrrhotite, and arsenopyrite are the dominant ore minerals of the carbonate replacement sulfide orebodies (Fig.7-6j).Silver is predominantly concentrated in galena by isomorphous substitution of Pb or as independent Ag-minerals such as pyrargyrite (Fig.7-6k), freibergite (Fig.7-6k and l), and freieslebenite. The galena/sphalerite ratio, pyrite/pyrrhotite ratio, and Ag grade of sulfide ores show positive correlations with the distance to the contact zone.Compared with the Tongshanling Cu-Pb-Zn deposit, the Jiangyong Pb-Zn-Ag deposit shows a relatively weak prograde anhydrous skarn stage with the formation of some wollastonite, garnet, and pyroxene in the contact zone and a strong retrograde stage dominated by carbonate replacement with the formation of abundant sulfide minerals and calcite in the peripheral zone but almost no quartz and chalcopyrite. The carbonate replacement ore bodies of the Jiangyong Pb-Zn-Ag deposit are similar to those of the Tongshanling Cu-Pb-Zn deposit in geometry, ore structure, mineral association, and paragenetic sequence. During Pb-Zn mineralization, galena was generally precipitated later and more distal than sphalerite. Galena/sphalerite ratio, pyrite/pyrrhotite ratio, and Ag grade progressively increased with time. Barren calcite veins were formed at the latest and cut the sulfide orebodies (Fig.7-4m).

  Yulong Mo deposit occurs in the periphery of the southern concealed contact zone between the Tongshanling granodiorite and country rocks (Figs. 3-1, 7-1c, and 7-3b). It is constituted by NW-SE-striking mineralized skarn veins in the Shidengzi limestone of the Datang Stage (Figs. 7-1c and 7-3b). These skarn veins are generally 0.1 -2 m in thickness (Fig. 7-4n and o) with an interval distance of 3 -10 m and a vertical extension of 10 -100 m.

Figure 7 - 8 .

 78 Figure 7-8. Paragenetic sequence of the Jiangyong Pb-Zn-Ag deposit. H &S = Hydrosilicate and sulfide.

Figure 7 - 9 .

 79 Figure 7-9. Paragenetic sequence of the Yulong Mo deposit.

  LA-ICP-MS U-Pb dating results of garnet in the proximal exoskarn from the Tongshanling Cu-Pb-Zn deposit are listed in Appendix 7-1. Twenty-five analyses revealed that the garnet in the proximal exoskarn has U, Th, and Pb contents of 7.25 -17.19 ppm, 0.02 -0.20 ppm, and 0.18 -0.61 ppm, respectively, and 207 Pb/ 206 Pb, 207 Pb/ 235 U, and 206 Pb/ 238 U ratios of 0.012337 -0.122815, 0.165985 -0.609241, and 0.023547 -0.029738, respectively (Appendix 7-1). A concordia age of 162.0 ± 3.7 Ma is obtained by the Wetherill concordia plots of the 207 Pb-corrected 207 Pb/ 235 U and 206 Pb/ 238 U ratios (Fig. 7-10). The weighted average value of the 207 Pb-corrected 206 Pb/ 238 U ages is 162.4 ± 4.2 Ma (Fig. 7-10) which is consistent with the concordia age.

Figure 7 -

 7 Figure 7-10. Wetherill U-Pb concordia plots and weighted average 206 Pb/ 238 U age of garnet in the proximal exoskarn from the Tongshanling Cu-Pb-Zn deposit.

Figure 7 -

 7 Figure 7-11. Re-Os isochrons and weighted average model ages of molybdenites from the (a) Tongshanling Cu-Pb-Zn deposit and (b) Yulong Mo deposit.

Figure 7 -

 7 Figure 7-12. (a) Wetherill and (b) Tera-Wasserburg U-Pb concordia plots and weighted average 206 Pb/ 238 U age of hydrothermal titanite in the altered granodiorite from the Tongshanling Cu-Pb-Zn deposit.

Figure 7 -

 7 Figure 7-13. S isotopic compositions of sulfide minerals from the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit. Mineral abbreviations: Ccp = chalcopyrite, Gn = galena, Mol = molybdenite, Po = pyrrhotite, Py = pyrite, Sp = sphalerite.

Note: a

 a Temperatures were calculated using the isotopic fractionation factors of sulfide mineral pairs from Ohmoto and Rye (1979), Δ 34 S A-B = C A-B × 10 6 / T (K) 2 , C Py-Sp = 0.30, C Py-Gn = 1.03, C Sp-Po = 0.00, C Sp-Ccp = 0.15, C Sp-Gn = 0.73, C Po-Ccp = 0.15, C Ccp-Gn = 0.58. Mineral abbreviations: Ccp = chalcopyrite, Gn = galena, Po = pyrrhotite, Py = pyrite, Sp = sphalerite.

  minerals from the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit show similar Pb isotopic compositions on the whole and are plotted above the average upper crust evolution lines (Fig. 7-14a and b). Notably, except for three discrete points, all the sulfide minerals of different mineralization types from the Tongshanling Cu-Pb-Zn deposit construct perfect positive linear correlations in the 206 Pb/ 204 Pb vs.208 Pb/ 204 Pb and 206 Pb/ 204 Pb vs.207 Pb/ 204 Pb diagrams with high squared correlation coefficients (R 2 ) of 0.97 (Fig.7-14c and d). In the same way, all the sulfide minerals of different mineralization types from the Jiangyong Pb-Zn-Ag deposit also construct perfect positive linear correlations (R 2 = 0.99) with similar but slightly steeper slopes and lower intercept values relative to those of the Tongshanling Cu-Pb-Zn deposit (Fig.7-14c and d).

Figure 7 - 14 .

 714 Figure 7-14. Pb isotopic compositions of sulfide minerals from the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit plotted with the evolution curves generated by the plumbotectonics model of Zartman and Doe (1981) (a and b) and the two-stage model of Stacey and Kramers (1975) (d). The Pb isotopic compositions of the Tongshanling granodiorite are from Cai et al. (2015). The data sources of Pb isotopic compositions of sulfide minerals from the Middle-Late Jurassic Cu-Pb-Zn (CDNR) and W (WDNR) deposits in the Nanling Range are listed in Appendix 7-5.

Figure 7 -

 7 Figure 7-15. H-O isotopic compositions of the fluids hosted by quartz from the Tongshanling (TSL) Cu-Pb-Zn deposit, Jiangyong (JY) Pb-Zn-Ag deposit, and Yulong (YL) Mo deposit. The fields of primary magmatic and metamorphic waters and the meteoric water line are from Taylor (1997). SMOW = standard mean ocean water. The data sources of H-O isotopic compositions of ore-forming fluids of the Middle-Late Jurassic Cu-Pb-Zn (CDNR) and W (WDNR) deposits in the Nanling Range are listed in Appendix 7-7.

  et al., 2015), indicating that the lead for sulfide mineralization in the Tongshanling polymetallic ore district was derived from the Tongshanling granodioritic intrusion. The sulfide minerals from the Tongshanling ore district show Pb isotopic compositions with upper crust affinities (Fig.7-14a and b). Based on detailed geochronological, geochemical, petrographic, and mineralogical studies,Huang et al. (2017a) and[START_REF] Huang | Reworked restite enclave: Petrographic and mineralogical constraints from the Tongshanling intrusion, Nanling Range, South China[END_REF] demonstrated that the Tongshanling granodiorite was originated from partial melting of the mafic amphibolitic lower crust. Thus, the lead for the metallogenesis in the Tongshanling ore district was in all probability extracted from the upper crust by the ascending granodioritic magma. The positive linear correlations of Pb isotopic compositions made up by the sulfide minerals from the Tongshanling ore district show steep slopes and do not construct isochrons (Fig.7-14c and d). Such Pb isotopic linear trends are probably indicative of a mixing between

  quartz veins in the granodiorite from the Tongshanling Cu-Pb-Zn deposit and Jiangyong Pb-Zn-Ag deposit and the quartz in the skarn of the Yulong Mo deposit show H-O isotopic compositions with evident magmatic water affinities (Fig. 7-15), indicating a magmatic origin of the ore-forming fluids. By contrast, the sulfide-quartz veins in the Tongshanling Cu-Pb-Zn deposit show a slight shift of oxygen isotope towards the meteoric water line (Fig. 7-15), indicating an additional influence of meteoric water during the migration of ore-bearing fluids from the granodiorite to the peripheral wall rocks with the temperature decreasing. However, the effect of meteoric water during mineralization was limited and did not change the magmatic water-dominant nature of the ore-forming fluids. In a word, the ore-forming fluids of the three ore deposits in the Tongshanling ore district are all dominated by magmatic water derived from the Tongshanling granodioritic intrusion.

  credible isotopic information supporting a wall-rock contribution of syndepositional ore-forming materials. They have similar magmatic δ 34 S values to those of the other mineralization types (Fig.7-13). The positive linear correlations made up by the sulfide Pb isotopic compositions of these different mineralization types in the Tongshanling Cu-Pb-Zn deposit (Fig.7-14c and d) which show a consistent variation with those of the Tongshanling granodiorite (Fig.7-14a) also indicate the same origin of ore-forming materials from the Tongshanling intrusion. According to the spatiotemporal evolution sequence from the irregular quartz within the proximal endoskarn (Fig.7-4a) through the barren vein-like quartz in the center of the proximal exoskarn (Fig.7-4b) or cutting the proximal exoskarn

  Figures 7-14-7-18.The S isotopic compositions of the sulfide minerals from the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range predominantly show narrow variations (δ 34 S values are -5.0 -6.5 ‰ and -2.9 -8.9 ‰, respectively) and are of an evident magmatic signature except for the Huangshaping Pb-Zn-W-Mo deposit (Fig.7-16).Ding et al. (2016a) proposed that the sulfur for Pb-Zn mineralization in the Huangshaping deposit has a mixing origin of partial magmatic sulfur and partial sulfur reduced from evaporite. The H-O isotopic compositions of the quartz from the Cu-Pb-Zn and W deposits are similar and show trends of oxygen isotope shift from magmatic water to meteoric water (Fig.7-15). These isotopic features indicate that granitoid magmas have played an important role in providing ore-forming materials and fluids for the Middle-Late Jurassic Cu-Pb-Zn and W mineralization in the Nanling Range. The Pb isotopic compositions of the sulfide minerals from these two types of mineral deposits are similar and show upper crust affinities (Fig.7-14a and b).Huang et al. (2017a) proposed that the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling Range were derived from non-simultaneous partial melting of the mafic amphibolitic basement in the lower crust and the muscovite-rich metasedimentary basement in the upper-middle crust, respectively. Thus, the upper-crust Pb isotopic signatures of the W deposits were probably inherited from the magma source, whereas, those of the

Figure 7 -

 7 Figure 7-16. S isotopic compositions of sulfide minerals from the Middle-Late Jurassic Cu-Pb-Zn and W deposits in the Nanling Range. The data sources are listed in Appendix 7-8.

Figure 7 -

 7 Figure 7-17. Molybdenite Re-Os ages of the Middle-Late Jurassic Cu-Pb-Zn (CDNR) and W (WDNR) deposits in the Nanling Range. The data sources are listed in Appendix 7-9.

Figure 7 -

 7 Figure 7-18. Re contents of molybdenites from the Middle-Late Jurassic Cu-Pb-Zn (CDNR) and W (WDNR) deposits in the Nanling Range. The data sources are the same as Figure 7-17.

Figure 8 - 1 .

 81 Figure 8-1. Geological map of the Weijia W deposit (modified after No. 418 Geological Team of Bureau of Geology and Mineral Exploration and Development of Hunan Province, unpub. report, 2016).

Figure 8 - 2 .

 82 Figure 8-2. Cross section A-B (section line shown in Fig. 8-1) of the Weijia W deposit (modified after No. 1 General Brigade of Hunan Geological and Mining Bureau for Nonferrous Metals, unpub. report, 2014; No. 418 Geological Team of Bureau of Geology and Mineral Exploration and Development of Hunan Province, unpub.

Figure 8 - 3 .

 83 Figure 8-3. Petrographic photographs of the Weijia W deposit at hand-specimen scale. (a) Porphyritic texture of the Weijia granite. (b) Altered granite with a green color. (c and d) Stockwork magnesian skarn veinlets hosted by dolostone. (e) Sulfide ore from the bottom of magnesian skarn. (f) Secondary weathering orebody over the calcic skarn. (g) Reaction front of the calcic skarn. (h) Three generations of garnet, two generations of pyroxene, and K-feldspar-quartz and quartz veinlets in the calcic skarn. (i) The first-generation garnet, late pyroxene, and (K-feldspar)-quartz veins in the calcic skarn. (j) The latest fluorite veinlets cut across all the other minerals, include quartz, in the calcic skarn. Mineral abbreviations: Ab = albite, Bt = biotite, Cal = calcite, Fl = fluorite, Grt = garnet, Kfs = K-feldspar, Px = pyroxene, Py = pyrite, Qz = quartz, Wo = wollastonite.

Figure 8 - 4 .

 84 Figure 8-4. Petrographic photomicrographs (crossed-polarized light) and backscattered electron (BSE) images of the Weijia granite. (a) Porphyritic texture of the Weijia granite (b) Embayment texture of the hexagonal bipyramidal quartz phenocryst. (c) Micrographic texture in K-feldspar. (d) "Pearlitic border" texture of the K-feldspar phenocryst. (e) Bleached biotite phenocryst. (f) Interstitial white mica in the matrix. (g) Bubble-like aggregate of white mica and fluorite. (h) Intergrowth of zircon, thorite, and xenotime. (i) Intergrowth of monazite and xenotime. Mineral abbreviations: Ab = albite, Bt = biotite, Fl = fluorite, Kfs = K-feldspar, Mnz = monazite, Qz = quartz, Thr = thorite, WM = white mica, Xtm = xenotime, Zrn = zircon.

  -7a), the second-generation (K-feldspar)-quartz veins (Fig.8-7b) or veinlets, and the third-generation stockwork quartz veinlets (Fig.8-7c). The K-feldspar-quartz pegmatite veins are several centimeters in thickness and comprise dominantly K-feldspar and quartz that are similar in contents (Fig.8-7a). Two generations of K-feldspar are recognized in the K-feldspar-quartz pegmatite veins (Fig.8-7a). By contrast, the (K-feldspar)-quartz veins or veinlets contain obviously less K-feldspar which is corresponding to the late-generation K-feldspar in the K-feldspar-quartz pegmatite veins (Fig.8-7a and b). The stockwork quartz veinlets have a thickness of several millimeters and are predominantly composed of quartz almost without

Figure 8 - 5 .

 85 Figure 8-5. Petrographic photomicrographs (crossed-polarized light) and BSE images of the altered Weijia granite near the magnesian skarn. (a) Serpentine cuts the granite as veinlet coexisting with abundant dolomite. (b) Serpentine brecciates and replaces the quartz phenocryst. (c) K-felspar phenocryst replaced by phlogopite and dolomite with a residual core. (d) Pseudomorphic replacement of a K-felspar phenocryst by phlogopite. (e) Alteration mineral clot constituted by a core of dolomite and fluorite and a rim of phlogopite. (f) Alteration mineral clot constituted by a core of calcite and a rim of phlogopite. Mineral abbreviations: Cal = calcite, Dol = dolomite, Fl = fluorite, Kfs = K-feldspar, Phl = phlogopite, Qz = quartz, Srp = serpentine.

Figure 8 - 6 .

 86 Figure 8-6. Equal-area lower hemisphere stereonet projection and density distribution of the poles of the stockwork veins at the apex of the Weijia granite.

Figure 8 - 7 .

 87 Figure 8-7. Petrographic photographs of the stockwork veins at the apex of the Weijia granite at hand-specimen scale. Mineral abbreviations are the same as Figure 8-3.

Figure 8 - 8 .

 88 Figure 8-8. Petrographic photomicrographs (crossed-polarized light) of micas in the stockwork veins and their adjacent zone at the apex of the Weijia granite. (a) White mica in the K-feldspar-quartz pegmatite veins. (b) White mica in the (K-feldspar)-quartz veinlets. (c) White mica in the stockwork quartz veinlets. (d) Bleached biotite in the granite with stockwork veins. (e) White mica in the matrix of granite with stockwork veins. (f) White mica in the bleached zone near stockwork veins. Mineral abbreviations are the same as Figure 8-4.

Figure 8 - 9 .

 89 Figure 8-9. Stockwork magnesian skarn veinlets hosted by the dolostone enriched with carbonaceous materials in the Weijia W deposit. Mineral abbreviations are the same as Figure 8-5.

Figure 8 - 10 .

 810 Figure 8-10. Petrographic photomicrographs (crossed-polarized light) and BSE images of the magnesian skarn in the Weijia W deposit. (a) Phlogopite, serpentine, and calcite formed by skarnization of dolostone. (b) Coexistence of phlogopite, serpentine, and fluorite in the magnesian skarn. (c) Outward zonation of magnesian skarn from serpentine with scheelite and fluorite in the center and magnetite in the rim through calcite with a few sellaite to dolomite. (d) Outward zonation of magnesian skarn from phlogopite + calcite through serpentine to phlogopite and then to serpentine + calcite with a few sellaite. (e) Outward zonation of magnesian skarn from phlogopite + fluorite and marialite through serpentine to phlogopite and to serpentine and fluorite with some phlogopite and then to calcite and sellaite. (f) Earlier garnet, phlogopite, and serpentine with a few scheelite cut by later calcite. (g) Outward zonation of magnesian skarn from serpentine and K-feldspar through fluorite + marialite to phlogopite and then to fluorite + serpentine. (h) Scheelite coexisting with garnet, fluorite, and calcite enveloped by serpentine. Mineral abbreviations: Cal = calcite, Dol = dolomite, Fl = fluorite, Grt = garnet, Kfs = K-feldspar, Mag = magnetite, Mar = marialite, Phl = phlogopite, Sch = scheelite, Sel = sellaite, Srp = serpentine.

Figure 8 -

 8 Figure 8-11. Paragenetic sequence of the magnesian skarn in the Weijia W deposit.

Figure 8 -

 8 Figure 8-12. BSE images of the calcic skarn in the Weijia W deposit. (a) The first-generation automorphic garnet with a zonal texture containing some pyroxene inclusions and enclosed and partially replaced by fluorite. (b) The second-generation vein-like garnet including some scheelite and enveloped by fluorite and pyroxene. (c) The third-generation interstitial garnet with a well-developed zonal texture. (d and e) Earlier garnet, pyroxene, wollastonite and fluorite cut by later wollastonite, the earlier wollastonite shows an intergrowth texture with fluorite and the later wollastonite occurs as veinlets. (f) Complex intergrowth texture of skarn minerals, calcite, fluorite, and quartz in the matrix of the calcic skarn. (g) Columnar vesuvianite with a zonal texture. (h) Late K-feldspar and quartz coexisting with fluorite. Mineral abbreviations: Cal = calcite, Fl = fluorite, Grt = garnet, Kfs = K-feldspar, Px = pyroxene, Qz = quartz, Sch = scheelite, Ves = vesuvianite, Wo = wollastonite.

Figure 8 -

 8 Figure 8-13. Paragenetic sequence of the calcic skarn in the Weijia W deposit.

  have a high content of fluorite (mostly > 10 wt.%, Figs. 8-14 and 8-15), however, the wall rocks (limestone) near the calcic skarn orebodies show a distinctly lower fluorite content (mostly < 5 wt.%, Fig.8-15). Weathering and leaching of the calcic skarn resulted in a sharp decrease of fluorite content to 0.4 -0.8 wt.%.

Figure 8 - 14 .

 814 Figure 8-14. Variations of WO 3 and CaF 2 grades in representative drill cores of the magnesian and calcic skarns in the Weijia W deposit. The data are from No. 1 General Brigade of Hunan Geological and Mining Bureau for Nonferrous Metals, unpub. report (2014) and No. 418 Geological Team of Bureau of Geology and Mineral Exploration and Development of Hunan Province, unpub. report (2016).

Figure 8 -

 8 Figure 8-15. Binary plot of CaF 2 and WO 3 grades in representative drill cores of the magnesian and calcic skarns in the Weijia W deposit. The data sources are the same as Figure 8-14.

Figure 8 -

 8 Figure 8-16. Raman spectra of carbonaceous material in carbonate rocks close to the magnesian and calcic skarns in the Weijia W deposit and temperatures calculated by the RSCM thermometry.

  8-18) relative to the fresh granite which may indicate a breakdown of albite during the hydrothermal alteration of granite.The analytical results of whole-rock major and trace element compositions of the altered Weijia granite are listed in Appendix 8-2 and shown in Figures 8-19 and 8-20. For major elements, the altered granite close to the magnesian skarn has distinctly higher CaO (0.69 -3.03 wt.%), MgO (0.11 -0.90 wt.%), FeOTotal (0.27 -1.57 wt.%), MnO (0.02 -0.10 wt.%), and LOI (loss on ignition) (2.33 -4.02 wt.%) contents and lower Na2O contents (0.10 -1.74

Figure 8 -

 8 Figure 8-17. Energy dispersive spectrometry (EDS) elemental mapping of the altered Weijia granite close to the magnesian skarn.

Figure 8 -

 8 Figure 8-18. EDS elemental mapping of the matrix of the altered Weijia granite close to the magnesian skarn.

Figure 8 -

 8 Figure 8-19. Binary plots of some major compositions, trace elements, and calculated parameters of the fresh and

( 105 -

 105 207 ppm) and LREE (59 -150 ppm) contents, similar HREE contents (43 -59 ppm), and slightly higher δEu values (0.04 -0.08) than that close to the calcic skarn (ΣREE: 117 -133 ppm, LREE: 51 -80 ppm, HREE: 51 -66 ppm, δEu: 0.02 -0.04) (Fig. 8-20b).

Figure 8 -

 8 Figure 8-20. Primitive mantle-normalized (Sun and Mcdonough, 1989) spider diagrams and chondrite-normalized (Boynton, 1984) REE patterns of the fresh and altered Weijia granite. The data source of fresh granite is the same as Figure 8-19.

Figure 8 -

 8 Figure 8-22. EDS elemental mapping of bleached biotite in the Weijia granite.

Figure 8 -

 8 Figure 8-23. (Fe Total +Mn+Ti-VI Al) (apfu)-(Mg-Li) (apfu) classification diagram of micas (after Tischendorf et al., 1997) from the Weijia W deposit.

Figure 8 -

 8 Figure 8-24. K 2 O and F contents of micas from the Weijia W deposit. Legends are the same as Figure 8-23.

Figure 8 -

 8 Figure 8-25. Histograms for F contents of different F-bearing minerals in the Weijia W deposit.(To be continued on the next page)

Figure 8 -

 8 Figure 8-26. EDS elemental mapping of white mica in the K-feldspar-quartz pegmatite veins at the apex of the Weijia granite.

Figure 8 -

 8 Figure 8-27. EDS elemental mapping of white mica in the (K-feldspar)-quartz veinlet at the apex of the Weijia granite.

  dolomite was decomposed to release Mg for the formation of serpentine firstly and then phlogopite, calcite and fluorite were formed contemporaneously. The serpentine in the magnesian skarn can be roughly divided into two types according to its occurrences. The first type of serpentine shows a disseminated distribution in the exteriors of the magnesian skarn veinlets and coexists with calcite and fluorite, whereas, the other type of serpentine occurs together with phlogopite and fluorite in the interiors of the magnesian skarn veinlets (Figs. 8-9, 8-10d-e and g, and 8-28). Reasonably, the serpentine in the veinlet interiors was formed later than that in the veinlet exteriors.Representative EMP analytical results and crystallochemical calculations of the serpentine in the magnesian skarn of the Weijia W deposit are listed in Appendix 8-5. The serpentine in the magnesian skarn veinlet exteriors contains SiO2 contents of 39.36 -46.74 wt.%, TiO2 contents of 0.00 -0.13 wt.%, Al2O3 contents of 0.47 -2.92 wt.%, FeO contents of 1.25 -3.56 wt.%, MnO contents of 0.00 -0.45 wt.%, MgO contents of 25.00 -40.61 wt.%, CaO contents of 0.04 -0.80 wt.%, Na2O contents of 0.00 -0.20 wt.%, K2O contents of 0.00 -0.31 wt.%, and F contents of 1.08 -5.88 wt.% with a peak value of 1.5 wt.% (Fig.8-25j). By contrast, the serpentine in the magnesian skarn veinlet interiors has distinctly lower SiO2 contents of 33.33 -42.38 wt.%, MgO contents of 20.93 -36.09 wt.%, and F contents of 0.00

Figure 8 -

 8 Figure 8-28. EDS elemental mapping of the magnesian skarn veinlets in the Weijia W deposit.(To be continued on the next page)

Figure 8 -

 8 Figure 8-29. EDS elemental mapping of phlogopite in the magnesian skarn of the Weijia W deposit.

Figure 8 -

 8 Figure 8-30. Compositions of garnets from the magnesian and calcic skarns in the Weijia W deposit. Mineral abbreviations: Ad = andradite, Al = almandine, Gr = grossularite, Py = pyrope, Sp = spessartine.

Figure 8 -

 8 Figure 8-31. EDS elemental mapping of the first-generation garnet in the calcic skarn of the Weijia W deposit.

Figure 8 -

 8 Figure 8-32. EDS elemental mapping of the second-generation garnet in the calcic skarn of the Weijia W deposit.

Figure 8 -

 8 Figure 8-33. EDS elemental mapping of the third-generation garnet in the calcic skarn of the Weijia W deposit.

  LA-ICP-MS analytical results of the garnet in the magnesian and calcic skarns of the Weijia W deposit are listed in Appendix 8-8 and shown in Figures 8-34 and 8-35. The garnet in the magnesian skarn shows rightward sloping REE patterns with (La/Yb)N values of 5.9 -62.0 and obvious negative Eu anomalies with δEu values of 0.02 -0.35 (Figs. 8-34a and 8-35a-b). It contains ΣREE contents of 10.8 -73.7 ppm (Fig. 8-35b). The first-generation garnet in the calcic skarn also shows rightward sloping REE patterns with (La/Yb)N values of 0.6 -62.8 but almost no Eu anomalies with δEu values of 0.44 -1.79 (Figs. 8-34b and 8-35ab). It contains ΣREE contents of 4.4 -26.8 ppm (Fig. 8-35b). In contrast, the second-generation and third-generation garnets in the calcic skarn show relatively flat REE patterns with obvious LREE depletions and negative Eu anomalies (Fig. 8-34c and d). They have (La/Sm)N values of 0.06 -0.19 and 0.02 -0.08, (La/Yb)N values of 0.07 -0.55 and 0.02 -0.10, ΣREE contents of 5.9 -36.4 ppm and 0.5 -4.2 ppm, and δEu values of 0.11 -0.40 and 0.16 -0.59, respectively (Fig. 8-35a-b).

Figure 8 -

 8 Figure 8-34. Chondrite-normalized (Boynton, 1984) REE patterns of garnets from the magnesian and calcic skarns in the Weijia W deposit.

Figure 8 - 35 .

 835 Figure 8-35. Trace element binary diagrams of garnets from the magnesian and calcic skarns in the Weijia W deposit. Legends are the same as Figure 8-34.

Figure 8 - 36 .

 836 Figure 8-36. Compositions of pyroxenes from the magnesian and calcic skarns in the Weijia W deposit. Mineral abbreviations: Di = diopside, Hd = hedenbergite, Jo = johannsenite.

Figure 8 -

 8 Figure 8-37. Binary plot of FeO (wt.%) vs. MnO (wt.%) contents of wollastonite in the calcic skarn of the Weijia W deposit.

  LA-ICP-MS analytical results of scheelite from the Weijia W deposit are listed in Appendix 8-12 and shown in Figures 8-38 and 8-39. The scheelite in the stockwork quartz veinlets shows flat REE patterns with (La/Yb)N values of 0.3 -2.4 and (La/Sm)N values of 0.3 -1.3 and strong negative Eu anomalies with low δEu values of 0.01 -0.06 (Figs. 8-38a and 8-39a-b). It contains high ΣREE contents of 1255.0 -4891.8 ppm (Fig. 8-39b). Two generations of scheelites with distinctly different REE patterns have been distinguished in the magnesian skarn (Fig. 8-38b and c). The early-generation scheelite in the magnesian skarn shows flat to slightly rightward sloping REE patterns with (La/Yb)N values of 0.1 -17.0 and (La/Sm)N values of 0.2 -2.2 and strong negative Eu anomalies with low

Figure 8 -

 8 Figure 8-38. Chondrite-normalized (Boynton, 1984) REE patterns of scheelites from the stockwork quartz veinlets of granite and the magnesian and calcic skarns in the Weijia W deposit.

Figure 8 -

 8 Figure 8-39. Trace element binary diagrams of scheelites from the stockwork quartz veinlets of granite and the magnesian and calcic skarns in the Weijia W deposit. Legends are the same as Figure 8-38.

  . The fresh biotite in the granite shows obviously lower IV (F) numbers than the bleached biotite (Fig.8-40a-c), however, they have similar IV (F/Cl) numbers (Fig.8-41a-c). Except for the core parts of the white micas in the K-feldspar-quartz pegmatite veins and (K-feldspar)-quartz veins or veinlets and some white micas in the matrix of granite, which were formed with high fluorine activities, all the other white micas indicate relatively low fluorine activities (Fig.8-40d-l). The phlogopite in the magnesian skarn has similar IV (F) numbers with the bleached biotite (Fig.8-40m) and distinctly higher IV (F/Cl) numbers than the fresh and bleached biotite (Fig.8-41d). In the IV (F) vs. IV (F/Cl) diagram (Fig.8-42), the fresh biotite in the granite plots in the field of porphyry Mo deposits, indicating an extremely high fluorine activity, whereas, the bleached biotite and phlogopite with distinctly higher IV (F) numbers indicate lower fluorine activities.[START_REF] Aksyuk | Estimation of fluorine concentrations in fluids of mineralized skarn systems[END_REF] proposed new biotite and phlogopite fluorimeters to estimate the fluorine concentrations in fluids associated with different skarn deposits, granitoids, pegmatites, and marble. Using the biotite fluorimeter, the HF concentrations calculated by the fresh biotite in the granite without stockwork veins are 10 -1.46 -10 -0.71 mole/dm 3 with a peak value of 10 -1.00 mole/dm 3 . The temperatures (569 -659 °C with a peak value of 635 °C ) used in the biotite fluorimeter are calculated by the Ti-in-biotite geothermometer according toHenry et al.

