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Article

Genesis of the Laoliwan Ag-Pb-Zn Deposit, Southern Margin of the North China Craton, China: Constrained by C-H-O-S-Pb Isotopes and Sulfide Rb-Sr Geochronology

by
Jianling Xue
1,2,
Zhenshan Pang
1,2,*,
Hui Chen
1,2,
Peichao Ding
3,
Ruya Jia
1,2,*,
Wen Tao
1,2,
Ruifeng Shen
3,
Banglu Zhang
1,2,
Nini Mou
1,2 and
Yan Yang
1,2
1
Development and Research Center, China Geological Survey, Beijing 100037, China
2
Technical Guidance Center for Mineral Exploration, Ministry of Natural Resources, Beijing 100037, China
3
Henan First Geology and Mineral Survey Institute Co., Ltd., Zhengzhou 450016, China
*
Authors to whom correspondence should be addressed.
Minerals 2025, 15(11), 1122; https://doi.org/10.3390/min15111122
Submission received: 24 August 2025 / Revised: 15 October 2025 / Accepted: 21 October 2025 / Published: 28 October 2025
(This article belongs to the Section Mineral Deposits)
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Abstract

The Laoliwan Ag-Pb-Zn deposit is situated in the southern margin of the North China Craton and represents the first large-scale Ag-Pb-Zn ore deposit discovered in the Xiaoshan District. Ag-Pb-Zn orebodies are structurally controlled by NW- and NNW-trending faults and primarily hosted within early Cretaceous granite porphyry intrusions. In this study, sulfide Rb-Sr isotope dating and C-H-O-S-Pb multiple isotope compositions were conducted to constrain the ore genesis of this deposit. The Rb-Sr isotopic data of sulfides yield a weighted mean isochron age of 132.8 ± 9.5 Ma and an initial 87Sr/86Sr ratio of 0.7115 ± 0.00016, indicating that mineralization occurred during the early Cretaceous and the ore-forming materials were derived from a crust–mantle mixed reservoir. The δ13 C (−1.3‰ to 0.7‰), δD (−96.3‰ to −86.7‰) and δ18OH2O (0.3‰ to 5.6‰) values suggest that the ore-forming fluids were mainly derived from magmatic water with a contribution of meteoric water during mineralization. The δ34S values of sulfides (+2.0‰ to +5.8‰) indicate a magmatic source. The Pb isotope data (206Pb/204Pb = 17.301–17.892, 207Pb/204Pb = 15.498–15.560, 208Pb/204Pb = 37.873–38.029) also reveal that the ore-forming materials originated from the lower crust with a small amount from the mantle source. By integrating geochronological and geochemical data, this study proposes that the Laoliwan Ag-Pb-Zn deposit is characterized as an epithermal deposit, with potential for the discovery of concealed porphyry Cu-Mo mineralization at depth. It is inferred to be related to tectonic–magmatic–fluid activities in the context of early Cretaceous lithospheric thinning along the southern margin of the North China Craton.

1. Introduction

The southern margin of the North China Craton (NCC) is regarded as one of the most important polymetallic metallogenic belts in China, which can be divided into the Xiaoqinling, Xiaoshan, Luanchuan, Xiong’ershan, and Waifangshan districts (Figure 1) [1,2,3,4,5,6,7,8,9]. The metallogenic belt hosts the world’s largest Mo resources (>1000 Mt), and the second largest Au resources in China (>1300 t) [10,11]. In recent years, a series of Ag-Pb-Zn deposits have been successively discovered in the southern margin of the North China Craton, including Lengshuigou and Luotuoshan deposits in the Nannihu ore field, Luanchuan district [3,10,12,13,14]; Shagou, Tieluping and Haopinggou deposits in the Xiayu ore field, Xiong’ershan district [8,15,16,17,18,19]; Laodaizhanggou, Sanyuangou, Donggou and Wangpingxigou deposits in the Fudian ore field, Waifangshan district [7,9,20,21]; Laoliwan and Zhonghe deposits in the Laoliwan ore field, Xiaoshan district [1,22]. Vein-type Ag-Pb-Zn deposits represent one of the vital sources of key metals like silver, lead, and zinc in China [8,23,24,25,26]. They occur prevalently in magmatic arcs and their related porphyry systems where they may be hosted by faults or the adjacent country rocks [27,28,29,30,31,32,33]. Research on vein-type Ag-Pb-Zn deposits not only helps understand their metallogenic mechanisms but also facilitates the interpretation of the geological tectonic settings conducive to ore formation [8]. Numerous studies have been conducted on these Ag-Pb-Zn deposits. However, the ore genesis and ore-forming process of these deposits are still controversial, largely because it is difficult to precisely define the age of Ag-Pb-Zn mineralization and to reliably identify the sources of ore-forming fluids and materials [10].
The Laoliwan Ag-Pb-Zn deposit is located in the eastern part of the Xiaoshan district, which is hosted by the Laoliwan granitic porphyry and controlled by NW-trending faults. As the first large-scale concealed Ag-Pb-Zn deposit discovered in the Xiaoshan district, its discovery rewrote the region’s record of lacking economically viable mineralization [22]. The Laoliwan Ag-Pb-Zn deposit has drawn significant attention from domestic research institutions, universities, and mining companies since it was first discovered. Previous studies have primarily focused on the geological characteristics, fluid inclusions, and geochemical characteristics of the Ag-Pb-Zn deposit [22,35,36]. However, the research on the Laoliwan Ag-Pb-Zn deposit remains inadequate in contrast with the medium- to large-scale Ag-Pb-Zn deposits in the southern margin of the North China Craton. Detailed studies of ore genesis, metallogenic epoch, sources of ore-forming fluids and materials, and ore-forming geodynamics are limited.
In this contribution, a detailed investigation of the geology, a systematic study of C-H-O-S-Pb isotopes, and Rb-Sr isotope dating of sulfides from the Laoliwan Ag-Pb-Zn deposit were carried out. Combined with previous geological, geochemical, and geochronological studies, the timing of Ag-Pb-Zn mineralization and the source of ore-forming fluids and materials are discussed. New information is provided to constrain the genesis of the deposit and important assist insights are offered into regional prospecting for potential Ag-Pb-Zn deposits in this district, which would help better understand the metallogenesis of the Ag-Pb-Zn deposits in the Xiaoshan district, the southern margin of the North China Craton.

