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Article

Sources and Ore-Forming Environment of the Jinchanghe Pb-Zn Polymetallic Skarn Deposit, Baoshan Block, SW China: Constraints from Cu-S Isotopic and Trace Elemental Compositions of Sulfides

by
Xiaolin Cheng
1,
Yunman Zhou
2,*,
Jiyuan Wang
2,
Chengfeng Zhao
2,
Jing Huang
2,
Pengju Li
1,
Hai Wang
2 and
Fuchuan Chen
1,2,*
1
Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093, China
2
Yunnan Gold and Mineral Group Co. Ltd., Kunming 650224, China
*
Authors to whom correspondence should be addressed.
Minerals 2024, 14(7), 644; https://doi.org/10.3390/min14070644
Submission received: 14 May 2024 / Revised: 22 June 2024 / Accepted: 23 June 2024 / Published: 25 June 2024
(This article belongs to the Special Issue Mineralogical and Geochemical Characterization of Zn-Pb Ore Deposits: Insights into Their Genesis, Implications for Exploration, and Environmental Issues)
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Abstract

:
The Jinchanghe Pb-Zn polymetallic deposit is a representative distal skarn deposit in the Baoshan block. Due to limited research on the sources of ore-forming metals and trace elemental geochemistry of sulfides, the sources and mineralization environments of the Jinchanghe skarn Pb-Zn polymetallic deposit are still controversial. In this study, copper and sulfur isotopes and trace elements of sulfides from the Jinchanghe Pb-Zn polymetallic deposit were analyzed to reveal the sources of ore-forming materials and the ore-forming environments. The trace elemental analysis results show abundant Co, Ni, Mn and Se elements, and less As, Tl and Sb elements dominantly enter pyrite by isomorphic substitution, except for some Zn and Cu that occur as sulfide inclusions in Py1. Abundant Fe and Mn elements could substitute Zn to enter the sphalerite crystal lattice by the isomorphic substitution mechanism of (Fe2+ + Mn2+) ↔ 2Zn2+, and less Ag and Sb elements could enter the sphalerite by the isomorphic substitution mechanism of (Ag+ + Sb3+) ↔ 2Zn2+. The Cu-S isotopic and trace elemental compositions jointly suggest that the Jinchanghe distal skarn Pb-Zn polymetallic deposit formed from magmatic hydrothermal fluids with a sedimentary host-rock contribution, under mesothermal conditions (260 °C on sphalerite).

1. Introduction

The Jinchanghe large scale Pb-Zn polymetallic deposit is one of the typical distal skarn deposits in the Sanjiang metallogenic belt, southwest China [1,2,3]. Previous studies about the Jinchanghe deposit mainly focused on deposit geology [3,4], timing of mineralization [5,6], ore-forming fluid [3,7] and isotopic geochemistry [3,4,8], providing some reliable evidence for revealing the formation and evolution processes of this deposit. However, the studies about the sources of ore-forming metals and trace elemental geochemistry of sulfides are still insufficient, which hinders the further understanding of the sources and mineralization processes of the Jinchanghe skarn Pb-Zn polymetallic deposit.
Sulfides are abundantly developed in the Jinchanghe skarn Pb-Zn polymetallic deposit. They recorded a large amount of important information of the mineralization processes, such as temperature, pH value and oxygen fugacity, and mainly reflected in changes in elemental compositions [9]. In recent years, laser-ablation inductively coupled plasma mass-spectrometry (LA-ICP-MS) has been proved to be an in-situ and accurate analysis method for the trace elemental compositions of sulfides, providing new insights into the mineralization processes [10,11]. For example, the trace elemental compositions of pyrite, sphalerite, galena and chalcopyrite have been used to reveal the sources of ores [12], the evolution of ore-forming fluids [13] and the mechanism for controlling ore precipitation [12]. In the Jinchanghe skarn Pb-Zn polymetallic deposit, pyrite is abundant in the sulfide-ore stage, while sphalerite, galena and chalcopyrite are the main ore minerals of the sulfide-ore stage.
In this study, the elemental compositions of pyrite, sphalerite and chalcopyrite were determined by LA-ICP-MS, combined with sulfur and copper isotopes, in order to discuss the sources of ore-forming materials and the mineralization processes of the Jinchanghe skarn Pb-Zn polymetallic deposit.

2. Geological Setting

2.1. Regional Geology

The Baoshan block, located in the southern part of the Sanjiang orogenic belt, southwest China, is the northern segment of the Sibumasu block and extends southward into the Shan Block of Myanmar (Figure 1a, [14]). It is bounded by the Changning-Menglian suture to the east and the Gaoligong shear zone to the west (Figure 1b).
The basement of the Baoshan block is composed of the Neoproterozoic to Middle Cambrian metamorphosed siliciclastic rocks of the Gongyanghe Group, intercalated with some volcanic rocks with zircon U-Pb age of 499 Ma [15]. The metamorphosed basement is covered by Late Cambrian to Mesozoic sedimentary rocks mainly consisting of siliciclastics and carbonates, and minor Permian volcanic rocks. The Cambrian to Ordovician, Middle Permian, Early Cretaceous and Late Cretaceous granitic intrusions emplaced in the Baoshan block, represented by Pinghe Pluton (500–450 Ma; [16,17]) Muchang Pluton (ca. 66 Ma; Ye et al., 2010) [18], Zhibenshan pluton (127 Ma; [19]) and Caojian plutons (80 Ma, [20,21]), respectively. Moreover, numerous Woniusi basaltic rocks are developed in the Baoshan block, with a zircon U-Pb age of ca. 240 Ma, which were considered to be related to the closure of the Paleo-Tethys Ocean [22]. The regional structures of the Baoshan block are mainly controlled by the Cenozoic collision between the Indian plate and the Eurasian plate [23]. The collision formed a series of NS trending folds (e.g., Hetaoping anticline), and many NS and NE trending faults in Baoshan block. The deposit types in the Baoshan block include magmatic Cu-Ni deposits (e.g., Daxueshan; [24]), Skarn Pb-Zn polymetallic deposits (e.g., Hetaoping, Jinchanghe, Luziyuan; [3,25,26]), epithermal Pb-Zn deposits (e.g., Xiyi, Dongshan; [27]) and magmatic-hydrothermal Sn-W deposit (e.g., Shiganghe, Tiechang; [22]).
Minerals 14 00644 g001
Figure 1. (a) Tectonic location of the Baoshan block [2]; (b) simplified geological and structural framework of the Baoshan block [12,25].
Figure 1. (a) Tectonic location of the Baoshan block [2]; (b) simplified geological and structural framework of the Baoshan block [12,25].
Minerals 14 00644 g001

