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Article

Origin of the Xulaojiugou Pb–Zn Deposit, Heilongjiang Province, NE China: Constraints from Molybdenite Re–Os Isotopic Dating, Trace Elements, and Isotopic Compositions of Sulfides

by
Gan Liu
1,
Yunsheng Ren
1,2,*,
Jingmou Li
1 and
Wentan Xu
2
1
School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China
2
School of Earth Sciences and Engineering, Institute of Disaster Prevention, Sanhe 065201, China
*
Author to whom correspondence should be addressed.
Minerals 2025, 15(5), 441; https://doi.org/10.3390/min15050441
Submission received: 18 March 2025 / Revised: 18 April 2025 / Accepted: 23 April 2025 / Published: 25 April 2025
(This article belongs to the Special Issue Genesis and Metallogeny of Non-ferrous and Precious Metal Deposits, 2nd Edition)
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Abstract

:
The Xulaojiugou Pb–Zn deposit, situated in the eastern Xing’an-Mongolia Orogenic Belt (XMOB), represents a medium-scale Pb–Zn deposit in central Heilongjiang Province, NE China. The mineralization occurs mainly near the contact zone of porphyritic biotite granite, medium-grained monzogranite, and marble in the Early Cambrian Qianshan Formation. Orebodies exhibit typical skarn characteristics and are structurally controlled by NE trending faults. To constrain the metallogenic age, ore-forming processes, and sources of ore-forming materials, we conducted integrated geochemical analyses, Re–Os isotope dating, in situ sulfur isotope analysis, and trace element analysis. Five molybdenite samples provided a Re–Os isochron age of 184.6 ± 3.0 Ma, indicating Early Jurassic mineralization. In situ δ34S values from 20 sphalerite and 9 galena samples ranged from 5.31‰ to 5.83‰, suggesting derivation of sulfur from a deep magmatic source. Trace element analysis of 42 spots from three sphalerite samples revealed formation temperatures of 248–262 °C, which are consistent with mesothermal conditions. Integrated with regional tectonic evolution, the Xulaojiugou deposit is genetically linked to medium-grained monzogranite emplacement and represents a typical skarn polymetallic deposit, which is genetically associated with the regional porphyry–skarn metallogenic system that developed during the Early Yanshanian (Jurassic) tectonic–magmatic event and was driven by the subduction of the Paleo-Pacific plate.

1. Introduction

The Lesser Xing’an Range, located in the eastern the Xing’an–Mongolia Orogenic Belt (XMOB), has undergone a complex tectonic evolution involving the superposition and transformation of both the Paleo-Asian Ocean and Paleo-Pacific tectonic domains from the late Paleozoic to Mesozoic [1,2,3,4]. This region is characterized by intricate geological structures and intensive magmatic activity, making it one of China’s most significant polymetallic metallogenic provinces. The Xulaojiugou Pb–Zn deposit, found in the southeastern part of the Lesser Xing’an Range, is a medium-scale Pb–Zn deposit [5]. Several studies have classified the Xulaojiugou deposit as a skarn mineralization based on integrated geological evidence, including mineralization settings, orebody characteristics, ore fabrics, and wall–rock alteration features [6]. However, existing geochronological data reveal discrepancies: Hu et al. [7] reported laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U-Pb ages of mineralized monzogranite ranging from 181.2 to 179.9 Ma, while Han et al. [8] obtained the crystallization age of ore-bearing granite in the Xulaojiugou deposit between 191 and 234 Ma. These conflicting age data indicate that critical metallogenic parameters, including the precise mineralization age, mineralizing intrusive rocks, metallic sources, and physicochemical conditions, remain poorly constrained and require systematic investigation.
In this study, we provide new molybdenite Re–Os ages to establish the mineralization age and tectonic setting. In situ sulfur isotope analysis of sulfide minerals was used to trace the source of metals. Additionally, we conducted in situ major and trace element analysis of sphalerite using electron probe microanalysis (EPMA) and LA-ICP-MS to constrain its formation temperature so as to constrain the petrogenesis of this ore deposit.

2. Regional Geology

The XMOB, situated between the Siberian and North China Craton (NCC), comprises four major crustal blocks from west to east: the Ergun, Xing’an, Songnen, and Jiamusi Blocks (Figure 1a). The study area is situated in the southeastern Lesser Xing’an Range, a region that records the Early Mesozoic closure of the Paleo-Asian Ocean and subsequent Mesozoic–Cenozoic tectonic interactions involving collision with the Mongol-Okhotsk Oceanic plate to the north and the Pacific Plate to the east. The superposition of the Paleo-Asian Ocean closure and Paleo-Pacific subduction regimes, along with their tectonic transition during the Mesozoic, triggered complex tectono-magmatic processes, thereby creating favorable geological conditions for mineralization [9,10,11].
The strata exposed in the study area primarily consist of volcanic, clastic, and carbonate rocks formed during the Cambrian, Ordovician, Devonian–Permian, and Cretaceous periods. The Cambrian strata are composed of marble and terrigenous clastic rocks. The Ordovician is scattered and consists of volcanic–sedimentary formations. The Devonian–Permian strata are widely developed in the area, mainly consisting of sandstone, tuff, and shale, with the majority having undergone regional metamorphism. The Cretaceous volcanic rocks are extensively distributed across the study area, comprising a diverse array of rock types, with terrestrial volcanic rocks, clastic rocks, and marble being the predominant rock types [12,13] (Figure 1b).
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Figure 1. (a) Tectonic framework of NE China (modified from Wu et al. [14]). F1: Mudanjiang fault. F2: Yitong–Yilan fault. F3: Yitong–Yilan fault. F4: Xilamulon–Changchun fault. F5: Nenjiang fault. F6: Nenjiang fault. (b) Detailed geological map of eastern Lesser Xing’an Range (after Hu et al. [13]). 1. Quaternary sediments. 2. Cretaceous volcanic rocks. 3. Permian clastic rocks. 4. Devonian clastic and carbonate rocks. 5. Ordovician volcanic and clastic rocks. 6. Cambrian clastic and carbonate rocks. 7. Jurassic–Cretaceous granitoids. 8. Permian–Triassic granitoids. 9. Ordovician granitoids. 10. Fault. 11. Ore deposit.
Figure 1. (a) Tectonic framework of NE China (modified from Wu et al. [14]). F1: Mudanjiang fault. F2: Yitong–Yilan fault. F3: Yitong–Yilan fault. F4: Xilamulon–Changchun fault. F5: Nenjiang fault. F6: Nenjiang fault. (b) Detailed geological map of eastern Lesser Xing’an Range (after Hu et al. [13]). 1. Quaternary sediments. 2. Cretaceous volcanic rocks. 3. Permian clastic rocks. 4. Devonian clastic and carbonate rocks. 5. Ordovician volcanic and clastic rocks. 6. Cambrian clastic and carbonate rocks. 7. Jurassic–Cretaceous granitoids. 8. Permian–Triassic granitoids. 9. Ordovician granitoids. 10. Fault. 11. Ore deposit.
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The regional structures are dominated by NW-, SN-, and NNE-trending fault systems. Jurassic–Cretaceous granites (monzogranite, porphyritic granite, and syenogranite) constitute the predominant plutonic rocks, occurring as stocks, with minor Ordovician and Permian–Triassic granitoids [15]. The study area hosts significant mineralization, including large-scale epithermal gold deposits, such as Tuanjiegou [16], large-scale porphyry molybdenum deposits, such as Luming and Huojihe [13,17], and medium- to small-scale skarn polymetallic deposits, such as Ergu, Xiaoxilin, Da’anhe, and Xulaojiugou [4,18,19].

