Geochronology and Geochemistry of Granodiorite Porphyry in the Baoshan Cu-Pb-Zn Deposit, South China: Insights into Petrogenesis and Metallogeny

Abstract

The Baoshan Cu-Pb-Zn deposit is situated at the intersection of the Qin-Hang Cu polymetallic and Nanling W-Sn polymetallic metallogenic belts. The age, lithology, petrogenesis, and tectonic setting of granodiorite porphyry within the deposit remain subjects of debate. Additionally, there is a lack of comparative studies with the W-Sn-related granites in the region. This study conducted whole-rock major and trace element analysis, Sr-Nd isotope analysis, and zircon U-Pb dating on the Baoshan granodiorite porphyry. The zircon U-Pb age of the granodiorite porphyry is 162 ± 1 Ma. The whole-rock SiO₂ and K₂O contents range from 65.87 to 68.21 wt.% and 3.42 to 5.62 wt.%, respectively, indicating that the granodiorite porphyry belongs to high-potassium calc-alkaline I-type granite. The granodiorite porphyry is characterized by enrichment in LREE and depletion in HREE (LREE/HREE ratio = 6.2–21.2). The samples of granodiorite porphyry generally exhibit weak negative Eu anomalies or no Eu anomalies (δEu = 0.62–1.04, mean = 0.82). The (⁸⁷Sr/⁸⁶Sr)_i and ε_Nd(t) values are 0.707717–0.709506 and −7.54 to −4.87, respectively. The whole-rock geochemical composition and Sr-Nd isotopic values indicate that the magma originated from the partial melting of the Mesoproterozoic ancient crust and Neoproterozoic mafic juvenile lower crust, with the addition of high oxygen fugacity and water-rich lithospheric mantle melts. The source of the granodiorite porphyry in the Baoshan deposit is significantly different from the crust-derived metapelite source of the W-Sn-related granite in the area, indicating that different magma sources might be the main reason for the co-spatial and nearly contemporaneous development of Cu-Pb-Zn and W-Sn mineralization in the southern Hunan region.

1. Introduction

The NE-trending Qin-Hang metallogenic belt in South China extends over 2000 km (Figure 1) [1] and is among the most significant Cu polymetallic metallogenic belts in China, comprising porphyry Cu deposits (e.g., Dexing), skarn Cu-Pb-Zn deposits (e.g., Tongshanling, Baoshan), and epithermal Cu-Pb-Zn-Ag deposits (e.g., Lengshuikeng and Yinshan). Conversely, the Nanling metallogenic belt is a world-class W-Sn metallogenic zone (Figure 1b) containing significant W deposits like Shizhuyuan, Yaogangxian, and Xintianling, as well as Sn deposits such as Xianghualing and Furong. These two metallogenic belts converge in the Baoshan area (Figure 1b), where the Baoshan Cu-Pb-Zn deposit stands as a prominent example of the deposits found within the intersection zone [2].

The granodiorite porphyry, as an ore-related intrusion in the Baoshan deposit, has attracted significant interest [4,5,6,7,8], prompting extensive studies on its petrology, geochronology, and geochemistry [4,5,7,8,9,10,11,12,13,14,15,16,17,18]. Due to differences in sample quality, analytical methods, and data processing, the age range of the Baoshan granodiorite porphyry samples obtained in various studies is relatively broad, ranging between 170 and 155 Ma [5,10,11,12,16,17,18,19]. Regarding the classification of granite, the majority of scholars consider that the Baoshan granodiorite porphyry possesses high-potassium calc-alkaline I-type granite characteristics [4,9,10,15,16,18], although some scholars propose that it might be classified as A-type granite [12]. There is also controversy regarding the petrogenesis of these rocks, mainly including (1) magma forming the Baoshan granodiorite porphyry originating from the mixing of melts from the lithospheric mantle metasomatized by subduction sediment melts and the partial melting of the lower crust [7,15,18], with the possible addition of Neoproterozoic island arc materials in the source region [10,11,16]; (2) the products of partial melting due to thickening of the lower crust [12,14]; (3) the partial melting products of mafic volcaniclastic rocks in the Neoproterozoic South China rift basin [9]; and (4) the partial melting of ancient mafic lower crust and Neoproterozoic juvenile crust [13]. In terms of the tectonic setting, some studies propose that Baoshan granodiorite porphyry developed in an extensional environment linked to the rollback of the Paleo-Pacific subducting slab [4,7,12,15,16,20], whereas others suggest it formed in a compressional environment associated with subduction [8,10,14]. In conclusion, the existing wide range of reported ages complicates the precise age determination of the Baoshan granodiorite porphyry. Moreover, significant disputes over rock types, petrogenesis, and tectonic settings hinder further understanding of the magmatism/mineralization relationship. There is a clear need for systematic studies on the Baoshan granodiorite porphyry. Additionally, while the granites linked to Cu-Pb-Zn and W-Sn mineralization share similar formation periods and tectonic settings within the intersection zone of Qin-Hang and Nanling metallogenic belts, the lack of comparative studies between these two granite types remains a critical gap in the research.

This study focuses on the granodiorite porphyry of the Baoshan deposit through the analysis of whole-rock major and trace elements, Sr-Nd isotopes, and zircon U-Pb geochronology. We have constrained the age of the Baoshan granodiorite porphyry and discussed its rock type, petrogenesis, and tectonic setting. The aim is to investigate the genetic relationship between magmatism and mineralization and to compare it with W-Sn-related granites. This study redefines the genetic mechanism of the ore-forming rock in the Baoshan Cu-Pb-Zn polymetallic deposit, revealing a distinct magma source compared to W-Sn-related granites.

2. Geological Setting

2.1. Regional Geology

The South China Block originated from the Neoproterozoic collision between the Yangtze Block in the northwest and the Cathaysian Block in the southeast (Figure 1) [21,22,23,24]. The South China Block was subsequently modified by three tectonic events. These include the (1) Early Paleozoic intracontinental orogeny [25,26,27]; (2) Early Mesozoic intracontinental orogeny [28,29]; and (3) Late Mesozoic subduction of the Paleo-Pacific Plate [30,31]. From the Early Paleozoic to the Late Mesozoic, four magmatic events occurred during the Caledonian, Hercynian, Indosinian, and Yanshanian periods, leading to the formation of numerous deposits [32,33]. The Yanshanian magmatism and associated mineralization events in the Late Jurassic were formed in an intracontinental extensional environment in response to the far-field effects of the Paleo-Pacific Plate subduction [20,23,34].