2.2. Deposit Geology

The Jinchanghe skarn Pb-Zn polymetallic deposit is located in the northern part of the Baoshan block. It is one of the largest distal Skarn Pb-Zn polymetallic deposits in the Baoshan block, with 0.29 Mt Zn at grade of 3.47% and 0.04 Mt Pb at grade of 0.51% [3].
The sedimentary units exposed in the Jinchanghe ore field include calcareous slate, limestone and marble of the Cambrian Hetaoping and Shahechang formations, and siltstone and mudstone of the Ordovician Pupiao formation (Figure 2a). The Late Cambrian Hetaoping formation is closely related to Pb-Zn polymetallic mineralization in the Jinchanghe deposit. The Hetaoping formation can be subdivided into three sections based on lithological differences: the upper section of the Hetaoping formation is composed of green-gray marbleized limestone and calcareous slate, the middle section is composed of blue-gray calcareous slate and marble, while the lower section is composed of calcareous slate and siltstone. Among them, the calcareous slate and marble in the middle section of Hetaoping formation is the main host rock for orebodies in the Jinchanghe deposit (Figure 2b). No relationship with granitic intrusion can be observed in the Jinchanghe mining area. Gabbro dikes of the Woniusi formation basaltic complex locally crop out in the mining area of the Jinchanghe deposit [28]. Controlled by the regional Hetaoping anticline, the faults in the Jinchanghe Pb-Zn polymetallic deposit are NW and NE trending. These faults do not show any relationship with the mineralization. Isotopic U-Pb dating of garnet from the Jinchanghe skarn deposit yielded an age of 520 to 496 Ma [6], probably implying that the formation of the Jinchanghe skarn Pb-Zn polymetallic deposit was the result of the subduction of Proto-Tethys Ocean.
Extensive hydrothermal activity has led to significant alteration of the wall rocks of Jinchanghe deposit, showing vertical zonation. As shown in Figure 2, the lower part is dominated by ilvaite skarn associated with Fe mineralization. The middle part is dominated by garnet skarn associated with Cu mineralization, while the upper part is dominated by pyroxene and actinolite skarn associated with Pb-Zn mineralization. A total of 174 orebodies have been identified in the Jinchanghe mining area, including 43 Pb-Zn orebodies at 2.37–8.26% Zn and 0.29–1.77% Pb, 57 Cu orebodies at 0.57–2.50% Cu, 65 Fe orebodies at 17.60–51.75 % Fe and 9 Au orebodies at 1–14 g/t Au [3,29]. These orebodies generally occur as lenses (Figure 2b). The gangue minerals in the Jinchanghe deposit mainly include garnet, pyroxene, ilvaite, epidote, actinolite, chlorite, fluorite, quartz and calcite. The ore-minerals mainly include magnetite, pyrite, chalcopyrite, pyrrhotite, sphalerite and galena.
Based on the systematic geological investigation and microscopic observation, four main mineralization stages have been identified, including the pre-ore stage characterized by prograde garnet and pyroxene, the oxide-ore stage represented by Fe mineralization associated with ilvaite, epidote and actinolite, a sulfide-ore stage characterized by Pb-Zn-Cu sulfides and post-ore stage with barren calcite and quartz veins (Figure 3).
The pre-ore stage could be divided into two substages, including syn-sedimentary stage and the prograde skarn stage. The syn-sedimentary stage is the diagenetic stage of wall rocks, which is characterized by the development of diagenetic pyrite (Py1) and calcite formed by Limestone recrystallization. The Py1 generally shows disseminated and euhedral distributed in wall rocks. The prograde skarn stager mainly developed anhydrous silicates represented by garnet and pyroxene (Figure 4a). The garnet from the Jinchanghe deposit is euhedral to subhedral, medium- to fine-grained with a yellow-green color. It was generally cut by the later minerals, such as oxide-ore stage actinolite, sulfide-ore stage quartz, galena and sphalerite (Figure 5a). The analysis of major elemental compositions showed that the garnet in the Jinchanghe skarn Pb-Zn polymetallic deposit is andradite [3]. Pyroxene from the Jinchanghe deposit is subhedral to anhedral, medium- to fine-grained with a blackish-green color. As the same as garnet, pyroxene was generally cut or replaced by later actinolite and calcite veins (Figure 5b). The major elemental analysis indicated that the pyroxene in the Jinchanghe skarn Pb-Zn polymetallic deposit belongs to hedenbergite [3].
The oxide-ore stage is characterized by the occurrence of abundant magnetite. Magnetite is mostly subhedral to anhedral and fine-grained, showing obvious metallic luster. In this stage, abundant hydrous silicates such as ilvaite, epidote and actinolite coexist with magnetite (Figure 4b). Locally, magnetite was filling the fractures of ilvaite crystals (Figure 5c), indicating that the magnetite formed slightly later than the ilvaite. Ilvaite is euhedral to subhedral and dark colored (Figure 5d), mainly occurring as aggregates and commonly replacing pre-ore stage pyroxene and garnet. Iron contents in ilvaite range from 43.00–50.49% [3]. Actinolite generally occurs as fibrous or radial aggregates. It usually cuts the pre-ore stage garnet and pyroxene, and the ilvaite and magnetite aggregates as well (Figure 4c), or develops around ilvaite crystals (Figure 5d), indicating the actinolite is later than ilvaite. In addition, actinolite is locally overprinted by epidote (Figure 5e), implying that epidote is later than actinolite.
In the sulfide-ore stage, abundant Cu-Zn-Pb-Fe sulfides developed associated with hydrothermal quartz and calcite, with minor chlorite and fluorite. The sulfides (e.g., chalcopyrite, sphalerite, galena, pyrite and pyrrhotite) mainly occur as veinlets or massive aggregates (Figure 4d,e), generally cutting or replacing the earlier silicates, such as pre-ore stage garnet and pyroxene, and oxide-ore stage ilvaite, magnetite, actinolite and epidote. The sulfide-ore stage could be further divided into two substages: early sulfide-ore stage and late sulfide-ore stage. The early sulfide-ore stage mainly developed quartz, arsenopyrite and pyrite (Py2). The Py2 grains were generally cut by the chalcopyrite and calcite veins of the late sulfide-ore stage (Figure 5f). The late sulfide-ore stage includes sphalerite, galena, chalcopyrite, pyrrhotite, pyrite (Py3), quartz and calcite (Figure 5g). These sulfides generally overprint the early minerals, such as the actinolite of oxide-ore stage (Figure 5h).
The post-ore stage is characterized by barren quartz and calcite veins with minor chlorite. The absence of ore minerals in this stage indicates that the hydrothermal mineralization in the Jinchanghe Pb-Zn polymetallic deposit has finished.