Figure 8 - 40 .

 840 Figure 8-40. Histograms for F intercept value [IV (F)] of micas in the Weijia W deposit.

Figure 8 -

 8 Figure 8-40. (Continued).

Figure 8 - 41 .

 841 Figure 8-41. Histograms for F/Cl intercept value [IV (F/Cl)] of biotite and phlogopite in the Weijia W deposit.

Figure 8 -

 8 Figure 8-42. F intercept value [IV (F)] vs. F/Cl intercept value [IV (F/Cl)] diagram (after Munoz, 1984) for biotite and phlogopite in the Weijia W deposit. IV (F) and IV (F/Cl) are quantitative parameters for F enrichment degree defined by Munoz (1984), both higher values indicate a lower F enrichment degree. Legends are the same as Figure 8-23.

  As the time flying away, the years shuttling again. With memory of the past and looking forward to the future, I am finally walking to the end of my career as a student. Since I firstly came to Nanjing at the beginning of September 2009, I have lived and studied here for nine years. Nanjing has become my second home town. During my five-year postgraduate period from September 2013 to December 2018, I was fortunate to have chances to study abroad in Orléans, France from February 2015 to July 2015 as a master student supported by an international student exchange program of Université d'Orléans and from February 2016 to February 2018 as a co-supervised Ph.D. student supported by the Sino-French Cai Yuanpei Program of China Scholarship Council. Here, at the end of the thesis, I would like to express my sincere gratitude to a lot of teachers, students, friends, technicians, and administration staff in NJU and ISTO and also many other persons who helped me a lot during my postgraduate study. Without their caring and help, I cannot finish this Ph.D. thesis. First of all, special appreciation is expressed to my Chinese supervisor Prof. LU Jian-Jun in NJU. He aroused my interest in Geology and led me into the field of Mineral DepositGeology. All stages of this thesis, include research topic selection, literature search, field observation, sample collection, processing and analysis, data interpretation, and scientific paper and thesis writing and revision, were accomplished under the meticulous guidance of Prof. LU. His rigorous academic attitude, sharp academic thinking, solid academic foundation, and strict academic criterion will benefit me all through my life. I have learned a lot from him, especially in the aspects of granitoid petrogenesis, deposit geology, and ore deposit geochemistry. In addition, Prof. LU is the role model for me also in his philosophy of life and particular personality charm. He encouraged and financially supported me to attend a number of international academic activities, such as the IAGOD2014, EGU2016, and SEG2017 conferences, and thus gave me an opportunity to visit the world famous Jiaodong Au deposits.I also want to gratefully acknowledge the training, help, and support from my French supervisor Prof. Stanislas SIZARET in ISTO. He is not only a teacher but also a friend. In my two and a half years' study and life in Orléans, he was always taking care of me and thus I could adapt myself to the new environment soon. He organized the Sino-French Cai YuanpeiProgram. With Prof. SIZARET, I have learned many new skills and knowledge and conducted some new studies to better understand the ore-forming process, such as electrical prospecting, paleo-fluid flow orientation and velocity estimation, crystal growth experiment, numerical modeling, RSCM thermometry, and permeability experiment. Prof. SIZARET encouraged and financially supported me to participate various academic activities, include the W-Sn international workshop in Nancy (2016), SGA2017 and MPC2017 conferences, and skarn deposits short course in Freiberg (2017). Prof. WANG Ru-Cheng and Prof. MA Dong-Sheng are the other two key members of our research group on granitoids and related mineralization in NJU. They are thanked for their general supervision and discussion on my research works. I have realized the importance of mineralogy in the study of metallogenesis from Prof. WANG and learned geochemistry from Prof. MA. I am also deeply grateful to CNRS Researcher Alain CHAUVET in Géosciences Montpellier and Associate Prof. Luc BARBANSON in ISTO. Working with Dr. CHAUVET in the field, I was trained by detailed field observation, geological sketching, and structural analysis. He helped me accomplish EBSD mapping in Géosciences Montpellier. Working with Dr. BARBANSON, I got new knowledge and skills on ore mineralogy and texture, paragenesis, and chemical exchange during metasomatic alteration. Special gratitude is expressed to Prof. CHEN Yan in ISTO and his wife Mrs. CHEN Li-Li. Their caring, enthusiasm, and hospitality made me feel at home in Orléans. Prof. CHEN helped me a lot in my two and a half years' study and life abroad and was always caring about the progress of my research works. I have learned geophysical knowledge from Prof. CHEN, include electricity, magnetism, seismology, and gravity. The numerous times of discussion with him on the topic of granitic magmatism and related mineralization in South China greatly benefited me for my research. Prof. CHEN provided me precious opportunities to participate the field excursions in the French Massif Central and the Western Alps. I am grateful to Prof. ZHOU Mei-Fu at The University of Hong Kong, Prof. SUN Xiao-Ming at Sun Yat-Sen University, and the other three anonymous reviewers for their valuable comments. The members of the examination board of my Ph.D. thesis defense, including Prof. JIN Zhen-Min at China University of Geosciences, Wuhan, Prof. WANG Ru-Cheng, Prof. ZHOU Mei-Fu, Prof. NI Pei at Nanjing University, CAS Researcher XIONG Xiao-Lin at Guangzhou Institute of Geochemistry, Prof. CHEN Yan, CNRS Researcher Alain CHAUVET, and Prof. Stanislas SIZARET, are sincerely thanked for their attendance and constructive suggestions. Academicians of Chinese Academy of Sciences Prof. CHEN Jun and Prof. WANG De-Zi are thanked for their recommendation letters for me to apply the Sino-French Cai Yuanpei Program. Prof. WANG Bo, Associate Prof. XIE Lei, CNRS Researcher Julien MERCADIER, and Ph.D. students ZHU Ze-Ying and Hélène LEGROS are thanked for their collaboration in executing the Sino-French Cai Yuanpei Program. The following teachers who enlightened my academic thinking are also thanked. They are Prof. HU Wen-Xuan, Prof. SHU Liang-Shu, Prof. XU Xi-Sheng, Prof. QIU Jian-Sheng, Prof. NI Pei, Prof. LING Hong-Fei, Prof. JIANG Yao-Hui, Prof. LU Hua-Yu, Prof. Michel FAURE, Prof. Bruno SCAILLET, Prof. Eric MARCOUX, Prof. Michel PICHAVANT, and Prof. Nicole LE BRETON. XING Gen-Sheng and ZHOU Pu-Cai at the Tongshanling Cu-Pb-Zn mine, OU Yue-Ming and CHANG Jia-Liang at the Jiangyong Pb-Zn-Ag mine, ZHU Xian and HE Li-Bin from the No. 418 Geological Team of Bureau of Geology and Mineral Exploration and Development of Hunan Province, and HE Zhong-Yuan from the No. 1 General Brigade of Hunan Geological and Mining Bureau for Nonferrous Metals are sincerely thanked for their kindly help and guidance during the fieldwork. I would like to express my appreciation to the following teachers, students, and technicians for their technical assistance with sample processing and analysis. They are Sylvain JANIEC for sample polishing, thin section making, and SEM analysis; Gabriel BADIN and ZHANG Guang-Hui for sample polishing and thin section making; Patricia BENOIST for thin section carbon coating and SEM analysis; WU Bing for LA-ICP-MS zircon U-Pb dating; YANG Tao and BIAN Xiao-Peng for LA-MC-ICP-MS zircon Hf isotopic analysis; LIU Qian for whole-rock trace element analysis; PU Wei for whole-rock Sr-Nd isotopic analysis; Ida DI CARLO for SEM, EMP, and RSCM analyses; LI Juan, ZHAO Xu, and ZHANG Rui for SEM analysis; ZHANG Wen-Lan, WU Bin, CHEN Wen-Di, YU Quan, XIANG Lu, and Saskia ERDMANN for EMP analysis; GAO Jian-Feng and LI Liang for LA-ICP-MS mineral trace element analysis and titanite U-Pb dating; HU Huan, ZHANG Rong-Qing, TIAN En-Nong, and SHAO Chun-Jing for the attempt of LA-ICP-MS calcite U-Pb dating; Thomas POITRENAUD, Hugues RAIMBOURG, and Romain AUGIER for RSCM analysis; Fabrice BAROU for EBSD mapping; Rémi CHAMPALLIER and Gaëtan LAUNAY for permeability experiment; DING Jun-Ying, LI Wen-Sheng, and LIU Zheng for fluid inclusion analysis. WU Xue-Min and WANG Chun-Qiao at the Education Office of the Embassy of the People's Republic of China in the French Republic are thanked for their help with the applications for the field trip in China during October 2016 and the SGA2017 and SEG2017 conferences. LU Xian-Cai, TANG Xiao-Qian, ZHANG Xiao-Qin, Marie-Noëlle PAILHÈS, Dominique FRERE, and Amélie SCHNEUWLY are thanked for their administrative management. ZHU Ye, Virginie LANCELOT, and Olivier GAUDEFROY are thanked for their help with financial reimbursement. I am also grateful to the other Ph.D. and master students of Prof. LU. They are ZHANG Rong-Qing, DING Teng, XIE Yin-Cai, ZHAO Zeng-Xia, ZHANG Shi-Tao, GAO Shou-Ye, ZHAO Xu, ZHANG Xue-Ai, ZHANG Qiang, LI Xiao-Yu, CHEN Guang-Hong, and ZHOU Wei-Fa. They greatly helped me with field works, sample collection, processing, and analysis, and some other daily works. We have similar research topics and frequently discussed with each other. Many new ideas in my research were derived from such general discussions. During my two and a half years' study and life abroad, a number of Chinese students and friends in Orléans provided me their enthusiastic help and precious academic thinking. They are LIU Hong-Sheng, HUANG Fang-Fang, YAN Chao-Lei, XUE Zhen-Hua, CHEN Jin-Yu, XIANG Lu, ZHU Xin, WEI Wei, XIA Wen-Jing, LU Yun-Qiao, FANG Ting, LI Shuai, HAN Si-Yu, REN Yan-Gang, WANG Ren-Lei, WEN Liang, YAN Rui, XU Chen, SUN Wen-Yu, LI Qian, ZHANG Feng-Feng, and CAI Min. The French Ph.D. students Hugo BOURQUE, Gaëtan LAUNAY, Thomas POITRENAUD, and Florent CHEVAL-GARABEDIAN are also sincerely thanked for their daily academic discussions with me. I want to thank my roommates in the office 433 of the Zhu Gongshan Building in NJU. They are WAN Ye, ZHANG Yang, CHEN Wen-Di, YU Quan, ZHU Shu-Qi, XIE Si-Wen, LIU Ding-Ding, BAI Li-Juan, LI Ming-Min, ZHAO Xu, XIANG Lu, ZHANG Yue-Xia, REN Qing-Qing, WANG Xiao-Yu, ZHU Qiang, LIU Chen, YANG Zhao-Yu, and QU Yang. I also deeply appreciate LI Lin and HAN Zhong who were my dormitory roommates during the master and doctoral stages, respectively. Finally, I would like to particularly thank my family. It is impossible for me to finish my doctoral study and Ph.D. thesis without the caring, help, and support from my parents and sister and her husband. This Ph.D. thesis is dedicated to my family. This Ph.D. thesis was financially supported by the National Natural Science Foundation of China (Grant No. 41273053, 41230315), the National Key Basic Research Program of China (Grant No. 2012CB416702, 2012CB416705), the China Geological Survey Program (Grant No. 1212011085407, 12120113067300), the French Labex Voltaire Project (Grant No. ANR-10-LABX-100-01), and the Sino-French Cai Yuanpei Program of China Scholarship Council. Xu-Dong HUANG November 14, 2018, Nanjing Munoz, J.L., 1984. F-OH and Cl-OH exchange in micas with applications to hydrothermal ore deposits. Reviews in Mineralogy 13, 469-493.

Full

  width at half maximum of the graphite band. d R1 = (D1 + D4) / (D1 + D2 + D3 + D4 + G) area ratio and D1 / G height ratio for samples with temperatures of 200 -320 °C and 330 -650 °C, respectively. e R2 = (D1 + D4) / (D2 + D3 + G) and D1 / (G + D1 + D2) area ratios for samples with temperatures of 200 -320 °C and 330 -650 °C, respectively. f T (°C) = 1250 × R1-469.75[START_REF] Lahfid | Evolution of the Raman spectrum of carbonaceous material in low-grade metasediments of the Glarus Alps (Switzerland)[END_REF] and -445 × R2

Table 1 - 1 .

 11 List of completed workload during my Ph.D. study

	Subject	Content	Quantity unit	Persons and/or organizations attending/completing this work
	Field	➢ 2012.10.12 -2012.10.21	10	days	Cheng, C.Z., Huang, X.D.,
	observation	Tongshanling Cu-Mo-Pb-Zn-Ag			Liu, Z., etc.
		ore district and Weijia W deposit
		➢ 2013.04.27	1	day	Lu, J.J., Wang, L.J., Huang,
		Magnetite-apatite deposits			X.D., etc.
		in the Ning-Wu Basin
		➢ 2013.06.04 -2013.06.05	2	days	Lu, J.J., Wang, L.J., Huang,
		Magnetite-apatite deposits			X.D., etc.
		in the Ning-Wu Basin
		➢ 2013.07.13 -2013.08.01	20	days	Lu, J.J., Ma, D.S., Ding, T.,
		Tongshanling Cu-Pb-Zn deposit,			Huang, X.D., Sun, Z.Y., etc.
		Yulong Mo deposit, Weijia W deposit,
		Baoshan Pb-Zn deposit, and
		Huangshaping Pb-Zn-W-Mo deposit
		➢ 2013.11.17 -2013.11.25	9	days	Huang, X.D., Sun, Z.Y., etc.
		Weijia granite,
		Jiangyong Pb-Zn-Ag deposit, and
		Tongshanling Cu-Pb-Zn deposit
		➢ 2014.08.01 -2014.08.08	8	days	Huang, X.D., Zhao, X., etc.
		Tongshanling granodiorite, Yulong Mo
		deposit, Jiangyong Pb-Zn-Ag deposit, and
		Weijia W deposit
		➢ 2014.08.23 -2014.08.24	2	days	Meinert, L.D., Lentz, D.R.,
		Beiya Au deposit and			Huang, X.D., Yao, C.Y., etc.
		Jinding Pb-Zn deposit
		➢ 2014.09.28 -2014.10.06 Weijia W deposit, Tongshanling Cu-Pb-Zn deposit, and Jiuyishan, Jianfengling, and Huashan-Guposhan granites Chen, Y.➢ 2014.12.08 -2014.12.18 9 days 11 days Huang, X.D., Tuo, X.S., etc.
		Tongshanling Cu-Pb-Zn deposit
		➢ 2015.09.08 -2015.09.14	7	days	Liu, H.S., Huang, X.D., etc.
		Jurassic granites in Fujian Province
		➢ 2015.09.27 -2015.10.15	19	days	Lu, J.J., Chauvet, A., Sizaret, S.,
		Regional geology of the			Barbanson, L., Guo, C.L.,
		Tongshanling-Weijia area,			Huang, X.D., Zhang, Q., Zhao,
		Tongshanling Cu-Pb-Zn deposit,			X., Xiang, L., Li, X.Y., etc.
		and Muguayuan W deposit
		➢ 2016.05.24 -2016.05.29	6	days	Chen, Y., Faure, M., Wang,
		Granites and associated			R.C., Li, X.H., Xu, X.S., Yang,
		Mineralization in the			J.H., Chauvet, A., Lin, W., Qiu,
		French Massif Central			J.S., Sizaret, S., Li, Q.L., Xie,
					L., Liu, X.C., Liu, H.S., Xue,

➢ 2014.01.25 -2014.01.26 Zhuxi W deposit 2 days Wang, R.C., Lu, J.J., Lu, X.C., Shu, L.S., Chen, G.H., Huang, X.D., Yu, Q., etc. , Faure, M., Scaillet, B., Lu, J.J., Sizaret, S., Wang, B., Guo, C.L., Liu, H.S., Huang, F.F., Huang, X.D., Zhao, X., Zhu, X., etc. Z.H., Huang, F.F., Zhu, Z.Y., Huang, X.D., etc.

Table 1

 1

	-1. (Continued)
	Subject	Content	Quantity unit	Persons and/or organizations attending/completing this work
		➢ 2016.09.13 -2016.09.16	4	days	Fan, H.R., Fontboté, L., Rhys,
		Jiaodong Au deposits			D., Liu, X., Qiu, K.F., Huang,
					X.D., etc.
		➢ 2016.10.12 -2016.10.21	10	days	Chauvet, A., Barbanson, L.,
		Regional geology of the			Huang, X.D., Chen, G.H., etc.
		Tongshanling-Weijia area,
		Tongshanling Cu-Pb-Zn deposit,
		and Weijia W deposit
		• Total	120	days
	Sample	➢ From surface outcrops	120	pieces Huang, X.D., etc.
	collection	➢ From underground galleries	246	pieces Huang, X.D., etc.
		➢ From drill cores	227	pieces Huang, X.D., etc.
		➢ From ore plots	147	pieces Huang, X.D., etc.
		• Total	740	pieces
	Sample	Mineral separation
	processing	➢ Zircon	7	pieces Langfang Geoservices Co. Ltd.
		➢ Sulfide minerals	116	pieces Huang, X.D. and Cheng, C.Z.
		➢ Scheelite	30	pieces Langfang Geoservices Co. Ltd.
		➢ Quartz	37	pieces Huang, X.D. and Cheng, C.Z.
		• Total	190	pieces
		Polished epoxy resin discs holding zircon	4	pieces Beijing GeoAnalysis Co. Ltd.
		Polished sections	65	pieces Langfang Geoservices Co. Ltd.,
					NJU, and ISTO
		Thin sections
		➢ Covered thin sections	316	pieces Langfang Geoservices Co. Ltd.
					and NJU
		➢ Uncovered thin sections	476	pieces Langfang Geoservices Co. Ltd.,
					ISTO, and NJU
		➢ Thin sections for fluid inclusion study	77	pieces Langfang Geoservices Co. Ltd.
					and ISTO
		• Total	869	pieces
		Whole-rock powder	54	pieces Langfang Geoservices Co. Ltd.
					and NJU
		Sample preparation for	8	pieces Huang, X.D. and Sizaret, S.
		permeability experiment			at ISTO
	Isotopic	LA-ICP-MS Zircon U-Pb dating	4	pieces	Huang, X.D. at LAMD, NJU
	dating		114	points
		Molybdenite Re-Os dating	13	pieces National Research Center of
					Geoanalysis, CAGS, Beijing
		LA-ICP-MS Titanite U-Pb dating	1	piece	Huang, X.D. at Nanjing
			21	points	FocuMS Technology Co. Ltd.
	Petrographic	By optical microscope	803	pieces Huang, X.D. at LAMD, NJU
	observation				and ISTO
		By SEM (BSE and CL images)	80	pieces	Huang, X.D. at LAMD, NJU
			23	days	and ISTO and Beijing
					GeoAnalysis Co. Ltd.

(To be continued on the next page)

Table 1

 1

	-1. (Continued)
	Subject	Content	Quantity unit	Persons and/or organizations attending/completing this work
	Mineral CPO	Calcite EBSD mapping	8	pieces Barou, F., Huang, X.D., and
	determination				Chauvet, A. at Géosciences
					Montpellier
	Composition	Whole-rock composition
	analysis	➢ Whole-rock major elements	54	pieces Analysis Center of No. 230
					Research Institute of the China
					National Nuclear Corporation,
					Changsha
		➢ Whole-rock trace elements	54	pieces Huang, X.D. and Liu, Q.
					at LAMD, NJU
		➢ Whole-rock Sr-Nd isotopes	17	pieces Huang, X.D. at LAMD, NJU
		In-situ mineral composition
		➢ Point and line analyses and	80	pieces	Huang, X.D. at LAMD, NJU
		elemental mapping by SEM	23	days	and ISTO
		➢ Major elements by EMP	5856	points	Huang, X.D. at LAMD, NJU
					and ISTO
		➢ Trace elements by LA-ICP-MS	411	points	Huang, X.D. at Nanjing
					FocuMS Technology Co. Ltd.
		➢ Zircon Hf isotope by LA-ICP-MS	4	pieces	Huang, X.D. at LAMD, NJU
			83	points
		Mineral and fluid isotopic composition
		➢ S isotope of sulfide minerals	112	pieces Ministry of Education Key
					Laboratory of Nuclear
					Resources and Environment,
					East China University of
					Technology
		➢ Pb isotope of sulfide minerals	41	pieces Analytical Laboratory of the
					Beijing Research Institute of
					Uranium Geology
		➢ H-O isotopes of quartz	37	pieces Analytical Laboratory of the
					Beijing Research Institute of
					Uranium Geology and
					LAMD, NJU
	Temperature	RSCM thermometry	47	pieces Huang, X.D. at BRGM
	measurement	Fluid inclusion thermometry	11	pieces Huang, X.D. at LAMD, NJU
	Experimental	Crystal growth experiment	20	rounds Huang, X.D. and Sizaret, S.
	study				at Polytech Orléans
		Permeability experiment	6	rounds Huang, X.D., Sizaret, S., and
					Champallier, R. at ISTO
	Numerical	Crystal growth and magma	2	cases	Huang, X.D. and Sizaret, S.
	modeling	emplacement-induced fluid flow			at ISTO

Notes: BRGM: Bureau de Recherches Géologiques et Minières, France; BSE: backscattered electron; CAGS: Chinese Academy of Geological Sciences; CL: cathodoluminescence; CPO: crystallographic preferred orientation; EBSD: electron backscatter diffraction; EMP: electron microprobe; ISTO: Institut des Sciences de la Terre d'Orléans, France; LA-ICP-MS: laser ablation-inductively coupled plasma-mass spectrometry; LAMD: State Key Laboratory for Mineral Deposits Research, China; NJU: Nanjing University, China; RSCM: Raman spectroscopy of carbonaceous material; SEM: scanning electron microscope.

  Twocrystallization ages of 435.3 ± 2.7 Ma and 436.2 ± 3.1 Ma and a crystallization age of 426.5 ± 2.5 Ma for the Penggongmiao medium to coarse grained biotite granite and the magmatic scheelite-bearing aplite veins therein, respectively, were obtained byZhang et al. (2011a)

	through LA-ICP-MS zircon U-Pb dating. However, Yuan et al. (2018) recently pointed out
	that the Zhangjialong W deposit was formed during Late Jurassic with a molybdenite Re-Os
	age of 160.2 ± 2.2 Ma and a muscovite 40Ar/39Ar age of 153.5 ± 1.0 Ma. The Xigang Nb-Ta
	deposit in eastern Jiangxi Province was recently confirmed as an Early Paleozoic (422 ± 3

  All of these different types of ore-bearing granitoids were formed from 165 Ma to 150 Ma. Dark microgranular enclaves and amphibole are commonly observed in the Cu-Pb-Zn-bearing granodioritic rocks and the

	Huashan-Guposhan and Qitianling A2-type Sn-bearing biotite granites but are absent in the
	other Sn-bearing granites and also the W-bearing and Nb-Ta-bearing granites. The Fe-Ti
	oxide minerals of the Cu-Pb-Zn-bearing granodiorites and the Huashan-Guposhan and
	Qitianling Sn-bearing granites are dominated by magnetite, whereas, the other ore-bearing
	granites mainly contain ilmenite. These different types of ore-bearing granitoids have various
	associations of accessory minerals. They also have different features in mineralization types.
	The Cu-Pb-Zn mineralization mainly consists of skarn, carbonate replacement, and
	sulfide-quartz vein. Skarn, greisen, and quartz vein are the dominant types for W and Sn
	mineralization. Besides, chloritized granite is also important for Sn mineralization. The Nb-Ta
	mineralization mainly comprises albite granite, greisen, and pegmatite.

. It holds the largest W production of South China and also of the whole world. Since the first question of "Where is Tongshanling, and Dabaoshan granodiorites (Fig.

1-1

).

Table 2 -1. Main

 2 features of the Middle-Late Jurassic ore-bearing granitoids in the Nanling Range (summarized

	from Chen et al., 2008, 2013; Huang et al., 2017a; Wang et al., 2017c)
	Ore-bearing granitoid Cu-Pb-Zn	Sn	W	Nb-Ta
	Tectonic setting		Intraplate extension
	Rock type	I-type granodioritic	A(A 2 )-type biotite	S-type two-mica,	Highly fractionated
		rocks	granites and S-type	muscovite, and	albite and
			two-mica, muscovite,	biotite granites	muscovite granites
			and biotite granites
	Age		165 -150 Ma
	Dark enclaves	Observed	Observed or not	Not observed	Not observed
	Amphibole	Observed	Observed or not	Not observed	Not observed
	Fe-Ti oxide minerals Mainly magnetite	Mainly Magnetite or	Mainly ilmenite	Mainly ilmenite
			mainly ilmenite
	Accessory minerals	Titanite, allanite,	Titanite, allanite,	Monazite, xenotime,	Columbite-tantalite,
		apatite, sulfide	apatite, cassiterite or	apatite, wolframite,	monazite, xenotime,
		minerals	monazite, xenotime,	scheelite	ferberite
			apatite, cassiterite
	Mineralization type	Skarn, carbonate	Skarn, greisen,	Skarn, greisen,	Albite granite,
		replacement,	quartz vein,	quartz vein	greisen, pegmatite
		sulfide-quartz vein	chloritized granite

. Results 4.4.1. Zircon U-Pb age

	the Analysis Center of No. 230 Research Institute of the China National Nuclear Corporation,
	Changsha. The analytical precision for all elements was better than 5 %. The detailed
	procedures are described in the China National Standards GB/T 14506.3-2010 -GB/T
	14506.14-2010.
	4.4Zircons of granitoids from the Tongshanling-Weijia area are mainly colorless and
	transparent through to light brown and subtransparent, and euhedral to subhedral prismatic
	grains with pyramidal termination, and exhibit well-developed growth zoning in CL images
	(Fig. 4-3). The analytical results of zircon U-Pb isotopes are listed in Appendix 4-1. Magmatic
	zircons from the Tongshanling granodiorite porphyry have a weighted mean 206 Pb/ 238 U age of
	162.5 ± 1.0 Ma (Fig. 4-4a), representing its crystallization age. Magmatic zircons in the
	dioritic dark enclaves generally consist of cores with a bright CL image and rims with a dark
	CL image. The rims have higher Th and U contents than the cores and both have the same
	206 Pb/ 238 U ages (Fig. 4-3b), giving a weighted mean value of 160.6 ± 1.4 Ma (Fig. 4-4b). The
	weighted mean 206 Pb/ 238 U age of the Tongshanling granite porphyry is 158.8 ± 1.2 Ma (Fig.
	4-4c), which is slightly younger than the granodiorite porphyry. There are two kinds of
	zircons in the Weijia granite porphyry. One has a bright CL image (Fig. 4-3d) and good
	transparency without cracks, while the other has a dark CL image (Fig. 4-3d) and is
	subtransparent with cracks. Metamictization happened in zircons with a dark CL image.
	Therefore, in this study zircons with a bright CL image were selected for dating. Their
	206 Pb/ 238 U ages vary from 157 Ma to 160 Ma and yield a weighted mean value of 158.3 ± 2.2

Table 4 -1. Main

 4 geochemical features of granitoids from the Tongshanling-Weijia area

	Geochemical indexes	Tongshanling granodiorite porphyry	Dioritic dark enclaves	Tongshanling granite porphyry	Weijia granite porphyry
	SiO 2 (wt.%)	63.71 -70.09	53.38 -59.35	71.35 -74.34	73.86 -76.73
	CaO/(Na 2 O+K 2 O)	0.32 -0.60	0.70 -1.22	0.09 -0.31	0.01 -0.09
	Mg/(Mg+Fe)	0.42 -0.48	0.42 -0.47	0.31 -0.41	0.04 -0.32
	ASI a	0.91 -1.03	0.83 -0.94	0.97 -1.17	1.00 -1.18
	DI b	68 -80	42 -58	83 -90	94 -97
	Rb/Sr	0.5 -1.3	0.5 -0.9	0.5 -1.2	10.3 -21.6
	Zr/Hf	30.6 -34.5	28.8 -32.9	27.4 -32.8	14.0 -16.9
	δEu c	0.64 -0.97	0.37 -0.73	0.73 -0.83	0.03 -0.05
	ΣREE (ppm)	82 -111	107 -202	124 -158	55 -100
	LREE/HREE	6.0 -7.7	2.9 -7.3	13.4 -15.9	1.8 -3.4
	HFSE d (ppm)	184 -241	219 -275	228 -261	142 -179
	T Zr e (°C)	747 -770	702 -764	763 -784	718 -741
	( 87 Sr/ 86 Sr) i	0.708955 -0.710682 0.710023 -0.711200 0.707011 -0.708124
	ε Nd (t) value	-6.9 --4.2	-6.7 --5.2	-2.8 --2.1	-5.4 --4.5
	T C DM (Nd) (Ga)	1.29 -1.51	1.38 -1.49	1.12 -1.18	1.32 -1.39
	Zircon ε Hf (t) value	-11.6 --6.3	-9.3 --6.9	-16.1 --0.2	-4.6 --1.7
	Zircon T C DM (Hf) (Ga) 1.60 -1.94	1.64 -1.79	1.22 -2.22	1.31 -1.50
	Notes: a ASI: aluminum saturation index, n(Al 2 O 3 )/n(CaO+Na 2 O+K 2 O). b DI: differentiation index, the sum of
	CIPW normative minerals Q, Or, Ab, Ne, Lc, and Kp. c δEu = 2Eu N /(Sm N +Gd N ). d HFSE: high field strength
	elements (Zr+Nb+Ce+Y). e T Zr : zircon saturation temperature, calculated by the method of