2. Geological Setting

2.1. Regional Geology

The Laoliwan Ag-Pb-Zn deposit is located in the Xiaoshan district of the southern margin of the North China Craton (Figure 1). It is bounded by the Sanmengxia-Lushan fault to the northeast, and the Luonan-Luanchuan fault to the southwest (Figure 1), separating it from the North Qinling orogenic belt to the south. The Xiaoshan district is dominated by the late Archean to early Paleoproterozoic basement of the Taihua Group and cover layer of Xiong’ er Group (Figure 2A). The Taihua Group consists of biotite-plagioclase gneiss, TTG gneiss, amphibole gneiss, amphibolite, granulite, and biotite-garnet gneiss or granulite [17,37], which formed from 2.6 to 2.07 Ga [38,39,40,41]. The Xiong’er Group is distributed extensively in the Xiaoshan district. Its lithologic assemblage mainly comprises andesite, amygdaloidal andesite, dacite, and rhyolite [42,43], with ages constrained to 1.80–1.75 Ga [37]. The Xiong’er Group is unconformably overlain by the Guandaokou Group in the southwestern part of the Xiaoshan district. The Guandaokou Group is characterized as a shallow marine to continental sedimentary system, which is dominated by interbedded sandstone and carbonate rocks [4].
Mesozoic granitoid intrusions are widespread in the Xiaoshan region. These intrusions primarily consist of small intermediate to acidic intrusive bodies that formed during the Yanshanian orogeny (145 Ma–117 Ma, Zircon U-Pb dating) [1], including granitic porphyry, monzogranite porphyry, and porphyritic granodiorite (Figure 2A). Examples include Longwogou (128 ± 1 Ma), Houhe (127.3–131.0 Ma), Xiaomeihe (131.5 ± 0.9 Ma), Baishiya (135 ± 3 Ma), Hangou (145.1 ± 0.7 Ma), Zhonghe (129–131 Ma), Zhangjiagudong (117 ± 2 Ma) and Laoliwan (129–137 Ma).
Numerous faults are well-developed in the Xiaoshan district. These faults include north–south (NS), east–west (EW), north–northwest (NNW), and northeast (NE)-striking faults (Figure 2A). Among them, the EW-trending and NE-trending faults are the most important structures. The EW-trending structures control the strike of strata, the distribution of magmatic rock belts, and the extension of the mountain ranges. The NE-trending structures govern the axial orientation of rift basin boundaries and are closely linked to the distribution of some gold, silver–lead–zinc deposits. The Xiaoshan District is characterized by small-scale gold deposits and a few large-scale silver–lead–zinc deposits, including Xiaoshan Au deposit (0.672 Mt @7.89 g/t Au) [44], Shizhaigou Au deposit (0.250 Mt @4.0 g/t Au) [45], Bankuan Au deposit (0.475 Mt @10.25 g/t Au) [46], Shenjiayao Au deposit (2.854 Mt @3.01 g/t Au) [11], Zhonghe Ag-Pb-Zn deposit (9.819 Mt @129.65 g/t Ag, 2.90% Pb, and 3.21% Zn) [1], and Laoliwan Ag-Pb-Zn deposit (11.250 Mt @157.0 g/t Ag, 0.70% Pb, and 0.50% Zn) [47].

2.2. Deposit Geology

The Laoliwan Ag-Pb-Zn deposit is located in Dongsong Town, Luoning County, Henan province, covering an area of 2.12 km2. It is situated in the shallowly-covered eastern Xiaoshan district. Quaternary sediments are widely exposed in the mining area. The Xiong’er Group is sporadically exposed in deeply eroded valleys or along steep slopes. In the Laoliwan ore field, the Xiong’er Group is mainly composed of grayish-green andesite, amygdaloidal andesite, and porphyritic andesite (Xushan Formation). There are many faults in the deposit, which mostly strike northwest, northeast, and north–south. Among them, the F1 fault mainly controls the distribution of orebodies in the Laoliwan Ag-Pb-Zn deposit and transects the Laoliwan granitic porphyry. The F1 fault is the largest fault in the mining area, with a length of approximately 1.2 km and a width of 10 m to 150 m; it strikes 310° to 330° with dips varying 50° to 70° [36]. The intrusive rock exposed in the mining area is the Laoliwan intrusive. The Laoliwan granite porphyry intrudes into the Xushan Formation, covering an area of 0.25 km2. The phenocrysts in the Laoliwan granite porphyry are mainly K-feldspar, plagioclase, and quartz, with a small amount of biotite and hornblende. The Laoliwan granite porphyry has a zircon LA-ICP-MS U-Pb age of 129~137 Ma [1]. Seven explosion breccia bodies have been identified in the mining area, predominantly exhibiting elliptical shapes and spatially distributed around the intrusive rock mass (Figure 2B) [36].
The Laoliwan Ag-Pb-Zn deposit consists of 20 orebodies which generally exhibit vein-like, pocket or lenticular forms, with estimated resources of 11.250 Mt @ 157.0 g/t Ag, 0.70% Pb, and 0.50% Zn [22,37]. The F1-1 orebody is the major orebody in the Laoliwan Ag-Pb-Zn deposit, hosted in the F1 fault. The F1-1 orebody exhibits a pocket morphology, with a strike of 330° and a dip of 60°. The orebody extends for 495 m along strike with an average thickness of 10.5 m, and a depth extends for 480 m (Figure 2C). Ore textures are mainly massive (Figure 3A), disseminated (Figure 3B), veinlet-disseminated (Figure 3C), veinlet (Figure 3D,E), and explosive breccia (Figure 3F). The primary sulfide minerals include galena, sphalerite, pyrite, chalcopyrite, tetrahedrite, and Ag sulfides (Figure 4A–D). The gangue minerals are predominately quartz, sericite, chlorite, and carbonates.
Pb and Zn are important coexisting elements of the Ag deposit. They are mainly distributed within Ag-Pb-Zn ores. The Zn/Pb ratio is 1.2. Au in the deposit, with an average grade of 0.21 g/t, shows a positive correlation with the grade of Ag and is mainly distributed in the shallow parts. The average grade of Cu is 0.01%, falling below the economic standard, but it tends to increase from top to bottom.
The wall-rock alteration is predominantly controlled by the F1 fault and its associated secondary tectonic structures, and exhibits planar or zonal distribution. The deposit exhibits extensive alteration including sericitization, kaolinization, pyritization, dolomitization, chloritization, epidotization, carbonatization, silicification and potassic alteration. Based on field and petrographic observation (Figure 5), three paragenetic stages are recognized at the Laoliwan Ag-Pb-Zn deposit: quartz-pyrite stage (stage I), quartz–polymetallic sulfides stage (stage II), and quartz–carbonate stage (stage III). The paragenetic sequence of the Laoliwan deposit is summarized in Figure 5.

3. Sampling and Analytical Methods

The study samples were collected from the −310 m and −360 m levels, drill holes, and stockpiles of ore bodies. Four sphalerite and three pyrite representative samples from the main mineralization stage (stage II) were collected for Rb-Sr isotopic dating. Additionally, five quartz samples from the main mineralization stage (stage II) were selected for H-O isotopic analyses. Moreover, three calcite samples from the stage III were chosen for C-O isotopic analyses. Twelve sulfide samples were selected for sulfur isotopic analyses, and eleven sulfide samples were collected to evaluate the lead isotopic variation. The Rb-Sr dating and C-H-O-S-Pb isotopic analyses were performed at the Analytical Laboratory, Beijing Research Institute of Uranium Geology, China.