3. Sampling and Analytical Methods

In order to investigate the sources and the ore-forming environment of the Jinchanghe Pb-Zn polymetallic deposit, 18 sulfide samples were selected for sulfur isotopic analysis, among them, 8 chalcopyrite samples were selected for copper isotopic analysis, and 2 disseminated pyrite (Py1) samples in the calcareous slate (Figure 4f and Figure 5i), 5 pyrite (Py2) samples from early sulfide-ore stage, 3 pyrite (Py3) and 5 sphalerite samples were chosen for in-situ trace element analysis in this paper.
Sulfur isotopic analyses were completed in the Stable Isotope Laboratory, China University of Geosciences (Beijing). Firstly, the sulfide samples were crushed into 0.2–0.5 mm. Then, sulfide grains (including chalcopyrite, sphalerite, galena and pyrite) were carefully handpicked under a binocular microscope, to ensure the purity of separated sulfide samples was greater than 99%. The sulfur isotopic compositions of samples were performed with an EA-ISOPRIME100 (Elementar, Frankfurt, Germany) with the temperature at 23 °C and the humidity at 20%. GBW04414 and GBW04415 standards were used to calibrate the results. The accuracy of sulfur isotopic analysis of the Jinchanghe Pb-Zn polymetallic deposit is estimated to be better than 0.2‰.
Copper isotopic analyses were completed in the Isotope Geochemistry Laboratory, China University of Geosciences (Beijing). Around 20 mg separated chalcopyrite samples were dissolved with 1 mL of 8 N HCl and 0.001% H2O2 at 160 °C in Teflon containers. The Cu mineral was purified using single-column ion exchange chromatography with the Bio-Rad strong anion resin AG-MP-1M [30]. Then, Cu isotopic analysis was determined using the Neptune plus MC-ICP-MS (Thermo Fisher Scientific, Waltham, MA, USA) following the procedure introduced by Liu et al. (2014) [31]. The Cu isotopic results are reported as δ65Cu values relative to the Cu standard NIST976 (65Cu/63Cu = 0.4456 ± 0.0004) with the equation δ65Cu = ((65Cu/63Cu)sample/(65Cu/63Cu)standard − 1) × 1000 [31]. The precision of Cu isotopic analysis is better than 0.05‰.
The in-situ elemental analysis was completed using a New Wave UP-213 nm laser ablation (Fremont, CA, USA) coupled with an Agilent 7700s Quadrupole ICP-MS (Lexington, MA, USA) at the CODES LA-ICP-MS facility at the University of Tasmania, Hobart, Australia, with a repetition rate of 5 Hz and laser-ablating spot diameters of 30 µm [12,32]. In order to correct analytical results, the contents of Fe and Zn were used as internal standards for pyrite and sphalerite, respectively. The calibrated standard is STDGL2b-2 [33], which is comprised of powdered sulfides doped with certified element solutions that were fused to a lithium borate glass disk. The accuracy of trace elemental analysis is better than 20% for most elements [11]. The detection limits for Mn, Fe, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sn, Sb, Te, Au, Tl, Pb and Bi are 0.11 ppm, 2.50 ppm, 0.02 ppm, 0.05 ppm, 0.05 ppm, 0.20 ppm, 0.36 ppm, 0.60 ppm, 0.01 ppm, 0.10 ppm, 0.11 ppm, 0.03 ppm, 0.02 ppm, 0.12 ppm, 0.01 ppm, 0.01 ppm, 0.01 ppm, 0.01 ppm, respectively.

4. Analytical Results

4.1. Sulfur and Copper Isotopes

All sulfur and copper isotopic compositions of sulfides from the Jinchanghe Pb-Zn polymetallic deposit have been listed in Table 1. The δ34S values of sulfide-ore stage pyrite, sphalerite, galena and chalcopyrite range from 5.9–7.1‰ (mean 6.5‰, n = 2), 4.5–7.3‰ (mean 5.9‰, n = 8), 4.3–5.9‰ (mean 4.9‰, n = 4), and 4.6–7.1‰ (mean 5.9‰, n = 8), respectively. The δ34S values obtained from the disseminated pyrite from wallrock are 12.3–15.1‰ (mean 13.9‰, n = 5), significantly higher than those of sulfide-ore stage sulfides. Besides, the δ65Cu values obtained from the sulfide-ore stage chalcopyrite range from −0.40 ± 0.02 ‰ to 0.22 ± 0.03‰ (mean 0.00‰, n = 8).