3. Deposit Geology

Only the Early Cambrian Qianshan Formation is exposed in the mine area (Figure 2a). It consists of shallow marine terrigenous clastic–carbonate rocks that have undergone regional metamorphism and interlayered brecciation. The structure in the ore district is dominated by SN-trending and NNE-trending faults, with the NNE-trending faults being crucial in controlling both mineralization and magmatic activity. The plutons in the mining area are primarily porphyritic biotite granites and medium-grained monzogranites.
Ore bodies occur in the contact zone between the medium-grained monzogranite and the marbles, with the majority of ore bodies being stratoid or veined in shape. The ore bodies are relatively small in scale, with lengths from 50 to 310 m, widths between 50 and 150 m, a mean thickness of 2–3 m, dips of 60°, and a mean burial depth of 150–350 m (Figure 2b).
The primary ores are characterized by fine-veined, disseminated, massive structures (Figure 3a–c). The metallic minerals in ores mainly include sphalerite, galena, molybdenite, chalcopyrite, pyrrhotite, and pyrite (Figure 4a–e), as well as non-metallic minerals such as clinohumite, calcite, potassium feldspar, chlorite, epidote, actinolite, and quartz (Figure 4f–h). Flaky molybdenite commonly occurs within quartz veins (Figure 4a), while sphalerite partially replaces galena (Figure 4b). Sphalerite encloses anhedral grain pyrrhotite, which is subsequently crosscut by later pyrite veins (Figure 4c). Chalcopyrite occurs as fine emulsion droplets in sphalerite (Figure 4e). Wall–rock alteration typically occurred by argillization, skarnization, silicification, carbonatization, and chloritization (Figure 3d and Figure 4f–h), with skarnization and silicification showing close spatial relationships with mineralization.
According to the crosscutting relationship and mineral assemblages, the formation process of the Pb–Zn deposit can be divided into two main periods: (1) skarn formation and (2) precipitation of quartz–sulfide assemblages (Figure 5). The skarn assemblage consists primarily of early anhydrous minerals: diopside, wollastonite, and scapolite (interstitials in wollastonite). These anhydrous minerals established the spatial framework of the skarn system with limited metal mineralization. Subsequent hydrothermal overprinting introduced water-bearing minerals such as tremolite and actinolite (replacing tremolite), which provided space for subsequent vein-type Pb–Zn mineralization. The quartz–sulfide period comprises three distinct stages: The (1) quartz-Fe-Cu sulfide stage (stage I) is marked by the occurrence of quartz veins containing disseminated pyrite and massive molybdenite. The (2) quartz-Pb–Zn sulfide stage (stage II) is the main stage of Pb–Zn mineralization and mainly includes plenty of galena and sphalerite, with minor chalcopyrite distributed in sphalerite as fine emulsion droplets. The (3) quartz–carbonate stage (stage III) is marked by the crystallization of quartz, calcite, and chlorite, with no significant mineralization.

4. Sample Description and Analytical Methods

4.1. Sample Description

Based on petrographic and mineralogical identification, Re–Os dating was performed on 5 molybdenite samples from medium-grained monzogranite. Three representative metallic sulfide ore samples were prepared as polished sections for in situ trace element analysis of sphalerite using both EPMA and LA-ICP-MS. Subsequently, in situ sulfur isotope analysis was conducted on the identical samples using laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). The characteristics of the analyzed samples are shown in Table 1.

4.2. Analysis Methods

4.2.1. Molybdenite Re–Os Isotopic Analyses

Molybdenites were separated and hand-picked to obtain molybdenite particles with >90 wt% purity, which was followed by Re–Os isotopic analysis at Beijing Yanduzhongshi Geological Analysis Laboratories Ltd., Beijing, China. The analyses were performed using a Thermo Electron TJAX series ICP-MS. The analytical procedure included sample digestion, Os separation by distillation, Re extraction, and final fractionation correction of the mass spectrometer, which was following those described by Qu et al. [20] and Li et al. [21,22]. Quality control was ensured using the GBW04435 (HLP) reference material. The Re–Os model age was calculated using the equation t = [ln(1 + 187Os/187Re)]/λ, where λ = 1.666 × 10−11/year [23], and isochron-weighted ages were processed using IsoplotR (ver 4.1) software.

4.2.2. In Situ Sulfur Isotope Analysis

We selected representative sphalerite and galena grains for in situ sulfur isotope analysis conducted at Beijing Yanduzhongshi Geological Analysis Laboratories Ltd., Beijing, China, using LA-MC-ICP-MS. The analytical system consisted of a Nu Plasma 1700 high-resolution MC-ICP-MS (Nu Instruments Ltd., Wrexham, UK) coupled with a Resonetics M50-LR excimer ArF laser ablation system (Australian Scientific Instruments, Canberra, Australia) operating at 193 nm wavelength with 20 ns pulse width.
The ablation parameters were set to a spot diameter of 30–37 μm (adjusted based on the size of the sulfide crystals to minimize contamination of adjacent minerals), a repetition frequency of 3 Hz, and an energy density of 3.6 J/cm2. Helium was used as the carrier gas (flow rate: 0.3 L/min) supplemented with 0.8 L/min of argon to enhance aerosol transport efficiency.
Mass bias drift was corrected using the Standard Sample Bracketing (SSB) method to ensure accurate measurements, with certified reference materials (Cpy-1/GC chalcopyrite: δ34SV-CDT = −0.7 ± 0.3‰; Py-4/PTST-2 pyrite: 32.5 ± 0.3‰; NBS123/PTST-3 sphalerite: 26.4 ± 0.3‰; uncertainties at 2SE) serving as quality controls. The laser parameters included a 30–37 μm spot diameter, a 3 Hz repetition rate, and an energy density of 3.6 J/cm2. The analytical precision for δ34S determinations was better than 0.1‰. The detailed analytical methods are described in Chen et al. [24] and Bao et al. [25].

4.2.3. EPMA

The electron probe microanalysis (EPMA) of sphalerite was conducted at the Shandong Institute of Geological Sciences using a JEOL JXA-8100 instrument (JEOL Ltd., Tokyo, Japan). The analytical parameters comprised an acceleration voltage set at 15 kV, a beam current of 20 nA, and a spot size ranging from 1 to 5 μm. The analyzed elements included Fe, Co, Ni, Cu, Pb, Sb, S, Au, As, Zn, Ag, Se, and Bi, with SPI (USA) reference materials serving as calibration standards. Quantitative analyses employed a 10 s peak/5 s background acquisition protocol coupled with ZAF correction, yielding major element contents with a <1% relative standard deviation based on repeated standard measurements.