3.1. Rb-Sr Isotope Dating

Fresh ore samples were crushed to 40–60 mesh for handpicking under a binocular microscope to ensure a purity level greater than 99%. The selected sphalerite and pyrite crystals were ground into a 200-mesh powder, then ultrasonically cleaned with Milli-Q water (manufactured by Merck KGaA, Darmstadt, Germany) for several minutes. After drying at low temperature, 200 mg of sample powder was transferred to Teflon vessels and spiked with a mixed 87Rb-84Sr tracer. Subsequently, the mixture was dissolved with mixed acid (HF + HNO3) for 48 h. After complete dissolution and evaporation of the sample, 6.0 mol/L hydrochloric acid was added to convert into chloride for evaporation. The residue was then dissolved in 0.5 mol/L hydrochloric acid solution and separated by centrifugation. The supernatant was loaded onto a cation exchange column (φ 0.5 cm × 15.0 cm, AG50W × 8 (H+), 100–200 mesh). Rubidium was eluted using 2.0 mol/L hydrochloric acid solution, while strontium was eluted with 3.0 mol/L hydrochloric acid solution. The eluates were subsequently evaporated to dryness for mass spectrometry analysis. Rb-Sr dating isotope analyses were performed using a Phoenix thermal ionization mass spectrometer. Sr isotopic data were normalized to 88Sr/86Sr = 8.375219, using power law fractionation correction. The standard used was NBS987 with a 87Sr/86Sr ratio of 0.710250 ± 0.000007 in the course of this study. All operations were carried out in a clean laboratory environment, with a laboratory process background of Rb = 2 × 10−10 g and Sr = 2 × 10−10 g.

3.2. C-H-O-S-Pb Isotope Analyses

The samples for hydrogen–oxygen, carbon–oxygen, sulfur and lead isotopes were crushed and sieved to obtain a particle size range of 40–60 mesh. Single-mineral separation was performed under a binocular microscope until purity exceeded 99%.
H-O isotopic analyses were conducted using a MAT-253 mass spectrometer (manufactured by Thermo Fisher Scientific, Bremen, Germany). Oxygen was extracted from quartz using the BrF5, and then reacted stepwise with carbon rods under platinum catalysis at 700 °C. The resultant CO2 was analyzed for oxygen isotopes. The procedure for hydrogen isotope analysis first involves releasing the water from the fluid inclusions using the crushing method. Before transferring it to the mass spectrometer, the water was reduced to H2 by passing it over depleted uranium. The analytical precisions were better than ±0.2‰ and ±0.1‰ for oxygen and hydrogen isotopes, respectively.
C-O isotope analysis was performed by MAT-251 mass spectrometer (manufactured by Thermo Fisher Scientific, Bremen, Germany). The carbon and oxygen isotopic compositions of carbonates were determined by measuring CO2. Within a vacuum system, the sample is reacted with 100% phosphoric acid at a constant temperature of 25 °C for over 4 h. The generated water is then separated by freezing, allowing the collection of pure CO2 gas. The measurement results were reported relative to the V-PDB and VSMOW standards, with an analytical precision better than ±0.2‰.
S isotope was measured with a MAT253EM mass spectrometer (manufactured by Thermo Fisher Scientific, Bremen, Germany). Sulfide compositions were reported as δ34S relative to V-CDT (Vienna Canyon Diablo Troilite) standard, achieving an analytical precision of ±0.2‰.
Pb isotope measurement was carried out on an ISOPROBE-T Thermal Ionization Mass Spectrometer (manufactured by GV Instruments, Manchester, UK), and the precisions were better than 0.005%. 200 mg of sample powder was put into PFA vessels and decomposed using a mixed solution of distilled HF and HClO4. After complete dissolution and evaporation of the sample, 6.0 mol/L hydrochloric acid was added to convert into chloride for evaporation. Then, 1 mL of 0.5 mol/L HBr solution was added to redissolve the dry residue. The mixture was centrifuged for 10 min and the supernatant was collected. The supernatant was transferred to an anion exchange column (250 μL of AG1—x8 resin, 100–200 mesh) and rinsed with 0.5 mol/L HBr solution to remove impurities. Next, 1 mL of 6 mol/L HCl was added to the column to elute Pb. After evaporation to dryness, Pb isotope measurements were conducted using thermal ionization mass spectrometry (TIMS) (manufactured by Thermo Fisher Scientific, Bremen, Germany). Analytical results for the standard NBS 981 and 208Pb/204Pb = 36.611 ± 0.004 (2σ), 207Pb/204Pb = 15.457 ± 0.02 (2σ), and 206Pb/204Pb = 16.937 ± 0.002 (2σ), in agreement with the reference value [48]. The lead isotope ratios are reported with a ±2‰ error (2σ).

4. Results

4.1. Rb-Sr Isochron Age

The Rb-Sr isotope compositions of three pyrite and four sphalerite samples are summarized in Table 1, and illustrated in Figure 6. The ISOPLOT software 3.00 [49] was used to calculate isochron age and initial 87Sr/86Sr ratio determination. The Rb and Sr contents of these pyrite and sphalerite samples range from 0.105 μg/g to 4.17 μg/g and 3.02 μg/g to 22 μg/g, respectively. The 87Rb/86Sr ratios range from 0.0347 to 3.0664, and 87Sr/86Sr ratios vary from 0.711623 to 0.717344. Seven samples yielded an isochron age of 132.8 ± 9.8 Ma with a low MSWD of 0.44 and initial 87Sr/86Sr ratio of 0.71151± 0.00016 (Table 1, Figure 6).

4.2. Hydrogen and Oxygen Isotopic Compositions

The measured and previously measured oxygen and hydrogen isotopes of quartz are summarized in Table 2 and graphically shown in Figure 7. The isotope fractionation equation used was 1000lnαquartz-water = 3.38 × 106 × T2 − 3.40, and the average homogenization temperature (300 °C) was obtained from microthermometric data. The δD values range from −96.3‰ to −86.7‰, and δ18OH2O values range from −1.82‰ to 3.43‰ for quartz in the main mineralization. In the δ18OH2O vs. δD plot (Figure 7), all these samples are plotted between the magmatic water field and meteoric water line.

4.3. Carbon Isotopic Compositions

Carbon–oxygen isotope data for calcite from the late stage of the Laoliwan Ag-Pb-Zn deposit and previous studies’ data are listed in Table 3 and illustrated in Figure 8. The δ18CV-PDB values for the calcite and siderite range from −5.6‰ to 0.7‰. The δ18OV-SMOW values for the calcite range from 4.4‰ to 17.4‰.

4.4. Sulfur Isotopic Compositions

The measured sulfur isotope data of ore sulfides of the Laoliwan Ag-Pb-Zn deposit and previous studies’ data are presented in Table 4 and shown in Figure 9. The δ34S values of ore sulfides range from 1.9‰ to 5.9‰, with an average of 3.8‰. The δ34S values of nine pyrite minerals, seven galena minerals, seven sphalerite minerals and one chalcopyrite range from 2‰ to 4.9‰, 1.9‰ to 4.9‰, 3.7‰ to 5.9‰, and 5.5‰, respectively.

4.5. Lead Isotopic Compositions

Lead isotopic data of ore are summarized in Table 5 and illustrated in Figure 10. The 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of ore sulfides range from 37.873 to 38.029, with an average of 37.941; 15.498 to 15.560, with an average of 15.528; and 17.301 to 17.892, with an average of 17.427. Five pyrite samples show 208Pb/204Pb values of 37.884–37.953, 207Pb/204Pb values of 15.507–15.560 and 206Pb/204Pb values of 17.343–17.892. Three galena samples have lead isotope ratios of 208Pb/204Pb from 37.992 to 38.029, 207Pb/204Pb from 15.540 to 15.548, and 206Pb/204Pb from 17.386 to 17.406. The 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204 ratios of three sphalerite minerals range from 37.873 to 37.93, 15.498 to 15.52, and 17.301 to 17.392, respectively.