The exposed strata in the Nanling area range from the Cambrian to the Quaternary, excluding the Silurian period. The lowermost part of the sedimentary sequence comprises Cambrian sandstone, slate, phyllite, and tuffaceous pyroclastic deposits, overlain by Ordovician rocks such as muddy and sandy sediments. The Devonian/Carboniferous clastic rocks are predominantly composed of siltstone, quartz sandstone, and conglomerate, along with shallow marine chemical sedimentary rocks like limestone and dolomite. During the Permian period, the primary components of the strata were shale and sandstone. Triassic layers, which are less frequently encountered, are mainly made up of carbonates and shale. The Jurassic to Cretaceous periods are notable for fluvial/lacustrine sediments that are typically found within fault basins [16,35,36].

The regional fault structures were primarily formed during the Indosinian and Yanshanian periods. Most faults are oriented N-S or NNE although others strike NW or NE. Additionally, there are a few E–W oriented faults. The region exhibits well-developed fold structures, predominantly consisting of complex folds. The major folds include the Jinziling-Xianghualing anticlinorium, Guiyang composite anticline, Wugaishan anticline, Xishan anticline, Yaogangxian-Rucheng composite anticline, Yangdiao-Zhangjiaping composite syncline, Chenzhou-Yizhang composite syncline, Gaochetou-Shatian composite syncline, and Zixing-Chishi composite syncline. These folds are primarily oriented in an NE and NNE direction.

The Nanling area is known for its widespread and diverse magmatic rocks (Figure 2). Jurassic magmatic activity played a significant role in the formation of various non-ferrous metal minerals occurring in two distinct periods: 195–170 Ma and 180–152 Ma [10]. The early-Middle Jurassic magmatic phase (195–170 Ma) involved the formation of basaltic rocks and rhyolites, which were associated with the emplacement of A-type granites, syenites, and calc-alkaline granites [37,38]. The magmatic phase from 180 to 152 Ma saw the production of Jurassic granitoids characterized by multistage intrusions and a direct connection to mineralization processes. The Jurassic intraplate granite/syenite/gabbro assemblage is interpreted as a response to far-field stress induced by the subduction of the Paleo-Pacific Plate [39]. The rocks from 180 to 152 Ma are interpreted as the products of the interactions between the lithospheric crust and asthenospheric mantle in a rift environment [3,37]. The Caledonian magmatic activity in the region likely had little impact on regional mineralization, while the Indosinian magmatic activity, although leading to the initial enrichment of W, Sn, and Fe elements, was relatively small in scale. In contrast, the Yanshanian magmatic activity (180–152 Ma) was the most intense and widespread, with all the known types of metallic deposits in the region closely associated with it. The large-scale highly fractionated granites exposed at the surface are closely related to the W-Sn polymetallic deposits, while the moderately fractionated oxidized small dikes are closely associated with the Cu-Pb-Zn polymetallic deposits.

2.2. Deposit Geology

The Baoshan Cu-Pb-Zn deposit comprises 0.24 Mt of Cu at a grade of 1.28%, 0.47 Mt of Pb at 3.82%, and 0.51 Mt of Zn at 4.34% [2]. Situated in the central part of the Nanling metallogenic belt, the Baoshan deposit includes the central Cu-Mo deposit, the northern Caishenmiao Pb-Zn-Ag deposit, the eastern Pb-Zn-Ag deposit, and the western Cu-Pb-Zn polymetallic deposits (Figure 3). The exposed formations in the Baoshan district consist mainly of Carboniferous carbonate rocks. The stratigraphic sequence comprises Devonian Xikuangshan Formation limestone, Carboniferous Menggong’ao Formation dolomitic limestone, Shidengzi Formation limestone, Ceshui Formation sand shale, Zimenqiao Formation dolomite, and Hutian Formation dolomite [46]. The primary NE- to ENE-trending faults and folds in this region are intersected by later-stage NW-trending shear zones. Jurassic granodiorite porphyry is extensively distributed and intrudes along these NW-trending structures (Figure 3).

This study examines granodiorite porphyry that is spatially associated with mineralization (Figure 4, Figure 5 and Figure 6). The granodiorite porphyry, found near the Cu-Pb-Zn mineralization, predominantly occurs in small blocks or dykes intruding Lower Carboniferous limestone, sandstone, and shale. The weathered surface of the rock appears gray–white, whereas the fresh surface is gray–green (Figure 6a,b). The rocks display massive and porphyritic textures, with phenocrysts (15%–20%) primarily consisting of quartz, K-feldspar, and biotite (Figure 6b). The matrix (80%–85%) is composed of cryptocrystalline hypidiomorphic plagioclase, xenomorphic quartz, K-feldspar, hornblende, and biotite. Accessory minerals include apatite, zircon, ilmenite, and magnetite. The quartz are colorless, transparent semi-idiomorphic grains with particle sizes ranging from 0.1 to 3 mm, exhibiting extensive erosion phenomena, accounting for approximately 40%–50% of the phenocrysts. K-feldspar are automorphic to semi-automorphic granules with particle sizes of 0.5 to 3 mm. Biotite appears as a flake with a multi-fractured surface, often associated with chlorite, making up 10%–20% of the rock content (Figure 6c,d). Numerous secondary carbonate veins (0.5–2 mm in width), primarily composed of calcite, are present in the rocks. The granodiorite porphyry samples display varying degrees of alteration, including sericitization, carbonatization, chloritization, silicification, and metal mineralization. Feldspar in the granodiorite porphyry has partially transformed into zoisite, with carbonatization and chloritization predominantly developed along fractures. The principal mineralizations observed are molybdenization, pyritization, and chalcopyrite mineralization.