4.2.4. LA-ICP-MS

The in situ trace element analysis of sphalerite was performed at Beijing Yanduzhongshi Geological Analysis Laboratories Ltd., Beijing, China, using a GeoLasPro 193 nm excimer laser ablation system (Coherent Inc., Santa Clara, CA, USA) integrated with a Neptune Plus MC-ICP-MS (multi-collector inductively coupled plasma mass Spectrometer). Key operational settings included a laser beam diameter of 44 μm, a repetition rate of 6 Hz, and an energy density ranging from 2.4 to 2.7 J/cm2. Helium served as the carrier gas, while argon was employed as the make-up gas, with both gases blended via a T-joint before entering the ICP. The signal collection involved a 20–30 s background measurement phase, which was succeeded by a 50 s analytical interval for sample data acquisition.
Calibration standards (NIST 610, NIST 612, and MASS-1) were analyzed at the beginning of each session and after every 10 samples to correct for instrumental drift and matrix effects. The calibration curves for each element were established using NIST 610 as the primary reference, with NIST 612 and MASS-1 validating the accuracy for low-concentration elements (e.g., Ga and Ge). The measured isotopes included 57Fe, 55Mn, 114Cd, 115In, 65Cu, 59Co, 60Ni, 71Ga, 72Ge, 75As, 78Se, 107Ag, 118Sn, 121Sb, 209Bi, 207Pb, and 66Zn. Raw data processing, involving selection of sample and blank signals, sensitivity drift correction, and quantitative calculations, was performed using ICPMSDataCal software (ver 12.2) [26] by applying the internal standard-free matrix normalization approach. The analytical precision for most trace elements (e.g., Mn, Cd, and Se) was better than 5% RSD and validated by repeated measurements of MASS-1 (n = 5).

5. Results

5.1. Molybdenite Re–Os Isotope Ages

The Re–Os isotopic analyses of five molybdenite samples from the Xulaojiugou Pb–Zn deposit are presented in Table 2 and illustrated in an isochron diagram in Figure 6. The 187Re and 187Os contents ranged from 20,891 to 38,153 ng/g and 64.66 to 117.64 ng/g, respectively. These samples yielded an isochron age of 184.6 ± 3.0 Ma (MSWD = 0.41), with an initial 187Os value of 0.3 ± 1.4 ng/g (Figure 6a). The model ages varied between 182.4 and 188.3 Ma, showing a weighted mean age of 185.2 ± 1.1 Ma (MSWD = 0.41) (Figure 6b).

5.2. In Situ Sulfur Isotopes

In situ sulfur isotope analyses of galena and sphalerite are listed in Table 3. The δ34SV-CDT values of sphalerite ranged from 5.31‰ to 5.83‰ (range = 0.52‰; mean = 5.63‰), while galena exhibited δ34SV-CDT values between 4.70‰ and 5.68‰ (range = 0.98‰; mean = 5.35‰). The δ34SV-CDT values of various sulfides exhibited minimal variation and uniformity, indicating a homogeneous sulfur source.

5.3. The Major and Trace Elements of Sphalerite

The sphalerite major and trace element compositions are shown in Table 4 and Table 5. The chemical composition of sphalerite in the Xulaojiuogu Pb–Zn deposit has the following characteristics: The content of Zn at different analytical spots does not change much (63.0–64.7 wt%; mean = 64.03 wt%), while relatively enriched Mn (2460–3780 ppm; mean = 3040 ppm), Bi (0.05–0.19 wt%; mean = 0.11 wt%), Co (150–171 ppm; mean = 159 ppm), Cd (0.27–0.31 wt%; mean = 0.29 wt%), and Se (350–870 ppm; mean = 590 ppm) exist. The contents of Pb (0.6–670 ppm; mean = 56.0 ppm) and As (0.6–19.0 ppm; mean = 8.4 ppm) display marked variability, while the deposit is poor in Fe (1.7–2.8 wt%; mean = 2.1 wt%), Cu (9.2–52 ppm; mean = 21.5 ppm), Ga (0.3–0.4 ppm; mean = 0.3 ppm), Ge (3.7–6.3 ppm; mean = 5.1 ppm), and In (0.04–1.3 ppm; mean = 0.11 ppm). Trace elements (Ag, Sn, and Sb) show low contents (0.1–1 ppm), without significant intersample variations. The analytical results suggest that these sphalerite samples are relatively homogeneous, lacking significant zoning characteristics, which suggests formation during a single hydrothermal event.

6. Discussion

6.1. Timing of Magmatism and Mineralization

Molybdenite does not incorporate Os during its crystallization; instead, it retains its initial Re–Os isotopic composition by substituting Mo in its crystal lattice, making Re–Os dating resistant to later thermal events and providing a reliable age for mineralization [27]. In contrast, zircon U-Pb dating primarily reflects the crystallization age of intrusive rocks rather than mineralization events and can be influenced by subsequent thermal or fluid activities [28]. Therefore, Re–Os dating is considered more reliable for metallogenic chronology studies.
The Re–Os isotopic dating of molybdenite samples yielded an isochron age of 184.6 ± 3.0 Ma for the molybdenite from the Xulaojiugou Pb–Zn deposit, providing a robust constraint on the timing of Pb–Zn mineralization. According to the mineral generation sequence, molybdenite crystallization predates Pb–Zn mineralization, so the Pb–Zn mineralization at the Xulaojiugou deposit is interpreted to postdate 184.6 ± 3.0 Ma. Recent studies have accumulated extensive geochronological data for magmatic rocks and mineralization ages in the Lesser Xing’an Range–Zhangguangcai Range metallogenic belt (Table 6) [13,15,18,29,30,31]. It is noteworthy that the zircon U-Pb age of the medium-grained monzogranite associated with mineralization in the Xulaojiugou Pb–Zn deposit (181.2 ± 1.1 Ma) overlaps with our Re–Os age [13]. In contrast, the crystallization age of the porphyritic biotite granite exhibited a significant discrepancy (179.9 ± 1.0 Ma), showing no temporal overlap with the Re–Os mineralization age within analytical uncertainty. This age disparity implies that the emplacement of the porphyritic biotite granite postdates the mineralization event, suggesting minimal direct contribution to ore formation [13]. Whole-rock geochemical analysis indicates that the ore-bearing medium-grained monzogranite formed in a subduction-related tectonic setting [6].
The Re–Os isochron age obtained by us is in good agreement with the metallogenic ages of Mesozoic deposits in the surrounding areas [13,15,18,29,30,31]. This suggests that the Xulaojiugou Pb–Zn deposit shares the same tectonic–magmatic evolutionary environment as other Mesozoic deposits in the region.