. Discussion 4.5.1. Timing of granitoids

	2, and Nd model ages of 1.29 -1.51 Ga and 1.38 -1.49 Ga, respectively. The
	Tongshanling granite porphyry has lower ( 87 Sr/ 86 Sr)i ratios (0.707011 -0.708124), higher εNd
	(t) values (-2.8 --2.1) (Fig. 4-8a), and younger Nd model ages (1.12 -1.18 Ga). It is difficult
	to thoroughly extract Rb from the samples of the Weijia granite porphyry which have high
	Rb/Sr ratios. Therefore, its Sr isotopic composition has not been determined. The εNd (t)
	values of the Weijia granite porphyry are -5.4 --4.5 and are plotted above the evolution
	region of the Precambrian metasedimentary basement of the Nanling Range (Fig. 4-8b). Its T
	C DM (Nd) values are 1.32 -1.39 Ga.
	4.5Wang et al. (2002b) reported a U-Pb age of 178.9 ± 1.7 Ma for the Tongshanling
	granodiorite porphyry by single-grain zircon dating. The SHRIMP zircon U-Pb dating results
	from Wei et al. (2007) and Jiang et al. (2009) are 149 ± 4 Ma and 163.6 ± 2.1 Ma, respectively.
	Zhao et al. (2016b) obtained three LA-ICP-MS zircon U-Pb ages of 160.7 ± 0.5 Ma, 160.5 ±
	0.9 Ma and 159.7 ± 0.8 Ma. Zircon dating of the Tongshanling granodiorite porphyry and its
	dark enclaves in this study gives consistent U-Pb ages of 162.5 ± 1.0 Ma and 160.6 ± 1.4 Ma
	(Fig. 4-4a and b), respectively, which are in accordance with the ages published by Jiang et al.
	(2009) and Zhao et al. (2016b). The zircon U-Pb age of the Weijia granite porphyry obtained
	in this study is 158.3 ± 2.2 Ma (Fig. 4-4d) and is consistent with the result of 157.8 ± 0.9 Ma
	acquired by Zhao et al. (2016a). The Tongshanling granite porphyry has a zircon U-Pb age of
	158.8 ± 1.2 Ma (Fig. 4-4c). From the above discussion, it is concluded that the Tongshanling
	granodiorite porphyry and both the Weijia and Tongshanling granite porphyries were formed
	at 160 -164 Ma and about 158 Ma and 158.8 Ma, respectively, and that the granite
	porphyries are slightly younger than the granodiorite porphyry. The metallogenic ages of the
	Tongshanling Cu-Pb-Zn deposit and Weijia W deposit obtained by Huang and Lu (2014) and

Table 4

 4

	-1 and Fig. 4-9a), and weak Ba, Sr, P, and Ti

Table 4 -

 4 2. Main features of the Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids in the Nanling

	Range
		Cu-Pb-Zn-bearing granitoids a	W-bearing granites b
	Location	Western part of the Nanling Range (South	Eastern part of the Nanling Range (South
		Hunan, North Guangdong)	Hunan, South Jiangxi, North Guangdong)
	Age (Ma)	155.2 -167.0 (peak value: 160.6)	151.1 -161.8 (peak value: 155.5)
	Tectonic setting	Intraplate extension	Intraplate extension
	Rock type	Granodiorites with the signatures of	S-type two-mica, muscovite, and biotite
		I-type granites	granites
	Source	Mainly mafic amphibolitic basement in	Mainly muscovite-rich metasedimentary
		the lower crust	basement in the upper-middle crust
	Dark enclaves	Observed	Not observed
	Amphibole	Observed	Not observed
	Fe-Ti oxide minerals	Mainly magnetite	Mainly ilmenite
	Accessory minerals	Zircon, titanite, allanite, etc.	Zircon, monazite, xenotime, thorite, etc.
	Redox condition	Oxidized	Reduced
	Degree of fractionation Weakly fractionated	Highly fractionated
	ASI	0.8 -1.0	1.0 -1.2
	CaO/(Na 2 O+K 2 O)	0.3 -0.8	<0.2
	Rb/Sr	<2	10 -250
	δEu	0.6 -1.0	<0.15
	ΣREE (ppm)	100 -240	60 -180
	LREE/HREE	5 -13	0.5 -3
	HFSE (ppm)	180 -290	150 -300
	T Zr (°C)	720 -790 (average value: 750)	690 -760 (average value: 735)
	( 87 Sr/ 86 Sr) i	0.708 -0.712	>0.712
	ε Nd (t) value

  intrusion show notably more juvenile isotopic compositions than the Tongshanling granodiorite and its enclaves, such as the Huziyan high-Mg basalt [ca. 150 Ma, ( 87 Sr/ 86 Sr)i: 0.705 -0.706,

	Nd (t): -1.3 -+0.7], Huilongxu lamprophyre [ca. 170 Ma, ( 87 Sr/ 86 Sr)i: 0.704 -0.705,

Nd (t): -1.7 --1.3], and Ninyuan alkaline basalt [ca. 170 Ma, ( 87 Sr/ 86 Sr)i: 0.704 -0.705, Nd (t): +5.4 -+6.1] (Wang

Table 5 -

 5 1. Geothermometry based on mineral chemical compositions of amphibole, plagioclase, and biotite from the Tongshanling granodiorite and its microgranular enclaves The low-Al and high-Si isolated amphibole was excluded for temperature calculation. b The pressure used for those pressure-dependent thermometers was 3 kbar for the II, OI, I, and RCE amphibole, 5 kbar for the MI amphibole, and 8 kbar for the CA and CCI amphibole. c The model liquid used the averaged whole-rock composition of the Tongshanling granodiorite based on the data reported byHuang et al.

	Geothermometer	Temperature a (°C) Tongshanling granodiorite Microgranular enclaves	Reference
	Amphibole	MI: 740 -840; II: 700 -770; OI: 690 -760	I: 700 -750; RCE: 690 -720	Ernst and Liu (1998)
	Amphibole	MI: 828 -931; II: 818 -844; OI: 801 -842	I: 803 -809; RCE: 783 -795	Ridolfi et al. (2010)
	Amphibole b	MI: 751 -807; II: 683 -744; OI: 663 -780	I: 654 -726; RCE: 662 -698	Ridolfi and Renzulli (2012)
	Amphibole-liquid c	MI: 962 -998; II: 976 -984; OI: 971 -989	I: 976 -984; RCE: 969 -974	Molina et al. (2015)
	Amphibole-liquid	MI: 897 -919; II: 903 -908; OI: 893 -910	I: 879 -886; RCE: 871 -887	Equation 4a of Putirka (2016)
	Amphibole-liquid	MI: 598 -616; II: 596 -603; OI: 594 -609	I: 595 -603; RCE: 593 -602	Equation 4b of Putirka (2016)
	Amphibole	MI: 769 -867; II: 771 -792; OI: 758 -789	I: 753 -759; RCE: 739 -751	Equation 5 of Putirka (2016)
	Amphibole	MI: 772 -865; II: 769 -787; OI: 757 -788	I: 753 -760; RCE: 740 -752	Equation 6 of Putirka (2016)
	Amphibole	MI: 764 -858; II: 774 -793; OI: 763 -784	I: 755 -763; RCE: 748 -764	Equation 8 of Putirka (2016)
	Amphibole-liquid	MI: 786 -877; II: 796 -809; OI: 788 -803	I: 784 -788; RCE: 774 -785	Equation 9 of Putirka (2016)
	Amphibole-plagioclase d	MI: 729 -896; II: 710 -782; OI: 698 -764	I: 703 -740; RCE: 682 -728	Blundy and Holland (1990)
	Amphibole-plagioclase (A) MI: 709 -863; II: 700 -801; OI: 682 -789	I: 682 -729; RCE: 679 -737	Holland and Blundy (1994)
	Amphibole-plagioclase (B) MI: 700 -849; II: 676 -775; OI: 661 -770; CA: 819 -847	I: 660 -739; CCI: 764 -848 RCE: 662 -751;	Holland and Blundy (1994)
	Plagioclase-liquid	Core: 1017 -1030; Intermediate: 990 -999; Rim: 956 -972	Core: 1025 -1031; Rim: 960 -973 Intermediate: 994 -995;	Putirka (2005)
	Biotite	680 -726	694 -733	Henry et al. (2005)
	Notes:

a MI: mineral inclusion; II: inner of isolated amphibole; OI: outer of isolated amphibole; CA: core of aggregated amphibole grains; I: isolated amphibole; CCI: core of clot interior amphibole grains; RCE: rim of clot exterior amphibole grains.

(2017a). d For the amphibole-plagioclase thermometers, the II, OI, I, and RCE amphibole, the MI amphibole, and the CA and CCI amphibole were supposed to be in equilibrium with the rim, intermediate, and core plagioclase, respectively.

Table 5 -

 5 2. Main features of the major Middle-Late Jurassic Cu-Pb-Zn-bearing granodiorites in the Nanling

	Range, South China
	Intrusion	Shuikoushan	Baoshan	Tongshanling	Dabaoshan
	Metal association	Pb-Zn-Au-Ag	(Cu, Mo)-Pb-Zn-Ag Cu(Mo)-Pb-Zn-Ag Mo(W)-Cu-Pb-Zn-Fe
	Dark enclaves	Have not been reported	Observed	Observed	Have not been reported
	Lithology	Porphyritic to equigranular biotite granodiorite with a dominant mineralogy of plagioclase + K-feldspar + quartz + biotite ± amphibole
	Accessory minerals	Apatite, zircon, titanite, allanite, rutile, sulfide minerals, and Fe-Ti oxide minerals (mainly magnetite)
	Zircon U-Pb age (Ma) 156.0 ± 1.0,	158.0 ± 2.0,	163.6 ± 2.1,	167.0 ± 2.5,
		158.8 ± 1.8,	156.7 ± 1.4,	160.7 ± 0.5,	162.2 ± 0.7,
		158.3 ± 1.2	157.7 ± 1.1	160.5 ± 0.9,	161.0 ± 0.9,
				159.7 ± 0.8,	160.2 ± 0.9,
				162.5 ± 1.0	166.3 ± 2.0,
					166.2 ± 2.7,
					162.1 ± 1.6
	Metallogenic age (Ma) (Molybdenite Re-Os dating)	157.8 ± 1.4	160 ± 2	161.8 ± 1.7, 160.1 ± 0.8, 162.2 ± 1.6 161 ± 1,	163.9 ± 1.3, 164.8 ± 0.8
	Evolutionary degree	Low	Low	Low	Low
	SiO 2 (wt.%)	59.6 -65.2	62.6 -68.8	63.7 -70.1	64.4 -72.9
	ASI a	0.9 -1.1	0.8 -1.0	0.9 -1.0	1.0 -1.1
	CaO/(Na 2 O+K 2 O)	0.3 -0.8	0.3 -0.9	0.3 -0.7	0.2 -0.8
	Mg/(Mg+Fe)	0.4 -0.6	0.4 -0.6	0.4 -0.5	0.3 -0.7
	Rb/Sr	0.2 -0.4	0.5 -2.9	0.4 -1.3	1.2 -2.1
	Eu b	0.8 -1.0	0.6 -0.8	0.6 -1.0	0.6 -0.8
	LREE/HREE	8.7 -16.1	7.0 -10.6	5.1 -11.3	10.3 -18.0
	ΣREE (ppm)	120 -234	124 -271	82 -189	134 -236
	HFSE c (ppm)	229 -267	198 -282	165 -264	175 -284
	T Zr d (°C)	726 -775	722 -760	738 -772	739 -774
	( 87 Sr/ 86 Sr) i	0.710 -0.711	0.710 -0.712	0.709 -0.711	0.704 -0.714

  -1). It was discovered in 1958 and mined since 1977 and is one of the oldest mines in the Nanling Range. Ancient mineral waste residues were remained on the surface and some pottery bowls of the Jin dynasty (from A.D. 265 to A.D. 420) were found in an ancient adit. The ore district contains about 53,000 t Cu (average 1.23 wt.% Cu), 6,000 t Mo (average 0.30 wt.% Mo), 126,000 t Pb (average 2.58 wt.% Pb), 138,000 t Zn (average 3.95 wt.% Zn), and 780 t Ag (average 144 g/t Ag) (No. 206 Exploring Team of HunanMetallurgical and Exploring Company, unpub. report, 1975; No. 409 Geological Team of Bureau of Geology and Mineral Exploration and Development of HunanProvince, unpub. report, 2008; Institute of Geological Survey of South Hunan, unpub. report, 2012). In addition, there are about 5,520 t Bi (average 0.16 wt.% Bi), 1,900 t Cd (average 0.016 wt.% Cd), 195 t Se (average 0.001 wt.% Se), and 95 t Te (average 0.003 wt.% Te)

within the Cu-Pb-Zn resources. It is constituted by three ore deposits distributed around the Tongshanling granodioritic intrusion, i.e., the Tongshanling Cu-Pb-Zn deposit, Jiangyong Pb-Zn-Ag deposit, and Yulong Mo deposit (Figs. 3-1, 7-1, 7-2, and 7-3). They are dominated by skarn, sulfide-quartz vein, and carbonate replacement mineralization. Although numerous geochronological and geochemical studies have been carried out on the Tongshanling

  and the 207 Pb-corrected206 Pb/ 238 U ages were used to calculate the weighted average age. Wetherill U-Pb concordia plots of garnet and titanite, Tera-Wasserburg U-Pb concordia plots of titanite, Re-Os isochrons of molybdenite, and weighted average age calculations of garnet, molybdenite, and titanite were constructed by the software Isoplot 4.15[START_REF] Ludwig | User's manual for Isoplot 3.75: A geochronology toolkit for Microsoft Excel[END_REF]. Sulfur isotopic compositions of sulfide minerals were analyzed by a Finnigan MAT-253 mass spectrometer coupled to a Flash EA 1112 elemental analyzer at the State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China University of Technology. Lead isotopic ratios were monitored and corrected by the analytical results of the standard NIST NBS 981. The external reproducibilities of Pb isotopic ratios were 0.001 -0.003 for 206 Pb/ 204 Pb and 207 Pb/ 204 Pb, and 0.002 -0.008 for 208 Pb/ 204 Pb at 2-sigma level.Hydrogen-oxygen isotopic compositions of quartz were analyzed using a Finnigan MAT-253 mass spectrometer at the Analytical Laboratory of the Beijing Research Institute of Uranium Geology, China. Water was released from quartz by heating to ca. 600 °C in an induction furnace and then reacted with heated zinc powder at 400 °C to produce H2 for hydrogen isotopic analysis. Quartz grains were ground to powder < 200 mesh and then reacted with BrF5 at 500 -600 °C for 14 h to generate O2. With the catalysis of platinum, the O2 reacted with graphite at 700 °C to produce CO2 for oxygen isotopic analysis. The analytical results of 2 H/ 1 H and 18 O/ 16 O ratios are expressed as the conventional δD and δ 18 O

	values in per mil relative to the Standard Mean Ocean Water (SMOW) with precisions of 1 ‰
	and 0.2 ‰, respectively.

For each sample, 20 -100 g sulfide powder was heated at 1020 °C to extract SO2 gas for S isotopic analysis. The analytical results of 34 S/ 32 S ratios are expressed as the conventional δ 34 S values in per mil relative to the Cañon Diablo Troilite (CDT). The analytical precision was better than 0.2 ‰.

Lead isotopic compositions of sulfide minerals were measured by a GV IsoProbe-T Thermal Ionization Mass Spectrometer (TIMS) at the Analytical Laboratory of the Beijing Research Institute of Uranium Geology, China. The analytical procedure involved dissolution of sulfide powder using HF and HClO4 in crucibles followed by basic anion-exchange resin chromatography to purify Pb.

  Yulong Mo deposit are listed in Appendix 7-2. Two molybdenite samples from the proximal endoskarn, one molybdenite sample from the proximal exoskarn, and two molybdenite samples from the distal skarn of the Tongshanling Cu-Pb-Zn deposit have respective Re contents of 16.28 -89.51 ppm, 24.60 ppm, and 47.97 -98.23 ppm, respective 187 Re contents of 10.23 -56.26 ppm, 15.46 ppm, and 30.15 -61.74 ppm, respective 187 Os contents of 27.84 -152.45 ppb, 41.32 ppb, and 81.02 -168.46 ppb, and respective model ages of 162.4 -163.1 Ma, 160.2 Ma, and 161.1 -163.5 Ma (Appendix 7-2). All these five samples yield a

187 Re-187 Os isochron age of 161.8 ± 1.7 Ma and a consistent weighted average model age of 161.9 ± 1.1 Ma (Fig.

7-11a

).

  Eight molybdenite samples from the skarn of the Yulong Mo deposit have Re,187 Re, and187 Os contents of 37.. Their Re-Os model ages vary from 158.9 Ma to 161.8 Ma and have a weighted average value of 160.1 ± 0.8 Ma (Appendix 7-2 and Fig.7-11b). The 187 Re-187 Os isochron age of these eight molybdenite samples is 160.0 ± 5.8 Ma (Fig.7-11b) which is consistent with the weighted average model age.

  Appendix 7-4. The 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of the sulfide minerals from

the Tongshanling Cu-Pb-Zn deposit vary from 18.643 to

18.785, 15.725 to 15.854, and 38.919

Table 7 -

 7 1. Sulfur isotopic fractionations and calculated temperatures of sulfide mineral pairs from the

	Tongshanling Cu-Pb-Zn deposit and Jiangyong Pb-Zn-Ag deposit
					Δ 34 S CDT (‰) [T °C] a
	Sample No. Level	Py-Sp	Py-Gn	Sp-Po	Sp-Ccp	Sp-Gn	Po-Ccp	Ccp-Gn
	Tongshanling Cu-Pb-Zn deposit
	Proximal endoskarn
	TSL121	00 m						-0.3
	TSL122	00 m						-0.3
	Proximal exoskarn
	TSL98	00 m				-0.6	0.3		0.9 [530]
	TSL123	00 m				-0.5	1.1 [541]		1.6 [329]
	Sulfide-quartz vein
	TSL04-1	60 m				0.7 [190] 1.6 [402]		0.9 [530]
	TSL04-5	60 m				-0.2	1.1 [541]		1.3 [395]
	TSL04-6	60 m				-0.2	1.0 [581]		1.2 [422]
	TSL04-9	60 m				-0.2
	TSL04-12	60 m				-0.9
	TSL04-15	60 m				1.0 [114]
	TSL25-2	90 m				-0.2	1.0 [581]		1.2 [422]
	TSL25-3	90 m				0.0	0.8 [682]		0.8 [578]
	TSL26-1	120 m				0.2 [593] 1.0 [581]		0.8 [578]
	TSL28-1	120 m				-0.3
	TSL28-2	120 m				-0.2	0.8 [682]		1.0 [488]
	TSL28-3	120 m				0.2 [593] 1.2 [507]		1.0 [488]
	TSL29-2	180 m				-0.1	1.2 [507]		1.3 [395]
	Distal skarn
	TSL91	231 m				-0.1	1.3 [476]		1.4 [371]
	TSL93	231 m					1.6 [402]
	TSL145	231 m				-0.5
	Carbonate replacement
	TSL17	60 m					2.8 [237]
	TSL40	231 m					2.8 [237]
	Jiangyong Pb-Zn-Ag deposit
	Skarn
	JY48	240 m			0.4
	Carbonate replacement
	JY59	200 m	-0.7
	JY47	160 m	-1.0	1.5 [556]			2.5 [267]
	JY63	160 m	-0.4	2.1 [427]			2.5 [267]
	JY50	240 m	-0.9	1.9 [463]			2.8 [237]
	JY56	200 m	-0.6	1.8 [483]			2.4 [278]
	JY58	200 m	-0.9	1.3 [617]			2.2 [303]
	JY66	240 m	-0.1	1.9 [463]			2.0 [331]

  to 39.352, respectively. Nine chalcopyrite samples show206 Pb/ 204 Pb,207 Pb/ 204 Pb, and208 Pb/ 204 Pb ratios of 18.703 -18.785, 15.730 -15.854, and 38.931 -39.350, respectively. The 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of nine sphalerite samples are 18.693 -18.752, The 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of the sulfide minerals from the Jiangyong Pb-Zn-Ag deposit range from 18.836 to 18.969, 15.712 to 15.875, and 38.997 to 39.535, respectively. Two pyrrhotite samples have 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of 18.921 -18.932, 15.818 -15.834, and 39.349 -39.408, respectively. The 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of two sphalerite samples are 18.853 -18.969, 15.727 -15.875, and 39.055 -39.535, respectively. Six galena samples show 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of 18.836 -18.880, 15.712 -15.752, and 38.997 -39.143, respectively. The 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of one pyrrhotite sample from the Yulong Mo deposit are 18.772, 15.729, and 39.022, respectively. In the 206 Pb/ 204 Pb vs. 208 Pb/ 204 Pb and 206 Pb/ 204 Pb vs. 207 Pb/ 204 Pb diagrams, the sulfide

	15.747 -15.821, and 38.993 -39.240, respectively. Eleven galena samples have 206 Pb/ 204 Pb,
	207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of 18.643 -18.743, 15.725 -15.834, and 38.919 -39.352,
	respectively. The 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb ratios of one molybdenite sample
	are 18.723, 15.770, and 39.073, respectively.

  Zn deposit are still not well constrained and the two molybdenite Re-Os model ages of the Yulong Mo deposit are not consistent and their corresponding 187 Re-187 Os isochron ages are unavailable or not precise[START_REF] Lu | Rock-forming and ore-forming ages of Tongshanling copper polymetallic ore-field in southern Hunan Province[END_REF] Zhao et al., 2016b).

	Lu et al. (2015)
	obtained a weighted average model age of 161 ± 1 Ma for the molybdenites from the
	sulfide-quartz veins of the Tongshanling Cu-Pb-Zn deposit. The weighted average Re-Os
	model ages of the molybdenites from the skarn ores of the Yulong Mo deposit published by
	Lu et al. (2015) and Zhao et al. (2016b) are 155 ± 3 Ma and 162.2 ± 1.6 Ma, respectively.
	However, the metallogenic ages of the dominant distal and proximal skarns in the
	Tongshanling Cu-Pb-deposit yield a 187 Re-187 Os isochron age of 160.0 ± 5.8 Ma (Fig. 7-11b) with a well consistent
	weighted average model age of 160.1 ± 0.8 Ma (Fig. 7-11b). These ages are consistent with
	the result of 162.2 ± 1.6 Ma published by Zhao et al. (2016b). Thus, the Tongshanling
	Cu-Pb-Zn deposit and Yulong Mo deposit were formed simultaneously with identical
	metallogenic ages of 160 -162 Ma.

In this study, the molybdenites from the proximal endoskarn, proximal exoskarn, and distal skarn of the Tongshanling Cu-Pb-Zn deposit yield consistent Re-Os model ages of 162.4 ± 2.2 -163.1 ± 2.3 Ma, 160.2 ± 2.4 Ma, and 161.1 ± 2.4 -163.5 ± 3.7 Ma (Appendix 7-2), respectively, with an integrated weighted average value of 161.9 ± 1.1 Ma (Fig.

7-11a

).

The 187 Re-187 Os isochron age of these molybdenites is 161.8 ± 1.7 Ma (Fig.

7-11a

) and perfectly coincides with the weighted average model age. These geochronological results are in accordance to the metallogenic age of the sulfide-quartz veins (161 ± 1

Ma, Lu et al., 2015)

. Therefore, it is concluded that the proximal endoskarn, proximal exoskarn, sulfide-quartz veins, and distal skarn are temporally indistinguishable by molybdenite Re-Os dating and there are no obvious time intervals between these different mineralization types in the Tongshanling Cu-Pb-Zn deposit. The molybdenites from the skarn ores of the Yulong Mo

  The Jiangyong Pb-Zn-Ag deposit and Yulong Mo deposit are dominated by carbonate replacement and skarn mineralization, respectively. Garnet U-Pb dating yields a 207 Pb/ 235 U-206 Pb/ 238 U concordia age of 162.0 ± 3.7 Ma with a weighted average 206 Pb/ 238 U age of 162.4 ± 4.2 Ma for the proximal exoskarn in the

	Tongshanling Cu-Pb-Zn deposit. Molybdenite Re-Os dating of the Tongshanling Cu-Pb-Zn
	deposit and Yulong Mo deposit yields 187 Re-187 Os isochron ages of 161.8 ± 1.7 Ma and 160.0
	± 5.8 Ma with weighted average model ages of 161.9 ± 1.1 Ma and 160.1 ± 0.8 Ma,
	respectively. U-Pb dating of the hydrothermal titanite in the altered granodiorite yields lower
	intercept ages of 155.5 ± 3.1 Ma and 155.6 ± 3.1 Ma in the Wetherill and Tera-Wasserburg
	U-Pb concordia plots, respectively, with a weighted average 206 Pb/ 238 U age of 154.4 ± 1.9 Ma.

  -26). EMP analyses show that the core contains SiO2 contents of 44.16 -49.59 wt.%, TiO2 contents of 0.00 -0.36 wt.%, Al2O3 contents of 25.73 -31.20 wt.%, FeO contents of 2.12 -9.79 wt.%, MnO contents of 0.00 -0.52 wt.%, MgO contents of 0.00 -

	0.27 wt.%, CaO contents of 0.00 -0.10 wt.%, Na2O contents of 0.03 -0.37 wt.%, K2O
	contents of 10.01 -11.07 wt.% (Fig. 8-24), and F contents of 2.99 -8.23 wt.% with a peak
	value of 4.5 wt.% (Figs. 8-24 and 8-25g), plotting in the lepidolite, zinnwaldite, Li phengite,

and Li muscovite fields (Fig.

8-23b

). Whereas, the rim contains distinctly higher Al2O3 contents of 30.44 -35.56 wt.% and lower FeO contents of 0.17 -3.39 wt.%, K2O contents of 8.40 -10.80 wt.% (Fig.

8

-24), and F contents of 0.00 -2.34 wt.% with a peak value of 0.3 wt.%

, plotting in the muscovite and Li muscovite fields (Fig.

8-23b

).

  -29).