The wall rocks within the Baoshan Cu-Pb-Zn deposit exhibit intense alteration, including potassic, silicification, sericitization, skarnization, carbonatization, and fluoridation (Figure 5). Among these, skarnization, silicification, fluoridation, and carbonatization are most closely associated with mineralization (Figure 5b,d). The central Cu orebodies in the Baoshan deposit typically appear as stratiform, vein-like, or lenticular, with a continuous distribution, large scale, and high grade, closely related to skarn formation. These orebodies are predominantly controlled by the overturned Baoling anticline, with the strike of the orebodies often consistent with that of the anticline. The primary host stratum for these orebodies is the Shidengzi Formation limestone. The most typical Cu orebodies are found in the 169-line profile, where five major Cu orebodies are identified (Figure 4). In the western and northern sections, Pb-Zn mineralization is primarily characterized by hydrothermal vein-type mineralization. These orebodies are mainly located within the northeast-trending fault fracture zones (F₂₁ and F₂₅) and the interlayer fracture zones in the footwalls of these faults, with some mineralization also occurring in the southern flank of the overturned Baoling anticline. The host strata for these Pb-Zn orebodies can be the Shidengzi Formation limestone, the Zimenqiao Formation dolomite, or the Ceshuishui Formation sandstone/shale.

The Baoshan Cu-Pb-Zn deposit can be categorized into two main ore types based on mineralization: Cu (Mo) ores and Pb-Zn (Ag) ores. The metallic minerals in the ores primarily include chalcopyrite, molybdenite, pyrite, sphalerite, and galena, with lesser amounts of tetrahedrite, scheelite, magnetite, arsenopyrite, native gold, and native silver. Non-metallic minerals mainly consist of garnet, diopside, actinolite, epidote, chlorite, quartz, fluorite, and carbonate minerals.

3. Samples and Analytical Methods

3.1. Samples

The granodiorite porphyry samples for major and trace element analysis, as well as Sr-Nd isotopic studies, were obtained from the core of the Baoling overturned anticline in the central part of the Baoshan deposit. Specifically, the samples were collected from the 165 line at the −270 m level and from the 162 and 156 lines at the −110 m level. The granodiorite porphyry sample used for zircon U-Pb dating was collected from the 169 line at the −190 m level. At these levels (−110 m, −190 m, and −270 m), the granodiorite porphyry occurs as dikes or veins that extend and interconnect at greater depths, intruding into the surrounding strata. The specific sampling location is shown in Figure 3 and Figure 4.

3.2. Analytical Methods

The analytical methods in this study for whole-rock major and trace element analyses, whole-rock Sr-Nd isotope analyses, and LA-ICP-MS zircon U-Pb dating analyses are provided in Supplementary Text I. Zircon U-Pb dating was carried out at the Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitoring, Ministry of Education, Central South University. The whole-rock major and trace element analyses were conducted at ALS Laboratory Group Co., Ltd. (Guangzhou, China). The whole-rock Sr-Nd isotope testing was performed at Beijing Kehui Testing Technology Co., Ltd. (Beijing, China)

4. Results

4.1. Whole-Rock Major and Trace Elements

In the Baoshan deposit, the granodiorite porphyry related to mineralization is very prone to post-magmatic hydrothermal alteration. This study selected fresh rock samples for the whole-rock geochemical analysis, revealing high loss on ignition (LOI) values ranging from 3.9 to 6.4 wt.%. Before undertaking the geochemical analysis, the influence of hydrothermal alteration on element concentrations was examined. On alteration box plots (Figure 7) [49], most samples plot in the least altered box. As the geochemical effects of alteration on the samples are limited, they can be used to investigate the petrogenesis and geochemical characteristics. As illustrated in Figure 8, there is a clear negative correlation between the contents of Al₂O₃, FeO, and Na₂O with LOI values. Among them, the Na₂O content is most significantly affected by the hydrothermal alteration, showing a notable decreasing trend when the LOI values approach four.

Due to the generally stable chemical properties of rare earth elements (REEs), their concentrations remain largely unchanged during hydrothermal activity. Thus, this study focuses solely on the impact of hydrothermal alteration on the trace elements and Sr-Nd isotopes, as discussed in the following sections. As shown in Figure 9, the trace elements and Sr-Nd isotopes in the Baoshan granodiorite porphyry do not exhibit trends in variation with changes in the LOI values. This indicates that the results indicated by the trace elements, rare earth elements, and Sr and Nd isotopes are reliable.

The whole-rock major element analysis results show that the Baoshan granodiorite porphyry has narrow content ranges for SiO₂ (65.87–68.21 wt.%), TiO₂ (0.31–0.39 wt.%), Al₂O₃ (13.87–14.36 wt.%), and FeO_T (2.37–3.37 wt.%) (Supplementary Table S1). In contrast, MgO (0.99–1.95 wt.%), CaO (1.82–3.91 wt.%), Na₂O (0.43–1.01 wt.%), and K₂O (3.42–5.62 wt.%) show relatively larger content ranges. MnO (0.07–0.12 wt.%) and P₂O₅ (0.15–0.16 wt.%) have relatively low contents (Supplementary Table S1). Among these, TiO₂, Al₂O₃, CaO, and P₂O₅ show negative correlations with SiO₂, while the correlations between SiO₂ and the other elements are not significant (Figure 10).

The trace element analysis results indicate that the Baoshan granodiorite porphyry is characterized by enrichment in light rare earth elements (∑LREE: 78.8–261.2 ppm) and depletion in heavy rare earth elements (∑HREE: 10.8–17.4 ppm), with ∑LREE/∑HREE ratios ranging from 6.2 to 21.2 (Supplementary Table S2). The rocks commonly show weak negative Eu anomalies or no Eu anomalies (δEu = [Eu_N/(Sm_N×Gd_N)^1/2] = 0.62–1.04, with an average value of 0.82), manifesting as a weak negative Eu anomaly and LREE enrichment in a right-leaning pattern in the REE distribution diagram (Figure 11a). Additionally, the rocks exhibit no significant Ce anomaly (δCe = [Ce_N/(La_N×Pr_N)^1/2] = 0.92–1.06, with an average value of 1.00). The trace element spider diagram (Figure 11b) reveals that the Baoshan granodiorite porphyry is enriched in Rb, Th, U, K, and LREE, but relatively depleted in Ba, Nb, Ta, Sr, P, and Ti.