6.2. Source of Ore-Forming Materials

Sulfur isotope compositions provide critical insights into ore-forming hydrothermal sources and deposit genesis [32]. However, interpreting δ34S values requires consideration of the ore-forming physicochemical parameters (such as pH and oxygen fugacity), and one should not rely solely on the δ34S value for judgment [33].
The Xulaojiugou Pb–Zn deposit features a simple sulfide assemblage dominated by galena, sphalerite, molybdenite, and pyrite, with no sulfate minerals detected, indicating low-pH conditions and low oxygen fugacity during mineralization. Equilibrium sulfur isotope fractionation typically follows the sequence pyrite → sphalerite → chalcopyrite → galena. It indicates the fractionation equilibrium between different sulfides. In this study, limited fractionation between sulfides (galena and sphalerite) was observed (sphalerite: 5.31‰–5.83‰, mean = 5.63‰; galena: 4.70‰–5.68‰, mean = 5.35‰), with δ34S values clustering within a narrow range of 4.7‰ to 5.83‰ (Figure 7). Based on the observation that δ34Ssphalerite > δ34Sgalena, it is concluded that isotopic equilibrium was reached during sulfide mineralization [34]. Consequently, the measured δ34S values of sulfides in the Xulaojiugou deposit closely approximate the total sulfur isotopic composition of the parental hydrothermal fluids [35]. Using the thermodynamic fractionation equation for sphalerite–galena pairs (Δ34S = 0.63 × 106/T2) [34] and the calculated mineralization temperature (248–262 °C), the theoretical Δ34S ranges from 0.89‰ to 1.02‰. The observed Δ34S (mean = 0.28‰) is less than theoretical values, suggesting either (1) near-equilibrium conditions with localized kinetic effects during rapid sulfide precipitation [36], or (2) isotopic homogenization due to fluid mixing prior to mineralization.
The isotopic data presented in Table 3 and Figure 8 demonstrate a limited compositional range of variation among the sulfide minerals in the Xulaojiugou Pb–Zn deposit, with the δ34S values consistently ranging from 4.7‰ to 5.83‰, which are close to typical magmatic reservoir sulfur characteristics (−3‰ to +7‰) [19]. These values of the Xu deposit are consistent with those of Xiaoxilin (1.5‰–7.3‰) [30], Da’anhe (−2.7‰–0.5‰) [37], and Erguxishan (2.2‰–4.6‰) [19]. Skarn deposits exist in the surrounding areas, but they are very different from the Lanping Jinding MVT Pb–Zn deposit (−27.3‰–5.73‰).
The δ34S values of the Xulaojiugou deposit exhibit typical magmatic sulfur isotopic signatures, which are distinct from both mantle-derived sulfur (0 ± 2‰) [38] and sedimentary sulfur reservoirs (−40‰–60‰). The absence of extreme δ34S values (<−10‰ or >15‰) precludes contributions from mantle degassing or the assimilation of crustal sulfur sources. These observations support a deep-seated magmatic–hydrothermal sulfur origin, most likely derived from the dehydration of subducted oceanic slabs metasomatized by mantle wedge fluids, with no isotopic evidence for thermochemical sulfate reduction (TSR) processes [39,40].
Integrated with Re–Os age constraints and sulfur isotopic evidence, it can be inferred that the Xulaojiugou Pb–Zn deposit and contemporaneous deposits in the surrounding areas collectively constitute a porphyry–skarn Pb–Zn-Fe-W-Mo-Ag metallogenic system. These deposits were formed through continuous differentiation of Early Mesozoic monzogranitic magmas, while their metallogenic characteristics were distinctly modified by varying wall rock compositions and structural settings.
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Figure 8. Distribution of δ34S of ore sulfides from the Xulaojiugou Pb–Zn deposit (derived from Shi et al. [16]). The published data of Jingding, Da’anhe, Ergu, Xiaoxilin deposits are from Li et al. [41], Yang [37], Zhao et al. [19], and Huang [30].
Figure 8. Distribution of δ34S of ore sulfides from the Xulaojiugou Pb–Zn deposit (derived from Shi et al. [16]). The published data of Jingding, Da’anhe, Ergu, Xiaoxilin deposits are from Li et al. [41], Yang [37], Zhao et al. [19], and Huang [30].
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6.3. Ore-Forming Temperature

The contents and ratios of trace elements in sphalerite provide critical insights into mineralization temperatures [42,43,44,45]. Sphalerite crystallizing in high-temperature environments (>300 °C) is typically enriched in Fe, In, and Sn, whereas sphalerite formed in medium- to low-temperature environments (<300 °C) is depleted in these elements but enriched in Ga and Ge [41,42].
In the Xulaojiugou Pb–Zn deposit, sphalerite exhibited significantly lower Fe (2.06 wt%), In (0.11 ppm), and Sn (0.49 ppm) contents compared to high-temperature sphalerite from the Laochang deposit (China), where the Fe, In, and Sn contents reached 13.1 wt%, 177 ppm, and 49 ppm, respectively [43]. A negative correlation between Zn and Cd (Figure 9a) reflects Cd substitution for Zn in the crystal lattice. Based on this phenomenon, the Zn/Cd ratio serves as a reliable geological thermometer [46], with high-temperature (>300 °C), medium-temperature (200–300 °C), and low-temperature (<200 °C) mineralization corresponding to Zn/Cd ratios of >500, 100–400, and <100, respectively. While Zn/Cd ratios are widely employed as a geothermometer, their reliability depends on the assumption of a closed system with minimal postdepositional alteration [47]. In the Xulaojiugou deposit, the absence of late-stage veins suggests limited overprinting, supporting the robustness of Zn/Cd-derived temperature estimates. The sphalerite geochemistry at Xulaojiugou reveals an average Zn/Cd ratio of 220.5, which belongs to the medium-temperature environment range.
The Fe content of sphalerite is closely related to the variation in physicochemical conditions, and therefore, the degree of Fe enrichment can indirectly reflect the ore-forming temperature [48]. The Fe and Zn contents of sphalerite in the Xulaojiugou Pb–Zn deposit show a good linear relationship (Figure 9b), which suggests that Fe partially substitutes for Zn in sphalerite. Keith et al. [49] summarized an empirical formula for estimating the crystallization temperature of sphalerite based on the study of the Zn-Fe element composition of sphalerite in massive sulfide deposits: Fe/Zn = 0.0013T (°C) − 0.2953, from which the crystallization temperature of sphalerite in the Xulaojiugou deposit was calculated to be in the range of 248–262 °C. However, it should be noted that this model assumes equilibrium conditions and minimal postcrystallization alteration, so it may not fully account for the effects of localized fluid mixing or redox fluctuations [44,49]. Zou et al. [50] pointed out that the change in Ga/In ratio has a strong correlation with the change in mineralization temperature. Sphalerite Ga/In ratios systematically decrease with increasing formation temperatures: high-temperature sphalerite yields ratios of 0.001–0.05, medium-temperature sphalerite yields 0.01–5, and low-temperature sphalerite yields 1–100. Nevertheless, uncertainties in these ratios may arise from heterogeneous fluid sources or kinetic effects during rapid mineral precipitation [43]. For instance, the availability of ligands (e.g., Cl−) in hydrothermal fluids can influence Ga/In ratios, and variations in ligand activity may occur independently of temperature [45]. The Ga/In ratios of sphalerite in the Xulaojiugou deposit exhibited a range of 0.09–30.1 (mean = 6.46), which indicates that the Xulaojiugou deposit’s formation occurred under mesothermal environment conditions.