5. Discussion

5.1. Timing of Ag-Pb-Zn Mineralization

The precise dating of Ag-Pb-Zn mineralization is crucial for understanding the mineralization process, the ore genesis and the metallogenic tectonic setting [60,61,62,63,64]. However, the ore-forming age of the Laoliwan Ag-Pb-Zn deposit has not been constrained yet. Rb-Sr isotopic dating of sulfides proved to be a reliable technique, and successfully used to directly determine the age of ore mineralization [65,66,67]. Previous studies have indicated that Rb-Sr dating on different hydrothermal mineral assemblages is more precise and meaningful than that of a single mineral [68,69]. The sphalerite and pyrite in the Laoliwan Ag-Pb-Zn deposit are two of the most important silver host minerals, suggesting that sphalerite and pyrite Rb-Sr dating can constrain the ore-forming age of the Ag-Pb-Zn deposit. In this study, direct dating of sphalerite and pyrite grains by the Rb-Sr technique yielded an age of 132.8 ± 9.8 Ma (MSWD = 0.44, Figure 6). The age is deemed reliable due to its minimal error and a comparatively low MSWD. The low MSWD value indicates that the isotopic systems of the sphalerite and pyrite grains selected for analysis remained undisturbed by subsequent thermal events [70]. Thus, the isochron age of 132.8 ± 9.8 Ma can be taken to represent the precise timing of mineralization of the Laoliwan Ag-Pb-Zn deposit. The mineralization age of the deposit is close to the Laoliwan granite porphyry (129~137 Ma) in the mining district obtained by Xu et al. [1], suggesting that the magmatic event and the mineralization process are closely related.
Similar ages have also been obtained for other Ag-Pb-Zn deposits in the southern margin of the North China Craton (Figure 1). In the Nannihu ore field, the garnet U-Pb ages of the Luotuoshan Ag-Pb-Zn deposit are 141~140 ± 1 Ma; the monazite U-Pb ages of the Lengshuigou Ag-Pb-Zn deposit are 140~139 ± 3 Ma; and the Re-Os ages of molybdenite from the Nannihu Mo deposit are 144.9 ± 0.7 and 142.8 ± 0.6 Ma [8]. The Shagou and Haopinggou Ag-Pb-Zn deposits in the Xiayu ore field have sericite 40Ar/39Ar plateau ages of 139.8 ± 1.2 Ma and 144.4 ± 1.6 Ma [53]. Li et al. [7,9] obtained sericite 40Ar/39Ar plateau ages of 124 ± 1.2 Ma from the Laodaizhuanggou Ag-Pb-Zn deposit and 115.1 ± 0.9 Ma from the Sanyuangou Ag-Pb-Zn deposit in the Fudian ore field. The zircon U-Pb age of the Donggou Ag-Pb-Zn deposit is 117.8 ± 0.9 Ma, and the Re-Os age of molybdenite from the Donggou Ag-Pb-Zn deposit, Fudian ore field is 117.5 ± 0.8 Ma [7]. Collectively, these ore-forming ages indicate that the early Cretaceous represents a significant period of Ag-Pb-Zn mineralization. Mineralization occurred between 110 Ma and 140 Ma, with a peak period at 130 ± 10 Ma, suggesting that it was constrained by a unified early Cretaceous magmatic–hydrothermal event.

5.2. Sources of Ore-Forming Fluids and Materials

The C-H-O isotopes are effective in constraining the source of ore-forming fluids [61]. The hydrogen and oxygen isotope data of quartz from several Ag-Pb-Zn deposits in the southern margin of the North China Craton are listed in Table 2. The δD and δ18OH2O values of the middle mineralization stage in the Laoliwan Ag-Pb-Zn deposit range from −96.3‰ to −86.7‰ and −1.82‰ to 3.43‰, respectively. In the δ18OH2O vs. δD diagram, H-O isotope data plot within the transitional zone between the magmatic fluid region and the meteoric water line, which is consistent with other nearby deposits, such as the Shagou, Tieluping, Longmendian, Bailugou, and Lengshuibeigou Ag-Pb-Zn deposits (Figure 7), indicating that ore-forming fluids of the Laoliwan Ag-Pb-Zn deposit may be originally derived from magmatic water and were mixed with meteoric water.
The δ18CV-PDB values of nine calcite samples from the late stage and four siderite samples from the early stage of the Laoliwan Ag-Pb-Zn deposit range from −5.6‰ to 0.7‰, showing a relatively narrow variation range. This is similar to carbonates formed in many hydrothermal ore deposits, suggesting that the carbon may have originated from deep sources or from a mixture of CO2 derived from carbonates and organic matter [71]. The δ18OV-SMOW values range from 4.4‰ to 17.4‰, with a relatively wide variation range. In the δ13CPDB vs. δ18OSMOW isotopic diagram, the C-O isotopic compositions predominantly fall within the regions between magmatic carbon and sedimentary organic carbon. The values cluster closer to the magmatic carbon range, similar to those of other Ag-Pb-Zn deposits in the southern margin of the North China Craton. This suggests a mixed origin for the carbon and oxygen in the ore-forming fluids (Figure 8). Studies on the timing of magmatism and mineralization reveal that the intrusion age of the Laoliwan granite porphyry is consistent with the mineralization age of the Laoliwan Ag-Pb-Zn deposit. This implies that the carbon in the calcite and siderite is of magmatic origin, since the wall rocks are predominantly composed of Proterozoic rocks and diorite dykes in the region, the influence of organic sediments can be excluded.
The sulfur isotopic composition of sulfide minerals constitutes a valuable tool for constraining the origin of materials [7,72,73]. The histogram depicting the sulfur isotopic composition of sulfides in the Laoliwan Ag-Pb-Zn deposit (Figure 9A,B) reveals that all the δ34S values are positive and relatively concentrated, exhibiting a tower-like distribution. Nine pyrite samples, seven galena samples, seven sphalerite samples, and one chalcopyrite sample collected from the Laoliwan Ag-Pb-Zn deposit yielded a narrow range of δ34S values (1.9‰–5.9‰) [47], with an average of 3.8‰, that were close to the range of magmatic sulfur (δ34S = 0‰ ± 3‰) [74]. Therefore, this indicates that these sulfides mainly originated from a deep-seated magma source [75,76].
Additionally, the δ34S values of the Laoliwan Ag-Pb-Zn deposit are consistent with those of typical Ag-Pb-Zn deposits in its neighboring areas (Figure 9B). For example, the δ34S values of sulfides in the Lengshuibeigou Ag-Pb-Zn deposit vary from 0.3‰ to 8.1‰, with an average of 3.3‰ [8,14]; in the Luotuoshan deposit, these values range from 0.2‰ to 6.5‰, with an average of 2.6‰ [53]; in the Haopinggou deposit, the δ34S values of sulfides range between 0.3‰ and 6.1‰, with an average of 4.0‰ [53]; and in the Shagou deposit they vary from 1.1‰ to 5.5‰, with an average of 3.6‰, suggesting these deposits could have a similar sulfur source. Compared with metamorphic rocks of the Xiong’er Group (δ34S = 2.5‰–5.4‰, average 4.1‰) [55] and the Taihua Group (δ34S = 1.3‰–5.7‰, average 3.2‰) [55], the sulfides from the Laoliwan deposit tend to have similar δ34S values. Thus, the sulfides have been partially sourced from the metamorphic rocks, and there is a certain inheritance relationship between the Laoliwan deposit and its surrounding rock.
Lead isotopes are utilized to trace the origin of ore-forming metals. Sulfides from the Laoliwan Ag-Pb-Zn deposit yield similar Pb isotope compositions, with 206Pb/204Pb ratios ranging from 17.301 to 17.892, 207Pb/204Pb ratios ranging from 15.498 to 15.560, 208Pb/204Pb ratios ranging from 37.873 to 38.029 (Figure 10). In the 207Pb/204Pb vs. 206Pb/204Pb and 208Pb/204Pb vs. 206Pb/204Pb diagram, all sulfide samples plot between the lower crustal to mantle evolution lines (Figure 10A,B). Notably, the samples in the 207Pb/204Pb vs. 206Pb/204Pb diagram tightly cluster near the Stacey & Kramers (S&K) model curves (Figure 10A). These characteristics suggest that the ore lead originates from deep sources, predominantly reflecting crustal signatures while not excluding minor contamination by mantle-derived materials. In addition, these samples in the Laoliwan Ag-Pb-Zn ores display notably high radiogenic lead isotope ratios, markedly distinct from those in the Xiong’er Group (Figure 10A,B). It is inferred that the lead of the Laoliwan ores does not originate from the Xiong’er Group. The lead isotopes of the Laoliwan Ag-Pb-Zn ores are located within the upper part of the Taihua Group and the lower part of the Yanshanian granitoids in the Xiaoshan region. This implies that the lead in Laoliwan ore deposits shares a similar origin with the Yanshanian granitoids in the Xiaoshan region but does not fully align with the provenance of early Cretaceous granitoids from the same region. It may be associated with the melting modification of the surrounding rocks by the ascending magma, or with the extraction of substances as these fluids percolate through the Taihua Group basement.
The initial ratio of 87Sr/86Sr serves as another highly effective tracer for identifying the source of ore-forming materials [77]. The initial 87Sr/86Sr ratios of the pyrite and sphalerite samples from the Laoliwan Ag-Pb-Zn deposit range from 0.711623 to 0.717344, which are higher than that of the mantle (0.707) [78], but lower than that of the continental crust (0.719), indicating that the ore-forming materials of the Laoliwan Ag-Pb-Zn deposit were mostly originated from the continental crust, with a small amount from the mantle.
Therefore, the ore-forming materials of Ag-Pb-Zn deposits in this region are not derived from the apparently associated wall rocks but originate from deep-seated fluids, exhibiting crust–mantle mixing characteristics. The ore-forming fluids are predominantly magmatic in origin, with minor meteoric water involvement in the mineralization process.