4.2. Whole-Rock Sr-Nd Isotope

Based on the zircon U-Pb geochronology results of the Baoshan granodiorite porphyry (162 ± 1 Ma in Section 4.3), the calculations of the initial Sr-Nd isotopic ratios (Supplementary Table S3) show that the ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios of the Baoshan granodiorite porphyry range between 0.714979 and 0.719998 and 0.512174 and 0.512276, respectively. The corresponding (⁸⁷Sr/⁸⁶Sr)_i and ε_Nd(t) values range from 0.707717 to 0.709506 and from −7.54 to −4.87, respectively. Additionally, the two-stage Nd isotopic model age (T_2DM) of the granodiorite porphyry is calculated to be 1.35–1.17 Ga.

4.3. Zircon U-Pb Geochronology

Cathodoluminescence (CL) images (Figure 12) reveal that the zircons from the Baoshan granodiorite porphyry appear mostly gray to grayish-white, exhibiting subhedral to euhedral prismatic structures (40 × 120–80 × 200 μm) with well-defined oscillatory zoning. Along the edges or fractures of zircon grains, alteration features from late-stage hydrothermal processes are visible, likely due to the proximity to the siliciclastic rock band. In this study, zircons showing signs of alteration from hydrothermal processes or with chaotic oscillatory zoning were excluded, along with data points having Th/U ratios less than 0.4 or significantly deviating from the concordia line. The remaining zircon samples exhibit U and Th contents ranging from 218 to 2096 ppm and 160 to 1176 ppm, respectively, with Th/U ratios ranging from 0.42 to 0.96, characteristic of typical magmatic zircons [51] (Supplementary Table S4). The zircon U-Pb analysis results a plot close to the concordia line, yielding a consistent isotopic age of 162 ± 1 Ma (MSWD = 2.3) (Figure 13).

5. Discussion

5.1. Age of Baoshan Granodiorite Porphyry

The Baoshan granodiorite porphyry is closely related to mineralization, with previous studies indicating that the age of the granodiorite porphyry ranges between 170 and 155 Ma [5,10,11,12,16,17,18,19]. In contrast, the U-Pb dating of garnet and the Re-Os dating of molybdenite suggest that the skarnization and Cu (Mo) mineralization in the central part occurred at 162.6 ± 2.9 Ma [5] and 160 ± 2 Ma [19], respectively (Figure 14). The broader range of magmatism ages does not match the relatively concentrated mineralization ages, with some emplacement ages notably younger than the mineralization ages (Figure 14). The sample for the zircon U-Pb dating used in this study was collected from the −190 m level along line 169, where the granodiorite porphyry, skarn, and Cu orebodies are continuously exposed, showing a clear genetic relationship between the magmatism and mineralization. This study obtained a zircon U-Pb age of 162 ± 1 Ma for the granodiorite porphyry, consistent with the previously reported ages for garnet and molybdenite [5,19], suggesting the reliability of this newly acquired age. Regionally, the zircon U-Pb age of the Baoshan granodiorite porphyry is slightly earlier than the magmatism ages of mineralizing intrusions in other typical deposits. However, it aligns with the timing of large-scale Mesozoic metallogenic events in South China proposed by Mao et al. [52], which occurred during 170–150 Ma and 140–125 Ma. It also corresponds with the metallogenic peak period of 160–150 Ma and the secondary peak period of 140–130 Ma identified by Fu et al. [53] in the Nanling metallogenic belt.

5.2. Petrogenesis of Granodiorite Porphyry

In the K₂O-SiO₂ diagram, most spots fall into the high-K calc-alkaline series rock zone (Figure 10). In the TAS rock type discrimination diagram, the spots mainly fall into the granodiorite zone (Figure 15a). In the A/NK-A/CNK diagram, some spots fall into the metaluminous zone, while others fall into the peraluminous zone (Figure 15b). As mentioned above, with the increase in the rock LOI values, the Na₂O content significantly decreases, leading to an increase in the A/NK and A/CNK values. Therefore, the fact that some spots fall into the peraluminous granite range in the A/NK-A/CNK diagram may be related to the high degree of alteration of the rocks. Further detailed discussion is needed to determine the rock type of the Baoshan granodiorite porphyry.

The primary mineral assemblage of the Baoshan granodiorite porphyry is plagioclase, K-eldspar, quartz, and biotite, with no peraluminous minerals such as cordierite observed. Additionally, it has been reported that the Baoshan granodiorite porphyry may contain small amounts of hornblende and other minerals characteristic of I-type granites [7,9]. In the rock type discrimination diagrams (Figure 16a,b), the spots all fall within the I-type granite field. Based on the impact of alteration on the Na₂O content, it can be anticipated that with increasing alteration, sample spots may shift into the S-type granite field (Figure 16b). However, in Figure 16b, all the spots fall within the I-type granite field, indicating that the Baoshan granodiorite porphyry should be classified as I-type granite. The whole-rock REE distribution pattern shows a right-leaning trend, with Eu displaying a slight negative anomaly or no anomaly (Figure 11a), which is distinctly different from the REE distribution pattern of the Mesozoic S-type granites in the region, characterized by moderate HREE fractionation and strong negative Eu anomalies [4]. There is a clear negative correlation between P₂O₅ and SiO₂ (Figure 10), and a distinct positive correlation between Th and Rb (Figure 16c), both indicative of the geochemical characteristics of I-type granites [63]. Apart from showing higher A/CNK and A/NK values due to hydrothermal alteration, the mineral assemblage, REE distribution pattern, and elemental evolution trends in the Baoshan granodiorite porphyry all indicate it should be classified as I-type granite.