6.4. Genetic Type and Metallogenic Processes

The trace element characteristics of sphalerite exhibit systematic variations in different genetic types of Pb–Zn deposit types (such as SEDEX, MVT, and skarn), as their crystallization processes occur under distinct physicochemical conditions; consequently, the elemental composition and relative proportions of sphalerite can be used to determine the genetic classification of the deposit [51]. The Cd/Mn ratio in sphalerite is particularly useful for identifying magmatic contributions to mineralization: MVT and SEDEX-type deposits typically exhibit Cd/Mn > 5, while magmatic–hydrothermal deposits show Cd/Mn < 5 [52]. Song [53] reported that magmatic–hydrothermal deposits and skarn deposits had the highest Cd content with Zn/Cd ratios < 250, sedimentary-modified deposits had the second highest Zn/Cd ratios of 417–531, and volcanic–sedimentary deposits had the lowest ratio, with Zn/Cd ratios ranging from 417 to 531. The Cd/Mn ratios of the sphalerite of the Xulaojiugou Pb–Zn ore ranged from 0.75 to 1.19 (mean = 0.96), indicating that the skarn mineralization of the deposit was greatly influenced by magmatic processes. Sphalerite from the Xulaojiugou deposit exhibited Zn/Cd ratios of 220–230, consistent with skarn deposits, and these results are significantly lower than those of the other two types of deposits.
Based on numerous previous experimental data, sphalerite in VMS-type deposits (such as in the Dabaoshan deposit, China) is relatively enriched in Fe, Mn, and In and relatively deficient in Co, Ga, and Ge [48]. The In, Sn, and Ni contents of sphalerite in skarn deposits (such as in the Dingjiashan deposit, China) are low. whereas Mn, Co, and Cd are high [16]. In contrast, MVT deposits (such as the Daliangzi deposit and Jinding deposit in China) display geochemical properties characterized by Ga-Ge-Cd enrichment and Fe-Mn-Co impoverishment [41,47]. The average contents of Mn, Co, Cd, In, Sn, and Ni in the Xulaojiugou deposit were found to be 3040 ppm, 159 ppm, 2900 ppm, 0.1 ppm, 0.4 ppm, and 8.2 ppm, respectively, and these values are consistent with the trace element distribution of skarn deposits.
The Xulaojiugou deposit exhibits characteristic trace element contents (Mn = 3038 ppm, Co = 159 ppm, Cd = 2900 ppm, In = 0.1 ppm, Sn = 0.39 ppm, Ni = 8.23 ppm) that align with skarn mineralization, particularly through its Mn-Co-Cd enrichment triad and suppressed In-Sn-Ni signature, which are consistent with typical skarn systems documented in South China.
In this paper, we collated sphalerite trace element data from VMS-type, high-temperature magmatic–hydrothermal, skarn, MVT, and SEDEX-type deposits [47,54,55,56], and we selected part of the data to make a scatter plot of sphalerite In-Ge elements (Figure 10), demonstrating conspicuous overlap between the sphalerite projection points of the Xulaojiugou deposit and the range of skarn deposits. Similarly, on the graphical representation of the relationship between genetic type and sphalerite trace elements (Figure 11), the Xulaojiugou deposit samples are all projected in the area of the skarn deposits and their vicinity.
Different genetic types of Pb–Zn deposits have distinct crystallization temperature ranges, ore-forming fluid characteristics, and high-temperature magmatic–hydrothermal deposits derived from fluids from postmagmatic hydrothermal systems, with ore-forming temperatures of 260–400 °C. SEDEX and MVT deposits are sedimentary deposits with ore-forming fluids sourced from deep-circulating basinal brines (potentially modified by evolved seawater) or evaporated seawater with high salinity and ore-forming temperatures ranging from 75 to 150 °C [58]. The metallogenic fluids of skarn deposits can be divided into magmatic fluids and mixed fluids (mixing of magmatic fluids with atmospheric precipitation or seawater), with crystallization temperatures ranging from 160 to 280 °C [59]. The ore-forming temperatures of the Xulaojiugou Pb–Zn deposit range from 248 °C to 262 °C, and the deposit features mixed fluid sources [13], which is consistent with the typical skarn deposits.
Recent regional geodynamic studies suggest that during the Late Triassic, the Lesser Xing’an Range region experienced the late collisional stage of the Paleo-Asian Ocean closure, generating calc-alkaline granites with geochemical affinities to active continental margins (such as high Sr/Y and LREE enrichment) [8]. The Early Jurassic marked the onset of the Paleo-Pacific plate subduction, triggering slab dehydration, mantle wedge melting, and large-scale crustal underplating that resulted in lithospheric thickening and subsequent delamination [60,61]. These magmas intruded into the early Cambrian Qianshan Formation strata, initiating contact metasomatism that leached and mobilized ore-forming metals (such as Pb and Zn) from the host rocks [62]. The synchronicity between Re–Os age and regional subduction-related magmatic pulses indicates that Xulaojiugou mineralization constitutes an integral component of this subduction-driven metallogenic framework.
Furthermore, the spatial association of the Xulaojiugou deposit with NNE-trending faults (Figure 1b) reflects the reactivation of pre-existing structures under subduction-induced transpressional stress [63]. These faults likely served as conduits for magma ascent and fluid circulation, enabling focused metal deposition at the stratabound skarn zone and contact zone accompanied by the generation of peridotite alteration such as argilliza-tion, skarnization, silicification, carbonatization, and chloritization. This model aligns closely with global skarn systems, where subduction-related compression and magmatic-hydrothermal activity synergistically govern metal mineralization [64]. Based on the integration of mineral parageneses, sphalerite geochemistry, sulfur isotopes, ore-forming temperature data, and geological characteristics, it is concluded that the Xulaojiugou Pb–Zn deposit can be classified as a skarn deposit formed in the tectonic setting of Paleo-Pacific plate subduction during the Early to Middle Jurassic.

7. Conclusions

  • The Re–Os isochron age of the molybdenite (184.6 ± 3.0 Ma, MSWD = 0.41) indicates that the Xulaojiugou Pb–Zn deposit was formed in the Early Jurassic, and its mineralization is related to the subduction of the Paleo-Pacific plate.
  • Geochemical analysis of rocks reveals that the major and trace element composition characteristics of sphalerite in the deposit are highly consistent with those of typical skarn deposits in China. This geochemical signature further supports the spatial association of the ore bodies with the contact zone between medium-grained monzogranite and marbles.
  • Sulfur isotope analysis exhibited homogeneous δ34S values ranging from 5.31‰ to 5.83‰ in sphalerite and 4.70‰ to 5.68‰ in galena, with sulfur source tracing confirming predominant derivation from the deep magmatic source area.
  • In situ trace element analysis of sphalerite in the Xulaojiugou Pb–Zn deposit shows that the Zn/Cd, Ga/In ratios indicate a mesothermal environment during mineralization, specifically within the range of 248–262 °C.