4.2. Trace Elements of Pyrite and Sphalerite

As listed in Table 2, abundant Co, Ni, As, Se and Sb elements are distributed in Py1, Py2 and Py3. The As, Sb, Ni, Co and Se contents in Py1 are 645.84–1102.55 ppm (averaging 884.08 ppm), 116.01–176.20 ppm (averaging 135.48 ppm), 57.25–132.26 ppm (averaging 93.27 ppm), 39.37–90.28ppm (averaging 53.61 ppm) and 8.41–20.38 ppm (averaging 14.58 ppm), respectively.
Those elements in Py2 are 13.04–926.75 ppm (averaging 300.01 ppm), 1.12–115.60 ppm (averaging 34.50 ppm), 0.13–159.82 ppm (averaging 29.51 ppm), 176.78–319.40 ppm (averaging 252.07 ppm) and 0.17–19.94 ppm (averaging 6.89 ppm), respectively. Those elements in Py3 are 126.38–299.20 ppm (averaging 205.96 ppm), 14.67–56.39 ppm (averaging 28.44 ppm), 27.28–102.08 ppm (averaging 51.06 ppm), 89.16–115.49 ppm (average of 105.87 ppm) and 5.14–15.15 ppm (averaging 9.25 ppm), respectively. Meanwhile, the economic metal element Cu, Zn and Ag are significantly enriched in both Py2 and show a wide range, with concentrations of 0.57–1057.71 ppm (averaging 105.71 ppm) for Cu, 2.99–3112.93 ppm (averaging 472.55 ppm) for Zn and 0.03–1103.81 ppm (averaging 163.46 ppm) for Ag. Likewise, it is noteworthy that the element Mn and Sb are obviously enriched in Py1 with concentrations of 98.15–163.22 ppm and 116.01–127.83 ppm, respectively.
Sphalerite in the Jinchanghe Pb-Zn polymetallic deposit contains abundant Mn, Fe, Co and Cd, with the lowest concentration greater than 100 ppm (Table 3). The Fe, Cd, Mn and Co in sphalerite are 14,119–43,927 ppm (averaging 27,147 ppm), 1603–3205 ppm (averaging 2551 ppm), 1215 ppm–1773 ppm (averaging 1443 ppm) and 116.59–244.47 ppm (averaging 192.89 ppm), respectively. The concentrations of Ni, Cu, Se, Ag, Sn, Sb and Pb are relatively lower, with average concentrations of 0.84 ppm, 40.20 ppm, 37.27 ppm, 3.90 ppm, 0.22 ppm, 3.03 ppm and 21.09 ppm, respectively. Furthermore, the contents of As, Te and Au in sphalerite are extremely low, below the detection limit in most samples, and with a maximum concentration of less than 0.5 ppm.

5. Discussion

5.1. Trace Element Distributions in Pyrite and Sphalerite

Previous studies have proved that trace elements in hydrothermal pyrite could occupy the mineral lattice with a solid solution or exist in the mineral lattice gaps as invisible nano-sulfide particles or visible micron-sized sulfide, silicate and oxide inclusions [34,35]. The time-resolved depth profiles are flat for most pyrite samples from the Jinchanghe Pb-Zn polymetallic deposit (Figure 6a), indicating that trace elements enter the pyrite crystal lattice by isomorphic substitution and invisible solid solution. Element Mn, Co, Ni, Tl, As and Sb could directly substitute Fe as Fe2+ ↔ (Co2+, Ni2+, Mn2+) and 2Fe2+ ↔ (Tl+, Cu+, Ag+) + (Sb3+, As3+) [36,37]. It was proven by the positive correlation between As and Ag in Py2 and Py3 (Figure 7a). Besides, Ag, Pb and Sb could combine with As, forming solid solutions to enter the pyrite lattice [38,39,40], consistent with the positive correlation between Pb and Sb in Py2 and Py3 (Figure 7b). There is a positive correlation between Pb and Bi contents in Py2 and Py3 (Figure 7c), probably implying that Pb and Bi occur in the pyrite as invisible galena inclusions [9,41]. Co and Ni show a positive correlation in Py2 and Py3 with Co/Ni > 1(Figure 7d), indicating that they enter the pyrite lattice by the isomorphic substitution of 2Fe2+ ↔ Co2+ + Ni2+ [42]. It is noteworthy that the concentrations of Cu and Zn in the Py2 range widely (Table 2). Both of them have several outliers with positive correlations (Figure 7e), probably implying that Cu and Zn occur as chalcopyrite and sphalerite inclusions in Py1 (Figure 5f), which was revealed by the Cu and Zn peaks in the time-resolved depth profile (Figure 6b).
In addition, the Py1 is disseminated in the calcareous slate and marble in the Jinchanghe deposit. It is considered to be sedimentary pyrite rather than hydrothermal pyrite. As shown in Figure 6c, the flat time-resolved depth profiles indicate that trace elements enter Py1 mainly by isomorphic substitution.
The flat time-resolved depth profiles of sphalerite from the Jinchanghe Pb-Zn polymetallic deposit suggest that the trace elements enter sphalerite dominantly by isomorphic substitution (Figure 6d). The Mn2+, Fe2+ and Cd2+ have the same valence state and similar ionic radii, so they could directly substitute the Zn2+ in sphalerite. The Mn content shows an obvious positive correlation with Fe content in the sphalerite from the Jinchanghe deposit (Figure 7g), indicating an isomorphic substitution of (Fe2+ + Mn2+) ↔ 2Zn2+. It also shows that Fe substituting Zn in the sphalerite may have a promoting effect on Mn entering the lattice of sphalerite [42]. Meanwhile, element Cd displays an obvious negative correlation with Fe (Figure 7h), indicating there is a mutual inhibitory effect between Fe and Cd when entering sphalerite [37,43]. Zhou et al. (2022) [42] proposed that the positive correlation between Ag and Sb probably implies an isomorphic substitution of Ag+ + Sb3+ ↔ 2Zn2+, which is consistent with the sphalerite from the Jinchanghe Pb-Zn polymetallic deposit.