	Representative EMP analytical results and crystallochemical calculations of the
	phlogopite in the magnesian skarn of the Weijia W deposit are listed in Appendix 8-6. The

phlogopite in the magnesian skarn contains SiO2 contents of 36.01 -43.85 wt.%, TiO2 contents of 0.00 -0.19 wt.%, Al2O3 contents of 9.96 -17.45 wt.%, FeO contents of 0.75 -22.26 wt.%, MnO contents of 0.00 -1.49 wt.%, MgO contents of 11.47 -31.57 wt.%, CaO

  04 -1.81 wt.%, FeO contents of 1.60 -13.50 wt.%, MnO contents of 0.05 -1.54 wt.%, MgO contents of 9.09 -17.98 wt.%, CaO contents of 23.42 -25.98 wt.%, Na2O contents of 0.00 -0.11 wt.%, and K2O contents of 0.00 -0.07 wt.%, showing a compositional variation between Di55.1Hd40.1 and Di99.6Hd0.0 (Fig.8-36b).The late-generation pyroxene has SiO2 contents of 46.22 -49.92 wt.%, TiO2 contents of 0.00 -0.15 wt.%, Al2O3 contents of 0.03 -2.31 wt.%, FeO contents of 20.61 -30.04 wt.%, MnO contents of 0.88 -2.84 wt.%, MgO contents of 0.00 -5.28 wt.%, CaO contents of 21.51 -23.47 wt.%, Na2O contents of 0.04 -0.40 wt.%, and K2O contents of 0.00 -0.10 wt.%,

Table 8 -

 8 1. F contents and some related parameters of different F-bearing minerals in the Weijia W deposit

	F content (wt.%)	IV (F) a	IV (F/Cl) a

  Major elements (wt.%), trace elements (ppm) and Sr-Nd isotopes of granitoids from the Tongshanling-Weijia area Representative EMP analyses of plagioclase (wt.%) from the Tongshanling granodiorite and its microgranular enclaves Notes: a All Fe as Fe 2+ . b An = anorthite, Ab = albite, Or = orthoclase. LA-ICP-MS analyses of amphibole and biotite (ppm) from the Tongshanling granodiorite and its microgranular enclaves Representative EMP analyses of biotite (wt.%) from the Tongshanling granodiorite and its microgranular enclaves Some parameters for Raman spectra of carbonaceous material in carbonate rocks from the Tongshanling Cu-Pb-Zn deposit and its adjacent area and temperatures calculated by the RSCM thermometry (mean value and standard deviation) The abbreviations and lithologies of different Formations refer toHuang et al. (2017a). b Raman shift center of the graphite band. c

	Tongshanling granite porphyry TSL138-01 230 1258 0.18 TSL138-02 743 1639 0.45 TSL138-03 880 1881 0.47 TSL138-04 410 1421 0.29 TSL138-05 667 1660 0.40 TSL138-06 483 683 0.71 TSL138-07 670 1229 0.55 TSL138-08 657 1723 0.38 TSL138-09 1120 1992 0.56 TSL138-10 325 1044 0.31 TSL138-11 935 1844 0.51 TSL138-12 735 1806 0.41 TSL138-13 676 1553 0.44 TSL138-14 525 1411 0.37 TSL138-15 598 1822 0.33 TSL138-16 245 620 0.39 TSL138-17 393 1110 0.35 TSL138-18 789 1600 0.49 TSL138-19 834 1899 0.44 TSL138-20 902 2107 0.43 TSL138-21 635 688 0.92 TSL138-22 659 1600 0.41 TSL138-23 610 1604 0.38 TSL138-24 188 437 0.43 TSL138-25 444 940 0.47 TSL138-26 729 552 1.32 TSL138-27 292 245 1.19 TSL138-28 287 151 1.90 TSL138-29 386 446 0.87 TSL138-30 538 284 1.90 TSL138-31 159 326 0.49 TSL138-32 1319 537 2.46 TSL138-33 288 409 0.70 Appendix 4-1. (Continued) Spot Elements (ppm) 232 Th 238 U Th/U 207 Pb/ 206 Pb 0.05021 0.00217 0.17069 0.00720 0.02467 0.00044 0.04933 0.00201 0.16719 0.00665 0.02460 0.00044 0.04782 0.00160 0.16299 0.00557 0.02473 0.00039 0.05079 0.00171 0.17277 0.00591 0.02468 0.00041 0.04713 0.00179 0.16049 0.00618 0.02470 0.00040 0.04918 0.00361 0.16852 0.01209 0.02486 0.00054 0.04919 0.00235 0.16827 0.00784 0.02484 0.00047 0.05252 0.00216 0.18023 0.00740 0.02489 0.00048 0.04932 0.00188 0.16929 0.00629 0.02490 0.00045 0.04992 0.00249 0.17166 0.00834 0.02497 0.00048 0.05323 0.00170 0.18275 0.00598 0.02491 0.00040 0.04926 0.00201 0.16893 0.00674 0.02490 0.00045 0.05074 0.00190 0.17426 0.00655 0.02492 0.00041 0.04932 0.00177 0.16970 0.00615 0.02496 0.00041 0.05236 0.00224 0.18015 0.00765 0.02495 0.00047 0.04924 0.00342 0.17052 0.01162 0.02512 0.00052 0.04914 0.00335 0.17067 0.01127 0.02520 0.00057 0.04921 0.00225 0.16995 0.00756 0.02509 0.00048 0.04961 0.00156 0.17155 0.00555 0.02508 0.00042 0.04935 0.00168 0.17139 0.00593 0.02519 0.00043 0.04922 0.00309 0.17113 0.01052 0.02523 0.00051 0.05005 0.00153 0.17407 0.00547 0.02523 0.00042 0.04931 0.00155 0.17153 0.00552 0.02523 0.00042 0.06932 0.00215 1.39889 0.04419 0.14638 0.00248 0.07284 0.00146 1.50132 0.03312 0.14951 0.00231 0.07108 0.00206 1.53689 0.04540 0.15684 0.00251 0.07779 0.00181 2.05875 0.05104 0.19200 0.00302 0.07851 0.00265 2.02175 0.06929 0.18684 0.00316 0.07943 0.00200 2.08608 0.05485 0.19054 0.00297 0.10423 0.00238 4.13516 0.10124 0.28778 0.00475 0.14988 0.00418 4.88191 0.14065 0.23626 0.00393 0.15273 0.00393 6.18107 0.16762 0.29356 0.00473 0.15826 0.00397 8.98428 0.23580 0.41175 0.00649 Isotopic ratios 1σ 207 Pb/ 235 U 1σ 206 Pb/ 238 U 1σ 207 Pb/ 206 Pb 1σ 207 Pb/ 235 U 1σ 206 Pb/ 238 U 1σ 205 102 160 6 157 164 95 157 6 157 90 76 153 5 157 231 80 162 5 157 56 83 151 5 157 156 166 158 11 158 157 110 158 7 158 308 96 168 6 158 163 89 159 5 159 191 116 161 7 159 339 74 170 5 159 160 95 158 6 159 229 89 163 6 159 163 85 159 5 159 301 100 168 7 159 159 158 160 10 160 155 155 160 10 160 158 106 159 7 160 177 75 161 5 160 164 81 161 5 160 158 143 160 9 161 197 73 163 5 161 163 75 161 5 161 908 65 888 19 881 1010 42 931 13 898 960 61 945 18 939 1142 47 1135 17 1132 1160 69 1123 23 1104 1183 51 1144 18 1124 1701 43 1661 20 1630 2345 49 1799 24 1367 2377 45 2002 24 1659 2437 43 2336 24 2223 (To be continued on the next page) Ages (Ma) Weijia granite porphyry WJ5-01 183 223 0.82 0.05617 0.00488 0.19085 0.01641 0.02464 0.00053 459 199 177 14 157 WJ5-02 975 942 1.03 0.05974 0.00276 0.20360 0.00931 0.02472 0.00046 594 103 188 8 157 WJ5-03 388 534 0.73 0.04923 0.00324 0.16797 0.01091 0.02476 0.00052 159 150 158 9 158 WJ5-04 99 136 0.73 0.04937 0.00955 0.16876 0.03239 0.02479 0.00077 165 357 158 28 158 WJ5-05 83 99 0.84 0.04922 0.01522 0.16889 0.05186 0.02489 0.00103 158 525 158 45 158 WJ5-06 47 66 0.71 0.04947 0.01829 0.16894 0.06209 0.02479 0.00110 170 633 158 54 158 WJ5-07 686 2573 0.27 0.04924 0.00185 0.16956 0.00635 0.02499 0.00042 159 88 159 6 159 WJ5-08 139 201 0.69 0.04940 0.00698 0.16972 0.02373 0.02492 0.00065 167 286 159 21 159 WJ5-09 257 215 1.20 0.07385 0.00670 0.25373 0.02247 0.02492 0.00067 1037 190 230 18 159 WJ5-10 257 501 0.51 0.04932 0.00343 0.17073 0.01174 0.02513 0.00052 163 158 160 10 160 WJ5-11 574 595 0.96 0.06024 0.00272 0.22010 0.00984 0.02656 0.00050 612 100 202 8 169 WJ5-12 136 208 0.65 0.04951 0.00611 0.18297 0.02231 0.02681 0.00070 172 262 171 19 171 WJ5-13 101 141 0.72 0.10832 0.01572 0.45749 0.06498 0.03063 0.00091 1771 281 383 45 194 WJ5-14 406 535 0.76 0.05117 0.00227 0.27302 0.01207 0.03873 0.00069 248 104 245 10 245 WJ5-15 484 868 0.56 0.06603 0.00286 0.55699 0.02360 0.06119 0.00110 807 93 450 15 383 WJ5-16 307 182 1.69 0.06361 0.00234 1.04873 0.03886 0.11962 0.00209 729 80 728 19 728 WJ5-17 61 66 0.92 0.06878 0.00272 1.98580 0.07835 0.20972 0.00379 892 84 1111 27 1227 WJ5-18 294 977 0.30 0.15223 0.00406 5.18185 0.14516 0.24692 0.00422 2371 47 1850 24 1423 WJ5-19 77 84 0.92 0.16010 0.00463 10.19107 0.29969 0.46186 0.00782 2457 50 2452 27 2448 Appendix 4-2. LA-ICP-MS zircon Hf isotope analyses of granitoids from the Tongshanling-Weijia area Spot Age (Ma) 176 Lu/ 177 Hf 2σ 176 Hf/ 177 Hf 2σ ( 176 Hf/ 177 Hf) i ε Hf (t) T DM(Hf) (Ga) T C DM(Hf) (Ga) Tongshanling granodiorite porphyry TSL001-01 0.001143 0.000013 0.282389 0.000020 0.282385 -10.2 1.23 1.85 TSL001-02 0.001599 0.000046 0.282438 0.000026 0.282434 -8.5 1.17 1.74 TSL001-03 0.000934 0.000003 0.282463 0.000022 0.282460 -7.5 1.12 1.68 TSL001-04 0.000774 0.000016 0.282397 0.000031 0.282395 -9.8 1.20 1.83 TSL001-05 0.001337 0.000011 0.282354 0.000023 0.282350 -11.4 1.28 1.92 TSL001-06 0.000443 0.000026 0.282345 0.000026 0.282344 -11.6 1.26 1.94 TSL001-07 0.001349 0.000040 0.282460 0.000024 0.282456 -7.6 1.13 1.69 TSL001-08 0.001151 0.000017 0.282453 0.000029 0.282449 -7.9 1.14 1.70 TSL001-09 0.000831 0.000023 0.282465 0.000021 0.282462 -7.4 1.11 1.67 TSL001-10 0.001320 0.000018 0.282449 0.000024 0.282445 -8.0 1.15 1.71 TSL001-11 0.000999 0.000006 0.282441 0.000019 0.282438 -8.2 1.15 1.73 TSL001-12 0.001893 0.000057 0.282499 0.000022 0.282493 -6.3 1.09 1.60 TSL001-13 0.001569 0.000020 0.282478 0.000024 0.282473 -7.0 1.11 1.65 TSL001-14 0.001592 0.000017 0.282428 0.000023 0.282423 -8.7 1.19 1.76 TSL001-15 0.001293 0.000009 0.282421 0.000025 0.282417 -8.9 1.19 1.77 TSL001-16 0.000790 0.000032 0.282107 0.000024 0.282100 -14.0 1.61 2.30 TSL001-17 0.001396 0.000021 0.282587 0.000020 0.282573 4.9 0.95 1.19 TSL001-18 0.000261 0.000003 0.281978 0.000024 0.281974 -11.3 1.76 2.37 TSL001-19 0.000694 0.000016 0.282342 0.000024 0.282330 4.0 1.28 1.51 TSL001-20 0.000190 0.000021 0.282206 0.000023 0.282202 -0.4 1.45 1.79 TSL001-21 0.001093 0.000015 0.282250 0.000023 0.282232 0.7 1.42 1.73 TSL001-22 0.000867 0.000032 0.282355 0.000022 0.282340 5.4 1.26 1.46 TSL001-23 0.000721 0.000016 0.282188 0.000036 0.282175 -0.4 1.49 1.83 TSL001-24 0.000511 0.000002 0.282024 0.000024 0.282014 -4.2 1.71 2.13 TSL001-25 0.000847 0.000009 0.281873 0.000023 0.281846 3.7 1.93 2.11 Dioritic dark enclaves JY55-01 0.002067 0.000019 0.282463 0.000024 0.282457 -7.7 1.15 1.69 JY55-02 0.001549 0.000009 0.282470 0.000022 0.282466 -7.4 1.12 1.67 JY55-03 0.001662 0.000037 0.282447 0.000021 0.282442 -8.2 1.16 1.72 JY55-04 0.001383 0.000026 0.282461 0.000024 0.282457 -7.7 1.13 1.69 JY55-05 0.001722 0.000060 0.282470 0.000029 0.282465 -7.4 1.13 1.67 JY55-06 0.001339 0.000020 0.282482 0.000022 0.282478 -6.9 1.10 1.64 JY55-07 0.001843 0.000030 0.282414 0.000022 0.282409 -9.3 1.21 1.79 JY55-08 0.001094 0.000018 0.282476 0.000021 0.282473 -7.1 1.10 1.65 (To be continued on the next page) Appendix 4-2. (Continued) Spot Age (Ma) 176 Lu/ 177 Hf 2σ 176 Hf/ 177 Hf 2σ ( 176 Hf/ 177 Hf) i ε Hf (t) T DM(Hf) (Ga) T C DM(Hf) (Ga) JY55-09 0.001723 0.000006 0.282453 0.000031 0.282447 -8.0 1.15 1.71 JY55-10 0.002152 0.000033 0.282476 0.000035 0.282470 -7.2 1.13 1.66 JY55-11 0.001205 0.000018 0.282424 0.000028 0.282421 -8.9 1.18 1.77 JY55-12 0.001468 0.000043 0.282451 0.000029 0.282446 -8.0 1.15 1.71 JY55-13 0.001454 0.000053 0.282445 0.000027 0.282441 -8.2 1.16 1.72 JY55-14 0.001419 0.000030 0.282448 0.000020 0.282444 -8.0 1.15 1.71 JY55-15 0.001284 0.000015 0.282313 0.000023 0.282303 -7.4 1.34 1.87 JY55-16 0.000830 0.000011 0.282434 0.000021 0.282427 -2.8 1.15 1.59 JY55-17 0.001375 0.000020 0.282187 0.000021 0.282171 -7.5 1.52 2.03 JY55-18 0.001815 0.000083 0.282275 0.000021 0.282243 2.3 1.41 1.67 JY55-19 0.001182 0.000056 0.282299 0.000040 0.282275 6.4 1.35 1.51 JY55-20 0.001281 0.000040 0.282244 0.000028 0.282215 6.9 1.43 1.57 Tongshanling granite porphyry TSL138-01 0.001435 0.000012 0.282535 0.000028 0.282531 -5.1 1.03 1.53 TSL138-02 0.001202 0.000027 0.282559 0.000033 0.282556 -4.2 0.99 1.47 TSL138-03 0.002067 0.000013 0.282612 0.000027 0.282606 -2.4 0.93 1.36 TSL138-04 0.002170 0.000048 0.282224 0.000035 0.282217 -16.1 1.50 2.22 TSL138-05 0.000894 0.000022 0.282387 0.000039 0.282384 -10.2 1.22 1.85 TSL138-06 0.002494 0.000019 0.282442 0.000054 0.282435 -8.4 1.19 1.74 TSL138-07 0.001451 0.000029 0.282517 0.000033 0.282512 -5.7 1.06 1.57 TSL138-08 0.001330 0.000036 0.282549 0.000038 0.282545 -4.5 1.01 1.49 TSL138-09 0.001231 0.000026 0.282670 0.000031 0.282666 -0.2 0.83 1.22 TSL138-10 0.000874 0.000012 0.282546 0.000027 0.282544 -4.6 1.00 1.50 TSL138-11 0.001635 0.000039 0.282519 0.000030 0.282514 -5.6 1.06 1.56 TSL138-12 0.001433 0.000014 0.282613 0.000020 0.282609 -2.3 0.92 1.35 TSL138-13 0.001663 0.000018 0.282518 0.000025 0.282513 -5.7 1.06 1.56 TSL138-14 0.000634 0.000039 0.282387 0.000031 0.282385 -10.2 1.21 1.85 TSL138-15 0.000482 0.000030 0.282597 0.000029 0.282596 -2.7 0.92 1.38 TSL138-16 0.001269 0.000011 0.282539 0.000022 0.282535 -4.9 1.02 1.51 TSL138-17 0.001147 0.000012 0.282560 0.000022 0.282557 -4.1 0.99 1.46 TSL138-18 0.002161 0.000009 0.282636 0.000028 0.282629 -1.5 0.90 1.30 TSL138-19 0.001075 0.000018 0.282306 0.000018 0.282288 2.3 1.34 1.61 TSL138-20 0.001502 0.000017 0.281938 0.000026 0.281912 -10.6 1.88 2.43 TSL138-21 0.001484 0.000079 0.282366 0.000032 0.282334 9.8 1.27 1.34 TSL138-22 0.001377 0.000055 0.282169 0.000034 0.282139 3.3 1.55 1.77 (To be continued on the next page) Appendix 4-2. (Continued) Spot Age (Ma) 176 Lu/ 177 Hf 2σ 176 Hf/ 177 Hf 2σ ( 176 Hf/ 177 Hf) i ε Hf (t) T DM(Hf) (Ga) T C DM(Hf) (Ga) TSL138-23 0.001369 0.000025 0.282004 0.000038 0.281973 -2.1 1.78 2.12 TSL138-24 0.001505 0.000029 0.281952 0.000033 0.281904 7.2 1.85 1.94 TSL138-25 0.000746 0.000008 0.281489 0.000029 0.281455 6.7 2.45 2.50 TSL138-26 0.000623 0.000024 0.281424 0.000033 0.281395 5.9 2.53 2.59 Weijia granite porphyry WJ5-01 0.000868 0.000007 0.282582 0.000027 0.282579 -3.4 0.95 1.42 WJ5-02 0.001934 0.000087 0.282634 0.000027 0.282628 -1.7 0.90 1.31 WJ5-03 0.000578 0.000015 0.282554 0.000030 0.282552 -4.3 0.98 1.48 WJ5-04 0.000792 0.000011 0.282571 0.000027 0.282569 -3.7 0.96 1.44 WJ5-05 0.000697 0.000007 0.282597 0.000029 0.282595 -2.8 0.92 1.38 WJ5-06 0.001100 0.000014 0.282577 0.000047 0.282574 -3.5 0.96 1.43 WJ5-07 0.001082 0.000006 0.282621 0.000019 0.282617 -2.0 0.90 1.33 WJ5-08 0.000856 0.000017 0.282624 0.000024 0.282622 -1.8 0.89 1.32 WJ5-09 0.000645 0.000005 0.282543 0.000025 0.282542 -4.6 0.99 1.50 WJ5-10 0.001379 0.000088 0.282547 0.000024 0.282537 0.1 1.01 1.37 WJ5-11 0.001141 0.000029 0.282420 0.000033 0.282401 6.6 1.18 1.35 WJ5-12 0.000886 0.000056 0.281501 0.000046 0.281459 8.7 2.44 2.44 Note: Zircons with ε Hf (t) > 0 using single-stage model ages T DM(Hf) (Ga); Zircons with ε Hf (t) < 0 using two-stage model ages T C DM(Hf) (Ga). Appendix 4-3. Sample Tongshanling granodiorite porphyry TSL58 TSL59 TSL60 JY23 JY36 JY38 JY40 YL49 YL50 SiO 2 68.23 68.12 65.94 65.74 63.71 65.02 65.84 68.21 70.09 TiO 2 0.37 0.43 0.47 0.52 0.52 0.56 0.48 0.44 0.37 Al 2 O 3 14.38 14.90 15.68 15.97 16.66 15.84 15.24 14.37 13.68 Fe 2 O 3 0.70 0.97 1.26 1.17 1.33 1.22 0.95 1.00 0.99 FeO 2.15 2.04 2.18 2.45 2.62 2.60 2.36 2.28 1.85 MnO 0.08 0.06 0.05 0.09 0.09 0.11 0.09 0.08 0.07 MgO 1.16 1.29 1.41 1.64 1.81 1.69 1.63 1.30 1.08 CaO 3.16 2.78 3.42 3.58 4.15 3.75 3.75 3.14 2.35 Na 2 O 2.77 2.89 3.19 2.89 3.03 2.95 3.14 2.94 2.57 K 2 O 4.63 4.64 3.97 3.97 3.92 4.22 4.42 4.20 4.79 P 2 O 5 0.13 0.15 0.18 0.19 0.21 0.20 0.18 0.18 0.15 LOI 2.56 2.52 2.08 1.48 2.02 2.01 1.44 1.20 1.32 Total 100.32 100.80 99.82 99.69 100.08 100.16 99.53 99.35 99.31 Ga 16.80 15.71 17.41 16.29 15.75 16.73 16.24 17.30 17.05 Rb 194.25 187.97 179.67 169.97 177.11 164.65 162.50 228.55 256.48 Sr 267.48 302.14 308.22 339.80 291.38 310.89 332.43 268.47 205.93 Y 18.41 24.32 21.85 18.33 19.42 20.25 19.90 17.49 18.26 Zr 123.44 138.31 154.91 129.48 142.41 152.77 143.96 118.88 127.29 Nb 14.43 21.02 23.52 14.65 15.05 15.79 13.55 17.93 16.85 Ba 601.26 858.21 749.22 1795.75 916.95 845.02 872.38 246.68 213.69 Hf 3.93 4.02 4.55 4.08 4.49 4.68 4.43 3.72 4.16 Ta 1.60 1.48 1.78 1.74 1.69 1.57 1.45 1.95 2.52 Th 23.21 15.19 16.62 13.47 13.26 13.78 14.75 15.12 20.42 U 10.55 4.56 5.59 5.91 5.78 5.46 5.18 11.88 15.17 La 17.91 22.42 23.88 20.80 21.13 22.12 21.19 13.40 16.00 Ce 34.69 42.22 40.23 40.83 39.83 42.56 41.09 29.51 34.78 Pr 4.77 5.16 5.03 5.71 5.96 5.97 5.82 4.61 5.17 Nd 16.80 19.42 19.41 19.92 20.80 20.88 20.23 17.92 19.11 Sm 3.42 3.76 4.01 4.01 4.22 4.31 4.25 3.82 3.90 Eu 1.01 1.17 1.21 1.47 1.21 1.20 1.20 0.85 0.78 Gd 3.26 3.53 3.80 3.81 3.89 3.84 3.95 3.40 3.41 Tb 0.53 0.55 0.62 0.59 0.62 0.64 0.65 0.54 0.54 Dy 3.16 3.16 3.64 3.40 3.58 3.72 3.74 3.00 3.01 Ho 0.63 0.61 0.71 0.66 0.69 0.72 0.72 0.58 0.59 Er 1.91 1.88 2.19 1.99 2.06 2.14 2.15 1.72 1.84 Tm 0.30 0.28 0.33 0.30 0.31 0.32 0.32 0.26 0.29 Yb 2.05 1.94 2.27 2.06 2.11 2.17 2.15 1.85 2.14 Lu 0.32 0.31 0.36 0.32 0.32 0.33 0.33 0.29 0.35 ASI a 0.94 1.00 0.99 1.03 0.99 0.97 0.91 0.95 1.00 DI b 76.08 76.88 72.69 70.80 67.52 70.24 72.74 75.51 79.64 ΣREE 90.76 106.42 107.69 105.87 106.73 110.92 107.79 81.75 91.91 HFSE c 190.97 225.86 240.51 203.29 216.71 231.37 218.50 183.81 197.18 T Zr d (°C) 749 764 770 758 758 764 752 747 761 87 Rb/ 86 Sr 2.10 1.80 1.45 1.76 1.53 1.41 2.46 3.60 87 Sr / 86 Sr 0.715467 0.714273 0.714026 0.713045 0.714132 0.713807 0.714646 0.717641 2σ 0.000008 0.000006 0.000006 0.000009 0.000007 0.000014 0.000008 0.000008 ( 87 Sr / 86 Sr) i 0.710612 0.710114 0.710682 0.708982 0.710592 0.710539 0.708955 0.709315 147 Sm/ 144 Nd 0.12 0.12 0.12 0.12 0.12 0.13 0.13 0.12 143 Nd/ 144 Nd 0.512208 0.512209 0.512231 0.512258 0.512212 0.512214 0.512351 0.512329 2σ 0.000006 0.000005 0.000008 0.000007 0.000006 0.000005 0.000006 0.000006 ε Nd (t) -6.9 -6.7 -6.4 -5.9 -6.8 -6.8 -4.2 -4.5 T C DM(Nd) (Ga) 1.51 1.50 1.47 1.43 1.51 1.51 1.29 1.32 (To be continued on the next page) SiO 2 55.70 48.61 59.35 53.38 55.13 58.79 57.56 TiO 2 0.85 1.00 0.80 1.16 0.90 0.85 0.86 Al 2 O 3 16.18 16.48 16.49 18.54 16.82 17.05 17.20 Fe 2 O 3 1.30 4.80 1.27 1.18 1.71 1.58 1.48 FeO 6.95 4.62 4.88 7.01 6.80 5.13 5.26 MnO 0.30 0.29 0.18 0.17 0.32 0.20 0.19 MgO 3.99 4.47 2.77 3.25 4.09 3.09 3.13 CaO 5.87 6.62 4.92 4.46 6.00 4.80 5.36 Na 2 O 3.27 3.38 3.08 3.23 3.46 3.48 3.26 K 2 O 2.52 2.03 3.17 2.99 2.87 3.39 2.85 P 2 O 5 0.26 0.24 0.29 0.34 0.30 0.33 0.32 LOI 2.57 6.72 2.03 3.43 1.23 1.57 1.77 Total 99.77 99.26 99.25 99.13 99.63 100.26 99.24 Ga 16.03 22.42 20.01 24.99 21.60 21.07 20.53 Rb 125.83 135.10 221.60 213.96 185.59 224.96 210.82 Sr 192.90 267.18 350.11 271.46 246.51 256.45 391.37 Y 53.29 58.85 30.82 38.47 61.81 47.11 24.09 Zr 105.97 134.91 121.57 144.20 146.16 190.58 133.43 Nb 19.80 24.34 19.16 33.14 23.37 23.24 21.06 Ba 268.94 400.17 592.37 428.28 479.41 515.45 617.02 Hf 3.67 4.48 3.89 4.51 4.71 6.09 4.06 Ta 2.12 2.50 1.73 3.83 2.67 2.80 0.88 Th 11.77 15.20 15.26 12.61 10.01 24.09 13.13 U 5.67 7.29 4.57 10.16 5.81 10.34 3.24 La 15.24 19.65 28.17 18.42 16.70 35.53 26.87 Ce 39.92 52.09 59.63 30.46 43.81 73.46 57.18 Pr 7.98 10.15 9.32 5.55 8.58 11.06 8.58 Nd 30.98 39.66 32.17 21.47 36.21 40.21 31.52 Sm 8.76 10.59 6.66 5.94 10.27 9.02 6.33 Eu 1.04 1.37 1.28 1.06 1.35 1.22 1.46 Gd 8.32 9.72 6.07 5.82 9.64 8.49 5.65 Tb 1.58 1.77 0.97 1.07 1.79 1.43 0.85 Dy 9.86 10.81 5.66 6.68 11.14 8.56 4.78 Ho 1.93 2.12 1.11 1.33 2.20 1.68 0.91 Er 5.69 6.30 3.35 4.05 6.57 5.08 2.70 Tm 0.86 0.96 0.50 0.63 0.99 0.76 0.38 Yb 5.63 6.46 3.40 4.25 6.65 5.06 2.55 Lu 0.82 0.97 0.51 0.67 0.99 0.77 0.39 ASI a 0.86 0.83 0.94 1.11 0.85 0.94 0.94 DI b 48.05 41.68 57.26 50.02 48.78 58.07 53.66 ΣREE 138.60 172.62 158.80 107.38 156.90 202.33 150.15 HFSE c 218.97 270.19 231.19 246.27 275.15 334.40 235.77 T Zr d (°C) 702 702 732 755 721 764 735 87 Rb/ 86 Sr 1.89 2.18 1.56 87 Sr / 86 Sr 0.714602 0.714997 0.714759 2σ 0.000005 0.000006 0.000005 ( 87 Sr / 86 Sr) i 0.710293 0.710023 0.711200 147 Sm/ 144 Nd 0.17 0.17 0.12 143 Nd/ 144 Nd 0.512270 0.512291 0.512290 2σ 0.000004 0.000005 0.000006 ε Nd (t) -6.7 -6.3 -5.2 T C DM(Nd) (Ga) 1.49 1.46 1.38 (To be continued on the next page) Appendix 4-3. (Continued) Sample Tongshanling granite porphyry TSL89 TSL90 TSL138 TSL139 TSL141 TSL142 TSL143 TSL146 SiO 2 71.57 71.35 72.29 73.07 71.80 72.17 72.68 74.34 TiO 2 0.22 0.24 0.21 0.23 0.22 0.22 0.22 0.22 Al 2 O 3 13.83 14.01 12.72 13.61 13.56 13.69 13.66 13.04 Fe 2 O 3 0.57 0.67 0.43 0.44 0.52 0.54 0.36 0.44 FeO 1.36 1.10 1.18 1.31 1.24 1.32 1.38 1.21 MnO 0.08 0.07 0.10 0.07 0.09 0.09 0.07 0.08 MgO 0.56 0.60 0.60 0.51 0.54 0.61 0.42 0.56 CaO 1.23 0.73 2.15 0.93 1.25 1.83 0.85 1.03 Na 2 O 2.95 2.62 2.73 2.82 3.21 2.44 3.98 4.04 K 2 O 5.16 5.81 4.30 4.94 4.87 5.04 4.41 3.98 P 2 O 5 0.10 0.09 0.08 0.08 0.08 0.08 0.08 0.08 LOI 2.17 1.77 2.84 1.63 2.27 2.47 1.27 1.22 Total 99.79 99.05 99.63 99.63 99.63 100.52 99.38 100.23 Ga 15.53 14.80 14.95 16.93 16.91 16.68 15.65 12.32 Rb 208.19 220.83 204.94 228.28 224.03 232.93 186.58 163.39 Sr 228.16 184.64 167.17 308.94 293.35 277.23 277.33 323.44 Y 12.64 10.95 13.02 14.07 13.35 13.13 13.81 13.88 Zr 137.78 130.61 127.83 134.44 143.31 132.92 142.62 134.92 Nb 35.00 32.91 34.68 38.50 37.15 37.30 37.15 38.42 Ba 635.01 556.30 633.86 650.21 650.26 679.25 611.55 778.21 Hf 4.39 4.76 3.95 4.21 4.39 4.18 4.35 4.19 Ta 2.70 2.91 2.46 2.71 2.67 2.70 2.68 2.65 Th 17.15 17.71 21.80 24.65 24.12 24.55 24.64 24.01 U 6.30 11.07 13.83 9.14 7.31 7.51 9.55 9.26 La 32.45 31.68 33.56 40.95 40.33 39.32 39.04 37.77 Ce 51.93 54.02 55.92 68.35 66.82 66.01 65.07 63.39 Pr 6.55 7.25 8.10 9.74 9.45 9.18 8.94 8.60 Nd 20.40 22.27 20.43 24.77 24.52 24.12 23.90 23.37 Sm 3.35 3.55 3.40 3.89 3.95 3.85 3.80 3.76 Eu 0.87 0.86 0.86 1.02 1.04 0.99 0.98 0.88 Gd 3.06 3.26 3.21 3.55 3.65 3.56 3.48 3.48 Tb 0.40 0.42 0.43 0.45 0.48 0.46 0.45 0.45 Dy 2.00 2.07 2.16 2.16 2.37 2.26 2.17 2.22 Ho 0.37 0.38 0.40 0.39 0.43 0.41 0.40 0.41 Er 1.12 1.17 1.22 1.20 1.34 1.28 1.24 1.28 Tm 0.17 0.17 0.18 0.18 0.20 0.19 0.18 0.19 Yb 1.20 1.24 1.28 1.23 1.38 1.33 1.28 1.34 Lu 0.19 0.20 0.20 0.20 0.22 0.21 0.21 0.22 ASI a 1.09 1.17 0.97 1.16 1.06 1.07 1.06 1.02 DI b 86.12 87.64 82.50 87.48 86.43 83.74 89.23 89.73 ΣREE 124.06 128.54 131.34 158.06 156.19 153.17 151.15 147.36 HFSE c 237.35 228.49 231.44 255.35 260.63 249.35 258.65 250.61 T Zr d (°C) 778 781 763 784 779 774 779 771 87 Rb/ 86 Sr 2.64 3.46 2.61 87 Sr / 86 Sr 0.713635 0.714824 0.714022 2σ 0.000007 0.000006 0.000009 ( 87 Sr / 86 Sr) i 0.707674 0.707011 0.708124 147 Sm/ 144 Nd 0.10 0.10 0.10 143 Nd/ 144 Nd 0.512431 0.512409 0.512391 2σ 0.000006 0.000006 0.000005 ε Nd (t) -2.1 -2.4 -2.8 T C DM(Nd) (Ga) 1.12 1.15 1.18 (To be continued on the next page) Appendix 4-3. (Continued) Weijia granite porphyry Appendix 5-1. Tongshanling granodiorite Microgranular enclaves Appendix 5-3. Amphibole Appendix 5-3. (Continued) Amphibole Appendix 5-4. Tongshanling granodiorite Microgranular enclaves Sample WJ-2 WJ-10 WJ-11 WJ-12 WJ-15 WJ-18 WJ-22 SiO 2 73.86 74.06 74.60 76.69 76.12 75.73 76.73 TiO 2 0.01 0.01 0.01 0.01 0.01 0.01 0.02 Al 2 O 3 13.84 14.27 14.08 13.30 13.70 13.69 13.06 Fe 2 O 3 0.07 0.29 0.11 0.02 0.00 0.01 0.22 FeO 0.22 0.28 0.27 0.11 0.13 0.11 0.11 MnO 0.01 0.01 0.01 0.00 0.00 0.00 0.00 MgO 0.04 0.17 0.04 0.01 0.01 0.03 0.14 CaO 0.88 0.15 0.63 0.28 0.12 0.17 0.25 Na 2 O 3.36 3.01 3.17 3.72 3.34 3.01 3.48 K 2 O 6.19 6.78 6.46 4.84 5.87 5.86 5.44 P 2 O 5 0.02 0.01 0.00 0.01 0.01 0.01 0.01 LOI 1.06 0.94 0.74 0.77 0.73 0.88 1.10 Total 99.57 99.98 100.12 99.74 100.04 99.51 100.57 Ga 17.08 22.24 16.06 28.72 25.08 27.43 21.03 Rb 300.62 310.95 259.64 318.89 345.79 355.98 291.60 Sr 27.20 19.93 15.97 14.77 17.69 21.75 28.45 Y 14.67 25.12 31.97 51.27 39.88 43.33 37.28 Zr 74.78 83.19 74.06 60.61 81.13 71.77 80.14 Nb 33.06 41.78 32.31 41.81 40.47 41.16 39.75 Ba 7.46 15.02 7.32 10.62 21.52 34.84 42.60 Hf 4.67 5.56 4.75 4.34 4.80 4.84 5.13 Ta 4.04 6.12 4.49 7.53 5.39 5.97 5.54 Th 12.04 18.05 15.83 26.76 27.31 27.78 27.60 U 13.69 6.78 11.44 18.79 7.79 9.16 8.69 La 7.14 8.52 8.12 15.20 11.55 14.67 13.33 Ce 19.16 15.58 14.47 23.48 16.45 22.77 14.81 Pr 1.92 2.38 2.17 5.49 3.85 5.08 4.54 Nd 10.51 13.48 12.24 16.73 12.34 15.34 13.57 Sm 3.86 5.26 4.89 7.40 5.97 6.61 5.88 Eu 0.04 0.07 0.06 0.09 0.09 0.10 0.10 Gd 4.05 5.88 5.26 8.32 7.02 7.45 6.49 Tb 0.69 1.02 0.99 1.71 1.48 1.52 1.37 Dy 3.91 5.96 6.13 10.11 8.83 8.95 8.25 Ho 0.65 1.01 1.08 1.78 1.56 1.57 1.46 Er 1.65 2.56 2.78 4.77 4.15 4.23 3.94 Tm 0.21 0.35 0.39 0.67 0.59 0.59 0.55 Yb 1.38 2.06 2.26 4.14 3.58 3.68 3.38 Lu 0.18 0.28 0.33 0.59 0.51 0.53 0.47 ASI a 1.00 1.13 1.05 1.12 1.13 1.18 1.08 DI b 93.59 95.46 94.85 95.93 96.82 95.44 96.58 ΣREE 55.35 64.41 61.17 100.47 77.97 93.08 78.14 HFSE c 141.67 165.67 152.81 177.17 177.93 179.02 171.97 T Zr d (°C) 722 741 726 718 741 735 737 87 Rb/ 86 Sr 87 Sr / 86 Sr 2σ ( 87 Sr / 86 Sr) i 147 Sm/ 144 Nd 0.22 0.24 0.24 143 Nd/ 144 Nd 0.512424 0.512446 0.512406 2σ 0.000006 0.000013 0.000009 ε Nd (t) -4.7 -4.5 -5.4 T C DM(Nd) (Ga) 1.33 1.32 1.39 156.0 ± 1.0 Zuo et al. (2014) SIMS 158.8 ± 1.8 Huang et al. (2015) SIMS 158.3 ± 1.2 Yang et al. (2016) Baoshan Cu-Mo-Pb-Zn-Ag Granodiorite porphyry SHRIMP 158.0 ± 2.0 Lu et al. (2006) LA-ICP-MS 156.7 ± 1.4 Xie et al. (2013) 157.7 ± 1.1 Granodioritic cryptoexplosion breccia SHRIMP 164.1 ± 1.9 Wu et al. (2005) 162.2 ± 1.6 Tongshanling Cu-Mo-Pb-Zn-Ag Granodiorite porphyry SHRIMP 163.6 ± 2.1 Jiang et al. (2009) LA-ICP-MS 160.7 ± 0.5 Zhao et al. (2016b) 160.5 ± 0.9 159.7 ± 0.8 LA-ICP-MS 162.5 ± 1.0 This study Dabaoshan Fe-Cu-Mo-Pb-Zn Granodiorite porphyry LA-ICP-MS 167.0 ± 2.5 Li et al. (2012b) Granodiorite porphyry LA-ICP-MS 162.2 ± 0.7 Mao et al. (2013b) 161.0 ± 0.9 Granodiorite 160.2 ± 0.9 Huangshaping Pb-Zn-W-Mo Dacite porphyry LA-ICP-MS 158.5 ± 0.9 Yuan et al. (2014) Quartz porphyry 160.8 ± 1.0 Granite porphyry 155.2 ± 0.4 Quartz porphyry LA-ICP-MS 160.5 ± 1.3 Ding et al. (2016b) W-bearing granites Dengfuxian W-Nb-Ta Medium-fine-grained two-mica granite LA-ICP-MS 154.4 ± 2.2 Cai (2013) Medium-grained porphyritic two-mica granite 151.1 ± 2.3 Yaogangxian W Coarse-grained biotite granite SHRIMP 155.4 ± 2.2 Li et al. (2011) Fine-grained porphyritic granite 157.6 ± 2.6 Quartz porphyry 158.4 ± 2.1 Weijia W Granite porphyry LA-ICP-MS 157.8 ± 0.9 Zhao et al. (2016a) Quartz porphyry 158.3 ± 1.4 Granite porphyry LA-ICP-MS 158.3 ± 2.2 This study Baxiannao W-Sn Medium-coarse-grained biotite granite SHRIMP 157.2 ± 2.2 Feng et al. (2011a) Maoping W-Sn Porphyritic biotite granite 151.8 ± 2.9 Taoxikeng W Biotite granite SHRIMP 158.7 ± 3.9 Guo et al. (2011) 157.6 ± 3.5 Piaotang W-Sn Medium-fine-grained porphyritic biotite granite Single-grain zircon dating 161.8 ± 1.0 Zhang et al. (2009) Muziyuan W-Mo Medium-fine-grained biotite-bearing granite 153.3 ± 1.9 Xihuashan W-Mo Coarse-grained porphyritic biotite granite LA-ICP-MS 155.7 ± 2.2 Wang et al. (2011c) Medium-grained porphyritic biotite granite LA-ICP-MS 155.5 ± 0.4 Yang et al. (2012) Medium-grained biotite granite 153.0 ± 0.6 Fine-grained two-mica granite 152.8 ± 0.9 Zhangtiantang W Fine-grained porphyritic muscovite granite SHRIMP 156.9 ± 1.7 Feng et al. (2007b) Huamei'ao W Biotite granite LA-ICP-MS 159.9 ± 1.2 Feng et al. (2015) Kuimeishan W Biotite granite SHRIMP 157.7 ± 2.7 Li et al. (2014c) Dajishan W-Nb-Ta Fine-grained muscovite granite Single-grain zircon dating 151.7 ± 1.6 Zhang et al. (2006) Sample No. TSL009 TSL016 YL49 JY55 From core to rim in the same grain From core to rim in the same grain Type Rim Rim Core Rim Rim Rim Rim Core Core Core Rim Rim Rim Rim SiO 2 61.19 60.92 49.89 51.51 54.34 57.42 61.14 49.72 48.75 52.02 57.85 60.47 61.05 62.69 TiO 2 0.04 0.01 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00 0.06 0.00 0.00 0.03 Al 2 O 3 23.40 24.06 30.89 29.81 28.70 26.51 23.26 31.74 32.17 29.32 25.63 23.93 23.85 22.43 FeO a 0.48 0.22 0.22 0.44 0.04 0.08 0.17 0.02 0.21 0.05 0.07 0.01 0.14 0.15 MnO 0.03 0.00 0.04 0.00 0.00 0.01 0.03 0.06 0.11 0.00 0.06 0.05 0.00 0.02 MgO 0.00 0.02 0.01 0.04 0.00 0.01 0.03 0.00 0.00 0.01 0.00 0.00 0.01 0.00 CaO 5.55 6.32 14.56 12.80 11.03 8.52 6.49 14.74 15.22 13.70 8.51 6.75 6.18 4.81 Na 2 O 8.46 7.55 3.03 3.84 4.93 6.11 7.76 2.95 2.71 3.95 6.95 7.93 8.26 8.96 K 2 O 0.21 0.25 0.13 0.12 0.20 0.49 0.33 0.05 0.06 0.13 0.11 0.16 0.22 0.29 Total 99.36 99.33 98.77 98.57 99.23 99.19 99.22 99.28 99.24 99.19 99.24 99.31 99.70 99.37 Cations based on 8 oxygen Si 2.742 2.725 2.304 2.373 2.467 2.592 2.743 2.282 2.246 2.384 2.613 2.713 2.726 2.798 Al 1.236 1.269 1.681 1.618 1.536 1.410 1.230 1.717 1.747 1.584 1.364 1.265 1.255 1.180 Ti 0.001 0.000 0.000 0.000 0.000 0.002 0.000 0.000 0.000 0.000 0.002 0.000 0.000 0.001 Fe 0.018 0.008 0.009 0.017 0.001 0.003 0.006 0.001 0.008 0.002 0.003 0.000 0.005 0.006 Mn 0.001 0.000 0.001 0.000 0.000 0.000 0.001 0.002 0.004 0.000 0.002 0.002 0.000 0.001 Mg 0.000 0.001 0.001 0.003 0.000 0.001 0.002 0.000 0.000 0.001 0.000 0.000 0.001 0.000 Ca 0.267 0.303 0.720 0.632 0.537 0.412 0.312 0.725 0.751 0.673 0.412 0.324 0.296 0.230 Na 0.735 0.655 0.271 0.343 0.434 0.535 0.675 0.262 0.242 0.351 0.609 0.690 0.716 0.776 K 0.012 0.014 0.008 0.007 0.012 0.028 0.019 0.003 0.003 0.008 0.006 0.009 0.013 0.016 End members b (%) An 26.30 31.16 72.08 64.33 54.63 42.27 31.00 73.24 75.36 65.20 40.08 31.69 28.90 22.50 Ab 72.49 67.39 27.15 34.94 44.18 54.85 67.12 26.48 24.31 34.04 59.29 67.41 69.88 75.91 Or 1.21 1.45 0.77 0.74 1.20 2.88 1.89 0.28 0.32 0.76 0.63 0.90 1.22 1.59 Tongshanling granodiorite Microgranular enclaves Sample No. TSL009 T1512 JY55 Type Isolated amphibole Isolated amphibole Isolated amphibole Core of clot interior amphibole grains Rim of clot interior amphibole grains Trace elements Sc 228.07 218.18 202.13 222.79 128.34 243.36 173.68 169.95 15.66 14.57 24.45 75.92 100.27 196.03 V 341.09 326.39 426.10 420.57 407.28 397.12 436.33 528.56 42.44 37.63 73.41 163.36 243.60 414.63 Cr 87.74 77.66 70.34 413.10 1006.91 391.54 77.45 86.36 368.61 390.45 278.45 783.18 382.77 143.75 Co 34.07 34.93 32.90 29.65 29.95 25.25 28.89 28.93 33.53 33.63 32.99 31.23 29.87 32.44 Ni 22.43 23.80 20.46 22.38 17.97 23.61 15.55 14.31 128.30 128.04 48.73 52.97 40.82 18.73 Zn 282.42 299.29 303.45 266.58 262.78 225.39 232.00 232.38 220.78 225.22 207.41 218.74 217.52 230.96 Ga 20.76 18.55 22.57 15.34 18.74 14.48 17.51 20.24 6.19 5.63 8.11 15.12 19.39 17.91 Rb 4.09 4.00 3.86 6.83 4.20 13.65 5.66 12.26 0.88 0.53 0.80 2.93 2.56 10.47 Sr 6.42 8.75 33.66 21.98 42.61 75.44 14.91 28.60 8.90 8.25 9.14 11.35 26.16 13.48 Y 505.48 470.00 299.36 278.26 210.98 268.25 337.02 234.40 78.69 69.43 91.37 255.97 180.42 419.30 Zr 41.60 33.06 48.20 19.98 43.93 17.53 45.21 64.16 6.84 5.73 9.73 26.51 31.42 37.40 Nb 56.33 60.42 45.91 21.55 18.57 20.31 34.89 29.20 3.99 3.42 6.16 25.98 26.61 37.54 In 0.80 0.76 0.92 0.89 0.79 0.88 0.73 0.79 0.29 0.24 0.39 0.71 0.77 0.77 Sn 20.01 19.53 16.85 17.15 11.85 14.98 19.07 17.88 5.11 4.25 6.45 17.90 12.22 25.56 Cs 0.00 0.37 0.00 3.04 0.95 5.78 0.98 2.53 0.08 0.00 0.05 0.43 0.10 1.87 Ba 1.78 5.14 35.25 4.66 31.29 5.74 10.64 31.46 0.69 1.06 2.05 6.09 16.95 8.58 1188.67 2485.56 2333.86 1400.97 1057.79 1013.68 Biotite Biotite Tongshanling granodiorite Microgranular enclaves TSL009 JY55 27.93 24.99 24.23 15.26 15.90 18.89 413.87 424.33 429.83 517.65 509.53 445.61 94.59 86.13 101.01 88.78 84.95 80.90 51.66 50.80 49.38 42.64 43.09 45.10 38.01 40.16 38.55 20.56 24.63 25.76 355.49 387.97 397.94 314.71 323.71 316.08 39.14 41.42 42.06 38.79 37.99 36.03 858.82 902.22 923.82 961.43 988.88 722.87 2.45 1.80 2.11 1.22 0.63 1.23 8.15 0.90 0.94 0.38 0.77 0.01 2.02 1.67 2.04 1.44 2.13 3.37 94.81 93.38 98.80 94.73 94.59 72.71 0.16 0.13 0.14 0.11 0.11 0.13 7.81 8.20 8.64 9.83 9.68 9.73 35.64 18.72 21.48 27.00 57.32 17.68 Hf 5.14 4.16 3.30 2.22 2.67 2.13 4.08 4.42 0.33 0.13 0.67 1.91 1.90 5.03 0.18 0.23 0.21 0.13 0.24 0.25 Ta 9.33 12.51 2.75 3.52 1.07 4.10 4.74 1.69 0.23 0.19 0.31 2.68 1.26 7.29 8.24 6.44 8.14 13.13 12.14 4.43 W 0.65 0.46 0.31 0.31 0.11 0.45 0.20 0.17 0.00 0.04 0.13 0.25 0.12 0.37 1.72 2.03 2.14 0.95 0.96 0.84 (To be continued on the next page) Tongshanling granodiorite Microgranular enclaves Tongshanling granodiorite Microgranular enclaves Sample No. TSL009 T1512 JY55 TSL009 JY55 Type Isolated amphibole Isolated amphibole Isolated amphibole Core of clot interior amphibole grains Rim of clot interior amphibole grains Pb 2.93 3.03 4.24 4.14 2.88 8.78 2.63 3.16 0.94 0.84 0.87 2.03 2.22 2.77 3.48 3.52 3.85 2.42 1.88 2.43 Th 0.36 0.26 0.34 0.41 0.53 1.37 0.16 0.16 0.01 0.00 0.07 0.13 0.16 0.17 0.03 0.00 0.00 0.00 0.00 0.00 U 0.54 0.39 0.59 0.74 0.28 1.22 0.22 0.21 0.00 0.04 0.09 0.17 0.21 0.20 0.11 0.00 0.13 0.01 0.00 0.00 Rare earth elements (REE) La 31.01 25.14 27.74 10.55 17.24 11.10 21.73 28.24 4.24 3.51 5.58 15.16 14.28 17.80 2.72 1.51 1.40 0.08 0.02 0.00 Ce 140.42 120.56 120.00 47.91 70.80 40.50 99.85 117.29 20.04 17.40 28.98 74.08 65.06 87.82 5.64 0.59 0.60 0.27 0.13 0.01 Pr 28.72 25.52 22.36 10.64 12.93 8.63 20.42 21.84 4.26 3.66 5.95 15.35 13.31 19.21 1.05 0.32 0.33 0.05 0.03 0.00 Nd 173.15 151.32 127.07 67.25 75.05 56.13 123.02 118.72 25.09 22.03 35.02 93.68 71.57 119.02 5.48 1.44 1.35 0.07 0.38 0.01 Sm 67.69 60.99 48.42 30.19 24.54 26.54 46.98 38.14 9.62 8.80 13.09 34.83 26.58 50.44 1.73 0.19 0.32 0.03 0.13 0.05 Eu 1.95 1.80 3.69 1.49 2.64 1.39 1.96 3.03 0.81 0.83 1.07 1.76 2.67 2.21 0.11 0.09 0.09 0.04 0.03 0.03 Gd 75.10 67.75 51.66 38.10 28.54 34.96 50.46 36.73 8.31 8.87 13.08 37.90 28.10 56.27 3.86 5.15 4.68 2.13 1.85 1.76 Tb 13.37 12.55 9.40 6.91 4.96 6.66 8.82 6.20 1.85 1.61 2.22 6.29 4.94 10.47 0.21 0.01 0.01 0.01 0.01 0.00 Dy 87.79 84.58 58.71 47.82 34.59 45.79 56.67 39.98 13.97 10.62 15.25 43.61 32.93 68.27 1.15 0.05 0.15 0.02 0.08 0.00 Ho 18.09 17.10 11.64 9.86 7.39 9.33 11.63 8.42 2.54 2.27 3.12 9.01 6.56 14.38 0.23 0.02 0.04 0.01 0.00 0.00 Er 54.83 53.50 33.61 30.26 24.14 29.19 36.34 26.39 9.09 7.45 9.28 27.13 20.73 44.45 0.71 0.05 0.06 0.04 0.04 0.00 Tm 7.73 7.47 4.56 4.15 3.59 4.10 5.08 3.92 1.29 1.23 1.36 3.73 2.79 6.50 0.07 0.00 0.01 0.01 0.02 0.01 Yb 56.06 55.59 31.84 30.35 26.39 28.04 36.70 31.11 11.57 9.23 10.84 27.48 24.15 45.39 0.56 0.00 0.06 0.08 0.09 0.00 Lu 7.76 7.89 4.29 4.39 3.73 4.21 5.13 4.50 1.74 1.25 1.57 4.03 3.42 6.74 0.10 0.03 0.00 0.02 0.00 0.02 Sample No. TSL009 TSL016 TSL58 YL49 JY55 SiO 2 36.12 35.76 36.13 35.90 35.57 36.30 35.78 35.02 35.44 36.09 35.61 35.31 TiO 2 3.44 3.49 3.83 3.76 3.58 3.40 3.87 4.12 3.78 3.67 3.68 3.74 Al 2 O 3 13.20 13.43 13.49 13.03 14.30 14.99 13.11 13.82 13.70 14.28 13.75 13.91 FeO 21.09 20.26 21.20 22.51 21.02 20.55 22.70 23.47 22.16 21.41 21.76 22.83 MnO 0.47 0.31 0.48 0.33 0.54 0.36 0.52 0.59 0.48 0.47 0.44 0.40 MgO 9.42 10.03 9.12 9.20 10.68 9.85 9.37 8.96 9.84 9.96 9.83 10.48 CaO 0.01 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Na 2 O 0.12 0.20 0.10 0.10 0.09 0.06 0.09 0.07 0.10 0.12 0.06 0.04 K 2 O 9.23 8.95 9.39 9.30 9.67 9.70 9.27 9.61 8.95 9.52 9.30 9.09 F 0.12 0.20 0.13 0.32 0.61 0.81 0.60 0.61 0.50 0.97 0.70 0.59 Cl 0.73 0.64 0.36 0.33 0.18 0.13 0.09 0.14 0.23 0.19 0.20 0.21 Total 93.94 93.35 94.24 94.78 96.24 96.16 95.39 96.40 95.20 96.68 95.33 96.57 Ions based on 22 oxygen T_Si 5.671 5.622 5.642 5.609 5.433 5.544 5.562 5.416 5.501 5.518 5.523 5.409 I_Na 0.037 0.060 0.031 0.030 0.027 0.018 0.027 0.020 0.031 0.036 0.019 0.012 I_K 1.848 1.795 1.870 1.854 1.884 1.890 1.838 1.897 1.772 1.858 1.839 1.776 ΣI 1.888 1.869 1.901 1.884 1.911 1.908 1.865 1.917 1.803 1.893 1.858 1.787 OH b 3.872 3.864 3.920 3.876 3.827 3.785 3.840 3.831 3.845 3.737 3.798 3.828 F 0.030 0.051 0.033 0.079 0.150 0.198 0.148 0.151 0.124 0.238 0.175 0.144 Cl 0.098 0.086 0.048 0.045 0.023 0.016 0.013 0.018 0.031 0.025 0.027 0.027 Formation a Number of G position b G FWHM c R1 ratio d R2 ratio e Temperature f (°C) Sample No. [Depth (m)] spectra Mean SD Mean SD Mean SD Mean SD Mean SD Regional carbonate samples collected from the surface far away from the Tongshanling intrusion D1509 D 3 x 16 1574.24 1.77 54.48 0.01 0.57 0.02 1.31 0.09 238 D1512 D 2 q 16 1566.77 1.46 54.48 0.01 0.66 0.01 1.96 0.11 347 D1515 D 3 s 11 1576.18 2.45 54.48 0.01 0.60 0.01 1.51 0.09 282 D1522 D 3 s 11 1574.51 2.55 54.48 0.01 0.68 0.00 2.10 0.03 340 D1524 C 1 y 13 1578.66 3.09 54.46 0.01 0.57 0.01 1.33 0.08 244 D1531 D 3 x 10 1603.38 2.01 50.17 4.18 0.66 0.02 1.96 0.16 347 T1610 C 1 y 14 1561.64 10.18 53.21 3.30 0.61 0.02 1.57 0.14 293 T1613 C 1 y 15 1579.77 10.86 59.89 6.25 0.62 0.02 1.64 0.16 305 T1615 D 3 s 17 1574.81 4.76 80.61 7.40 0.66 0.01 1.92 0.06 348 T1637A D 3 s 15 1599.22 11.34 40.30 3.89 0.63 0.01 1.74 0.06 324 Metamorphosed carbonate samples collected from the surface and a drill core (ZK1001) in the Tongshanling ore district D1507B C 1 d 11 1579.94 1.45 18.05 1.45 0.11 0.05 0.16 0.07 570 T1532 C 1 d 15 1579.67 0.73 18.51 1.83 0.06 0.02 0.09 0.05 599 T1533 C 1 d 24 1579.33 1.30 19.68 2.16 0.11 0.04 0.15 0.05 572 T1641 C 1 d 20 1580.51 0.55 18.26 0.90 0.07 0.02 0.11 0.03 593 T1645 C 1 y 22 1580.63 0.37 22.56 1.32 0.09 0.03 0.12 0.04 587 ZK1001-08 C 1 d [1146] 15 1579.25 0.57 17.03 1.35 0.06 0.03 0.09 0.05 601 ZK1001-10 C 1 d [1110] 11 1579.12 1.45 18.53 1.41 0.15 0.05 0.17 0.07 564 ZK1001-15 C 1 d [980] 16 1579.21 0.91 20.91 0.92 0.20 0.05 0.22 0.06 544 ZK1001-18 C 1 d [851] 18 1579.38 0.69 21.94 1.31 0.23 0.12 0.24 0.09 532 ZK1001-22 C 1 d [651] 10 1580.46 0.49 25.05 2.23 0.28 0.10 0.28 0.06 516 ZK1001-23 C 1 d [601] 16 1581.33 0.54 22.97 0.75 0.56 0.15 0.36 0.05 480 ZK1001-24 C 1 d [550] 20 1580.88 2.05 23.58 2.11 1.19 0.66 0.49 0.10 421 ZK1001-25 C 1 d [500] 20 1582.92 4.75 39.44 6.47 1.75 0.36 0.60 0.07 372 ZK1001-26 C 1 d [404] 18 1587.09 5.77 51.14 8.45 1.96 0.31 0.67 0.04 343 ZK1001-29 C 1 d [203] 16 1596.68 2.63 53.22 4.95 2.21 0.17 0.71 0.02 326 ZK1001-31 C 1 d [42] 17 1586.72 3.84 37.39 5.31 2.26 0.40 0.72 0.03 320 Metamorphosed carbonate samples collected from the underground adits of the Tongshanling Cu-Pb-Zn deposit Samples close to the proximal endoskarn TSL1403 D 2 q 20 1580.48 0.61 17.20 1.68 0.03 0.02 0.04 0.02 624 TSL1410 D 2 q 18 1577.42 4.41 17.94 2.84 0.04 0.03 0.05 0.04 618 Samples close to the proximal exoskarn TSL1404 D 2 q 24 1579.89 2.73 18.39 3.41 0.08 0.04 0.10 0.05 595 TSL1407 D 2 q 22 1579.81 2.88 18.20 6.98 0.05 0.03 0.07 0.05 610 T1534A D 2 q 20 1580.51 0.95 18.16 1.52 0.04 0.03 0.05 0.04 619 Samples close to the sulfide-quartz vein TSL1411 D 3 s 21 1580.92 0.45 24.58 2.13 0.33 0.06 0.32 0.04 500 TSL1412 D 2 q 17 1580.71 0.72 25.00 1.23 0.23 0.05 0.23 0.04 539 TSL1413 D 2 q 20 1579.81 1.39 22.74 0.90 0.19 0.04 0.21 0.04 547 Samples close to the distal skarn T1507 D 3 x 15 1580.87 1.04 26.91 0.94 0.30 0.06 0.28 0.04 515 T1530A D 3 x 13 1581.06 1.12 27.48 1.47 0.52 0.14 0.41 0.06 461 Notes: LA-ICP-MS Hukeng W Muscovite granite LA-ICP-MS 151.6 ± 2.6 Liu et al. (2008a) Hongtaoling W Biotite granite SHRIMP 151.4 ± 3.1 Feng et al. (2007a) Mg/(Mg+Fe) 0.44 0.47 0.43 0.42 0.48 0.46 0.42 0.40 0.44 0.45 0.45 0.45 Fe 3+ /(Fe 2+ + Fe 3+ ) 0.14 0.15 0.13 0.16 0.23 0.16 0.16 0.19 0.16 0.18 0.17 0.20 Notes: a