Author Contributions

Conceptualization, G.L. and Y.R.; Formal analysis, G.L., J.L. and W.X.; Investigation, G.L. and Y.R.; Data curation, G.L. and W.X.; Writing—original draft, G.L.; Writing—review and editing, Y.R. and J.L.; Visualization, G.L. and J.L.; Supervision, Y.R.; Project administration, Y.R.; Funding acquisition, Y.R. All authors have read and agreed to the published version of the manuscript.

Funding

This research was financially supported by the National Key Research and Development Program of China (2017YFC0601304).

Data Availability Statement

The original contributions presented in this study are included in the article. Further inquiries can be directed to the corresponding authors.

Acknowledgments

We would like to express sincere gratitude to Qun Yang from Jilin University for his constructive suggestions, which have significantly improved the quality of this manuscript. We are also deeply grateful to the anonymous reviewers for their insightful comments and valuable feedback.

Conflicts of Interest

The authors declare no conflicts of interest.

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Minerals 15 00441 g002
Figure 2. Geologic map (a) and cross-section of the No. 3 prospecting line (b) of the Xulaojiugou Pb–Zn deposit (modified from Han et al. [5]).
Figure 2. Geologic map (a) and cross-section of the No. 3 prospecting line (b) of the Xulaojiugou Pb–Zn deposit (modified from Han et al. [5]).
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Minerals 15 00441 g003
Figure 3. Characteristics of the ore hand specimens in the Xulaojiugou Pb–Zn deposits. (a) quartz–molybdenite vein crosscut skarn; (b) molybdenite in medium-grained monzogranite; (c) sphalerite and galena in skarn; (d) chlorite porphyritic biotite granite. Scale bars: 1 cm (black-and-white grid segments common to all figures). Abbreviations: Mo: molybdenite; Sp: sphalerite; Gn: galena; Qtz: quartz.
Figure 3. Characteristics of the ore hand specimens in the Xulaojiugou Pb–Zn deposits. (a) quartz–molybdenite vein crosscut skarn; (b) molybdenite in medium-grained monzogranite; (c) sphalerite and galena in skarn; (d) chlorite porphyritic biotite granite. Scale bars: 1 cm (black-and-white grid segments common to all figures). Abbreviations: Mo: molybdenite; Sp: sphalerite; Gn: galena; Qtz: quartz.
Minerals 15 00441 g003
Minerals 15 00441 g004aMinerals 15 00441 g004b
Figure 4. Representative photomicrographs showing mineral assemblages and textural features from the Xulaojiugou Pb–Zn deposit: (a) flaky molybdenite in quartz veins; (b) sphalerite replaced galena; (c) sphalerite contained anhedral grain pyrrhotite later filled with pyrite vein; (d) sphalerite replaced chalcopyrite; (e) chalcopyrite occurring as emulsion inside sphalerite; (f) skarnization and silicified associated with marble; (g) carbonated skarn; (h) argillization associated with porphyritic biotite granite; (i) chloritization associated with medium-grain monzogranite granite. Abbreviations: Mo: molybdenite; Sp: sphalerite; Gn: galena; Po: pyrrhotite; Py: pyrite; Ccp: chalcopyrite; Qtz: quartz; Cal: calcite; Scp: scapolite; Di: diopside; Chl: chlorite; Kfs: K-feldspar; Pl: plagioclase; Bt: biotite; Tr: tremolite.
Figure 4. Representative photomicrographs showing mineral assemblages and textural features from the Xulaojiugou Pb–Zn deposit: (a) flaky molybdenite in quartz veins; (b) sphalerite replaced galena; (c) sphalerite contained anhedral grain pyrrhotite later filled with pyrite vein; (d) sphalerite replaced chalcopyrite; (e) chalcopyrite occurring as emulsion inside sphalerite; (f) skarnization and silicified associated with marble; (g) carbonated skarn; (h) argillization associated with porphyritic biotite granite; (i) chloritization associated with medium-grain monzogranite granite. Abbreviations: Mo: molybdenite; Sp: sphalerite; Gn: galena; Po: pyrrhotite; Py: pyrite; Ccp: chalcopyrite; Qtz: quartz; Cal: calcite; Scp: scapolite; Di: diopside; Chl: chlorite; Kfs: K-feldspar; Pl: plagioclase; Bt: biotite; Tr: tremolite.
Minerals 15 00441 g004aMinerals 15 00441 g004b
Minerals 15 00441 g005
Figure 5. Mineral paragenesis for the Xulaojiugou Pb–Zn deposit.
Figure 5. Mineral paragenesis for the Xulaojiugou Pb–Zn deposit.
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Minerals 15 00441 g006
Figure 6. Re–Os isochron (a) and model ages (b) for molybdenite samples from Xulaojiugou Pb–Zn deposit.
Figure 6. Re–Os isochron (a) and model ages (b) for molybdenite samples from Xulaojiugou Pb–Zn deposit.
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Minerals 15 00441 g007
Figure 7. Histogram of δ34S values hydrothermal sulfides from Xulaojiugou Pb–Zn deposit.
Figure 7. Histogram of δ34S values hydrothermal sulfides from Xulaojiugou Pb–Zn deposit.
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Minerals 15 00441 g009
Figure 9. Plot of Zn vs. Cd (a) and Fe vs. Zn (b) for sphalerites from the Xulaojiugou Pb–Zn deposit.
Figure 9. Plot of Zn vs. Cd (a) and Fe vs. Zn (b) for sphalerites from the Xulaojiugou Pb–Zn deposit.
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Minerals 15 00441 g010
Figure 10. Plot of In vs. Ge for sphalerites from the Xulaojiugou Pb–Zn deposit compared with other deposit types (derived from Lan et al. [57]).
Figure 10. Plot of In vs. Ge for sphalerites from the Xulaojiugou Pb–Zn deposit compared with other deposit types (derived from Lan et al. [57]).