5.3. Ore Genesis and Prospecting Direction

The Laoliwan Ag-Pb-Zn deposit represents a large-scale ore deposit that has been discovered in recent years. Currently, fundamental research in this area remains relatively underdeveloped, and studies on the ore genesis of the Laoliwan Ag-Pb-Zn deposit are limited. Previous studies suggest that the Laoliwan Ag-Pb-Zn deposit in the Xiaoshan district belongs to a porphyry-type system [79], considering the close spatio-temporal relationship between the deposit and the Yanshanian Laoliwan granite porphyry. However, this study reveals some geological and geochemical characteristics indicating that the Laoliwan deposit represents distal, vein-type Ag-Pb-Zn mineralization associated with the periphery of a porphyry system.
The following supplementary lines of evidence support the Laoliwan Ag-Pb-Zn deposit as a distal epithermal deposit associated with magmatic activity. (a) The ore bodies are controlled by the F1 fracture structural belt and their secondary structures. Moreover, a large amount of silver–lead–zinc mineralization and alterations such as sericitization, silicification and kaolinization have developed in the structural belts. (b) The Laoliwan granite porphyry, distant from the fault zones, displays relatively weak silver–lead–zinc mineralization and even lacks alteration. (c) The wall-rock alteration and mineral paragenetic assemblage of the Laoliwan deposit exhibit characteristics typical of medium- to low-temperature conditions. These features are essentially consistent with those of epithermal Ag-Pb-Zn deposits [9,53]. (d) Fluid inclusion thermometry indicates that the ore-forming temperature is below 300 °C [22]. The C-H-O isotopic compositions provide evidence indicating that the ore-forming fluids predominantly originated from magmatic water. (e) The S-Pb composition of sulfides, combined with Sr isotopes, shows that the ore-forming material came from deep-seated magma. (f) The Rb-Sr dating indicates that the Ag-Pb-Zn mineralization in the Laoliwan deposit formed at 132 Ma, which is consistent with age of the Laoliwan intrusion. (g) Comparing the Laoliwan deposit with the Ag-Pb-Zn deposits in the periphery of porphyry molybdenum deposits in the Nannihu and Fudian ore fields, although there are differences in the occurrence and morphology of ore bodies, they are relatively similar in terms of wall-rock alteration types, ore types, and mineral assemblages [7,9,10,14,53]. However, the Laoliwan deposit differs markedly from those in the Xiayu ore field. In the Xiayu ore field, the host rocks are metamorphic rocks of the Taihua Group, and the ore bodies are hosted within large-scale NNE-trending faults, with a comparatively weak spatial association with Mesozoic magmatic rocks [4,17,18,52,80]. Previous studies suggest that the Ag-Pb-Zn deposits in the Xiayu ore field belong to orogenic Ag-Pb-Zn deposits [16,81]. Recently, the discovery of molybdenum ore veins in the deep part of Shagou in the Xiayu ore field may indicate the potential existence of underlying molybdenum deposits and porphyry bodies, which suggests that the molybdenum and silver–lead–zinc mineralization in the area is a product of the same geological event [17,19,82]. Thus, the Laoliwan deposit does not belong to either porphyry-type or orogenic-type deposit; rather, it is classified as a distal epithermal deposit. Porphyry Mo (Cu) deposit and distal Ag-Pb-Zn hydrothermal veins make up a giant magmatic-hydrothermal Mo (Cu)-Pb-Zn-Ag metallogenic system [28,29,31,83,84,85,86,87,88].
The interaction between the North China Block and surrounding plates, combined with the subduction of the Paleo-Pacific Plate, resulted in a transition from a compressional to an extensional tectonic regime at the southern margin of the North China Craton, and triggered lithospheric thinning of the North China Craton during the early Cretaceous [3,5,89,90]. This process resulted in mantle upwelling, large-scale crustal extension and uplift, and intense crust–mantle material exchange and mixing, thereby providing favorable geological settings and material conditions for the ascent of deep-sourced components and their participation in mineralization (Figure 11A). Compared with the deposits in the Xiaoqinling and Xiong’ershan districts, those in the Xiaoshan district are fewer in number and smaller in scale. This may be related to its relatively shallow denudation degree, and it also indirectly indicates that there is still significant prospecting potential in the Xiaoshan region. Regionally, regions with well-developed faults, especially where granite porphyry is present and exhibits significant wall-rock alterations such as sericitization, pyritization, and carbonatization, are considered favorable areas for ore prospecting. Based on the metallogenic model of porphyry molybdenum deposit—skarn Pb-Zn deposit—hydrothermal vein-type Ag-Pb-Zn deposit in the region [7,87], the Ag-Pb-Zn ore veins in the Laoliwan deposit may represent the external end-member of the Mo-Fe-Ag-Pb-Zn metallogenic series [53,87].
The geological, geophysical and geochemical data of the Laoliwan Ag-Pb-Zn deposit indicate its ore-forming body is a deeply buried intrusive body [35,36]. The ore bodies are distributed in the upper section and the peripheral areas of the concealed intrusive body, displaying a mineralization structure characterized by veins within the upper structural belt, explosion breccia in the peripheral contact zone and massive ore bodies at the apex of the intrusive body. The ore-forming temperature, being below 300 °C, indicates characteristics of epithermal magmatic hydrothermal mineralization. Distinct alteration mineral assemblages, including silicification, sericitization, kaolinization, chloritization, and carbonatization, have formed in the intrusive body and surrounding rocks, displaying disseminated and banded distributions. Based on regional metallogenic geological conditions and deposit geological characteristics, it is considered to be a porphyry-type metallogenic system. The metallogenic model of the Laoliwan Ag-Pb-Zn deposit is shown in Figure 11B. The copper grade of the Laoliwan ore bodies exhibits a tendency to increase from the upper to the lower parts [35]. Additionally, Boreholes ZK804 and ZK812 have revealed three molybdenum ore bodies (with Mo grades ranging from 0.04% to 0.20%) in the Zhonghe mining area, which is situated in the north of the Laoliwan mining area. Deep-seated molybdenum mineralization has been identified in this area. There is also potential for the discovery of concealed porphyry Cu-Mo mineralization at depth.