5.2. Origin of Ore-forming Materials

Copper is one of the most important economic metals in the Jinchanghe skarn Pb-Zn polymetallic deposit. As listed in Table 1, the chalcopyrite samples from the Jinchanghe Pb-Zn polymetallic deposit yield δ65Cu values of −0.40 ± 0.02‰ to 0.17 ± 0.05‰, similar to the δ65Cu values of magmatic rocks and magmatic hydrothermal fluids [44,45]. As shown in the δ65Cu vs. δ34S diagram (Figure 8a), all chalcopyrite samples are plotted in the magmatic field as well, implying that copper in the Jinchanghe deposit has a magmatic origin [45]. Chen et al. (2022) [8] analyzed the iron isotopic compositions of pre-ore stage garnet, oxide-ore stage magnetite and sulfide-ore stage pyrite and chalcopyrite, proposing that the mineralized iron in the Jinchanghe deposit mainly originated from concealed granitic rocks. It indicates that the ore-forming metals in the Jinchanghe Pb-Zn polymetallic deposit have a granitic magmatic source.
Sulfur is the main ore-forming material in the Jinchanghe skarn Pb-Zn polymetallic deposit. The δ34S values of sulfides (including pyrite, chalcopyrite, sphalerite and galena) from the sulfide-ore stage in the Jinchanghe deposit vary from 4.3 to 7.3‰ (Table 1), which are similar to or slightly higher than those of typical magmatic sulfur (−3 to 7‰, [46]), but lower than the δ34S values of the disseminated pyrite from wallrocks (calcareous slate and marble), which yield 12.3 to 15.1‰ (Table 1). Hence, it is indicated that sulfur in the ore-forming fluid of the Jinchanghe Pb-Zn polymetallic deposit was dominantly magmatic. Besides, the wallrocks, such as the Cambrian Hetaoping formation calcareous slate and marble, probably contributed some sulfur to the ore-forming fluids with fluid–rock interaction. The fluid–rock interaction could dissolve the diagenetic sulfates and sulfide in wallrocks, resulting in sulfur with higher δ34S values being mixed into the ore-forming fluids.
Besides, the Co/Ni ratios have been proved to be an indicator of pyrite origin, because the physicochemical environment for pyrite formation dominantly controls the Co-Ni contents and Co/Ni ratios in pyrite [47,48]. Pyrite formed in the reducing environments in sedimentary rocks prefers to absorb more Ni, leading to low Co/Ni ratios. Many previous studies have revealed that pyrite with low Co/Ni ratios (Co/Ni < 1) generally has sedimentary origins, while pyrite with high Co/Ni ratios (Co/Ni > 1) is mainly attributed to magmatic-hydrothermal fluid. As listed in Table 2 and shown in Figure 7d, the Co/Ni ratios of Py1 vary from 0.30–0.86, consistent with the pyrite of a sedimentary origin. The Co/Ni ratios of Py2 and Py3 vary from 1.89–24.61 and 3.07–16.92, respectively, implying that the pyrite from sulfide-ore stage in the Jinchanghe Pb-Zn polymetallic deposit was dominantly originated from magmatic-hydrothermal sources.
In summary, the Cu-S isotopic and trace elemental compositions jointly suggest a magmatic-hydrothermal origin for the Jinchanghe Pb-Zn polymetallic deposit with some sedimentary host-rock contributions.

5.3. Implications for Ore-forming Temperature

During the mineralization of hydrothermal deposits, processes such as fluid mixing and boiling could significantly change the physicochemical condition of ore-forming fluids [49,50]. Meanwhile, the trace element incorporation into sulfides is generally controlled by the physicochemical parameters, including fluid composition, temperature, pH and oxygen fugacity [13,32,48]. Hence, sulfide chemistry has been considered to be a robust method to reveal the ore-forming environment of hydrothermal deposits.
The concentration of Se in hydrothermal pyrite is controlled by the ore-forming fluid temperature [35,51]. The Se content of Py2 (176.78–319.40 ppm) is significantly higher than that of Py3 (89.16–115.49 ppm), indicating that the temperature of ore-forming fluid decreases from the early sulfide-ore stage to the late sulfide-ore stage. Meanwhile, meteoric water generally has a lower Se concentration than magmatic fluid [35,52,53], and abundant meteoric water characterized by lower temperature has been mixed into ore-forming fluids during the mineralization processes [3]. Hence, the variation of Se content in Py2 and Py3 implies a mixture of low-temperature meteoric water mixed into ore-forming fluids during the mineralization of the sulfide-ore stage. Furthermore, an ore-forming fluid decrease could result in the enrichment of As in pyrite [52], consistent with rising As concentration from Py2 (average of 29.51 ppm) to Py3 (average of 51.06 ppm).
The trace elemental composition of sphalerite could constrain the ore-forming environments as well. The sphalerite from medium- to high-temperature ore-forming fluids is generally enriched in Fe, Mn, Co, Te and In elements, while the sphalerite from low-temperature ore-forming fluids is enriched in Ga, Ge, As and Tl elements [10,18,43,54,55]. As shown in Figure 9, the trace elemental compositions of sphalerite from the Jinchanghe skarn Pb-Zn polymetallic deposit are similar to that of Luziyuan skarn Fe-Pb-Zn deposit and Hetaoping skarn Pb-Zn deposit in Baoshan block. Compared to other type deposit (e.g., MVT, VMS and Epithermal deposits), the sphalerite from the Jinchanghe skarn Pb-Zn polymetallic deposit is enriched in Fe (14,119–43,927 ppm, average of 27,147 ppm), Mn (1215.26–1773.02 ppm, average of 1443.07 ppm) and Co (166.59–2444.47 ppm, average of 192.89 ppm), relatively depleted in As (0.00–0.46 ppm, average of 0.11 ppm) and Tl (below detection limit), probably indicating that the ore-forming fluid of sulfide-ore stage in the Jinchanghe deposit is medium to high temperature. In the elemental binary diagram (Figure 10a–d), the Mn, Fe, Co and Cd contents in sphalerite from the Jinchanghe deposit are similar to the deposits related to medium to high ore-forming temperature (e.g., skarn, VMS and epithermal deposits), and are distinct from the sphalerite from MVT deposit, which is generally related to medium to low ore-forming temperature. The Zn/Cd value of sphalerite is also controlled by ore-forming temperature [56,57]. The Zn/Cd values of sphalerite from the Jinchanghe Pb-Zn polymetallic deposit are 200.1–393.8 (average of 271.7, n = 24), belonging to the range of sphalerite from medium temperature deposit (100 < Zn/Cd < 500). In addition, Keith et al. (2014) [58] proposed that the ore-forming temperature could be calculated by Fe/Zn value of sphalerite with a formula of Fe/Znsphalerite = 0.0013(T) − 0.2953. The calculated average ore-forming temperature of the Jinchanghe Pb-Zn polymetallic deposit is 260 °C (average Fe/Zn value is 0.043, n = 24), approximate to the homogenization temperature of the fluid inclusions in sphalerite (191–244 °C, [3]).

6. Conclusions

(1)
In the Jinchanghe skarn Pb-Zn polymetallic deposit, trace element Mn, Co, Ni, Cu, Zn, As, Cd, Sn, Sb, Te, Tl, Pb and Bi were detected in pyrite, and Mn, Fe, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sn, Sb, Te, Au, Pb and Bi were detected in sphalerite. Those elements dominantly enter the pyrite and sphalerite crystal lattice by isomorphic substitution, except for some Zn and Cu occuring as sulfide inclusions in Py1.
(2)
Cu-S isotopic and trace elemental compositions jointly demonstrate a magmatic-hydrothermal origin for the Jinchanghe Pb-Zn polymetallic deposit with some sedimentary host-rock contributions.
(3)
The trace elemental compositions of pyrite and sphalerite indicate that the ore-forming temperature of the sulfide-ore stage in the Jinchanghe distal skarn Pb-Zn polymetallic deposit is medium (ca. 260 ℃).