The variation trend in a pair of highly incompatible elements can distinguish partial melting from fractional crystallization during the rock-forming process [66,67]. The Zr/Nd and La/Sm ratios of the Baoshan granodiorite porphyry are positively correlated with the Zr and La contents, respectively (Figure 17), with a few spots forming an upward convex parabolic distribution in Figure 17a. These characteristics indicate that partial melting dominated the rock-forming process of the granodiorite porphyry with relatively weak fractional crystallization. Whole-rock oxides such as TiO₂, Al₂O₃, CaO, and P₂O₅ show negative correlations with SiO₂ (Figure 10), along with relative depletion in elements like Ba, Sr, and Ti (Figure 11b), suggesting that the fractional crystallization of minor amounts of K-feldspar- and Ti-bearing minerals (e.g., biotite, titanite, and amphibole) may have occurred. Mineral fractional crystallization discrimination diagrams (Figure 18) also show that the Baoshan granodiorite porphyry underwent the fractional crystallization of K-feldspar, amphibole, and minor plagioclase. The whole-rock Eu content shows a slight negative anomaly or no anomaly, and the non-dominant role of fractional crystallization during the rock-forming process suggests that plagioclase fractional crystallization was not significant, and residual plagioclase may not be present in the magma source. Experimental studies have shown that amphibole crystallizes in andesite melt at 800 to 850 °C when the melt contains more than 4 wt.% H₂O [68,69]. However, when the melt is unable to dissolve such an amount of water under low pressure, amphibole becomes unstable [70]. Therefore, the Baoshan granodiorite porphyry, which underwent amphibole fractional crystallization with suppressed plagioclase fractional crystallization, suggests high water content in the magma.

As previously mentioned, the formation of the Baoshan granodiorite porphyry was primarily dominated by partial melting with insignificant fractional crystallization. The REE distribution pattern shows a slight negative Eu anomaly or no anomaly (Figure 11a), indicating that there is almost no residual plagioclase in the magma source region. Figure 18c,d indicate that the granodiorite porphyry underwent hornblende fractional crystallization. Garnet is relatively enriched in Y, whereas plagioclase is relatively enriched in Sr. Therefore, garnet crystallization can result in an increased Sr/Y ratio in the magma. The whole-rock data of the Baoshan granodiorite porphyry exhibits LREE enrichment and HREE depletion, a high (La/Yb)_N ratio (5–32, averaging 15.8), and a low Sr/Y ratio (3–23), suggesting that residual garnet may be present in the source region without participating in the partial melting process.

Regionally, the coexistence in time and space of ultrabasic to basic rocks with granites can effectively indicate whether granites originate from mantle-derived mafic magma fractional crystallization [66,71]. Typical basic volcanic rocks in southern Hunan include Daoxian high-Mg olivine basalt (151.6 ± 1.0 Ma) and Ningyuan alkaline basalt (266–199 Ma; 177–174 Ma; 165 Ma) [72]. The eruption times of these two types of basalts in Hunan, which are close to the magmatic activity of the Baoshan granodiorite porphyry, can approximately reflect the compositional characteristics of mantle-derived materials during the same period. Utilizing differences in the partition coefficients of various trace elements between solids and liquids, one can effectively discern the fractional crystallization relationship between coexisting ultrabasic to basic rocks and granites in both time and space.

Figure 19a shows a significant variation trend in the Rb content as the Sr content decreases. This contrasts significantly with the relatively stable Rb content characteristic of fractional crystallization processes, indicating that the Baoshan granodiorite porphyry did not originate from the fractional crystallization of mantle-derived mafic magma in the region. As mentioned above, the formation of the Baoshan granodiorite porphyry was primarily dominated by partial melting processes (Figure 17), which also suggests that it is unlikely to have formed directly from the weak fractional crystallization of mantle-derived mafic material [66]. This is consistent with the whole-rock Sr-Nd isotope results, where the Baoshan granodiorite porphyry exhibits (⁸⁷Sr/⁸⁶Sr)_i and ε_Nd(t) values ranging from 0.7077 to 0.7095 and −7.54 to −4.87, respectively, showing significant differences compared to the two types of volcanic rocks in the region (Ningyuan: 0.7037–0.7096, 3.97–9.5; Daoxian: 0.7058–0.7072, −1.92–3.81) [72,73], indicating they do not originate from the same magma source region. In summary, this indicates that the Baoshan granodiorite porphyry did not directly result from the fractional crystallization of deep mantle-derived mafic magma.

The relatively low ε_Nd(t) values (−7.54 to −4.87) and Nd isotopic two-stage model ages (1.17–1.35 Ga) of the Baoshan granodiorite porphyry indicate the magma source region may be composed of mafic rocks from the Middle Proterozoic ancient crust (Figure 19b). However, the ε_Nd(t) values of the Baoshan granodiorite porphyry are significantly different from those of S-type granites directly derived from Precambrian metamorphic basement rocks (−12 to −16) [4], suggesting that the partial melting of a single ancient crustal source material may not have formed the Baoshan granodiorite porphyry magma.

The whole-rock Sr and Nd isotopic compositions of the Baoshan granodiorite porphyry lie between the pre-Cambrian metamorphic basement and the depleted mantle in the Xiangnan region. This suggests a hybridization process involving ancient crustal material and isotopically depleted material in the magma source region [4]. With variations in the SiO₂ and MgO contents, the (⁸⁷Sr/⁸⁶Sr)_i ratio and ε_Nd(t) values of the rocks display weak trends (Figure 20), which are distinct from those expected from the crystallization or partial melting of a single source material. Differences in the elemental and isotopic compositions between the crustal and mantle materials result in a decrease in (⁸⁷Sr/⁸⁶Sr)_i ratio and an increase in ε_Nd(t) values with decreasing whole-rock SiO₂ content during the incorporation of mantle melts. This is consistent with the relationship between the Baoshan granodiorite porphyry and its mafic enclaves (Figure 20a,b), indicating the formation of the mafic enclaves due to the addition of mantle-derived melts, consistent with previous findings [15]. However, the (⁸⁷Sr/⁸⁶Sr)_i and ε_Nd(t) values of the Baoshan granodiorite porphyry itself do not follow this pattern, suggesting the involvement of other isotopically depleted materials.

Studies indicate that juvenile crust and mantle material have similar isotopic compositions, but the former typically generates felsic melts during melting, while the latter typically produces mafic melts [74,75]. The addition of isotopically depleted felsic melts formed by re-melting juvenile crust significantly influences the large fluctuations in the (⁸⁷Sr/⁸⁶Sr)_i ratio and ε_Nd(t) values of the Baoshan granodiorite (⁸⁷Sr/⁸⁶Sr)_i, along with being a key factor in the non-linear variations between the SiO₂ and MgO contents. Baoshan granodiorite contains abundant inherited zircons from the Neoproterozoic (892 ± 20 Ma, 891.5 ± 15 Ma) [15], with ε_Hf(t) values (+6) consistent with the characteristics of Neoproterozoic arc magmas (ε_Hf(t) = 2.89–16.2) [76,77]. Recent studies indicate that isotopically enriched granites like the Baoshan granodiorite with high ⁸⁷Sr/⁸⁶Sr ratios and negative ε_Nd(t) values can be produced by partial melting interactions between juvenile and ancient crustal materials [71]. Meanwhile, in the southern Hunan region, the phenomenon of juvenile crustal melt addition during the formation of polymetallic Cu-Pb-Zn deposits (e.g., Tongsanling, Shuikoushan) has also been widely recognized [9,10], suggesting that the incorporation of juvenile crustal material may play a crucial role in the formation of these deposits.