6. Conclusions

Based on geological survey and comprehensive studies of Rb-Sr geochronology and C-H-O-S-Pb isotopes in the Laoliwan Ag-Pb-Zn deposit, the following conclusions are drawn:
  • The Laoliwan Ag-Pb-Zn deposit district is the first large-scale deposit discovered in the shallow-covered eastern Xiaoshan district. The ore bodies mainly occur within the Laoliwan granite porphyry intrusion and are controlled by NW-trending faults. The wall-rock alteration and mineral paragenetic assemblage show typical medium- to low-temperature characteristics.
  • The Rb-Sr isochron age of sulfides (sphalerite and pyrite) is determined to be 132.8 ± 9.8 Ma (MSWD = 0.44). It is interpreted as the timing of Ag-Pb-Zn mineralization occurring in the early Cretaceous.
  • The C-H-O-S-Pb isotopic compositions, combined with the initial ratio of 87Sr/86Sr, indicate that the ore-forming material originated from deep-seated magma.
  • The Laoliwan Ag-Pb-Zn deposit is classified as an epithermal deposit, which formed in a lithospheric thinning tectonic setting related to the subduction of the Paleo-Pacific Plate during the early Cretaceous.
  • The metallogenic model for the Laoliwan Ag-Pb-Zn deposit has been established, and there is potential for the discovery of concealed porphyry Cu-Mo mineralization at depth. Silver–lead–zinc and molybdenum–copper mineralization belong to the same metallogenic system.

Author Contributions

Conceptualization, J.X. and Z.P.; methodology, J.X.; formal analysis and investigation, J.X., Z.P., H.C., P.D., W.T. and R.S.; writing—original draft preparation, J.X., R.J., B.Z. and N.M.; writing—review and editing, J.X., Y.Y. and N.M.; supervision, Z.P.; project administration, J.X.; funding acquisition, Z.P. and H.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Key Research and Development Program of China (grant number 2021YFC2901805), the National Natural Science Foundation of China (grant number 42302079), and the China Geological Survey Project (grant numbers DD20230355, DD20230356, DD20221692, DD20190570 and DD20160052).

Data Availability Statement

The data presented in this study are available upon request from the corresponding author due to internal privacy considerations.

Acknowledgments

The authors extend their gratitude to Zhizhong Chen, Weizhi Sun, Yunzhen Chang, Tianyou Liang, Hongsong Li, and Henan Fuguang Mining Industry Co., Ltd. for supporting this field investigation. We also thank the academic editors and anonymous reviewers for their valuable suggestions and feedback.