Author Contributions

Methodology, X.C. and J.W.; investigation, Y.Z. and J.H.; data curation, X.C., J.W. and C.Z.; writing—original draft preparation, X.C., P.L. and F.C.; writing—review and editing, C.Z. and H.W.; funding, Y.Z. and F.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was jointly supported by the National Natural Science Foundation of China (42262011) and the special selection program for high-level technology talents and innovation teams “formation mechanism and resource potentiality assessment of W, Be, and other strategic minerals in the Geza–Mahuaping area of Shangri-la” (grant no. 202305AT350004).

Data Availability Statement

Data are contained within the article.

Conflicts of Interest

Yunman Zhou, Jiyuan Wang, Chengfeng Zhao, Jiyuan Wang, Hai Wang and Fuchuan Chen are employees of Yunnan Gold and Mineral Group Co., Ltd. The paper reflects the views of the scientists and not the company.

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Figure 2. (a) Geological map of the Jinchanghe Pb-Zn polymetallic deposit (Modified from [8]); (b) alteration and mineralization characteristics of No. 8 exploration line in the Jinchanghe Pb-Zn polymetallic deposit (Modified from [8]).
Figure 2. (a) Geological map of the Jinchanghe Pb-Zn polymetallic deposit (Modified from [8]); (b) alteration and mineralization characteristics of No. 8 exploration line in the Jinchanghe Pb-Zn polymetallic deposit (Modified from [8]).
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Figure 3. Mineral paragenesis of the Jinchanghe Pb-Zn polymetallic deposit.
Figure 3. Mineral paragenesis of the Jinchanghe Pb-Zn polymetallic deposit.
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Figure 4. Representative photographs of selected ore samples. (a) pre-ore stage garnet and pyroxene skarn; (b) oxide-ore stage ilvaite and epidote skarn coexisting with magnetite, crosscut by post-ore stage barren calcite vein; (c) pre-ore stage garnet altered by oxide-ore stage ilvaite and magnetite, all of them were crosscut by actinolite vein; (d) massive sphalerite and galena ore; (e) sulfide-ore stage sphalerite-galena-quartz veins; (f) Disseminated pyrite in calcareous slate.
Figure 4. Representative photographs of selected ore samples. (a) pre-ore stage garnet and pyroxene skarn; (b) oxide-ore stage ilvaite and epidote skarn coexisting with magnetite, crosscut by post-ore stage barren calcite vein; (c) pre-ore stage garnet altered by oxide-ore stage ilvaite and magnetite, all of them were crosscut by actinolite vein; (d) massive sphalerite and galena ore; (e) sulfide-ore stage sphalerite-galena-quartz veins; (f) Disseminated pyrite in calcareous slate.
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Figure 5. Representative photomicrographs of the Jinchanghe Pb-Zn polymetallic deposit. (a) pre-ore stage garnet cut by sulfide-ore stage sphalerite; (b) pre-ore stage pyroxene cut by oxide-ore stage actinolite vein; (c) oxide-ore stage magnetite filling in fractures of ilvaite grains; (d) oxide-ore stage actinolite and magnetite surrounding ilvaite grains; (e) oxide-ore stage actinolite overprinted by epidote; (f) early sulfide-ore stage pyrite (Py2) cut by late sulfide-ore stage chalcopyrite-calcite veins and overprinted by late sulfide-ore stage sphalerite; (g) late sulfide-ore stage pyrite (Py3) coexisting with chalcopyrite, galena, sphalerite, pyrrhotite and quartz; (h) oxide-ore stage actinolite overprinted by sulfide-ore stage sphalerite; (i) disseminated pyrite in calcareous slate. Abbreviations: Act = actinolite, Cal = calcite, Ccp = chalcopyrite, Ep = epidote, Grt = garnet, Ilv = ilvaite, Mt = magnetite, Po = pyrrhotite, Py = pyrite, Px = pyroxene, Qz = quartz. Sp = sphalerite.
Figure 5. Representative photomicrographs of the Jinchanghe Pb-Zn polymetallic deposit. (a) pre-ore stage garnet cut by sulfide-ore stage sphalerite; (b) pre-ore stage pyroxene cut by oxide-ore stage actinolite vein; (c) oxide-ore stage magnetite filling in fractures of ilvaite grains; (d) oxide-ore stage actinolite and magnetite surrounding ilvaite grains; (e) oxide-ore stage actinolite overprinted by epidote; (f) early sulfide-ore stage pyrite (Py2) cut by late sulfide-ore stage chalcopyrite-calcite veins and overprinted by late sulfide-ore stage sphalerite; (g) late sulfide-ore stage pyrite (Py3) coexisting with chalcopyrite, galena, sphalerite, pyrrhotite and quartz; (h) oxide-ore stage actinolite overprinted by sulfide-ore stage sphalerite; (i) disseminated pyrite in calcareous slate. Abbreviations: Act = actinolite, Cal = calcite, Ccp = chalcopyrite, Ep = epidote, Grt = garnet, Ilv = ilvaite, Mt = magnetite, Po = pyrrhotite, Py = pyrite, Px = pyroxene, Qz = quartz. Sp = sphalerite.