High-temperature melting experiments indicate that amphibole from newly formed mafic lower crust can release up to 6.5 wt.% H₂O under conditions of 1.2–1.4 GPa and 850–1150 °C [78,79,80,81]. This contrasts with the higher water content (9.5–11.5 wt.%) and relatively lower melting temperature (<800 °C) of the Baoshan granodiorite magma. In addition, the lower oxygen fugacity characteristics of the local Archean crust (ΔFMQ = −2.4–0.7) are also unfavorable for the formation of high oxygen fugacity granodiorite magma [82]. Therefore, it is speculated that the mantle-derived melt forming dark enclaves in the Baoshan granodiorite should exhibit high oxygen fugacity and be enriched in water.

The deep portions of the Yangtze Block and the North China Block are characterized by EM I and EM II lithospheric mantle, respectively [83,84,85]. The former is characterized by high water content and oxygen fugacity [9,84]. The Jiangshan-Shaoxing Fault marks the boundary where the Neoproterozoic Yangtze Block and North China Block collided [86,87]. There has been significant debate over the southwestern extension of this boundary, with the Chenzhou-Linwu Fault potentially serving as the passage for its extension to the southwest [4,15,83,88,89,90]. Wang et al. [85] conducted a comparative study of Mesozoic basaltic volcanic rocks and mafic dykes on both sides of the Chenzhou-Linwu Fault, indicating that the western deep part of the fault is composed of EM I lithospheric mantle while the eastern deep part is EM II lithospheric mantle. The Baoshan polymetallic Cu-Pb-Zn deposit is located precisely on the western side of the Chenzhou-Linwu Fault, and the Sr-Nd isotopic compositions of the enclaves in the granodiorite of Baoshan are consistent with those of EM I lithospheric mantle. This further suggests the possible addition of EM I lithospheric mantle melts characterized by high oxygen fugacity and enriched in water.

There has been ongoing debate regarding the tectonic environment and dynamic background of the South China region [4,39,78,91,92]. Recently, Hou et al. [78] summarized significant geological events of the Yanshanian period in South China, pointing out that the subduction of the Paleo-Pacific Plate and the compression between the northern and southern blocks led to multi-phase orogeny in South China, resulting in unconformable contacts between the Early, Middle, and Late Jurassic strata [93]. A series of NE-trending and nearly EW-trending intraplate OIB-type basalts, A-type granites, and bimodal volcanic rock associations formed in the Middle Jurassic indicate that the lithosphere transitioned from brief compression to an extensional state (180–158 Ma) [33,78,94,95,96,97,98]. By the Late Yanshanian period, South China experienced three peaks of magmatic activity at 158 Ma, 125 Ma, and 93 Ma, along with intense lithospheric extension [39,99,100,101,102]. In the extensional tectonic setting, the upwelling of deep asthenospheric mantle material causing large-scale magmatic activity in the Nanling region during the Middle–Late Jurassic has gained wide scholarly support [31,103,104]. Zhang et al. [83], using a joint seismic algorithm, mapped a high-resolution velocity model of the lithosphere in South China, revealing that the large-scale delamination of the lithospheric mantle and mafic lower crust during the Middle Jurassic was a key factor inducing asthenospheric mantle upwelling (180–160 Ma). In this study, zircon U-Pb geochronology determined the crystallization age of the Baoshan granodiorite porphyry to be 162 ± 1 Ma, indicating its formation in the extensional tectonic setting of South China during the Middle Jurassic. In the granite tectonic setting discrimination diagrams (Figure 21), the granodiorite porphyry sample points mainly fall into the post-collisional granite area, also indicating its formation in a post-collisional extensional tectonic setting [105].

In summary, this study indicates that the formation of the Baoshan granodiorite magma occurred during the Middle Jurassic extensional tectonic environment in South China. The underlying intrusion of hydrous, high oxygen fugacity lithospheric mantle melts triggered partial melting interactions between the ancient Archean crustal material and newly formed mafic lower crust during the Neoproterozoic, leading to the formation of the Baoshan granodiorite magma.

5.3. Metallogenic Significance

Some studies have pointed out that the partial melting of the magma source area, located in the lower crust (25–29 km) and experiencing conditions characteristic of the amphibolite facies, may be an important source of Cu in the Cu deposit granodiorite porphyry at Tongshanling [108]. However, recent studies suggest that the magmatic source areas of the Cu-Pb-Zn polymetallic deposits in Baoshan, Shuikoushan, etc., in the area may exceed 30 km [9], which is inconsistent with the above-mentioned amphibolite facies source depth, implying that Cu may come from deeper sources. In the southern Hunan area, the characteristics of the addition of juvenile crustal melts to the ore-forming plutons of the Cu-Pb-Zn polymetallic deposits (such as Tongshanling and Shuikoushan) have been widely recognized [9,10], revealing the extensive link between the juvenile crustal material and Cu-Pb-Zn polymetallic deposits in the area. Recently, studies on the genesis of the ore-forming plutons of the Dexing porphyry Cu deposit in the Qin-Hang metallogenic belt have shown that its porphyry magma comes directly from the partial melting of the juvenile crust [78,94]. The remelting and decomposition of Cu-bearing metal sulfides in the juvenile crust provide a large amount of metallic Cu for the Dexing porphyry magma [109,110,111]. Thus, it is inferred that the addition of juvenile crustal melts may also provide an important source of ore-forming materials for the formation of the Cu-Pb-Zn polymetallic deposits in southern Hunan.