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Minerals 15 00441 g011
Figure 11. Genetic type identification of Fe/Mn vs. Cd/Fe, Fe/Mn vs. (Fe + Mn)/(Cd + 100Ga) in sphalerite (derived from Lan et al.) [57]. The published data of other deposits: VMS types from Cook et al. [54]; magmatic–hydrothermal types from Kang et al. [56]; MVT types from Yuan et al. [47]; SEDEX and skarn from George et al. [55].
Figure 11. Genetic type identification of Fe/Mn vs. Cd/Fe, Fe/Mn vs. (Fe + Mn)/(Cd + 100Ga) in sphalerite (derived from Lan et al.) [57]. The published data of other deposits: VMS types from Cook et al. [54]; magmatic–hydrothermal types from Kang et al. [56]; MVT types from Yuan et al. [47]; SEDEX and skarn from George et al. [55].
Minerals 15 00441 g011
Table 1. Xulaojiugou deposit Sample description.
Table 1. Xulaojiugou deposit Sample description.
Sample No.Ore TypeMineral Association
XLJ-3 (1)massive oreGn + Sp + Py + skarn minerals
XLJ-3 (2)submassive oreGn + Sp + Ccp + Py + skarn minerals
XLJ-3 (3)submassive oreGn + Sp + Po + skarn minerals
Table 2. Re–Os isotopes of molybdenite from the Xulaojiuogu Pb–Zn deposit.
Table 2. Re–Os isotopes of molybdenite from the Xulaojiuogu Pb–Zn deposit.
Sample No.Weight (g)Re (μg/g)Os (ng/g)187Re (μg/g)187Os (ng/g)Model Ages (Ma)
Measured2σMeasured2σMeasured2σMeasured2σMeasured2σ
XLJ-1-10.0100043.690.146.7960.60727.460.0985.041.03185.62.9
XLJ-1-20.0100056.460.180.7150.12135.490.12109.870.81185.62.4
XLJ-1-30.0100060.700.200.8940.08138.150.13117.640.84184.82.3
XLJ-1-50.0100033.240.100.6990.08920.890.0764.660.46185.52.3
XLJ-1-60.0100043.860.141.4210.14227.570.0984.950.60184.72.3
Table 3. Sulfur isotope compositions of sulfides from the Xulaojiugou Pb–Zn deposit.
Table 3. Sulfur isotope compositions of sulfides from the Xulaojiugou Pb–Zn deposit.
No.Sulfideδ34SV-CDT%2SENo.Sulfideδ34SV-CDT%2SE
1Sphalerite5.670.1116Sphalerite5.390.11
2Sphalerite5.710.1217Sphalerite5.550.13
3Sphalerite5.640.1118Sphalerite5.470.13
4Sphalerite5.750.1119Sphalerite5.500.13
5Sphalerite5.700.1120Sphalerite5.630.13
6Sphalerite5.810.1221Galena5.560.15
7Sphalerite5.310.1122Galena5.520.16
8Sphalerite5.720.1323Galena5.470.17
9Sphalerite5.780.1424Galena5.680.15
10Sphalerite5.830.1125Galena5.310.15
11Sphalerite5.830.1326Galena5.460.14
12Sphalerite5.660.1227Galena5.150.14
13Sphalerite5.410.1328Galena5.270.15
14Sphalerite5.480.1229Galena4.700.19
15Sphalerite5.780.12
Table 4. Major element compositions (wt%) of sphalerite analyzed by electron probe microanalysis (EPMA) from the Xulaojiugou Pb–Zn deposit.
Table 4. Major element compositions (wt%) of sphalerite analyzed by electron probe microanalysis (EPMA) from the Xulaojiugou Pb–Zn deposit.
Sample No.FeCoNiCuPbSbSAuAsZnSeBi
XLJ-3(1)-12.380.020.01 ---32.50--63.71-0.15
XLJ-3(1)-22.330.02----32.640.03-63.78-0.12
XLJ-3(1)-32.350.04-0.01--32.39-0.0163.450.050.19
XLJ-3(1)-42.350.02----32.57--63.830.060.10
XLJ-3(1)-52.380.03----32.580.02-63.960.020.12
XLJ-3(1)-62.320.02--0.040.0232.84--64.060.020.13
XLJ-3(1)-72.410.02----32.86--64.100.070.06
XLJ-3(2)-12.270.02-0.02--32.700.07-64.27-0.14
XLJ-3(2)-22.290.02----32.67--64.35-0.14
XLJ-3(2)-32.350.02--0.01-32.59--64.470.040.11
XLJ-3(2)-42.350.02----32.760.04-64.660.080.11
XLJ-3(2)-52.320.02----32.79--64.23-0.10
XLJ-3(2)-62.380.03-0.03--32.750.01-64.72-0.11
XLJ-3(2)-72.390.020.03---32.760.19-63.86-0.12
XLJ-3(2)-82.400.01-0.03--32.800.04-64.130.020.11
XLJ-3(2)-92.380.02--0.070.0332.690.070.0364.59-0.11
XLJ-3(2)-102.410.02-0.010.01-32.88--64.370.020.11
XLJ-3(2)-112.400.02----32.61-0.0164.76-0.06
XLJ-3(2)-122.370.02--0.05-32.480.04-64.32-0.12
XLJ-3(2)-132.310.010.010.03--32.64--64.680.020.07
XLJ-3(2)-142.340.02----32.59--64.220.010.14
XLJ-3(2)-152.360.040.01--0.0133.41--64.240.020.13
XLJ-3(2)-162.390.020.01-0.02-32.740.08-64.28-0.12
XLJ-3(2)-172.350.030.01-0.04-32.47--64.070.020.11
XLJ-3(2)-182.400.020.00--0.0232.54--63.56-0.15
XLJ-3(2)-192.400.020.01---32.590.02-63.840.020.10
XLJ-3(2)-202.410.03----32.600.15-64.07-0.09
XLJ-3(2)-212.430.020.01--0.0132.42--63.87-0.16
XLJ-3(2)-222.410.03----32.430.04-63.69-0.10
XLJ-3(3)-12.460.02----32.31--63.050.030.10
XLJ-3(3)-22.490.02----32.410.04-63.980.040.15
XLJ-3(3)-32.450.01----32.510.02-63.97-0.17
XLJ-3(3)-42.470.02---0.0132.36-0.0463.66-0.16
XLJ-3(3)-52.500.03----32.030.020.0163.000.020.11
XLJ-3(3)-62.450.02----32.470.02-63.80-0.15
XLJ-3(3)-72.430.02---0.0132.47--64.120.010.10
XLJ-3(3)-82.440.030.01---32.58--64.37-0.08
XLJ-3(3)-92.460.02-0.01--32.630.030.0563.870.040.16
XLJ-3(3)-102.440.02--0.020.0132.440.02-63.790.010.10
XLJ-3(3)-112.430.020.01-0.03-32.44--63.10-0.12
XLJ-3(3)-122.500.03-0.01--32.40--63.750.030.11
XLJ-3(3)-132.540.03----32.520.01-63.44-0.05
XLJ-3(3)-142.400.020.02---32.60-0.0264.500.010.10
XLJ-3(3)-152.460.040.01--0.0032.660.040.0263.98-0.10
XLJ-3(3)-162.350.02---0.0032.58--64.51-0.11
XLJ-3(3)-172.370.02----31.88--63.41-0.11
XLJ-3(3)-182.460.03---0.0132.91--64.13-0.12
XLJ-3(3)-192.430.03----32.740.01-64.40-0.10
XLJ-3(3)-202.480.020.01---32.58--64.41-0.12
XLJ-3(3)-212.450.02-0.01--32.63--64.30-0.05
Table 5. Trace element compositions (ppm) of sphalerite analyzed by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-ICP-MS) from the Xulaojiugou Pb–Zn deposit.
Table 5. Trace element compositions (ppm) of sphalerite analyzed by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-ICP-MS) from the Xulaojiugou Pb–Zn deposit.