a ASI: aluminum saturation index, n(Al 2 O 3 )/n(CaO+Na 2 O+K 2 O). b DI: differentiation index, the sum of CIPW normative minerals Q, Or, Ab, Ne, Lc, and Kp. c HFSE: high field strength elements (Zr+Nb+Ce+Y). d T Zr : zircon saturation temperature. Notes: General formula: IM 3 T 4 O 10 (OH, F, Cl) 2 . a Fe 3+ was calculated by the surplus oxygen method after Zheng (1983). b The estimation of OH was based on OH+F+Cl = 2. Appendix 6-1.

  LA-ICP-MS U-Pb dating results of garnet in the proximal exoskarn from the Tongshanling Cu-Pb-Zn deposit Some parameters for Raman spectra of carbonaceous material in carbonate rocks close to the magnesian and calcic skarns in the Weijia W deposit and temperatures calculated by the RSCM thermometry (mean value and standard deviation)

	Appendix 6-2. Representative EMP analyses of garnets (wt.%) from the proximal endoskarn and exoskarn of the Tongshanling Cu-Pb-Zn deposit
	Skarn Generation Point No. SiO 2 TiO 2 Al 2 O 3 FeO MnO MgO CaO Na 2 O K 2 O F Cl Total Ions based on 12 oxygen 1 36.93 0.02 16.11 12.01 1.66 0.02 33.32 0.00 0.03 0.00 0.04 100.09 T_Si 2.868 T_Al 0.132 ΣT 3.000 Cl 0.003 End members b (%) Gr 62.92 Ad 32.99 Appendix 7-1. Spot Elements (ppm) Pb Th U 207 Pb/ 206 Pb Proximal endoskarn 2 3 4 36.66 36.85 36.92 0.08 0.01 0.10 15.17 15.98 15.80 12.56 11.70 11.64 1.65 1.65 1.66 0.00 0.00 0.00 33.58 33.71 33.51 0.00 0.00 0.00 0.04 0.02 0.02 0.00 0.00 0.00 0.04 0.03 0.04 99.74 99.92 99.65 2.867 2.868 2.880 0.133 0.132 0.120 3.000 3.000 3.000 0.003 0.002 0.003 60.63 63.34 63.20 35.63 32.92 33.04 Isotopic ratios 5 36.18 0.00 14.47 13.65 1.56 0.01 33.81 0.00 0.01 0.00 0.03 99.68 2.844 0.156 3.000 0.002 57.77 38.67 1σ 207 Pb/ 235 U 1-2-01 0.26 0.03 9.72 0.048939 0.019178 0.223433 0.100543 0.026977 0.001657 6 7 36.53 35.09 34.92 8 0.01 0.00 0.00 16.50 2.30 2.06 10.79 27.49 27.56 1.96 0.38 0.44 0.01 0.05 0.06 33.45 34.24 34.28 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.03 0.04 0.02 99.26 99.55 99.35 2.860 2.889 2.885 0.140 0.111 0.115 3.000 3.000 3.000 0.002 0.003 0.001 65.24 10.47 9.41 30.28 88.11 89.35 1σ 206 Pb/ 238 U 1σ 207 Pb/ 206 Pb First generation 9 10 34.87 35.14 0.03 0.06 3.73 4.44 25.35 24.73 0.20 0.24 0.10 0.10 34.70 34.67 0.00 0.00 0.01 0.00 0.00 0.00 0.03 0.03 98.99 99.38 2.872 2.874 0.128 0.126 3.000 3.000 0.002 0.002 17.02 19.99 82.14 79.05 Ages (Ma) 11 35.17 0.00 3.81 24.70 0.31 0.16 34.20 0.00 0.00 0.00 0.03 98.34 2.907 0.093 3.000 0.002 17.60 81.05 1σ 207 Pb/ 235 U 146.4 725.8 204.8 83.4 1σ 206 Pb/ 238 U 1σ Proximal exoskarn Second generation 12 13 14 15 35.17 35.04 35.03 35.26 0.00 0.00 0.00 0.00 4.34 5.75 4.95 6.54 23.38 23.32 24.39 22.35 0.33 0.64 0.53 0.59 0.15 0.02 0.03 0.00 34.50 34.01 33.79 34.35 0.00 0.09 0.09 0.08 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.03 0.05 0.04 0.05 97.87 98.88 98.83 99.18 2.915 2.868 2.875 2.869 0.085 0.132 0.125 0.131 3.000 3.000 3.000 3.000 0.002 0.003 0.003 0.003 20.44 25.37 21.95 28.79 78.22 73.06 76.72 69.87 171.6 10.4 1-2-02 0.38 0.03 9.50 0.096833 0.024945 0.448277 0.152093 0.029738 0.002805 1564.8 500.0 376.1 106.6 188.9 17.6 1-2-03 0.37 0.03 10.29 0.054834 0.019057 0.204357 0.075525 0.026576 0.001561 405.6 633.3 188.8 63.7 Formation a Number of G position b G FWHM c R1 ratio d R2 ratio e Temperature f (°C) Appendix 8-1. Sample No. [Depth (m)] spectra Mean SD Mean SD Mean SD Mean SD Mean SD 169.1 9.8 1-2-04 0.18 0.02 7.25 0.012337 0.007236 0.202635 0.103736 0.024695 0.001777 187.4 87.6 Carbonate rocks close to the magnesian skarn 157.3 11.2 1-2-05 0.44 0.11 14.56 0.035332 0.010679 0.208372 0.117544 0.026316 0.001677 192.2 98.8 ZK803-6 D 2 q [601] 21 1580.10 3.01 24.00 2.46 0.51 0.17 0.36 0.07 481 29 167.5 10.5 1-2-06 0.41 0.08 13.38 0.046970 0.013289 0.219194 0.085812 0.026908 0.001432 55.7 557.3 201.2 71.5 ZK803-7 D 2 q [624] 22 1580.30 2.11 22.32 1.94 0.46 0.17 0.35 0.08 486 35 171.2 9.0 1-2-07 0.45 0.12 15.08 0.052511 0.016047 0.184665 0.069402 0.026084 0.001374 309.3 577.7 172.1 59.5 ZK803-9 D 2 q [565] 20 1581.36 0.57 22.77 1.50 0.59 0.20 0.37 0.07 477 33 166.0 8.6 1-2-08 0.31 0.05 7.53 0.122815 0.032590 0.609241 0.183162 0.029443 0.001852 1998.2 487.5 483.1 115.6 ZK803-17 D 2 q [615] 14 1579.81 2.64 24.36 3.71 0.54 0.08 0.38 0.02 470 10 187.1 11.6 1-2-09 0.39 0.19 12.50 0.065390 0.019121 0.259003 0.056590 0.027293 0.001422 787.0 646.2 233.9 45.6 ZK803-20 D 2 q [628] 25 1580.66 2.55 25.35 2.75 0.55 0.17 0.38 0.06 473 29 173.6 8.9 1-2-10 0.51 0.18 16.77 0.080256 0.018175 0.224366 0.044099 0.028541 0.001349 1203.4 459.4 205.5 36.6 ZK803-25 D 2 q [666] 12 1580.90 0.61 22.35 2.74 0.44 0.04 0.33 0.02 496 9 181.4 8.5 1-2-11 0.50 0.16 14.49 0.071699 0.021054 0.206117 0.058539 0.028077 0.001605 977.5 625.0 190.3 49.3 Carbonate rocks close to the calcic skarn 178.5 10.1 1-2-12 0.61 0.19 15.71 0.073554 0.014188 0.279307 0.047431 0.027565 0.001355 1029.3 394.0 250.1 37.6 WJ23 D 2 q [0] 16 1579.94 0.82 23.55 2.06 0.13 0.05 0.15 0.05 573 22 175.3 8.5 1-2-13 0.59 0.17 15.97 0.090933 0.023792 0.255400 0.072031 0.023547 0.001180 1455.6 516.7 231.0 58.3 WJ24 D 2 q [0] 15 1579.93 0.65 23.01 1.50 0.14 0.04 0.16 0.04 568 17 150.0 7.4 1-2-14 0.42 0.14 15.72 0.053655 0.016171 0.165985 0.042760 0.026614 0.001352 366.7 557.4 155.9 37.2 ZK7'02-4 D 2 q [42] 18 1580.11 0.26 21.42 1.05 0.20 0.05 0.20 0.04 554 18 169.3 8.5 1-2-15 0.44 0.13 14.06 0.085756 0.022678 0.244963 0.070105 0.025858 0.001392 1332.4 531.2 222.5 57.2 ZK7'02-17 D 2 q [176] 18 1579.71 0.75 20.33 3.20 0.15 0.07 0.15 0.05 576 21 164.6 8.7 1-2-16 0.39 0.15 15.37 0.089366 0.024653 0.284113 0.105711 0.023639 0.001177 1413.0 550.0 253.9 83.6 150.6 7.4 ZK7'02-18 D 2 q [180] 18 1579.89 0.45 21.35 6.13 0.16 0.13 0.16 0.04 572 16	16 35.42 0.01 6.37 22.25 0.74 0.01 34.02 0.08 0.02 0.00 0.05 98.93 2.887 0.113 3.000 0.004 28.25 70.02	Third generation 18 19 37.23 37.23 0.05 0.00 14.41 16.46 12.50 12.17 0.69 1.36 0.07 0.04 35.76 33.64 0.00 0.00 0.01 0.00 0.00 0.00 0.03 0.03 100.27 100.71 100.89 100.31 17 20 37.41 37.39 0.03 0.04 17.24 16.93 10.27 10.45 0.84 0.88 0.09 0.05 34.38 34.56 0.00 0.00 0.01 0.01 0.00 0.00 0.03 0.04 2.880 2.888 2.865 2.881 0.120 0.112 0.135 0.119 3.000 3.000 3.000 3.000 0.002 0.002 0.002 0.002 68.71 60.82 63.59 68.05 29.06 37.43 32.37 29.81
	B_Al Py + Al + Sp 1-2-17 0.30 0.07 10.46 1.342 4.09	1.266 3.74 0.026099 0.009569 0.177004 0.085985 0.024113 0.001568 1.334 1.332 1.185 1.382 0.113 0.086 3.74 3.76 3.56 4.48 1.42 1.24	0.234 0.84	0.302 0.95	0.277 1.35 165.5 74.2	0.338 1.34 153.6 9.9 0.423 1.57	0.354 1.33	0.495 1.34	0.499 1.73	1.443 2.23	1.206 1.74	1.358 4.04	1.419 2.14
	1-2-18 Notes: General formula: A 3 B 2 T 3 O 12 . a Fe 3+ was calculated based on the stoichiometric criteria after Droop (1987). b Mineral abbreviations: Ad = andradite, Al = almandine, Gr = grossularite, Py = pyrope, Sp = 0.24 0.06 9.71 0.043009 0.016189 0.220661 0.089927 0.023937 0.001480 202.5 74.8 152.5 9.3 1-2-19 0.33 0.07 10.81 0.040697 0.012388 0.196150 0.060537 0.025212 0.001469 181.9 51.4 160.5 9.2 spessartine. 1-2-20 0.43 0.16 14.94 0.077035 0.022432 0.213394 0.056517 0.024789 0.001317 1121.9 609.7 196.4 47.3 157.9 8.3
	1-2-21	0.48 0.15 16.06	0.090418 0.019451 0.303659 0.080001 0.023926 0.001317	1435.2 415.7	269.3 62.3	152.4 8.3
	1-2-22	0.50 0.19 17.19	0.072609 0.020124 0.207200 0.056798 0.025658 0.001214	1002.8 588.9	191.2 47.8	163.3 7.6
	1-2-23	0.49 0.19 15.45	0.091629 0.026971 0.246048 0.055312 0.025958 0.001400	1461.1 585.3	223.4 45.1	165.2 8.8
	1-2-24	0.46 0.20 13.79	0.114048 0.031148 0.372318 0.123122 0.027943 0.001567	1865.1 506.0	321.4 91.1	177.7 9.8
	1-2-25	0.44 0.07 12.34	0.041993 0.012332 0.303210 0.057434 0.027684 0.001758			268.9 44.7	176.0 11.0

  Appendix 8-2. Whole-rock major and trace element compositions of the altered Weijia granite

	Appendix 8-2. (Continued)
	Sample No. ZK802-6 ZK803-29 ZK1001-2 ZK1001-3 ZK1001-5 ZK1001-6 ZK1001-7 ZK1001-9 Sample No. ZK802-6 ZK803-29 ZK1001-2 ZK1001-3 ZK1001-5 ZK1001-6 ZK1001-7 ZK1001-9	WJ29 WJ29	WJ35 ZK706-1 ZK706-2 WJ35 ZK706-1 ZK706-2
	Depth (m) Depth (m)	565 565	548 548	642 642	634 634	616 616	604 604	594 594	573 573	0 0	0 0	286 286	279 279
	Major elements (wt.%) Ta 4.79	7.64	4.95	5.05	5.11	5.82	5.96	7.20	8.91	7.42	6.47	7.04
	SiO 2 W		73.85 14.16	72.81 38.83	71.19 3.88	74.62 4.42	75.38 3.73	74.93 4.69	73.10 5.38	74.98 4.86	76.82 5.43	75.82 264.89	73.87 3.42	74.12 3.01
	TiO 2 Pb		0.06 39.36	0.02 37.42	0.05 56.34	0.05 38.93	0.05 40.49	0.04 51.87	0.05 36.57	0.04 36.53	0.01 20.27	0.02 37.68	0.02 43.90	0.02 42.19
	Al 2 O 3 Th	12.79 26.63	12.40 23.09	13.52 25.61	13.85 28.60	12.92 27.43	12.88 20.91	13.58 25.19	12.53 22.87	12.72 26.71	12.74 27.79	13.46 26.28	13.65 26.39
	Fe 2 O 3 U	0.31 15.89	0.12 16.27	0.83 12.72	0.26 19.41	0.72 18.92	0.81 11.42	0.31 18.05	0.25 17.22	0.15 8.14	0.21 16.32	0.15 18.95	0.24 18.32
	FeO		0.49	0.16	0.81	0.84	0.66	0.83	0.73	1.00	0.07	0.40	0.36	0.51
	MnO Rare earth elements (REE) 0.07	0.02	0.05	0.03	0.06	0.10	0.10	0.09	0.00	0.02	0.01	0.01
	MgO La	0.90 17.32	0.11 12.62	0.39 28.98	0.21 28.30	0.22 27.30	0.16 25.04	0.17 26.59	0.11 24.89	0.04 9.96	0.19 15.39	0.09 13.10	0.13 13.50
	CaO Ce		0.69 42.72	3.03 20.49	2.64 66.29	1.18 63.72	0.98 61.92	1.39 57.66	1.62 60.05	1.36 57.32	0.18 18.26	1.26 29.85	1.16 29.26	1.04 27.88
	Na 2 O Pr	0.22 5.60	0.54 4.63	0.10 8.29	0.14 12.21	1.48 12.00	0.94 7.30	1.51 11.65	1.74 11.48	1.59 3.64	2.36 6.14	3.19 6.24	3.00 5.93
	K 2 O Nd		7.78 31.67	8.28 14.65	5.71 31.95	5.72 34.98	5.54 34.18	4.58 28.01	5.45 32.76	5.00 33.47	5.78 12.24	5.57 19.82	5.45 19.35	5.23 18.30
	P 2 O 5 Sm		0.02 9.86	0.01 6.63	0.02 10.49	0.02 11.08	0.02 10.99	0.02 9.16	0.02 10.43	0.02 11.98	0.02 7.26	0.01 8.29	0.01 8.33	0.01 8.06
	LOI Eu		2.49 0.28	2.66 0.12	4.02 0.25	3.08 0.21	2.33 0.19	2.36 0.15	2.94 0.19	2.33 0.17	1.87 0.06	1.79 0.11	1.70 0.09	2.02 0.09
	Total Gd	99.66 11.30	100.16 8.90	99.32 10.46	99.98 12.65	100.36 12.42	99.05 9.01	99.57 11.97	99.43 13.21	99.26 11.38	100.38 10.23	99.46 10.90	99.99 10.83
	Tb		2.34	2.16	2.48	2.66	2.61	2.17	2.56	2.78	2.99	2.38	2.57	2.61
	Trace elements (ppm) Dy 15.80	14.53	15.15	17.26	16.90	13.18	16.60	17.59	21.32	16.00	17.58	18.00
	Li Ho		18.62 3.05	5.16 2.80	20.13 2.91	22.08 3.34	30.96 3.24	39.19 2.46	31.28 3.17	35.35 3.29	5.84 4.18	12.23 3.11	9.98 3.45	13.18 3.56
	Be Er		6.25 8.60	10.84 7.97	12.01 7.79	7.69 9.53	5.67 9.23	18.03 6.61	4.70 9.07	18.13 9.49	2.17 11.89	9.47 8.85	5.12 9.95	9.36 10.21
	Sc Tm		8.13 1.27	5.35 1.17	15.74 1.34	10.76 1.39	10.15 1.35	13.99 1.17	10.17 1.35	10.26 1.46	4.14 1.76	8.53 1.31	9.70 1.48	9.69 1.53
	Ti Yb		386.31 7.89	196.16 1094.95 7.32 7.96	443.71 8.61	399.34 1073.45 8.44 7.13	446.10 8.63	313.66 9.57	73.19 10.90	197.55 8.28	177.25 9.36	192.69 9.63
	Mn Lu		691.13 1.11	186.83 1.03	539.26 1.15	217.43 1.24	469.80 1.21	898.70 1.04	753.27 1.24	701.25 1.40	64.31 1.55	215.16 1.18	118.50 1.35	153.76 1.38
	Cu		2.34	1.55	2.90	0.54	0.49	2.48	1.13	0.45	0.27	0.55	1.47	2.40
	Zn ΣREE	99.28 158.81	31.82 105.02	62.91 195.47	65.14 207.19	62.75 201.98	100.14 170.08	75.16 196.26	67.18 198.11	16.04 117.40	25.82 130.93	16.70 133.01	22.64 131.51
	Ga La/Yb	26.88 2.20	25.84 1.72	33.73 3.64	28.24 3.29	26.24 3.23	32.24 3.51	29.18 3.08	27.92 2.60	28.38 0.91	28.54 1.86	27.98 1.40	30.58 1.40
	Rb K/Rb	619.16 104.28	535.09 128.46	496.16 95.50	435.02 109.09	412.27 111.47	505.75 75.14	499.94 90.41	500.77 82.87	308.68 155.32	350.27 132.02	398.48 113.39	409.01 106.00
	Sr Y/Ho	37.72 26.97	25.92 27.10	43.58 33.24	25.35 27.55	40.99 27.57	44.24 34.70	41.68 28.52	26.60 29.60	23.85 28.31	29.16 25.63	20.03 27.92	23.01 27.84
	Y Zr/Hf	82.26 18.47	75.98 15.09	96.69 18.90	92.15 16.79	89.36 17.23	85.41 18.28	90.29 16.73	97.53 15.57	118.23 12.13	79.59 14.66	96.44 14.29	99.10 13.75
	Zr Sr/Eu	115.45 134.71	65.52 213.20	81.35 177.14	84.82 120.09	89.35 220.93	74.42 296.91	83.39 218.62	78.29 159.17	69.41 407.80	75.16 267.52	69.64 216.07	65.42 248.60
	Nb δEu a		36.99 0.08	49.47 0.05	50.49 0.07	41.33 0.05	40.23 0.05	48.15 0.05	39.64 0.05	36.20 0.04	49.09 0.02	47.96 0.04	49.23 0.03	46.65 0.03
	Sn TE 1,3	b	55.04 1.02	3.00 1.10	6.46 1.14	8.62 1.18	9.81 1.19	13.44 1.15	13.66 1.20	24.88 1.20	0.79 1.14	1.76 1.13	4.63 1.19	10.30 1.17
	Cs		13.10	15.22	13.80	13.39	14.41	12.99	15.03	13.56	7.90	14.90	7.91	9.52
	Ba		195.34	130.39	158.30	135.26	123.84	66.38	112.91	110.79	24.50	35.00	24.75	38.41
	Hf		6.25	4.34	4.31	5.05	5.19	4.07	4.98	5.03	5.72	5.13	4.87	4.76
											(To be continued on the next page)

Dong HUANG Les granitoïdes du jurassique moyen et les skarns à Cu-Pb-Zn et à W associées dans la région de Nanling (Chine du Sud): les gisements de Tongshanling et de Weijia Middle-Late Jurassic Cu-Pb-Zn-bearing and W-bearing granitoids and their skarn mineralization in the Nanling Range, South China: the Tongshanling and Weijia deposits

  Representative EMP analyses of garnet in the magnesian and calcic skarns of the Weijia W deposit LA-ICP-MS analyses of garnet in the magnesian and calcic skarns of the Weijia W deposit General formula: ABT 2 O 6 . a Fe 3+ is calculated based on the stoichiometric criteria after[START_REF] Droop | A general equation for estimating Fe 3+ concentrations in ferromagnesian silicates and oxides from microprobe analyses, using stoichiometric criteria[END_REF]. b Mineral abbreviations: Di = diopside, Hd = hedenbergite, Jo = johannsenite. Representative EMP analyses of vesuvianite in the calcic skarn of the Weijia W deposit General formula: I 19 M 13 T 18 O 68 (OH, F, Cl) 10 . a All Fe as Fe 2+ . b The estimation of OH is based on OH + F + Cl = 10. Representative LA-ICP-MS analyses of scheelite from the Weijia W deposit