Additionally, the water content and oxygen fugacity conditions of magma are important indicators for the formation of copper deposits. The amount of water determines whether the magmatic fluid can become saturated and when exsolution occurs, while the level of oxygen fugacity directly determines the saturation state of metal sulfides [78,112,113,114]. Magma with high water content and high oxygen fugacity is conducive to the entry of Cu and other chalcophile elements into the magmatic melt phase and exsolving at shallow depths to form mineral-rich magmatic-hydrothermal fluids [115,116,117].

This study indicates that the Baoshan granodiorite porphyry originated from the partial melting of ancient and new crust; the magma is characterized by high oxygen fugacity and high water content. Based on the above inference, the juvenile crustal magma source can provide a large amount of Cu to the Baoshan granodiorite porphyry; the high oxygen fugacity and water-rich magma conditions are favorable for bringing deep-seated Cu to the shallow crust. The coupling of these two factors provides favorable magmatic conditions for the formation of large Cu deposits in Baoshan.

5.4. Comparison of W-Sn-Related Granites in the Region

This study suggests that the mineralized granodiorite porphyry in the Baoshan deposit is a low-differentiation I-type granite, with magma originating from the partial melting of ancient and newly formed crust, and accompanied by the addition of high oxygen fugacity, water-rich lithospheric mantle melts. The interaction between the crust and mantle and the addition of new crustal materials have been widely recognized in the formation of many Cu-Pb-Zn polymetallic ore-forming plutons in the region (e.g., Tongshanling, Shuikoushan, etc.) and are considered representative [9,10]. Studies indicate that the granites associated with tin in the area are mainly alkali feldspar granites, followed by syenogranites, while those associated with tungsten are mainly biotite or muscovite granites (Table 1). Due to the highly differentiated characteristics of W-Sn-related granites, their petrogenetic classification (I-, S-, and A-type) is somewhat constrained, leading to differing views on their magmatic source regions [118,119]. However, it is generally believed that tungsten/tin-bearing granites originate from the re-melting of crust-derived metapelitic magma sources [119,120]. This differs significantly from the clay-poor, mafic-rich characteristics of the magmatic source regions of mineralized plutons like Baoshan and Tongshanling [103].

Regarding the formation age of ore-forming rocks, the formation age of the Baoshan granodiorite porphyry is slightly earlier than that of the typical tungsten/tin polymetallic ore-forming plutons in the region (Table 1), which is consistent with the characteristic that the formation age of the Cu-Pb-Zn-related granites in the region is slightly earlier than that of the W-Sn-related granites (age of Cu-Pb-Zn-related granites: 167–155 Ma [5,10,11]; age of the W-Sn-related granites: 180–150 Ma, peaking at 160–150 Ma [44,121,122,123,124,125,126,127,128]. A comparison of oxygen fugacity characteristics shows that the Baoshan ore-forming granodiorite porphyry has higher oxygen fugacity characteristics, whereas the tungsten/tin ore-forming plutons show a decreasing trend in oxygen fugacity, which is consistent with previous findings [119,129]. Water promotes the fractionation of Ti and Sc into early-crystallizing minerals, leading to higher Al₂O₃/TiO₂ and V/Sc ratios in the residual melt [70]. Previous studies have shown that whole-rock Al₂O₃/TiO₂ and V/Sc ratios increase with rising SiO₂ during hydrous mafic-to-felsic magmatic differentiation, whereas these ratios remain constant or decrease with increasing SiO₂ during weakly hydrous or dry mafic-to-felsic magmatic differentiation [70,130]. The Baoshan ore-forming granodiorite porphyry shows a positive correlation between the Al₂O₃/TiO₂ and V/Sc ratios and SiO₂ content, indicating the characteristics of water-rich magma, while the Al₂O₃/TiO₂ and V/Sc ratios of the W-Sn granites decrease with increasing SiO₂ content, indicating the characteristics of water-poor magma (Figure 22). In summary, the Baoshan ore-forming granodiorite porphyry differs significantly from the typical W-Sn ore-forming plutons in the region in terms of magmatic source, degree of crystal differentiation, magma oxygen fugacity, and water content.

Table 1

Comparison of characteristics between Baoshan granodiorite porphyry and W-Sn-related granites.

Comparison Aspects	Cu-Related Baoshan Granodiorite Porphyry	W-Sn-Related Granites
		Furong Deposit	Xianghualing Deposit	Yaogangxian Deposit
Rock types	Granodiorite porphyry	Alkali feldspar granite	Alkali feldspar granite; sodium feldspar granite	Two-mica granite; muscovite granite
Evolution process	Partial melting	Fractional crystallization
Differentiation degree	Rb/Sr = 0.47–2.9	Rb/Sr = 7–116	Rb/Sr = 97–245	Rb/Sr = 14.5–175.6
Oxygen fugacity	ΔNNO +3.1	ΔNNO −1.3	-	ΔNNO +2.7
Magma source	Ancient and new crust	Crust-derived metamorphic mudstone
Incorporation of mantle-derived material	Yes	Yes	Yes	No

Data for Furong deposit primarily based on Chen et al. [45]; Xianghualing deposit based on Yuan et al. [131]; Yaogangxian deposit based on Dong et al. [132] and Li et al. [133]; oxygen fugacity calculation for Baoshan granodiorite porphyry based on Eugster and Wones et al. [134].

6. Conclusions

Based on whole-rock major and trace elements, Sr-Nd isotopes, and zircon U-Pb geochronology of the granodiorite porphyry in the Baoshan deposit, the following conclusions are drawn:

• (1). The Baoshan granodiorite porphyry has a zircon U-Pb age of 162 ± 1 Ma.

• (2). The granodiorite porphyry is classified as a high-potassium calc-alkaline I-type granite. It originated from the partial melting of ancient Mesoproterozoic crust and Neoproterozoic mafic juvenile lower crust, with contributions from water-rich, high oxygen fugacity melts derived from the lithospheric mantle.

• (3). The magma formed in an extensional tectonic setting during the Middle Jurassic period in South China.

• (4). A comparison with the diagenesis of the ore-bearing intrusions in the W-Sn deposits suggests that different magma source regions may be the primary cause for the spatial and temporal development of Cu-Pb-Zn versus W-Sn mineralization in southern Hunan.