Conflicts of Interest

Author Peichao Dings and Ruifeng Shen were employed by the company Henan First Geology and Mineral Survey Institute Co., Ltd. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Figure 1. Geological map of the southern margin of the North China Craton (modified after Xu et al. [1], Li et al. [8], Mao et al. [34]).
Figure 1. Geological map of the southern margin of the North China Craton (modified after Xu et al. [1], Li et al. [8], Mao et al. [34]).
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Figure 2. (A) Geological map of the Xiaoshan district (modified after Li et al. [8]; Xu et al. [1]; Tang et al. [11]); (B) Geological map of the Laoliwan Ag-Pb-Zn deposit (modified after Ding et al. [36]); (C) Geological cross-section along line 11 of the Laoliwan Ag-Pb-Zn deposit (after Ding et al. [36]). 1—Quaternary sediments; 2—Late Cretaceous-Tertiary terrestrial clastic rocks; 3—Meso-Proterozoic carbonates of the Guandaokou Group; 4—Meso-Proterozoic volcanic rocks of the Xiong’ er Group; 5—Archean gneiss and migmatite of the Taihua Group; 6—Fault and its number; 7—Ag-Pb-Zn deposit; 8—Au deposit; 9—Granitoid intrusion; 10—Massive andesite;11—Amygdaloidal andesite; 12—Porphyritic andesite;13—Granite porphyry; 14—Explosion breccia; 15—Tectonic belt; 16—Exploration line.
Figure 2. (A) Geological map of the Xiaoshan district (modified after Li et al. [8]; Xu et al. [1]; Tang et al. [11]); (B) Geological map of the Laoliwan Ag-Pb-Zn deposit (modified after Ding et al. [36]); (C) Geological cross-section along line 11 of the Laoliwan Ag-Pb-Zn deposit (after Ding et al. [36]). 1—Quaternary sediments; 2—Late Cretaceous-Tertiary terrestrial clastic rocks; 3—Meso-Proterozoic carbonates of the Guandaokou Group; 4—Meso-Proterozoic volcanic rocks of the Xiong’ er Group; 5—Archean gneiss and migmatite of the Taihua Group; 6—Fault and its number; 7—Ag-Pb-Zn deposit; 8—Au deposit; 9—Granitoid intrusion; 10—Massive andesite;11—Amygdaloidal andesite; 12—Porphyritic andesite;13—Granite porphyry; 14—Explosion breccia; 15—Tectonic belt; 16—Exploration line.
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Figure 3. Hand specimen and field photographs of representative ores of the Laoliwan Ag-Pb-Zn deposit. (A) Massive ore; (B) Disseminated ore; (C) Veinlet—disseminated ore; (D) Polymetallic sulfide veinlet ore; (E) Carbonate–sulfide veinlet ore; (F) Breccia ore.
Figure 3. Hand specimen and field photographs of representative ores of the Laoliwan Ag-Pb-Zn deposit. (A) Massive ore; (B) Disseminated ore; (C) Veinlet—disseminated ore; (D) Polymetallic sulfide veinlet ore; (E) Carbonate–sulfide veinlet ore; (F) Breccia ore.
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Figure 4. Photomicrographs of mineral assemblages in the Laoliwan Ag-Pb-Zn deposit. (A) Anhedral galena, sphalerite and chalcopyrite coexistence with euhedral–subhedral pyrite; (B) Anhedral chalcopyrite coexists with subhedral cataclastic pyrite; (C) Coarse euhedral–subhedral pyrite cut across by chalcopyrite; (D) Coarse-grained native silver is intergrown with stromeyerite and chalcopyrite. Gn—Galena; Sp—Sphalerite; Py—Pyrite; Ccp—Chalcopyrite; Ag—Silver; Smy—Stromeyerite.
Figure 4. Photomicrographs of mineral assemblages in the Laoliwan Ag-Pb-Zn deposit. (A) Anhedral galena, sphalerite and chalcopyrite coexistence with euhedral–subhedral pyrite; (B) Anhedral chalcopyrite coexists with subhedral cataclastic pyrite; (C) Coarse euhedral–subhedral pyrite cut across by chalcopyrite; (D) Coarse-grained native silver is intergrown with stromeyerite and chalcopyrite. Gn—Galena; Sp—Sphalerite; Py—Pyrite; Ccp—Chalcopyrite; Ag—Silver; Smy—Stromeyerite.
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Figure 5. Paragenetic sequence of the Laoliwan Ag-Pb-Zn deposit.
Figure 5. Paragenetic sequence of the Laoliwan Ag-Pb-Zn deposit.
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Figure 6. Rb-Sr isotope isochron age of sulfides in the Laoliwan Ag-Pb-Zn deposit.
Figure 6. Rb-Sr isotope isochron age of sulfides in the Laoliwan Ag-Pb-Zn deposit.
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Figure 7. δD vs. δ18OH2O isotopic diagram of quartz from the Laoliwan Ag-Pb-Zn deposit (modified after Taylor [51]). The published data on Shagou, Tieluping, Longmengou, Bailugou, and Lengshuibeigou Ag-Pb-Zn deposits are from Han et al. [16]; Franco et al. [15]; Chen et al. [50]; Yang et al. [33]; Wang et al. [14].
Figure 7. δD vs. δ18OH2O isotopic diagram of quartz from the Laoliwan Ag-Pb-Zn deposit (modified after Taylor [51]). The published data on Shagou, Tieluping, Longmengou, Bailugou, and Lengshuibeigou Ag-Pb-Zn deposits are from Han et al. [16]; Franco et al. [15]; Chen et al. [50]; Yang et al. [33]; Wang et al. [14].
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Figure 8. δ13CV-PDB vs. δ18OV-SMOW isotopic diagram of calcite and siderite from the Laoliwan Ag-Pb-Zn deposit (modified after Li et al. [54]). The published data for typical deposits are from [8,9,22,52,53].
Figure 8. δ13CV-PDB vs. δ18OV-SMOW isotopic diagram of calcite and siderite from the Laoliwan Ag-Pb-Zn deposit (modified after Li et al. [54]). The published data for typical deposits are from [8,9,22,52,53].
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Figure 9. S isotope composition for sulfides from the Laoliwan Ag-Pb-Zn deposit. (A) Histogram showing the sulfur isotope compositions of sulfides from the Laoliwan deposit; (B) The δ34S data of sulfides from the Laoliwan deposit and other representative Ag-Pb-Zn deposits in southern margin of the North China Craton. The published data on Nannihu and Xiayu ore fields are from references [8,9,14,47,53,55].
Figure 9. S isotope composition for sulfides from the Laoliwan Ag-Pb-Zn deposit. (A) Histogram showing the sulfur isotope compositions of sulfides from the Laoliwan deposit; (B) The δ34S data of sulfides from the Laoliwan deposit and other representative Ag-Pb-Zn deposits in southern margin of the North China Craton. The published data on Nannihu and Xiayu ore fields are from references [8,9,14,47,53,55].
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Figure 10. (A) Diagrams of 207Pb/204Pb vs. 206Pb/204Pb and (B) 208Pb/204Pb vs. 206Pb/204Pb of ore sulfides in the Laoliwan Ag-Pb-Zn deposit. The evolution curves of mantle, upper crust and lower crust are from Zartman and Doe [56]. S&K is the evolution curve of the Stacey and Kramers [57] model, Pb evolution curve u = 9.735 (A), ω = 36.950 (B). The published data on Pb isotope ratios of whole-rock samples from Xiong’er Group, Taihua Group, and Yanshanian granitoid intrusions in the Xiaoshan region refer to Fan et al. [55]; Ni et al. [58]; Li et al. [59].