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Figure 6. Typical time-resolved analytical signals LA-ICP-MS. (a) early sulfide-ore stage pyrite with isomorphic trace elemental substitutions; (b) early sulfide-ore stage pyrite with Zn-Cu inclusions; (c) syn-sedimentary stage pyrite with isomorphic trace elemental substitutions; (d) late sulfide-ore stage sphalerite with isomorphic trace elemental substitutions.
Figure 6. Typical time-resolved analytical signals LA-ICP-MS. (a) early sulfide-ore stage pyrite with isomorphic trace elemental substitutions; (b) early sulfide-ore stage pyrite with Zn-Cu inclusions; (c) syn-sedimentary stage pyrite with isomorphic trace elemental substitutions; (d) late sulfide-ore stage sphalerite with isomorphic trace elemental substitutions.
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Figure 7. Binary plots of (a) Ag vs. As, (b) Pb vs. Sb, (c) Bi vs. Pb, (d) Ni vs. Co, (e) Zn vs. Cu, (f) Se vs. Co/Ni in pyrite, and (g) Mn vs. Fe, (h) Cd vs. Fe, (i) Sb vs. Ag in sphalerite from the Jinchanghe Pb-Zn polymetallic deposit.
Figure 7. Binary plots of (a) Ag vs. As, (b) Pb vs. Sb, (c) Bi vs. Pb, (d) Ni vs. Co, (e) Zn vs. Cu, (f) Se vs. Co/Ni in pyrite, and (g) Mn vs. Fe, (h) Cd vs. Fe, (i) Sb vs. Ag in sphalerite from the Jinchanghe Pb-Zn polymetallic deposit.
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Figure 8. (a) Plot of δ34SCDT vs. δ65Cu (Modified from [45]) for chalcopyrite, (b) histogram of δ34S values of sulfides from the Jinchanghe Pb-Zn polymetallic deposit.
Figure 8. (a) Plot of δ34SCDT vs. δ65Cu (Modified from [45]) for chalcopyrite, (b) histogram of δ34S values of sulfides from the Jinchanghe Pb-Zn polymetallic deposit.
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Figure 9. Comparative box of trace elemental concentrations in sphalerite from the the Jinchanghe Pb-Zn polymetallic deposit (Other data are cited [9,10,18,54,59,60]). HTP = Hetaoping skarn Pb-Zn deposit; LZY = Luziyuan skarn Pb-Zn-Fe deposit.
Figure 9. Comparative box of trace elemental concentrations in sphalerite from the the Jinchanghe Pb-Zn polymetallic deposit (Other data are cited [9,10,18,54,59,60]). HTP = Hetaoping skarn Pb-Zn deposit; LZY = Luziyuan skarn Pb-Zn-Fe deposit.
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Figure 10. Binary plots of (a) Cd vs. Mn, (b) Co vs. Mn, (c) Fe vs. Mn and (d) Mn vs. Cd/Fe in sphalerite from the Jinchanghe Pb-Zn polymetallic deposit (Other data are cited [9,10,18,54,59,60]).
Figure 10. Binary plots of (a) Cd vs. Mn, (b) Co vs. Mn, (c) Fe vs. Mn and (d) Mn vs. Cd/Fe in sphalerite from the Jinchanghe Pb-Zn polymetallic deposit (Other data are cited [9,10,18,54,59,60]).
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Table 1. Sulfur and copper isotopes of the sulfides from the Jinchanghe deposit.
Table 1. Sulfur and copper isotopes of the sulfides from the Jinchanghe deposit.
Sample No.MineralSample Descriptionδ34S(CDT)‰δ65Cu (‰)2SD
JCH-16-02SphaleriteSphalerite massive ore4.5NDND
JCH-16-04ChalcopyriteChalcopyrite-quartz-calcite vein7.10.000.03
JCH-16-05ChalcopyriteChalcopyrite-sphalerite-galena massive ore5.1NDND
Galena4.6NDND
Sphalerite6.2NDND
JCH-16-08ChalcopyriteChalcopyrite-quartz vein5.30.220.03
JCH-16-09SphaleriteSphalerite stockwork ore4.5NDND
JCH-16-10ChalcopyriteChalcopyrite-galena-sphalerite vein6.2−0.400.02
Galena4.7NDND
Sphalerite5.8NDND
JCH-16-11ChalcopyriteSphalerite-chalcopyrite massive ore5.50.170.05
Sphalerite7.3NDND
JCH-16-12PyritePyrite-chalcopyrite-sphalerite vein5.9NDND
Chalcopyrite6.5−0.060.02
Sphalerite6.7NDND
JCH-16-13ChalcopyriteChalcopyrite-quartz vein4.60.080.02
JCH-16-15SphaleritePyrite-sphalerite massive ore5.2NDND
Pyrite7.1NDND
JCH-16-16ChalcopyriteChalcopyrite-quartz vein5.8−0.060.04
JCH-16-19GalenaChalcopyrite-sphalerite-galena massive ore4.3NDND
Sphalerite6.6NDND
JCH-16-22ChalcopyriteGalena-chalcopyrite-quartz vein6.10.070.02
Galena5.9NDND
JCH-16-25PyriteDisseminated pyrite in calcareous slate14.5NDND
JCH-16-26PyriteDisseminated pyrite in calcareous slate12.3NDND
JCH-16-27PyriteDisseminated pyrite in marble15.1NDND
JCH-16-28PyriteDisseminated pyrite in marble14.2NDND
JCH-16-29PyriteDisseminated pyrite in marble13.6NDND
Note: SD = standard deviation; ND = not determined.
Table 2. Trace elemental contents of pyrite from the Jinchanghe Pb-Zn polymetallic deposit.
Table 2. Trace elemental contents of pyrite from the Jinchanghe Pb-Zn polymetallic deposit.
Pyrite GenerationSample No.Analysis SpotMnCoNiCuZnAsSeAgCdSnSbTeTlPbBiCo/Ni
(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)
Py1JCH-16-261163.2239.37132.26B.D.L0.331102.5512.561.08B.D.L0.09127.830.280.971.320.250.3
298.1545.5557.250.120.25645.8420.380.620.160.13116.970.160.515.630.160.8
3117.6490.28105.410.080.22806.378.412.370.280.11116.01B.D.L0.3618.260.130.86
JCH-16-291145.0542.6582.350.050.251008.2515.221.53B.D.L0.15176.20.250.5810.050.20.52
2148.7350.1989.090.060.26857.3816.350.090.120.11140.410.180.658.470.160.56
Py2JCH-16-011B.D.L416.12115.61057.71409.2916.72274.392.529.050.7619.160.190.5118.4210.073.6