Author Contributions

Conceptualization, K.C. and J.Z.; methodology, J.Z. and X.D.; software, Y.L.; validation, M.H.; investigation, Z.L.; resources, Z.L.; data curation, X.D.; writing—original draft preparation, X.D.; writing—review and editing, K.C.; visualization, X.D.; supervision, Z.L.; project administration, Z.L.; funding acquisition, Z.L. All authors have read and agreed to the published version of the manuscript.

Data Availability Statement

Data are contained within the article.

Conflicts of Interest

All the authors (Xue-Ling Dai, Ke Chen, Jun-Ke Zhang, Yong-Shun Li, Ming-Peng He, and Zhong-Fa Liu) declare that they have no financial and personal relationships with other people or organizations that can inappropriately influence their work. There is no professional or other personal interest of any nature or kind in any product, service, or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled.

Footnotes

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Figures and Table

Figure 1. (a) Sketch map of the regional tectonic framework. (b) The distributions of the Jurassic granites and deposits in the South China Block (modified from [3]).

Figure 2. Sketch map of the regional geology showing the tectonic framework and mineralization resources (modified from [19]). Geochronological data from [11,40,41,42,43,44,45].

Figure 3. Simplified geologic map of the Baoshan Cu-Pb-Zn deposit (after [47]).

Figure 4. Cross section along the No. 169 prospecting line from the Baoshan Cu-Pb-Zn deposit (after [48]).

Figure 5. Hydrothermal alteration characteristics of the Baoshan deposit. (a) Development of potassic alteration, epidotization, chloritization, and silicification in the ore-forming granodiorite porphyry. (b) Skarnization and silicification are closely associated with Cu mineralization. (c) Skarnization in wall rocks. (d) Silicitization and fluoropylitization are closely related to sphalerite and galena. Ep = epidote; Qtz = quartz; Chl = chlorite; Ccp = Chalcopyrite; Grt = garnet; Cb = Carbonate minerals; Cpx = pyroxene; ls = limestone; Fl = fluorite; Py = pyrite; Sp = sphalerite.

Figure 6. Petrographic characteristics of granodiorite porphyry in the Baoshan deposit. (a,b) Granodiorite porphyry; (c,d) K-feldspar and biotite in granodiorite porphyry (Crossed polar and transmitted light). Kfs = K-feldspar; Pl = Plagioclase; Bt = Biotite; Qtz = Quartz; Amp = Aamphibole.

Figure 7. Alteration box plots (after [49]) showing that all the samples from the Dongguashan and Xinqiao in this study have relatively weak hydrothermal alteration. Previous data based on the literature [4,9,16], the same below. AI = 100 × (K2O + MgO)/(K2O + MgO + Na2O + CaO); CCPI = 100 × (MgO + FeO)/(MgO + FeO + K2O + Na2O). Additional abbreviation: ab = albite; calc = calcite; carb = carbonate; chl = chlorite; ep = epidote; Kfs = K-feldspar; ms = muscovite; py = pyrite.

Figure 8. Impact of hydrothermal alteration on major elements.

Figure 9. Impact of hydrothermal alteration on trace elements.

Figure 10. Harker diagram of Baoshan granodiorite porphyry.

Figure 11. (a) REE distribution pattern diagram of granodiorite porphyry. (b) The trace element spider diagram of granodiorite porphyry. Data from [4]. Chondrite normalization based on the literature [50].

Figure 12. Cathodoluminescence image of zircon from Baoshan granodiorite porphyry.

Figure 13. (a) U-Pb concordant age and (b) U-Pb weighted mean age of zircons from Baoshan granodiorite porphyry.

Figure 14. Geochronological constraints on the formation of magmatic rocks and mineralization events in Southern Hunan. Age data source [5,10,11,12,16,17,18,19,54,55,56,57,58,59,60]. Bt = biotite; Zrn = zircon; Ttn = titanite; Mol = molybdenite; Grt = garnet.

Figure 15. (a) TAS diagram for classification of intrusive rock types [61]. (b) Whole-rock A/NK-A/CNK diagram [62].

Figure 16. Discrimination diagrams for granite rock types. (a) Zr-10000*(Ga/Al) diagram [64]; (b) Al-Na-K–Ca–Fe+Mg diagram [65]; (c) Th-Rb diagram [63].

Figure 17. Partial melting and fractional crystallization trends in rocks. (a) Zr/Nb-Zr diagram; (b) La/Sm-La diagram.

Figure 18. Discrimination diagrams for fractional crystallization. (a) Sr-Eu diagram; (b) Ba-Sr diagram; (c) Dy-Er diagram; (d) Yb-DyN/(LaN4/13 × YbN9/13)-Dy/Yb diagram. (a–c) according to Kong et al. [10]; (d) according to Liu et al. [9].

Figure 19. (a) Whole-rock Rb-Sr diagram and (b) εNd(t)-t diagram.

Figure 20. Relationship between whole-rock (87Sr/86Sr)i and εNd(t) with SiO2 and MgO contents. (a) (87Sr/86Sr)i-SiO2 diagram; (b) εNd(t)-SiO2 diagram; (c) (87Sr/86Sr)i-MgO diagram; (d) εNd(t)-MgO diagram.

Figure 21. Discrimination diagrams for tectonic settings of Baoshan granodiorite porphyry. (a) Rb-Y+Nb tectonic discrimination diagram [106]; (b) Rb/30-Hf-3Ta tectonic discrimination diagram [107]. syn-COLG = syn-collisional granites; VAG = volcanic arc granites; Late and post-COLG = late- and post-collisional granites; WPG = within-plate granites; ORG = ocean ridge granites.

Figure 22. Comparison of water content characteristics between the Baoshan granodiorite porphyry and W-Sn-related granites. (a) Al2O3/TiO2-SiO2 diagram; (b) V/Sc-SiO2 diagram. W-Sn-related granite data from the literature [45,131,132].

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min14090897/s1, Text I [135,136,137]; Table S1. Major element characteristics of granodiorite porphyry and mafic enclave in Baoshan Cu-Pb-Zn deposit; Table S2. Trace element characteristics of granodiorite porphyry and mafic enclave in Baoshan Cu-Pb-Zn deposit; Table S3. Sr-Nd isotopic characteristics of granodiorite porphyry in Baoshan Cu-Pb-Zn deposit; Table S4. U-Pb isotopic composition and age of zircon from Baoshan granodiorite porphyry.

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