	Nov. 2018 Xu-	X.D. HUANG
	Appendix 8-3. Representative EMP analyses of fresh and bleached biotite in the Weijia granite Occurrence Biotite in the granite without stockwork veins Sample No. WJ2 Type Fresh Bleached Fresh SiO 2 (wt.%) 32.30 31.94 31.42 32.36 32.21 29.65 33.84 33.76 TiO 2 0.59 0.30 0.19 0.35 0.43 0.36 2.45 2.60 Al 2 O 3 18.64 19.04 20.56 20.66 21.78 19.35 15.09 15.35 FeO 28.51 30.41 31.66 31.95 30.60 35.15 29.89 33.19 MnO 0.86 0.96 0.94 0.93 0.87 1.34 0.60 0.66 MgO 0.27 0.36 0.37 0.64 0.34 0.33 2.97 1.03 CaO 0.00 0.00 0.10 0.05 0.04 0.08 0.11 0.00 Na 2 O 0.19 0.10 0.06 0.07 0.06 0.08 0.37 0.37 K 2 O 8.62 7.89 5.30 5.23 4.40 3.89 8.54 8.21 F 3.64 2.42 0.59 0.48 0.03 0.91 4.84 3.06 Cl 0.13 0.12 0.10 0.08 0.02 0.06 0.44 0.29 Total 93.75 93.55 91.28 92.80 90.78 91.19 99.15 98.51 Li 2 O a 1.74 0.93 0.11 0.08 0.00 0.21 2.71 1.33 Ions based on 22 oxygen T_Si 5.360 5.333 5.274 5.319 5.316 5.092 5.343 5.434 T_Al 2.640 2.667 2.726 2.681 2.684 2.908 2.657 2.566 ΣT 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 Appendix 8-3. (Continued) Occurrence Biotite in the granite without stockwork veins Sample No. WJ2 Type Fresh Bleached Fresh M_Al 1.005 1.078 1.342 1.322 1.551 1.007 0.151 0.347 M_Ti 0.073 0.038 0.024 0.043 0.054 0.047 0.290 0.314 M_Fe 3.956 4.246 4.445 4.392 4.224 5.048 3.947 4.467 M_Mg 0.066 0.090 0.093 0.157 0.083 0.083 0.699 0.247 M_Mn 0.120 0.136 0.133 0.129 0.122 0.195 0.080 0.090 M_Li 1.162 0.624 0.072 0.050 0.001 0.142 1.720 0.861 ΣM 6.383 6.212 6.109 6.093 6.034 6.522 6.887 6.326 I_Ca 0.000 0.000 0.018 0.009 0.007 0.014 0.018 0.000 I_Na 0.061 0.033 0.021 0.023 0.018 0.027 0.114 0.114 I_K 1.825 1.680 1.134 1.096 0.926 0.851 1.720 1.685 ΣI 1.886 1.713 1.173 1.128 0.951 0.892 1.853 1.799 OH b 2.054 2.687 3.657 3.729 3.978 3.487 1.462 2.365 Fe 2+ 2.570 3.353 4.445 4.392 4.224 4.891 1.883 3.287 Notes: General formula: IM 2-3 T 4 O 10 (OH, F, Cl) 2 . a Li 2 O is estimated using the equations Li 2 O = 0.237 × F 1.544 (trioctahedral micas) and Li 2 O = 0.3935 × F 1.326 (dioctahedral micas) after Tischendorf et al. (1997). b The estimation Biotite in the granite with stockwork veins ZK902-1 WJ1616B WJ1617B Bleached Bleached Bleached 33.46 30.45 30.44 30.01 37.14 40.38 37.95 42.61 45.14 45.72 43.34 41.65 2.41 2.91 2.95 0.85 1.40 0.64 0.44 1.17 0.18 0.00 0.09 0.04 15.51 16.79 16.98 20.31 17.93 18.04 16.71 18.71 24.03 22.58 19.39 15.27 33.53 36.24 34.27 35.54 23.02 22.29 25.55 18.16 12.02 13.96 17.12 25.49 0.60 0.65 0.82 0.65 0.31 0.29 0.24 0.33 0.10 0.21 0.21 0.06 1.27 1.48 2.48 1.18 0.34 0.52 0.46 0.69 0.36 0.40 0.48 0.58 0.00 0.00 0.02 0.28 0.44 0.67 0.74 1.03 0.61 0.98 1.31 1.70 0.40 0.18 0.11 0.06 0.06 0.11 0.08 0.05 0.00 0.02 0.10 0.10 8.62 5.10 4.07 3.32 6.10 5.47 4.85 4.45 6.35 4.63 2.74 0.88 2.42 1.17 0.85 0.53 0.65 0.60 1.04 0.35 0.00 0.00 0.11 0.24 0.47 0.26 0.27 0.16 0.17 0.04 0.05 0.03 0.04 0.00 0.00 0.00 98.68 95.23 93.25 92.88 87.55 89.04 88.10 87.58 88.84 88.48 84.87 86.00 0.92 0.30 0.19 0.09 0.12 0.11 0.25 0.10 0.00 0.00 0.02 0.03 5.407 5.072 5.093 5.007 6.155 6.447 6.286 6.660 6.691 6.805 6.831 6.781 2.593 2.928 2.907 2.993 1.845 1.553 1.714 1.340 1.309 1.195 1.169 1.219 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 (To be continued on the next page) Biotite in the granite with stockwork veins ZK902-1 WJ1616B WJ1617B Bleached Bleached Bleached 0.360 0.368 0.442 0.999 1.656 1.841 1.548 2.107 2.889 2.765 2.433 1.712 0.293 0.365 0.371 0.107 0.174 0.077 0.055 0.137 0.020 0.000 0.011 0.005 4.531 5.050 4.796 4.958 3.190 2.977 3.539 2.374 1.490 1.738 2.257 3.470 0.305 0.367 0.619 0.293 0.083 0.123 0.112 0.161 0.080 0.088 0.112 0.141 0.082 0.092 0.117 0.091 0.043 0.039 0.033 0.043 0.013 0.026 0.027 0.008 0.601 0.201 0.125 0.059 0.081 0.069 0.168 0.062 0.000 0.000 0.013 0.017 6.172 6.443 6.468 6.508 5.228 5.126 5.456 4.885 4.492 4.618 4.853 5.353 0.000 0.000 0.003 0.050 0.077 0.114 0.130 0.173 0.097 0.155 0.221 0.297 0.127 0.059 0.037 0.018 0.020 0.035 0.027 0.016 0.000 0.005 0.030 0.033 1.776 1.084 0.869 0.707 1.290 1.113 1.024 0.887 1.201 0.879 0.550 0.182 1.903 1.143 0.908 0.775 1.388 1.262 1.181 1.076 1.299 1.039 0.800 0.512 2.638 3.313 3.473 3.675 3.612 3.687 3.442 3.818 3.990 4.000 3.946 3.878 3.423 4.644 4.692 4.958 3.190 2.977 3.539 2.374 1.490 1.738 2.257 3.470 of OH is based on OH + F + Cl = 2. c Fe 3+ is calculated based on the surplus oxygen method after Zheng (1983). 303 Appendix 8-4. Representative EMP analyses of white mica in the Weijia granite and its stockwork veins Occurrence White mica in the matrix of granite without stockwork veins White mica coexisting with fluorite as aggregates in the granite without stockwork veins White mica in the matrix of granite with stockwork veins White mica in the bleached zone near stockwork veins White mica in the K-feldspar-quartz pegmatite veins Sample No. WJ2 ZK706-2 WJ13 WJ1616B WJ1617B WJ1616A Type Core Core Core Rim SiO 2 (wt.%) 44.48 47.33 48.57 49.27 48.28 46.13 46.57 46.48 44.43 42.72 47.81 49.06 46.03 49.03 48.71 49.85 45.55 47.35 49.22 49.17 TiO 2 0.00 0.31 0.29 0.27 0.00 0.00 0.17 0.10 0.04 0.18 0.08 0.04 0.06 0.13 0.20 0.07 0.00 0.03 0.01 0.00 Al 2 O 3 28.98 30.41 32.42 31.43 37.39 36.98 33.76 36.41 25.16 27.72 28.98 32.46 31.57 28.08 28.03 30.88 26.37 27.63 28.84 34.07 FeO 6.04 3.05 3.24 3.58 0.08 0.32 1.19 0.67 8.83 9.61 4.00 2.14 2.60 4.54 4.08 2.67 8.74 6.12 5.48 1.07 MnO 0.29 0.00 0.07 0.00 0.00 0.00 0.10 0.01 0.06 0.18 0.14 0.10 0.03 0.03 0.07 0.04 0.22 0.39 0.21 0.04 MgO 0.08 0.19 0.22 0.26 0.01 0.02 0.40 0.09 0.16 0.16 0.33 0.06 0.02 0.29 0.31 0.39 0.07 0.03 0.07 0.05 CaO 0.09 0.00 0.03 0.00 0.00 0.00 0.00 0.10 0.00 0.01 0.09 0.21 0.01 0.15 0.10 0.40 0.00 0.00 0.00 0.00 Na 2 O 0.32 0.04 0.04 0.08 0.20 0.26 0.40 0.42 0.20 0.23 0.03 0.08 0.30 0.03 0.02 0.05 0.20 0.05 0.06 0.07 K 2 O 10.55 10.27 9.52 9.88 10.15 10.58 9.83 9.99 9.81 10.53 9.17 8.82 10.32 9.60 9.06 8.31 10.41 10.59 10.20 9.94 F 4.38 1.54 0.70 0.40 0.81 0.15 1.14 0.35 7.09 4.36 1.67 0.22 2.32 1.61 1.03 0.49 7.90 5.58 3.59 0.38 Cl 0.01 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.02 0.02 Total 95.21 93.13 95.09 95.17 96.92 94.45 93.55 94.62 95.75 95.69 92.28 93.19 93.26 93.48 91.61 93.16 99.43 97.77 97.69 94.80 Li 2 O a 2.32 0.69 0.24 0.12 0.30 0.03 0.47 0.10 4.88 2.30 0.77 0.05 1.20 0.74 0.41 0.15 5.76 3.37 2.14 0.11 Ions based on 22 oxygen T_Si 6.217 6.520 6.491 6.589 6.248 6.151 6.311 6.188 6.214 6.075 6.638 6.599 6.349 6.744 6.785 6.714 6.121 6.404 6.556 6.509 T_Al 1.783 1.480 1.509 1.411 1.752 1.849 1.689 1.812 1.786 1.925 1.362 1.401 1.651 1.256 1.215 1.286 1.879 1.596 1.444 1.491 ΣT 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 (To be continued on the next page) Appendix 8-4. (Continued) Occurrence White mica in the matrix of granite without stockwork veins White mica coexisting with fluorite as aggregates in the granite without stockwork veins White mica in the matrix of granite with stockwork veins White mica in the bleached zone near stockwork veins White mica in the K-feldspar-quartz pegmatite veins Sample No. WJ2 ZK706-2 WJ13 WJ1616B WJ1617B WJ1616A Type Core Core Core Rim M_Al 2.991 3.458 3.597 3.543 3.950 3.962 3.702 3.899 2.361 2.721 3.381 3.744 3.481 3.297 3.387 3.616 2.297 2.808 3.083 3.824 M_Ti 0.000 0.032 0.029 0.027 0.000 0.000 0.018 0.010 0.004 0.019 0.009 0.004 0.006 0.013 0.021 0.007 0.000 0.003 0.001 0.000 M_Fe 0.706 0.351 0.362 0.401 0.009 0.035 0.135 0.074 1.033 1.142 0.464 0.241 0.300 0.522 0.476 0.301 0.982 0.692 0.610 0.118 M_Mg 0.016 0.038 0.045 0.052 0.002 0.005 0.080 0.018 0.032 0.034 0.068 0.012 0.004 0.059 0.065 0.078 0.013 0.006 0.014 0.010 M_Mn 0.035 0.000 0.008 0.000 0.000 0.000 0.011 0.001 0.007 0.022 0.016 0.012 0.003 0.003 0.008 0.004 0.024 0.045 0.023 0.005 M_Li 1.301 0.385 0.131 0.062 0.154 0.016 0.255 0.053 2.743 1.315 0.432 0.029 0.667 0.409 0.229 0.084 3.112 1.831 1.147 0.058 ΣM 5.049 4.264 4.172 4.085 4.115 4.019 4.201 4.055 6.179 5.253 4.370 4.041 4.462 4.303 4.185 4.091 6.429 5.386 4.879 4.015 I_Ca 0.013 0.000 0.004 0.000 0.000 0.000 0.000 0.015 0.000 0.001 0.013 0.031 0.001 0.022 0.015 0.058 0.000 0.000 0.000 0.000 I_Na 0.086 0.011 0.010 0.020 0.049 0.067 0.105 0.108 0.053 0.063 0.007 0.020 0.080 0.009 0.006 0.012 0.052 0.012 0.015 0.017 I_K 1.881 1.804 1.622 1.686 1.676 1.799 1.699 1.697 1.750 1.909 1.624 1.514 1.817 1.684 1.610 1.427 1.785 1.827 1.733 1.678 ΣI 1.981 1.816 1.636 1.707 1.725 1.866 1.804 1.819 1.803 1.973 1.643 1.564 1.898 1.715 1.631 1.498 1.837 1.840 1.748 1.695 OH b 2.063 3.330 3.705 3.832 3.670 3.935 3.511 3.852 0.864 2.041 3.269 3.906 2.987 3.300 3.546 3.788 0.644 1.615 2.484 3.837 F 1.934 0.669 0.295 0.168 0.329 0.062 0.489 0.148 3.136 1.959 0.731 0.094 1.013 0.700 0.454 0.210 3.356 2.385 1.512 0.158 Appendix 8-4. (Continued) Occurrence White mica in the K-feldspar-quartz pegmatite veins White mica in the (K-feldspar)-quartz veins or veinlets White mica in the stockwork quartz veinlets Sample No. WJ1617A WJ3 WJ1620 WJ1628A WJ1628B Type Core Core Core Rim Rim Rim Core Core Core Rim Core Core Core Core Rim Rim SiO 2 (wt.%) 45.45 47.18 45.97 45.52 46.23 46.85 45.89 45.82 47.39 49.40 46.94 46.65 45.27 45.43 46.86 47.79 49.24 49.47 49.26 48.30 TiO 2 0.00 0.18 0.21 0.06 0.00 0.04 0.05 0.11 0.00 0.00 0.04 0.13 0.15 0.00 0.00 0.00 0.03 0.01 0.00 0.00 Al 2 O 3 25.99 27.82 30.14 31.73 34.40 34.65 27.19 26.12 30.04 33.37 25.54 30.23 32.02 31.82 32.88 34.65 31.93 32.33 32.50 32.10 FeO 7.36 4.87 3.80 2.85 0.50 0.24 6.94 8.91 2.67 1.09 8.19 4.95 2.81 2.47 1.57 0.43 1.22 1.31 1.13 1.00 MnO 0.27 0.19 0.07 0.09 0.27 0.11 0.26 0.18 0.92 0.19 0.52 0.24 0.21 0.12 0.31 0.04 0.00 0.10 0.00 0.11 MgO 0.03 0.02 0.02 0.01 0.05 0.05 0.04 0.09 0.05 0.29 0.07 0.11 0.03 0.02 0.02 0.02 0.19 0.38 0.49 0.60 CaO 0.00 0.00 0.00 0.00 0.05 0.06 0.00 0.12 0.00 0.12 0.01 0.14 0.00 0.00 0.00 0.02 0.13 0.24 0.23 0.28 Na 2 O 0.17 0.15 0.30 0.28 0.22 0.09 0.14 0.13 0.06 0.06 0.14 0.25 0.47 0.43 0.11 0.07 0.06 0.05 0.04 0.08 K 2 O 10.62 10.92 10.73 10.60 10.21 10.19 10.13 9.78 9.78 9.21 9.65 9.57 10.59 10.21 9.98 9.82 8.36 9.14 8.30 8.25 F 6.11 5.04 3.59 2.34 1.31 0.33 8.02 6.25 3.28 0.34 6.39 4.55 3.60 2.87 1.25 0.27 0.57 0.13 0.24 0.00 Cl 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.02 0.04 0.05 0.00 0.02 0.00 0.02 0.02 0.03 0.01 Total 96.01 96.36 94.84 93.49 93.24 92.60 98.65 97.51 94.18 94.09 97.51 96.84 95.19 93.36 93.01 93.11 91.74 93.17 92.21 90.74 Li 2 O a 3.88 2.88 2.14 1.22 0.57 0.09 5.90 4.02 1.90 0.10 4.15 2.46 2.15 1.59 0.53 0.07 0.18 0.02 0.06 0.00 Ions based on 22 oxygen T_Si 6.328 6.449 6.311 6.292 6.282 6.354 6.139 6.289 6.472 6.564 6.409 6.301 6.168 6.268 6.404 6.421 6.679 6.635 6.634 6.607 T_Al 1.672 1.551 1.689 1.708 1.718 1.646 1.861 1.711 1.528 1.436 1.591 1.699 1.832 1.732 1.596 1.579 1.321 1.365 1.366 1.393 ΣT 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 (To be continued on the next page) Appendix 8-4. (Continued) Occurrence White mica in the K-feldspar-quartz pegmatite veins White mica in the (K-feldspar)-quartz veins or veinlets White mica in the stockwork quartz veinlets Sample No. WJ1617A WJ3 WJ1620 WJ1628A WJ1628B Type Core Core Core Rim Rim Rim Core Core Core Rim Core Core Core Core Rim Rim M_Al 2.593 2.930 3.188 3.460 3.791 3.893 2.425 2.515 3.308 3.790 2.518 3.113 3.309 3.443 3.699 3.907 3.785 3.745 3.793 3.783 M_Ti 0.000 0.018 0.021 0.006 0.000 0.004 0.005 0.011 0.000 0.000 0.004 0.013 0.015 0.000 0.000 0.000 0.003 0.001 0.000 0.000 M_Fe 0.856 0.557 0.437 0.329 0.057 0.027 0.777 1.022 0.305 0.121 0.935 0.559 0.320 0.285 0.180 0.048 0.138 0.147 0.128 0.115 M_Mg 0.007 0.003 0.005 0.003 0.009 0.011 0.008 0.019 0.010 0.058 0.015 0.022 0.005 0.005 0.004 0.004 0.038 0.077 0.097 0.122 M_Mn 0.031 0.022 0.008 0.011 0.031 0.012 0.029 0.021 0.106 0.022 0.060 0.028 0.024 0.014 0.036 0.005 0.000 0.011 0.000 0.013 M_Li 2.172 1.583 1.184 0.676 0.309 0.050 3.175 2.218 1.044 0.051 2.281 1.337 1.179 0.885 0.292 0.037 0.101 0.013 0.033 0.000 ΣM 5.659 5.113 4.842 4.485 4.197 3.996 6.419 5.805 4.773 4.042 5.813 5.072 4.853 4.632 4.210 4.001 4.065 3.994 4.051 4.033 I_Ca 0.000 0.000 0.000 0.000 0.007 0.008 0.000 0.018 0.000 0.018 0.002 0.020 0.000 0.000 0.000 0.003 0.019 0.034 0.033 0.041 I_Na 0.047 0.039 0.079 0.074 0.058 0.023 0.035 0.034 0.015 0.016 0.037 0.065 0.124 0.114 0.028 0.017 0.016 0.013 0.011 0.022 I_K 1.887 1.904 1.879 1.869 1.770 1.763 1.728 1.712 1.704 1.561 1.681 1.649 1.841 1.797 1.740 1.683 1.447 1.563 1.425 1.440 ΣI 1.934 1.942 1.958 1.943 1.834 1.794 1.763 1.764 1.718 1.595 1.719 1.733 1.965 1.911 1.768 1.703 1.482 1.610 1.470 1.503 OH b 1.308 1.821 2.437 2.976 3.435 3.855 0.606 1.285 2.584 3.854 1.236 2.047 2.438 2.746 3.452 3.885 3.753 3.943 3.890 3.997 F 2.692 2.179 1.560 1.024 0.565 0.143 3.394 2.715 1.416 0.144 2.759 1.945 1.551 1.254 FeO b 3.40 3.17 1.60 6.61 5.34 5.73 6.55 5.54 5.70 5.81 5.53 2.58 2.46 3.18 2.27 3.38 1.35 1.25 4.53 4.86 MnO 0.14 0.24 0.07 0.28 0.19 0.31 0.21 0.15 0.39 0.29 0.15 0.04 0.11 0.08 0.00 0.01 0.09 0.00 0.43 0.39 MgO 39.54 40.03 40.61 32.15 32.62 34.84 34.01 36.09 33.83 36.03 35.29 32.56 34.42 32.96 30.30 31.55 31.65 36.26 30.92 30.39 CaO 0.11 0.11 0.11 0.41 0.29 0.06 0.02 0.07 0.26 0.09 0.04 0.38 0.22 0.30 0.48 1.34 0.46 0.26 0.14 0.12 Na 2 O 0.01 0.03 0.00 0.03 0.03 0.02 0.04 0.06 0.04 0.07 0.00 0.05 0.05 0.00 0.00 0.00 0.00 0.03 0.04 0.00 K 2 O 0.00 0.00 0.00 0.00 0.00 0.00 1.53 0.05 0.07 0.02 0.03 0.01 0.14 0.00 0.04 0.02 0.01 0.00 0.00 0.00 F 1.57 2.42 3.01 1.88 2.31 0.66 1.29 1.91 1.27 1.54 0.20 2.36 3.25 2.50 2.92 3.04 1.52 2.13 0.00 0.68 Cl 0.00 0.01 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.01 0.00 0.00 0.00 0.02 0.00 0.01 0.00 0.00 0.01 0.00 Total 87.82 88.54 88.86 84.10 84.00 84.36 89.95 87.29 84.35 88.36 86.86 86.27 89.15 85.07 78.83 83.83 79.28 84.76 77.80 78.10 Ions based on 14 oxygen T_Si 3.891 3.849 3.871 4.200 4.233 3.892 3.804 3.875 4.128 3.847 3.760 4.356 4.305 4.410 4.410 4.373 4.398 4.278 4.042 4.213 FeO 2.15 3.45 4.26 7.58 5.03 7.35 9.61 11.19 15.44 9.91 12.02 20.10 21.86 22.06 1.95 2.64 1.98 1.53 1.02 1.89 MnO 0.10 0.10 0.08 0.41 0.16 0.38 0.37 0.33 0.36 0.64 0.52 0.66 1.24 1.49 0.29 0.01 0.10 0.12 0.00 0.13 MgO 27.89 30.80 31.57 23.20 25.10 25.00 21.34 19.95 17.73 20.99 20.65 15.22 12.56 11.88 25.58 26.59 27.60 27.36 28.01 26.97 CaO 0.00 0.00 0.04 0.03 0.06 0.03 0.08 0.08 0.07 0.02 0.05 0.02 0.06 0.04 0.02 0.00 0.00 0.10 0.02 0.00 Na 2 O 0.17 0.14 0.09 0.13 0.17 0.16 0.17 0.23 0.10 0.15 0.10 0.02 0.10 0.00 0.29 0.35 0.22 0.25 0.27 0.31 K 2 O 10.41 6.94 7.04 8.00 9.84 8.74 9.79 9.36 7.33 9.72 9.28 8.48 8.36 8.55 9.63 9.58 9.43 9.47 9.73 9.95 F 4.57 5.23 6.27 3.65 4.45 4.06 4.27 2.93 1.72 3.75 4.15 3.29 2.05 1.74 2.46 2.81 3.21 4.02 3.00 2.40 Cl 0.00 0.01 0.00 0.00 0.03 0.00 0.00 0.00 0.01 0.01 0.03 0.01 0.04 0.04 0.01 0.00 0.01 0.00 0.00 0.00 Total 99.24 98.52 99.06 96.02 98.26 97.10 98.13 95.98 92.95 98.20 99.30 98.14 95.39 95.32 96.96 98.24 98.53 97.26 97.66 97.20 Ions based on 22 oxygen T_Si 5.933 6.082 5.799 5.478 5.805 5.600 5.787 5.921 5.632 6.142 6.026 5.981 5.901 5.938 5.700 5.811 5.931 5.945 6.064 5.947 T_Al 2.011 1.503 1.609 2.522 2.195 2.332 2.213 2.079 2.368 1.858 1.974 2.019 2.099 2.062 2.300 2.189 2.069 2.055 1.936 2.053 ΣT 7.943 7.585 7.407 8.000 8.000 7.932 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 8.000 (To be continued on the next page) M_Fe 0.255 0.409 0.513 0.936 0.609 0.907 1.191 1.405 2.006 1.216 1.477 2.576 2.892 2.915 0.230 0.308 0.231 0.182 0.120 0.222 M_Mg 5.887 6.514 6.788 5.110 5.415 5.498 4.713 4.464 4.107 4.592 4.524 3.478 2.962 2.800 5.373 5.539 5.733 5.812 5.833 5.649 M_Mn 0.012 0.012 0.010 0.051 0.020 0.047 0.047 0.042 0.047 0.079 0.064 0.086 0.166 0.200 0.034 0.001 0.011 0.015 0.000 0.015 ΣM 6.154 6.935 7.317 6.354 6.118 6.452 6.079 6.037 6.341 5.958 6.085 6.163 6.126 6.080 6.040 6.078 6.096 6.077 6.025 6.024 I_Ca 0.000 0.000 0.006 0.004 0.010 0.005 0.012 0.012 0.011 0.003 0.007 0.003 0.010 0.006 0.003 0.000 0.000 0.015 0.003 0.000 I_Na 0.047 0.038 0.026 0.038 0.047 0.045 0.049 0.065 0.030 0.043 0.027 0.007 0.029 0.000 0.078 0.096 0.060 0.069 0.073 0.084 I_K 1.881 1.257 1.294 1.507 1.818 1.644 1.850 1.791 1.453 1.820 1.740 1.657 1.688 1.724 1.731 1.707 1.677 1.721 1.734 1.784 ΣI 1.929 1.295 1.327 1.550 1.874 1.694 1.912 1.869 1.494 1.867 1.774 1.667 1.727 1.730 1.813 1.803 1.736 1.806 1.811 1.868 OH a 1.954 1.651 1.142 2.294 1.958 2.105 2.002 2.611 3.150 2.255 2.060 2.404 2.963 3.120 2.900 2.758 2.582 2.187 2.674 2.934 F 2.046 2.345 2.858 1.706 2.036 1.895 1.998 1.389 0.846 1.742 1.931 1.595 1.026 0.869 1.097 Magnesian skarn Calcic skarn 1.242 Appendix 8-7. Skarn Sample No. ZK7'08-7 ZK7'08-9 ZK803-14 ZK803-15 ZK803-16 ZK1202-1 ZK7'02-1 ZK9'02-3 Generation First generation First generation Second generation Third generation Point No. 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 SiO 2 (wt.%) 35.82 35.29 35.87 35.88 36.46 35.75 35.50 35.88 37.04 36.70 36.84 36.42 35.97 35.46 36.62 36.31 37.46 36.95 37.21 36.89 TiO 2 0.00 0.03 0.04 0.00 0.00 0.01 0.06 0.03 0.04 0.00 0.14 0.00 0.10 0.02 0.00 0.03 0.03 0.15 0.00 0.00 Al 2 O 3 16.72 17.15 17.15 16.80 17.01 17.99 17.58 17.03 19.49 17.34 16.02 16.08 2.57 1.53 4.87 2.84 14.11 9.44 16.46 16.03 FeO 3.15 2.96 4.04 3.78 2.48 3.11 3.10 2.96 6.21 4.01 4.49 4.61 26.60 27.72 22.46 25.43 12.34 16.93 7.14 9.00 MnO 1.12 1.02 0.51 0.80 0.94 0.30 0.97 1.00 0.55 0.43 0.39 0.37 0.53 0.56 0.37 0.58 1.87 1.04 1.52 1.50 MgO 2.81 2.87 2.73 2.92 2.07 2.22 2.50 2.40 0.12 2.13 2.28 2.26 0.26 0.05 0.10 0.04 0.05 0.05 0.06 0.02 CaO 34.44 34.51 35.61 35.51 35.07 35.75 35.31 35.43 35.09 35.94 34.31 34.32 33.42 32.98 33.93 32.74 32.61 33.45 34.84 33.82 Na 2 O 0.02 0.00 0.04 0.04 0.04 0.00 0.01 0.01 0.00 0.12 0.01 0.00 0.05 0.01 0.00 0.00 0.00 0.00 0.00 0.00 K 2 O 0.02 0.05 0.00 0.04 0.01 0.00 0.00 0.01 0.00 0.00 0.04 0.00 0.05 0.00 0.00 0.00 0.00 0.00 0.03 0.03 F 3.82 4.83 2.96 3.92 2.45 3.76 2.44 3.74 2.71 4.09 2.65 4.24 0.09 0.18 0.03 0.09 1.23 1.36 2.37 1.22 Cl 0.07 0.06 0.18 0.12 0.00 0.06 0.02 0.03 0.00 0.02 0.06 0.05 0.01 0.02 0.00 0.00 0.00 0.00 0.01 0.02 Total 98.00 98.76 99.14 99.81 96.54 98.96 97.49 98.51 101.24 100.76 97.22 98.33 99.65 98.51 98.37 98.05 99.69 99.37 99.63 98.54 Ions based on 12 oxygen T_Si 2.920 2.885 2.872 2.883 2.964 2.878 2.870 2.909 2.875 2.912 2.980 2.963 2.951 2.964 3.003 3.023 2.970 2.988 2.953 2.932 T_Al 0.080 0.115 0.128 0.117 0.036 0.122 0.130 0.091 0.125 0.088 0.020 0.037 0.049 0.036 0.000 0.000 0.030 0.012 0.047 0.068 ΣT 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.003 3.023 3.000 3.000 3.000 3.000 B_Al 1.526 1.537 1.490 1.474 1.594 1.584 1.545 1.536 1.658 1.533 1.507 1.505 0.199 0.115 0.470 0.278 0.000 0.000 0.000 0.000 0.003 0.003 ΣA 3.090 3.097 3.096 3.122 3.127 3.104 3.126 3.148 2.954 3.102 3.005 3.017 3.050 3.054 3.030 3.017 2.989 3.017 3.041 2.984 F 0.497 0.629 0.379 0.503 0.317 0.483 0.315 0.483 0.338 0.518 0.343 0.552 0.013 0.026 0.004 0.013 0.159 0.182 0.303 0.157 Cl 0.005 0.004 0.012 0.008 0.000 0.004 0.002 0.002 0.000 0.001 0.004 0.004 0.001 0.001 0.000 0.000 0.000 0.000 0.000 0.001 End members b (%) Gr 77.43 78.20 76.64 76.17 82.14 81.48 79.35 79.72 80.19 78.69 75.74 75.55 11.84 7.25 23.45 13.83 59.70 43.41 73.74 69.02 Ad 10.35 9.58 12.79 12.16 8.51 10.00 9.92 9.84 18.12 12.91 15.06 15.36 83.53 87.29 72.64 79.01 32.79 51.62 22.70 27.50 Py + Al + Sp 12.23 12.22 10.56 11.67 9.35 8.53 10.72 10.44 1.69 8.40 9.19 9.09 4.63 5.46 3.91 7.16 7.51 4.97 3.57 3.49 (To be continued on the next page) Appendix 8-8. Skarn Magnesian skarn Calcic skarn Generation First generation Sample No. ZK803-15 ZK803-16 ZK7'02-1 ZK9'02-3 ZK9'02-9-1 Type Core Core Rim Rim Core Major elements (wt.