Sample No.MnFeZnNiCuCoGaGeAsSeAgCdInSnSbBiPb
XLJ-3-1-02325319,285643,11411.021.91610.015.2918.55543.8128840.020.150.040.192.58
XLJ-3-1-03316319,234642,3843.9920.61600.925.815.196514.2028620.031.090.370.315.02
XLJ-3-1-04323718,707642,97711.024.71550.074.846.045994.4328600.03-0.462.936.03
XLJ-3-1-05348618,434640,3865.0222.81560.095.522.225344.2628190.020.601.392.2710.43
XLJ-3-1-06297718,587642,1475.7022.11580.394.042.865744.2227800.050.110.961.3067
XLJ-3-1-07304818,768642,846-22.11600.075.035.875596.1027560.030.602.822.8973.6
XLJ-3-1-08370718,989638,26917.225.31600.405.916.365654.0828090.030.680.260.2426.6
XLJ-3-1-09310018,188642,4575.3022.41590.304.9413.14943.9728140.07-0.641.149.76
XLJ-3-1-10288217,874645,080-21.11550.095.439.204923.8627600.050.390.040.1614.6
XLJ-3-1-11307818,669642,17612.523.91710.435.3913.45724.1628410.020.410.821.2439.5
XLJ-3-1-12293719,720637,922-18.21630.166.265.184415.0128050.030.741.614.1064.2
XLJ-3-1-13303618,343641,697-23.41700.005.8913.64104.8228780.061.030.835.0638.4
XLJ-3-1-19295018,670644,370-20.81670.245.108.315994.9028810.060.120.150.538.08
XLJ-3-1-20304219,111643,28811.125.41620.195.540.635344.2327620.090.000.020.124.40
XLJ-3-1-21258718,966640,48813.322.61650.115.5510.665064.6529511.230.640.173.27673
XLJ-3-1-22333219,423638,980-18.91680.324.902.65064.2930280.050.090.072.25611
XLJ-3-1-23300618,654643,09016.220.61640.254.7212.15174.1827300.011.500.590.8727.25
XLJ-3-2-24293217,619644,21512.518.31530.044.868.777673.7328970.030.410.060.071.51
XLJ-3-2-25297118,694642,25013.823.71550.234.648.156894.7728580.040.26-0.438.61
XLJ-3-2-27310320,854642,07618.919.91570.174.639.715333.7829840.05-0.210.303.50
XLJ-3-2-28353621,325637,5110.1620.31590.475.3110.56144.2429220.060.761.123.1611.6
XLJ-3-2-29288822,584639,51918.429.91520.264.7511.67553.8829091.300.420.310.842.61
XLJ-3-2-30297223,390636,835-21.81580.265.505.437843.8530260.040.212.230.131.82
XLJ-3-2-31283123,552639,2259.3620.01540.215.2912.97093.7229170.030.060.120.223.29
XLJ-3-2-32281125,770634,9381.989.21550.545.198.123523.5029960.060.130.010.031.21
XLJ-3-2-33304226,364634,2228.8910.91580.514.8710.77023.4430460.050.000.070.159.67
XLJ-3-2-34301026,983630,068-20.61590.184.4812.18713.8630230.040.610.161.12245
XLJ-3-2-35281628,123634,34310.719.81560.025.007.218143.5830090.06--0.082.51
XLJ-3-2-36323528,074631,62717.520.31590.385.069.797383.5529850.510.630.130.253.07
XLJ-3-2-37287028,660631,17618.723.11590.135.8815.07453.5429400.060.600.200.238.04
XLJ-3-3-38320119,195638,7627.5218.81520.243.796.735335.1130580.030.270.444.7318.3
XLJ-3-3-39335719,306638,1275.9419.01560.264.224.796014.1328300.060.300.201.149.41
XLJ-3-3-40289918,451642,9863.4520.21500.335.0715.35345.3327620.060.360.353.63190
XLJ-3-3-41332719,449636,66019.521.11580.294.994.575764.0828080.040.400.471.83102
XLJ-3-3-42265919,259642,9722.6823.31570.145.3410.35445.1730720.070.180.613.6419.2
XLJ-3-3-43285220,096641,2247.4220.51590.394.923.335474.4129560.020.660.160.666.06
XLJ-3-3-44254619,864642,87012.620.21630.115.979.705373.7929820.070.160.120.565.56
XLJ-3-3-45254319,730641,59116.120.41580.095.527.374983.8830000.060.560.090.002.03
XLJ-3-3-46246420,433642,4949.6412.91620.484.691.603773.5629480.050.270.010.050.63
XLJ-3-3-47299319,532639,763-25.41590.515.8515.25944.0428410.050.610.521.1910.2
XLJ-3-3-48317420,511635,8605.5719.01600.435.512.375824.3329030.040.330.762.8333.1
XLJ-3-3-49378221,072630,44712.320.41610.335.497.846094.2729170.050.220.441.3011.8
Table 6. Comparative geochronological data of the Xulaojiugou deposit and regional deposits.
Table 6. Comparative geochronological data of the Xulaojiugou deposit and regional deposits.
DepositLithologySample AnalyzedAnalytical MethodAge (Ma)References
Xulaojiugoumedium-grained monzograniteMolybdeniteRe–Os184.6 ± 3.0This study
medium-grained monzograniteZirconU-Pb181.2 ± 1.1[13]
porphyritic biotite graniteZirconU-Pb179.9 ± 1.0
LumingmonzograniteZirconU-Pb180.7 ± 1.6[13]
HuojihemonzograniteZirconU-Pb186 ± 1.7[15,29]
porphyritic graniteZirconU-Pb176.3 ± 5.1
Cuihongshanporphyritic graniteZirconU-Pb196.5–193.7[18]
XiaoxilingranodioriteZirconU-Pb200 ± 2[30]
Ergubiotite granodioriteZirconU-Pb186.5 ± 5[31]
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Liu, G.; Ren, Y.; Li, J.; Xu, W. Origin of the Xulaojiugou Pb–Zn Deposit, Heilongjiang Province, NE China: Constraints from Molybdenite Re–Os Isotopic Dating, Trace Elements, and Isotopic Compositions of Sulfides. Minerals 2025, 15, 441. https://doi.org/10.3390/min15050441

AMA Style

Liu G, Ren Y, Li J, Xu W. Origin of the Xulaojiugou Pb–Zn Deposit, Heilongjiang Province, NE China: Constraints from Molybdenite Re–Os Isotopic Dating, Trace Elements, and Isotopic Compositions of Sulfides. Minerals. 2025; 15(5):441. https://doi.org/10.3390/min15050441

Chicago/Turabian Style

Liu, Gan, Yunsheng Ren, Jingmou Li, and Wentan Xu. 2025. "Origin of the Xulaojiugou Pb–Zn Deposit, Heilongjiang Province, NE China: Constraints from Molybdenite Re–Os Isotopic Dating, Trace Elements, and Isotopic Compositions of Sulfides" Minerals 15, no. 5: 441. https://doi.org/10.3390/min15050441

APA Style

Liu, G., Ren, Y., Li, J., & Xu, W. (2025). Origin of the Xulaojiugou Pb–Zn Deposit, Heilongjiang Province, NE China: Constraints from Molybdenite Re–Os Isotopic Dating, Trace Elements, and Isotopic Compositions of Sulfides. Minerals, 15(5), 441. https://doi.org/10.3390/min15050441

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