2B.D.L77.2633.2712.152131.4121.52298.290.6732.860.557.610.350.2411.533.222.32
JCH-16-0310.43123.8740.9254.363112.9315.72293.381.337.360.6514.060.230.4113.25.083.03
2B.D.L54.9129.123.486.5914.35319.40.238.60.191.230.350.160.4411.89
JCH-16-0610.22926.7563.921.6235.360.13259.438.62.320.143.690.130.127.557.3314.5
20.23420.5430.219.08208.910.32234.697.0120.073.15B.D.L0.393.512.9913.92
310.65493.7544.4416.354.18114.09176.781103.816.640.148.44B.D.L0.292.263.3411.11
JCH-16-0818.55536.5421.85.494.69159.82202.81783.234.220.154.62B.D.L0.120.650.5424.61
24.45483.3831.326.762.9930.9188.98216.6915.10.243.55B.D.L0.141.653.6915.43
JCH-16-141B.D.L270.5527.50.5710.252.42234.870.230.520.110.170.270.070.110.439.84
2B.D.L13.042.675.043.983.5257.350.6B.D.L0.1419.940.270.2832.1413.64.88
3B.D.L15.331.120.875.151.5241.840.05B.D.L0.12.580.120.250.320.213.69
4B.D.L68.136.611.087.362.67294.740.030.130.111.430.230.130.630.7210.31
Py3JCH-16-04171.94198.943.570.273.0333.33115.490.52B.D.L0.1510.13B.D.L0.082.731.134.57
286.61170.1219.330.492.2629.44111.510.45B.D.L0.138.65B.D.L0.161.870.58.8
3103.96248.2614.671.192.5476.24104.7727.51B.D.L0.155.14B.D.L0.251.40.416.92
JCH-16-11186.57173.2356.393.694.5453.7111.225.472.70.158.32B.D.L0.142.520.323.07
294.62299.221.630.072.87102.08100.739.18B.D.L0.1312.08B.D.L0.120.870.1613.83
JCH-16-15181.22126.3828.226.915.3635.3689.160.250.560.225.260.150.121.420.484.48
272.23225.6515.2615.4220.1327.28108.220.380.250.1715.15B.D.L0.295.310.7514.79
Table 3. Trace elemental contents of sphalerite from the Jinchanghe Pb-Zn polymetallic deposit.
Table 3. Trace elemental contents of sphalerite from the Jinchanghe Pb-Zn polymetallic deposit.
Sample No.Analysis No.MnFeCoNiCuZnAsSeAgCdSnSbTeAuPbBi
(ppm)(ppm)(ppm)(ppm)(ppm)(wt.%)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)(ppm)
JCH-16-021177343,243138.59B.D.L13.9562.52%B.D.L49.792.3117270.210.260.10B.D.L0.870.52
2153442,949139.64B.D.L14.5562.55%B.D.L41.152.6617490.190.920.09B.D.L2.211.68
3153743,927140.87B.D.L72.2162.45%B.D.L41.634.5317680.192.490.060.0139.394.89
JCH-16-051147043,631138.92B.D.L506.1562.48%B.D.L36.024.8217250.212.260.130.029.806.29
2149743,853136.79B.D.L12.3162.46%B.D.L33.563.1617290.210.760.23B.D.L2.991.99
JCH-16-091139214,340240.591.5811.7365.58%B.D.L29.083.0030700.210.320.05B.D.L1.220.01
2141814,803238.751.442.1965.53%0.1321.102.1830610.220.760.13B.D.L1.000.01
3131914,333239.481.552.8265.58%0.358.432.6730520.240.280.05B.D.L0.770.01
4141114,119244.471.453.3265.60%0.165.503.5430440.250.120.050.010.880.01
JCH-16-101148736,659117.16B.D.L92.8563.22%0.20132.414.9516810.232.910.110.01310.743.79
2172837,325118.785.437.4363.15%0.24119.634.5516030.213.370.110.025.301.45
3148837,349117.98B.D.L4.6763.15%0.14129.092.4716670.210.230.04B.D.L0.900.32
4149036,847116.59B.D.L125.4363.20%0.02107.454.5116210.233.330.080.0215.182.32
JCH-16-121146127,367220.100.845.8364.20%0.267.562.3430190.221.200.130.012.98B.D.L
2144427,137220.800.973.1464.22%0.156.821.9430120.250.080.03B.D.L1.190.01
3141826,361221.800.843.3264.31%0.467.591.8529740.260.100.100.011.13B.D.L
4148227,115224.380.604.4964.23%B.D.L5.273.0631580.177.130.100.025.39B.D.L
5150027,987225.240.654.6264.13%B.D.L6.333.4932050.193.590.02B.D.L5.41B.D.L
JCH-16-151130615,178235.330.1824.6465.49%0.198.0712.3631560.2527.790.110.1074.960.01
2151815,166231.561.067.4965.49%B.D.L14.603.7031660.236.460.010.018.12B.D.L
JCH-16-191128515,213227.961.268.4565.48%0.1848.243.0830450.22B.D.L0.120.011.68B.D.L
2122715,043230.830.8111.8265.50%0.1711.235.1030540.245.100.040.018.27B.D.L
3121515,595231.200.808.0265.44%B.D.L12.074.0629480.150.37B.D.LB.D.L1.340.01
4122115,986231.480.8213.2665.40%0.0211.777.1529950.252.910.030.014.400.01
Note: B.D.L = below detection limit.
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Cheng, X.; Zhou, Y.; Wang, J.; Zhao, C.; Huang, J.; Li, P.; Wang, H.; Chen, F. Sources and Ore-Forming Environment of the Jinchanghe Pb-Zn Polymetallic Skarn Deposit, Baoshan Block, SW China: Constraints from Cu-S Isotopic and Trace Elemental Compositions of Sulfides. Minerals 2024, 14, 644. https://doi.org/10.3390/min14070644

AMA Style

Cheng X, Zhou Y, Wang J, Zhao C, Huang J, Li P, Wang H, Chen F. Sources and Ore-Forming Environment of the Jinchanghe Pb-Zn Polymetallic Skarn Deposit, Baoshan Block, SW China: Constraints from Cu-S Isotopic and Trace Elemental Compositions of Sulfides. Minerals. 2024; 14(7):644. https://doi.org/10.3390/min14070644

Chicago/Turabian Style

Cheng, Xiaolin, Yunman Zhou, Jiyuan Wang, Chengfeng Zhao, Jing Huang, Pengju Li, Hai Wang, and Fuchuan Chen. 2024. "Sources and Ore-Forming Environment of the Jinchanghe Pb-Zn Polymetallic Skarn Deposit, Baoshan Block, SW China: Constraints from Cu-S Isotopic and Trace Elemental Compositions of Sulfides" Minerals 14, no. 7: 644. https://doi.org/10.3390/min14070644

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