%) SiO 2 39.42 39.44 40.16 39.75 39.18 35.98 38.13 37.84 39.77 37.70 39.14 40.18 CaO 35.35 35.05 32.01 35.00 35.66 40.06 34.29 34.89 34.58 36.28 34.29 35.57 Al 2 O 3 19.23 19.18 19.65 19.02 2.77 3.83 1.38 2.45 4.41 4.42 2.81 0.82 FeO 2.23 2.19 5.80 3.18 19.34 17.82 23.53 22.14 17.71 20.09 22.23 21.72 MnO 0.98 1.04 1.79 0.31 0.90 0.60 1.89 1.78 0.61 0.31 0.58 0.30 MgO 2.61 2.89 0.13 2.21 1.25 0.75 0.04 0.18 2.15 0.22 0.15 0.31 Trace elements (ppm) Na 107.32 157.90 21.39 427.92 99.94 56.33 14.19 18.55 90.69 64.69 67.63 20.49 P 82.34 85.21 28.22 46.93 69.38 22.77 39.56 30.49 14.90 27.58 23.20 28.89 K 24.99 125.44 704.12 37.31 26.53 28.63 15.84 2.49 53.65 62.45 58.59 14.22 Sc 6.69 6.11 16.48 2.82 2.54 2.30 1.42 1.91 1.95 1.97 1.23 1.73 Ti 1.94 0.01 7.31 6.17 518.66 1068.36 36.31 287.47 330.02 443.70 141.52 78.23 V 1.07 0.73 2.47 0.45 7.79 9.53 1.60 6.88 11.35 14.73 4.19 2.78 Cr 0.03 1.14 0.00 0.00 105.84 108.80 0.29 3.12 33.68 12.09 16.93 22.75 Co 0.33 0.24 0.13 0.23 0.59 0.39 0.23 0.34 0.44 0.14 0.16 0.25 Ni 0.00 0.61 0.38 0.68 3.12 1.90 0.15 0.56 2.70 0.55 0.61 0.65 Cu 0.57 0.35 0.09 0.66 0.58 0.89 0.11 0.24 0.41 0.61 0.54 0.22 Zn 105.61 142.51 138.26 1872.47 542.07 56.00 36.62 70.15 162.38 15.02 30.65 16.24 Ga 13.79 12.84 43.35 33.54 34.82 37.66 34.89 36.72 48.62 31.76 57.87 52.21 Ge 25.88 25.57 34.91 20.80 28.80 31.05 22.43 24.12 61.43 64.30 48.02 40.98 Rb 0.54 3.50 19.10 1.05 0.35 0.57 0.29 0.03 0.95 1.14 1.10 0.26 Sr 23.53 27.83 0.54 145.36 2.33 2.54 1.48 1.72 1.40 0.29 0.80 1.63 Y 0.19 0.31 21.44 0.60 3.95 4.08 1.09 1.43 1.80 2.68 2.33 2.33 Zr 0.24 0.27 1.50 0.94 5.78 3.96 2.17 4.59 5.22 6.74 9.71 3.16 Nb 19.99 14.72 14.19 1.39 3.69 2.10 2.71 2.14 3.78 8.57 3.24 0.54 (To be continued on the next page) Appendix 8-8. (Continued) Skarn Magnesian skarn Calcic skarn Generation First generation Sample No. ZK803-15 ZK803-16 ZK7'02-1 ZK9'02-3 ZK9'02-9-1 Type Core Core Rim Rim Core Mo 0.74 0.67 0.84 0.17 17.03 33.96 4.50 3.13 1.08 1.06 4.19 79.44 Sn 446.29 553.60 1179.39 742.80 491.85 496.95 133.28 206.78 1115.17 2385.19 825.67 2294.44 Sb 4.64 4.64 0.10 10.51 8.58 0.88 0.02 0.23 0.78 0.10 0.15 0.01 Cs 0.16 1.41 0.36 0.29 0.07 0.10 0.05 0.00 0.14 0.19 0.34 0.04 Ba 0.11 0.43 7.88 0.89 0.08 0.05 0.00 0.01 0.07 0.07 0.02 0.05 Hf 0.04 0.03 0.17 0.02 0.21 0.09 0.05 0.14 0.16 0.21 0.33 0.11 Ta 0.07 0.04 0.08 0.02 0.05 0.05 0.01 0.02 0.04 0.11 0.05 0.04 W 1.00 1.33 17.56 1.65 551.36 1180.95 236.02 91.14 32.30 7.09 37.77 1128.32 Pb 5.54 5.93 0.22 47.28 8.46 2.17 0.18 0.34 5.28 2.46 1.49 0.94 Th 0.22 0.10 0.04 2.90 0.95 0.83 0.35 0.39 0.10 0.23 0.50 0.45 U 1.29 0.77 0.08 1.54 0.39 0.27 0.32 0.13 0.18 0.34 0.32 1.59 Rare earth elements (REE) La 2.03 1.94 0.04 9.33 5.27 4.00 7.75 1.45 0.26 0.31 0.27 1.61 Ce 6.84 5.89 1.73 36.75 11.53 9.12 10.33 3.77 1.21 2.41 1.48 4.54 Pr 0.80 0.69 1.19 5.15 1.22 1.02 0.71 0.40 0.21 0.43 0.25 0.56 Nd 2.15 1.45 12.64 16.24 4.64 4.17 2.06 1.76 1.05 1.93 1.29 2.29 Sm 0.47 0.29 13.20 4.19 1.13 1.00 0.24 0.41 0.32 0.58 0.38 0.45 Eu 0.02 0.02 0.01 0.02 0.24 0.26 0.08 0.07 0.12 0.17 0.06 0.14 Gd 0.11 0.09 6.74 1.07 0.83 1.03 0.25 0.34 0.33 0.53 0.40 0.40 Tb 0.03 0.02 1.82 0.16 0.13 0.16 0.03 0.05 0.06 0.09 0.07 0.06 Dy 0.11 0.10 8.93 0.60 0.76 0.88 0.19 0.28 0.33 0.51 0.33 0.33 Ho 0.01 0.01 1.10 0.05 0.15 0.16 0.03 0.06 0.07 0.11 0.09 0.07 Er 0.04 0.03 2.72 0.07 0.42 0.36 0.11 0.15 0.18 0.25 0.25 0.19 Tm 0.02 0.01 0.65 0.01 0.06 0.05 0.01 0.02 0.02 0.04 0.05 0.02 Yb 0.23 0.18 5.83 0.10 0.32 0.27 0.08 0.16 0.18 0.23 0.32 0.13 Lu 0.03 0.03 0.72 0.01 0.05 0.04 0.01 0.02 0.02 0.03 0.05 0.02 (To be continued on the next page) Appendix 8-8. (Continued) Skarn Calcic skarn Generation First generation Second generation Third generation Sample No. ZK9'02-9-1 ZK9'02-3 ZK9'02-3 ZK9'02-9-1 Type Rim Rim Major elements (wt.%) SiO 2 40.09 40.31 37.52 37.63 38.60 39.99 38.80 40.06 39.13 38.63 38.15 38.21 CaO 34.99 35.39 34.94 35.27 34.23 34.15 32.34 32.92 33.54 33.01 34.01 34.11 Al 2 O 3 1.40 0.74 10.51 9.25 14.28 11.08 14.26 11.86 17.03 21.30 19.76 19.91 FeO 21.92 22.12 14.99 16.00 11.14 12.60 11.81 12.85 8.44 4.57 6.19 5.98 MnO 0.27 0.25 1.51 1.28 1.17 0.94 2.38 1.09 1.51 2.28 1.54 1.34 MgO 0.30 0.20 0.05 0.04 0.11 0.65 0.03 0.74 0.04 0.03 0.04 0.04 Trace elements (ppm) Na 63.40 68.38 47.54 50.35 212.62 378.87 9.78 137.39 8.61 13.17 252.84 303.98 P 25.65 29.79 24.71 17.86 20.68 21.53 25.73 16.97 15.17 27.84 26.19 39.65 K 27.07 1216.34 32.79 35.25 173.23 359.77 1.29 122.03 2.85 0.36 224.56 953.09 Sc 1.80 1.76 2.23 3.19 1.42 23.15 1.05 13.45 1.21 1.53 1.41 1.52 Ti 60.27 15.47 72.58 147.68 33.35 122.21 106.87 120.81 19.28 0.00 5.57 11.87 V 4.38 1.29 3.59 4.70 1.28 3.97 4.41 4.63 2.08 0.00 0.25 0.78 Cr 67.71 111.52 18.03 6.45 116.29 68.87 9.01 25.63 166.29 2.90 63.93 62.38 Co 0.20 0.17 0.19 0.18 0.16 0.24 0.23 0.35 0.18 0.29 0.24 0.31 Ni 0.69 0.58 0.29 0.26 0.41 1.23 0.23 1.81 0.38 0.41 0.63 0.57 Cu 0.28 0.48 0.34 0.39 1.37 2.33 0.20 0.68 0.16 0.00 1.02 1.30 Zn 12.45 11.50 21.40 16.63 32.27 75.68 32.71 63.02 18.61 33.98 46.31 40.62 Ga 34.93 32.14 52.21 51.78 48.92 49.62 55.88 49.82 50.53 31.90 61.73 63.31 Ge 36.55 22.94 34.22 38.50 20.66 23.60 25.36 20.59 28.46 30.31 23.37 26.73 Rb 0.43 11.05 0.60 0.62 2.96 7.05 0.00 2.12 0.06 0.04 3.77 7.96 Sr 0.76 1.72 0.33 0.46 0.64 1.23 0.29 1.05 0.21 0.10 3.94 11.84 Y 0.55 1.27 6.09 10.28 0.52 1.89 2.18 2.05 2.07 0.49 2.01 3.35 Zr 0.72 1.60 0.89 2.17 1.00 7.52 0.81 6.89 0.33 0.01 0.09 0.13 Nb 1.76 0.25 6.60 13.76 6.79 9.18 21.45 12.95 2.35 1.83 6.26 5.35 (To be continued on the next page) Appendix 8-8. (Continued) Skarn Calcic skarn Generation First generation Second generation Third generation Sample No. ZK9'02-9-1 ZK9'02-3 ZK9'02-3 ZK9'02-9-1 Type Rim Rim Mo 28.25 10.88 1.36 1.46 37.03 1.66 1.40 1.13 2.86 1.49 1.72 2.32 Sn 2331.71 1271.10 108.69 135.31 406.54 538.79 50.08 334.52 63.71 131.56 220.51 224.95 Sb 0.61 0.09 0.26 0.00 1.51 0.71 0.08 0.30 0.00 0.10 0.43 1.21 Cs 0.08 1.18 0.08 0.07 0.54 1.12 0.00 0.34 0.00 0.01 0.58 1.00 Ba 0.10 0.08 0.04 0.78 0.14 0.11 0.03 0.07 0.00 0.02 0.13 0.45 Hf 0.02 0.05 0.02 0.06 0.04 0.45 0.01 0.28 0.00 0.00 0.01 0.01 Ta 0.02 0.01 0.12 0.25 0.13 0.42 0.08 0.35 0.02 0.00 0.02 0.02 W 630.04 149.44 6.32 5.36 17.57 9.08 13.37 5.60 167.70 100.97 80.44 126.53 Pb 1.44 1.03 7.56 0.91 45.98 12.11 0.04 7.89 0.18 0.05 2.84 3.11 Th 0.10 0.25 0.74 1.06 0.13 0.25 0.21 0.14 0.07 0.00 0.01 0.01 U 0.43 0.62 0.94 0.80 0.10 0.12 0.26 0.05 0.10 0.00 0.15 0.01 Rare earth elements (REE) La 0.87 1.06 0.43 0.52 0.16 0.25 0.12 0.09 0.05 0.00 0.52 0.02 Ce 3.06 3.48 5.29 5.41 1.49 1.58 1.82 0.76 0.54 0.02 0.68 0.06 Pr 0.44 0.41 1.55 1.58 0.42 0.42 0.55 0.25 0.16 0.01 0.06 0.02 Nd 1.77 1.67 9.11 9.63 2.22 2.32 3.26 1.88 0.95 0.05 0.25 0.10 Sm 0.27 0.33 3.75 4.90 0.53 0.98 1.35 0.99 0.52 0.08 0.15 0.15 Eu 0.14 0.08 0.14 0.16 0.06 0.06 0.05 0.05 0.03 0.01 0.07 0.04 Gd 0.20 0.26 2.33 3.57 0.30 0.77 0.75 0.66 0.47 0.08 0.28 0.26 Tb 0.02 0.04 0.52 0.82 0.05 0.17 0.14 0.14 0.12 0.02 0.05 0.06 Dy 0.11 0.23 2.57 4.57 0.31 1.07 0.77 0.82 0.62 0.09 0.32 0.50 Ho 0.02 0.05 0.41 0.68 0.05 0.21 0.12 0.16 0.11 0.02 0.07 0.11 Er 0.04 0.11 0.99 1.72 0.11 0.59 0.28 0.42 0.24 0.06 0.18 0.30 Tm 0.01 0.02 0.19 0.33 0.02 0.14 0.04 0.09 0.05 0.01 0.03 0.06 Yb 0.03 0.08 1.24 2.20 0.19 1.48 0.30 0.86 0.29 0.07 0.32 0.54 Lu 0.01 0.01 0.16 0.27 0.04 0.26 0.04 0.13 0.04 0.01 0.04 0.09 FeO 2.01 2.67 1.82 1.01 1.46 1.16 4.73 2.24 2.99 3.61 6.17 25.89 26.62 26.69 27.80 26.68 27.34 25.66 24.22 23.68 MnO 0.31 0.39 0.15 0.15 0.09 0.23 0.31 0.26 0.28 0.32 0.65 2.84 0.88 1.29 1.60 1.38 1.23 1.59 1.15 1.31 MgO 17.13 17.23 17.66 17.97 18.38 18.77 15.84 17.07 16.50 16.25 14.65 0.01 0.23 0.51 0.09 0.26 0.56 1.23 2.05 3.09 CaO 25.95 25.75 26.02 25.73 25.58 25.69 25.33 25.52 25.95 25.82 25.17 22.32 22.51 22.49 22.28 22.76 22.27 22.38 22.86 23.23 Na 2 O 0.09 0.09 0.05 0.00 0.02 0.00 0.02 0.04 0.01 0.01 0.02 0.06 0.32 0.16 0.27 0.22 0.29 0.07 0.16 0.15 K 2 O 0.00 0.02 0.05 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.02 0.00 0.03 0.00 0.00 0.05 0.00 Total 98.99 100.35 99.78 98.88 100.10 100.22 99.61 98.63 99.24 99.08 99.75 99.80 99.20 99.84 99.37 99.81 99.79 99.28 99.18 100.16 Cations based on 6 oxygen T_Si 1.952 1.950 1.961 1.969 1.944 1.952 1.904 1.945 1.960 1.954 1.958 1.984 1.971 1.988 1.936 1.981 1.957 1.987 1.980 1.934 T_Al 0.017 0.020 0.009 0.011 0.035 0.018 0.071 0.033 0.011 0.007 0.016 0.016 0.029 0.012 0.026 0.015 0.023 0.005 0.012 0.028 ΣA 1.029 1.009 1.021 1.011 1.015 1.021 1.001 1.011 1.024 1.023 1.003 1.000 1.022 1.004 1.010 1.022 1.004 1.000 1.016 1.012 End members b (%) Di 98.99 98.74 99.54 99.53 99.71 99.31 96.17 99.16 96.67 96.13 85.02 0.04 1.52 3.24 0.63 1.72 3.66 7.63 13.17 20.34 Hd 0.00 0.00 0.00 0.00 0.00 0.00 2.76 0.00 2.40 2.79 12.84 89.80 95.16 92.12 93.18 93.18 91.75 86.75 82.65 74.78 Jo 1.01 1.26 0.46 0.47 0.29 0.69 1.07 0.84 0.93 1.08 2.14 10.16 3.33 4.63 6.20 5.10 4.59 5.62 4.19 4.88 Notes: Appendix 8-11. Sample No. ZK9'02-5 Point No. 1 2 3 4 5 6 7 8 9 10 11 12 SiO 2 (wt.%) 35.66 34.73 34.50 34.60 35.36 34.71 35.30 35.18 35.67 35.96 35.14 36.55 TiO 2 0.01 0.03 0.00 0.03 0.00 0.00 0.00 0.02 0.03 0.14 0.06 0.00 Al 2 O 3 14.59 16.91 16.66 15.92 16.08 17.07 16.48 16.13 15.20 14.98 16.36 16.05 FeO a 5.44 3.92 3.96 5.09 4.25 3.09 4.81 5.94 4.99 6.09 6.36 6.72 MnO 0.22 0.07 0.32 0.38 0.23 0.37 0.26 0.49 0.13 0.42 0.35 0.34 MgO 2.57 2.12 1.71 1.71 2.37 1.78 1.88 1.06 2.76 2.30 1.39 1.30 CaO 35.56 35.44 35.33 35.54 35.46 35.42 35.34 35.82 35.96 36.01 35.57 35.77 Na 2 O 0.02 0.04 0.01 0.02 0.01 0.04 0.03 0.08 0.01 0.01 0.07 0.01 K 2 O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 F 1.04 1.37 1.86 1.97 2.58 2.77 2.92 3.04 3.43 3.62 3.84 4.03 Cl 0.20 0.22 0.17 0.16 0.15 0.16 0.17 0.22 0.20 0.15 0.23 0.21 Total 95.31 94.84 94.52 95.43 96.50 95.40 97.18 97.99 98.39 99.66 99.35 100.97 Ions based on 73 oxygen T_Si 18.101 17.616 17.681 17.710 17.873 17.702 17.812 17.792 17.936 17.970 17.672 18.073 T_Al 0.000 0.384 0.319 0.290 0.127 0.298 0.188 0.208 0.064 0.030 0.328 0.000 ΣT 18.101 18.000 18.000 18.000 18.000 18.000 18.000 18.000 18.000 18.000 18.000 18.073 M_Al 8.730 9.729 9.743 9.315 9.451 9.964 9.614 9.410 8.941 8.792 9.369 9.351 M_Ti 0.004 0.011 0.000 0.011 0.000 0.000 0.000 0.009 0.011 0.052 0.022 0.000 M_Fe 2.308 1.664 1.695 2.179 1.797 1.316 2.031 2.512 2.097 2.545 2.673 2.777 M_Mg 1.945 1.602 1.309 1.306 1.789 1.353 1.413 0.800 2.066 1.711 1.044 0.955 M_Mn 0.094 0.031 0.139 0.164 0.097 0.158 0.111 0.208 0.053 0.176 0.149 0.141 ΣM 13.081 13.037 12.886 12.975 13.134 12.791 13.169 12.938 13.168 13.276 13.256 13.224 I_Ca 19.339 19.261 19.397 19.491 19.200 19.354 19.105 19.412 19.372 19.285 19.167 18.948 I_Na 0.018 0.036 0.009 0.021 0.009 0.041 0.025 0.079 0.013 0.012 0.067 0.012 I_K 0.000 0.000 0.000 0.000 0.000 0.003 0.000 0.000 0.008 0.000 0.000 0.000 ΣI 19.357 19.297 19.406 19.511 19.209 19.397 19.130 19.492 19.392 19.297 19.234 18.961 OH b 8.159 7.611 6.834 6.664 5.744 5.395 5.195 4.945 4.366 4.161 3.695 3.521 F 1.669 2.203 3.020 3.195 4.127 4.467 4.663 4.864 5.460 5.716 6.111 6.304 Cl 0.172 0.186 0.147 0.141 0.129 0.138 0.142 0.190 0.174 0.124 0.194 0.175 (To be continued on the next page) Appendix 8-12. (Continued) (To be continued on the next page) (To be continued on the next page) Appendix 8-12. (Continued) Notes: Appendix 8-12. Occurrence Scheelite in the stockwork quartz veinlets Scheelite in the magnesian skarn Generation Early generation Late generation Sample No. WJ35 WJ35 WJ35 ZK801-27 ZK801-33 ZK801-41 ZK802-15 ZK802-17 ZK803-2 ZK801-39 ZK801-40 ZK802-9 Major elements (wt.%) WO 3 70.01 79.72 80.91 79.27 78.67 78.34 74.47 62.96 77.17 80.21 75.21 78.75 CaO 27.62 16.84 16.28 20.19 20.50 20.45 20.98 22.23 18.00 18.87 21.88 20.38 MoO 3 0.02 0.03 0.09 0.01 0.50 0.86 4.25 14.39 0.47 0.64 1.49 0.00 Trace elements (ppm) Na 120.47 124.56 213.01 116.49 29.49 31.89 6.11 20.63 42.60 16.96 52.37 7.71 Mg 105.21 73.44 201.77 285.76 366.90 265.29 33.00 165.51 5027.73 80.58 2798.11 1224.54 Al 804.14 1220.50 741.54 12.20 1.49 1.80 0.00 398.91 1086.17 0.28 396.91 462.45 Si 3562.27 5424.47 2231.54 688.08 679.72 957.68 927.13 723.19 6317.25 1071.16 3462.98 2105.52 P 12.89 19.62 22.44 38.39 42.13 34.41 24.40 35.71 9.16 9.47 17.74 35.11 K 62.50 454.14 223.19 2.18 1.98 9.62 0.00 0.49 107.42 5.77 97.37 Occurrence Scheelite in the Scheelite in the magnesian skarn Occurrence Scheelite in the magnesian skarn Scheelite in the calcic skarn stockwork quartz veinlets Generation Early generation Generation Late generation Early generation Late generation Late generation Sample No. WJ35 WJ35 Sample No. ZK803-14 ZK803-14 ZK803-14 ZK7'04-2 ZK9'02-3 ZK9'02-3 ZK9'02-9-2 ZK9'02-10 ZK9'02-10 ZK9'02-7 ZK9'02-7 ZK9'02-7 WJ35 ZK801-27 ZK801-33 ZK801-41 ZK802-15 ZK802-17 ZK803-2 ZK801-39 ZK801-40 ZK802-9 Zr 8.97 12.07 4.80 6.23 5.17 7.30 5.61 4.94 35.16 0.02 0.02 Zr 0.02 0.01 0.01 1.36 0.01 0.02 0.02 0.25 0.18 0.08 0.01 0.03 6.63 Nb 1212.42 1535.87 584.69 148.32 43.36 97.70 98.62 94.54 1104.77 2.71 40.52 Nb 3.40 2.81 2.82 2480.59 420.02 180.68 721.06 477.04 308.49 24.06 16.29 77.11 0.90 Sn 0.90 4.91 1.00 0.00 0.64 0.33 0.86 0.13 18.12 4.68 2.56 Sn 0.79 0.63 0.54 1.87 0.21 0.28 0.34 12.03 5.42 0.47 0.43 0.38 1.06 Sb 15.37 8.55 2.27 0.16 0.08 0.00 0.29 0.24 0.68 0.05 0.07 Sb 0.00 0.03 0.03 45.96 0.01 0.07 0.07 6.15 0.81 0.13 0.90 0.18 0.25 Cs 0.15 0.45 0.06 0.00 0.09 0.10 0.00 0.00 1.33 0.01 0.09 Cs 0.43 0.00 0.01 0.11 0.09 0.00 0.02 0.11 0.05 0.06 0.04 0.03 0.12 Ba 0.46 0.25 0.10 0.00 0.14 0.25 0.00 0.00 1.94 0.14 1.33 Ba 0.35 0.16 0.18 0.31 0.39 0.32 0.23 0.78 0.37 1.32 1.33 0.74 1.01 Hf 0.37 0.66 0.30 0.00 0.00 0.00 0.15 0.04 2.32 0.00 0.00 Hf 0.00 0.00 0.00 0.11 0.00 0.00 0.02 0.01 0.01 0.01 0.00 0.00 0.00 Ta 32.60 42.42 21.98 1.72 0.29 0.03 0.14 0.19 2.73 0.06 0.05 Ta 0.06 0.06 0.05 101.96 4.53 1.09 13.17 1.41 0.94 0.06 0.04 0.14 0.00 Pb 17.62 13.14 13.92 10.67 12.39 12.74 7.15 4.14 19.58 21.52 6.27 Pb 14.53 10.94 9.69 335.08 5.23 3.07 7.55 8.02 3.43 39.29 232.47 12.71 0.15 Th 36.95 34.03 21.92 8.84 3.05 2.21 0.10 0.65 9.24 0.63 4.29 Th 1.25 6.61 0.19 35.05 9.26 6.62 5.22 4.34 1.59 0.19 0.08 1.23 0.04 U 703.35 108.24 25.38 12.37 2.58 9.00 0.25 0.83 47.44 2.11 34.51 P 189.25 12.51 9.80 15.56 9.27 7.95 10.46 13.08 6.31 11.77 17.31 16.03 U 5.38 24.98 1.20 67.09 6.89 5.87 3.88 3.73 1.46 0.22 0.13 3.17 0.65 K 296.76 0.97 7.29 162.74 13.91 2.59 251.91 85.39 8.96 8.74 6.43 4.57 74.97 Sc 20.59 133.34 36.72 0.27 0.55 0.22 0.00 0.12 176.04 0.01 0.03 0.04 Ti 56.39 96.37 82.76 0.00 0.00 0.00 2.08 0.30 4.65 0.49 1.43 0.00 V 0.08 0.28 0.30 0.13 0.00 0.32 0.00 0.07 0.06 0.01 0.01 0.09 Cr 13.24 14.16 2.14 0.90 0.00 0.00 0.00 3.61 3.61 0.00 0.50 0.00 Mn 996.97 1936.14 1976.93 43.62 241.25 96.82 32.40 12.50 3743.52 5.16 84.08 4.23 Fe 4182.01 7348.49 9663.02 17.37 161.14 17.47 0.00 110.13 8829.23 153.26 576.20 370.15 Co 3.53 0.11 0.09 0.03 0.00 0.15 0.00 0.00 0.07 0.05 0.09 0.00 Ni 0.62 0.10 0.12 1.68 0.00 0.00 0.53 0.00 0.13 0.14 0.17 1.08 Cu 1.03 7.16 0.43 0.68 0.00 0.00 0.17 0.11 0.30 0.24 1.32 0.51 Zn 12.26 16.94 18.72 0.00 0.00 0.76 0.96 542.47 33.50 6.81 7.47 0.87 Ga 5.00 6.47 6.57 1.11 0.82 0.59 0.18 0.53 1.15 0.03 0.58 0.39 Ge 5.14 2.60 1.22 0.01 0.54 1.46 1.80 0.10 1.80 0.17 0.24 0.00 Rb 1.02 6.05 3.20 0.00 0.00 0.10 0.15 0.00 3.83 0.09 0.48 3.10 Sr 21.98 31.46 40.23 49.77 16.64 59.56 35.81 42.07 28.23 22.65 28.02 420.77 Y 1414.39 1221.18 774.84 824.54 12.76 4.01 117.44 47.52 313.78 1.53 1.84 1.34 Sc 0.03 0.06 0.00 0.77 0.04 0.03 0.08 0.04 0.03 0.10 0.01 0.04 Rare earth elements (REE) Rare earth elements (REE) La 120.52 180.44 259.92 156.79 50.02 60.81 14.70 45.26 9.30 2.70 37.45 Ti 1.87 1.25 1.01 18.11 1.64 1.81 1.29 7.16 9.89 7.07 8.50 4.87 La 1.53 15.83 4.76 420.74 180.12 97.17 207.46 177.43 148.54 19.70 11.14 43.84 1.08 Ce 312.40 422.20 542.81 388.15 180.71 185.56 78.63 145.05 35.26 3.53 41.04 V 0.02 0.01 0.00 0.05 0.20 0.00 0.10 0.73 0.58 0.01 0.00 0.00 Ce 4.59 72.12 18.16 1380.33 514.90 204.95 704.46 394.84 357.29 30.17 16.68 73.72 3.52 Pr 46.12 59.09 71.05 48.00 24.03 21.50 16.19 18.74 7.63 0.29 1.70 Cr 11.87 2.80 0.26 84.80 0.66 5.20 48.48 4.39 208.88 44.48 3.75 2.95 Pr 0.36 7.19 1.88 220.59 73.77 21.79 116.89 49.18 43.48 2.35 1.29 5.82 0.70 Nd 232.62 300.18 320.31 189.07 74.09 61.27 89.75 58.44 46.77 0.82 2.70 Mn 42.35 105.94 25.38 53.76 20.05 15.23 45.49 19.86 27.02 114.88 11.90 42.41 Nd 0.58 10.56 3.21 1108.41 273.61 63.59 512.06 187.21 158.33 5.80 3.55 13.24 2.84 Sm 142.22 141.86 126.08 84.79 22.08 17.08 57.17 20.52 39.04 0.15 0.37 Fe 293.71 189.53 159.62 335.08 137.89 134.95 167.70 1568.35 1260.58 331.18 235.82 340.23 Sm 0.07 1.34 0.46 444.27 92.88 13.25 199.95 48.63 34.05 0.58 0.33 1.38 0.81 Eu 0.74 0.61 0.72 0.29 0.00 0.37 0.16 0.29 0.15 0.18 0.19 Co 0.06 0.04 0.05 1.25 0.05 0.03 0.05 0.07 0.06 0.05 0.07 0.08 Eu 0.02 0.12 0.07 3.45 1.49 1.03 1.59 2.02 2.12 0.14 0.11 0.34 0.08 Gd 254.97 225.84 170.56 90.70 8.90 4.62 48.51 13.44 42.13 0.12 0.35 Ni 0.02 0.05 0.06 0.48 0.09 0.04 0.04 0.12 0.16 0.22 0.15 0.17 Gd 0.03 0.30 0.09 494.53 59.06 8.24 142.81 44.50 25.17 0.27 0.20 0.71 0.79 Tb 57.21 51.37 35.97 18.72 2.07 1.38 11.23 3.20 11.84 0.02 0.05 Cu 0.08 0.06 0.05 2.80 0.12 0.05 0.09 0.60 0.17 0.18 0.22 0.04 Tb 0.00 0.04 0.02 91.86 12.76 1.70 30.76 8.55 4.35 0.02 0.02 0.09 0.20 Dy 367.79 331.12 232.50 115.20 10.66 6.30 63.79 20.13 73.79 0.18 0.30 Zn 17.77 0.57 0.55 0.44 0.88 0.08 0.18 2.39 6.12 1.04 0.92 0.44 Dy 0.03 0.18 0.08 489.41 61.75 8.46 156.10 45.42 21.63 0.08 0.08 0.34 0.76 Ho 81.51 74.49 53.06 22.67 1.30 0.66 8.16 2.86 13.86 0.04 0.07 Ga 0.11 0.51 0.10 16.65 4.56 1.60 7.61 3.78 3.41 0.26 0.12 0.55 Ho 0.00 0.03 0.01 87.30 8.87 1.36 23.51 7.89 3.61 0.01 0.01 0.05 0.19 Er 202.80 194.17 140.08 72.28 3.40 1.42 19.82 7.65 39.84 0.10 0.15 Ge 0.00 0.00 0.00 4.59 0.68 0.17 1.30 0.49 0.47 0.01 0.00 0.07 Er 0.01 0.06 0.04 180.31 17.79 2.92 48.22 14.62 6.54 0.02 0.02 0.12 0.35 Tm 28.75 30.76 22.16 13.98 0.70 0.31 3.01 1.45 9.23 0.01 0.02 Rb 12.32 0.00 0.27 2.39 0.22 0.03 1.73 0.62 0.19 0.18 0.17 0.11 Tm 0.00 0.01 0.01 21.33 2.63 0.40 6.75 1.46 0.72 0.00 0.00 0.01 0.16 Yb 178.35 201.06 140.40 121.59 6.26 2.66 16.97 10.61 84.01 0.08 0.20 Sr 52.21 33.91 30.63 61.83 55.40 66.61 31.77 38.96 52.30 66.53 66.48 72.75 Yb 0.01 0.15 0.07 104.41 13.05 1.72 34.82 4.90 2.75 0.01 0.01 0.08 0.64 Lu 22.79 28.30 20.35 18.40 0.69 0.33 1.83 1.02 12.29 0.02 0.04 0.10 Y 0.13 0.54 0.25 961.20 33.54 11.54 155.73 134.86 41.06 0.17 0.18 0.59 Lu 0.00 0.02 0.01 11.74 1.28 0.13 3.63 0.34 0.24 0.00 0.00 0.00

Institut des Sciences de la

Terre d'Orléans, Orléans 45071, France School of Earth Sciences and Engineering, Nanjing University, Nanjing 210023, China

  Mo-Pb-Zn-Ag de Tongshanling sont génétiquement lié à l'hydrothermalisme et à son évolution lors du développement du skarn. Le granite de Weijia a cristallisé à partir d'un magma saturé en eau et riche en Fluor. Les facteurs qui ont contrôlé la formation de ce skarn magnésien riche en W, suppose l'existence d'une source enrichie en W dans les sources métasédimentaires et d'un magma riche en Fluor très différentia par cristallisation fractionnée.

Mots clés: Granitoïdes; Skarns; Enclave; Contrôle structuraux; Petrogènèse; Métallognénèse; Jurassique Moyen; Tongshanling; Weijia; Nanling

Acknowledgements

East Qinling molybdenum belt, Shanxi Province, China. Economic Geology 92, 827-835.

Stein, H.J., Markey, R.J., Morgan, J.W., Hannah, J.L., Scherstén, A., 2001. The remarkable Re-Os chronometer in molybdenite: how and why it works. Terra Nova 13, 479-486.

Stephens, W.E., 2001. Polycrystalline amphibole aggregates (clots) in granites as potential I-type restite: an ion microprobe study of rare-earth distributions. Australian Journal of Earth Sciences 48, 591-601. Stern, R.A., 1997. The GSC sensitive high resolution ion microprobe (SHRIMP): analytical techniques of zircon U-Th-Pb age determinations and performance evaluation. Radiogenic Age and Isotopic Studies: Report 10.

Geological Survey of Canada Current Research 1997-F, 1-31. Sun, S.-S., Mcdonough, W.F., 1989. Chemical and isotopic systematics of oceanic basalts: Implications for mantle composition and processes, in: Saunders, A.D., Norry, M.J. (Eds.), Magmatism in the ocean basins.

Geological Society, London, Special Publications 42, 313-345. Sun, T., 2006. A new map showing the distribution of granites in South China and its explanatory notes.

Geological Bulletin of China 25, 332-335 (in Chinese with English abstract). Sun, T., Zhou, X.M., Chen, P.R., Li, H.M., Zhou, H.Y., Wang, Z.C., Shen, W.Z., 2005. Strongly peraluminous granites of Mesozoic in Eastern Nanling Range, southern China: Petrogenesis and implications for tectonics.

Science in China Series D: Earth Sciences 48, 165-174.

Tartèse, R., Boulvais, P., 2010. Differentiation of peraluminous leucogranites "en route" to the surface. Lithos 114, 353-368.

Taylor, H.P., 1997. Oxygen and hydrogen isotope relationships in hydrothermal mineral deposits, in: Barnes, H.L.

(Ed.), Geochemistry of hydrothermal ore deposits, third ed. Wiley,New York, Taylor, S.R., McLennan, S.M., 1995. The geochemical evolution of the continental crust. Reviews of Geophysics 33, 241-265.

The Granitoid Research Group of the Nanling Project, MGMR (Ministry of Geology and Mineral Resources of P.R. China), 1989. Geology of granitoids of Nanling Region and their petrogenesis and mineralization.

Geological Publishing House, Beijing (in Chinese with English abstract). Thompson, A.B., 1982. Dehydration melting of pelitic rocks and the generation of H 2 O-undersaturated granitic liquids. American Journal of Science 282, 1567-1595. Ting, V.K., 1929. The orogenic movements in China. Bulletin of the Geological Society of China 8, 151-170. Tischendorf, G., Gottesmann, B., Förster, H.-J., Trumbull, R.B., 1997. On Li-bearing Tong, Q.M., Wu, R.H., Peng, J.L., Wang, S.M., 1995. Metallogeny of W, Sn, Pb-Zn, Au, and Ag deposits in the Chenxian-Guiyang region, south Hunan, China. Geological Publishing House, Beijing (in Chinese with English abstract).

Appendices

Appendix 4-1. LA-ICP-MS zircon U-Pb isotope analyses of granitoids from the Tongshanling-Weijia area

Spot

Elements (ppm) Isotopic ratios Ages (Ma) 232 Th 238 U Th/U 207 -2.6 -3.9 -2.9 -1.4