Figure 10. (A) Diagrams of 207Pb/204Pb vs. 206Pb/204Pb and (B) 208Pb/204Pb vs. 206Pb/204Pb of ore sulfides in the Laoliwan Ag-Pb-Zn deposit. The evolution curves of mantle, upper crust and lower crust are from Zartman and Doe [56]. S&K is the evolution curve of the Stacey and Kramers [57] model, Pb evolution curve u = 9.735 (A), ω = 36.950 (B). The published data on Pb isotope ratios of whole-rock samples from Xiong’er Group, Taihua Group, and Yanshanian granitoid intrusions in the Xiaoshan region refer to Fan et al. [55]; Ni et al. [58]; Li et al. [59].
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Figure 11. Tectonic evolution and genetic model for the Laoliwan deposit. (A) Schematic diagram showing the geodynamic setting of southern margin of the NCC (modified from Xu et al. [1]; Chao et al. [91]; Li et al. [6]; Mao et al. [92]). (B) Metallogenic model for the exploration of the Laoliwan Ag-Pb-Zn gold deposit. 1—Massive andesite; 2—Amygdaloidal andesite; 3—Porphyritic andesite; 4—Granite porphyry; 5—Orebody; 6—Granite porphyry dike; 7—Breccia orebody; 8—Fault; 9—Migration direction of meteoric water; 10—Migration direction of ore-forming materials; 11—Extent of alteration zone; 12—Pyritization; 13—Chalcopyritization; 14—Sphaleritization; 15—Galenitization; 16—Silicification; 17—Phyllic alteration; 18—Sericitization; 19—Clay mineralization; 20—Epidotization; 21—Chloritization; 22—Carbonatization.
Figure 11. Tectonic evolution and genetic model for the Laoliwan deposit. (A) Schematic diagram showing the geodynamic setting of southern margin of the NCC (modified from Xu et al. [1]; Chao et al. [91]; Li et al. [6]; Mao et al. [92]). (B) Metallogenic model for the exploration of the Laoliwan Ag-Pb-Zn gold deposit. 1—Massive andesite; 2—Amygdaloidal andesite; 3—Porphyritic andesite; 4—Granite porphyry; 5—Orebody; 6—Granite porphyry dike; 7—Breccia orebody; 8—Fault; 9—Migration direction of meteoric water; 10—Migration direction of ore-forming materials; 11—Extent of alteration zone; 12—Pyritization; 13—Chalcopyritization; 14—Sphaleritization; 15—Galenitization; 16—Silicification; 17—Phyllic alteration; 18—Sericitization; 19—Clay mineralization; 20—Epidotization; 21—Chloritization; 22—Carbonatization.
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Table 1. The Rb-Sr isotope data of sulfides in the Laoliwan Ag-Pb-Zn deposit.
Table 1. The Rb-Sr isotope data of sulfides in the Laoliwan Ag-Pb-Zn deposit.
Sample No.MineralsRb
(μg/g)		Sr
(μg/g)		87Rb/86Sr87Sr/86Sr2σ87Sr/86Sr (Isr)
KSD-3Pyrite1.5006.380.68210.7127350.0000250.711448
KSD-8Pyrite1.6906.380.76570.7128010.0000190.711356
KSD-13Pyrite4.1703.943.06640.7173440.0000140.711556
LLW-360Sphalerite0.3993.020.38210.7122570.0000220.711536
KSD-1Sphalerite0.1053.780.08010.7118020.0000190.711651
KSD-2Sphalerite0.1159.590.03470.7116680.0000140.711603
LLW-310Sphalerite0.86722.000.11400.7116230.0000210.711408
Table 2. D-O isotopic data of quartz from the Laoliwan Ag-Pb-Zn deposit.
Table 2. D-O isotopic data of quartz from the Laoliwan Ag-Pb-Zn deposit.
Ag-Pb-Zn DepositsSample No.Mineralization StageMineralsTh
(°C)		δD
(‰)		δ18OMineral
(‰)		δ18OH2O
(‰)		Data Sources
LaoliwanLLW310-5-1Middle (stage II)Quartz300−89.18.31.4this paper
LLW310-5-3Middle (stage II)Quartz300−86.77.20.3
LLW310-5-4Middle (stage II)Quartz300−90.58.61.7
LLW1507-6-1Middle (stage II)Quartz300−94.111.64.7
LLW1507-6-2Middle (stage II)Quartz300−96.312.55.6
ShagouSG071EarlyQuartz236−102.117.27.6[16]
SG112EarlyQuartz236−110.518.79.1
SG153EarlyQuartz236−96.217.17.5
11SG03MiddleQuartz203−100.513.82.3
11SG04MiddleQuartz203−106.2131.5
SG012MiddleQuartz203−88.213.82.3
SG041MiddleQuartz203−100.915.74.2
SG231MiddleQuartz203−104.416.85.3
SG35MiddleQuartz203−75.6153.5
SG391MiddleQuartz203−110.715.43.9
SG311LateQuartz182−8713.91.0
TielupingTS7EarlyQuartz373−8915.69.8[15]
TS8EarlyQuartz373−9615.59.7
TS15EarlyQuartz373−8414.28.4
TS20EarlyQuartz373−9013.77.9
TS17MiddleQuartz233−10913.02
TS13MiddleQuartz210−7310.1−2.5
TS10LateCalcite158−8811.8−0.2
TS11LateCalcite158−6010.5−1.6
TS14LateCalcite158−7410.9−1.2
TS16LateCalcite158−7011.4−0.7
BT3LateQuartz203−7011.5−1.5
BT5LateQuartz203−689.8−3.2
BT10LateQuartz203−608.9−4.1
LongmendianZK1002EarlyQuartz −8315.97.6[50]
ZK1002EarlyQuartz −9214.86.5
ZK301EarlyQuartz −7614.15.8
ZK702EarlyQuartz −8915.16.8
ZK901MiddleQuartz −639.7−3.0
ZK1014MiddleQuartz −818.3−4.4
ZK1014MiddleQuartz −697.4−5.3
ZK2701MiddleQuartz −7611.2−1.5
ZK1002LateQuartz −797.9−8.9
ZK1002LateQuartz −717.1−9.7
ZK301LateCalcite −736.8−10.0
LengshuibeigouS031-2MiddleQuartz229−8012−0.03[14]
S027-5MiddleQuartz209−8313.90.53
S027-21MiddleQuartz255−8012.51.93
LSBG-3MiddleQuartz258−80.112.31.64
LSBG-6MiddleQuartz257−77.415.024.52
LSBG-14MiddleQuartz230−7216.994.97
BailugouBLC-30EarlyQuartz380−8518.714.2[33]
BGL-5EarlyQuartz300−8212.75.8
BLC-11EarlyQuartz340−8112.67.0
BLC-33MiddleQuartz250−8115.06.0
BLC-32MiddleQuartz280−7814.97.3
BLC-13MiddleQuartz330−7612.26.3
BLY-12MiddleQuartz280−7413.45.8
BLC-30LateDolomite250−6715.47.4
BGL-12LateDolomite280−669.83.0
BJD-2LateDolomite250−659.92.0
BLY-21LateDolomite250−6011.43.5
Table 3. C-O isotopic data of quartz from the Laoliwan Ag-Pb-Zn deposit.
Table 3. C-O isotopic data of quartz from the Laoliwan Ag-Pb-Zn deposit.
Ag-Pb-Zn DepositsSample No.Mineralsδ18CV-PDB(‰)δ18OV-SMOW
(‰)		δ18OV-PDB
(‰)		Data Resources
LaoliwanLLWKSD-2-1Calcite0.74.4−25.7this paper
LLWKSD-2-2Calcite0.15.0−25.2
LLWKSD-2-3Calcite−1.35.8−24.4
LLW-73-4Siderite−3.711.6−18.8[22]
LLW-119Siderite−4.712.9−17.5
LLW-123Siderite−4.712.9−17.5
LLW-126Siderite−4.912.9−17.5
LLW-21-2Calcite−5.617.4−13.1
LLW-22-1Calcite−4.314.4−16
LLW-27Calcite−5.412.8−17.6
LLW-K-1Calcite−1.211.2−19.1
LLW-K-2Calcite−0.27.7−22.5
LLW-KD-2Calcite−1.211.5−18.9
ShagouSG52-1Siderite−2.911.2 [8]
SG80Siderite−2.010.9
SC12Siderite−2.611.0
SG57Siderite−2.811.2
SG52-2Ankerite−1.513.6
SG40Ankerite−1.413.8
SG41Ankerite−1.613.4
SG53Calcite−5.114.7
SG55Calcite−5.215.0
TielupingTLP-4Siderite−1.9211.86−18.48[52]
TLP-28-1Siderite−3.0312.26−18.09
TLP-11-2Siderite−2.5612.93−17.44
TLP-38Siderite−2.5713.29−17.09
TLP-76Siderite−2.8513.73−16.67
TLP-2Dolomite−1.0010.78−19.52
TLP-25Dolomite−0.618.73−21.52
TLP-71Calcite−0.988.25−21.98
TLP-38-1Calcite−0.897.93−22.29
HaopinggouHP56Siderite−5.7314.88−15.55[53]
HP57Siderite−5.8214.32−16.09
HP58Siderite−5.0414.56−15.86
HP65Siderite−5.0914.62−15.80
HP68-1Siderite−5.3814.69−15.73
HP76Siderite−5.4514.39−16.02
HP52Ankerite−3.0916.06−14.40
HP68-2Ankerite−5.6617.61−12.90
HP69Ankerite−5.6017.59−12.92
HP71Ankerite−4.9714.20−16.21
HP07Calcite−2.849.62−20.65
HP21Calcite−3.3110.47−19.83
HP61Calcite−1.8411.75−18.59
LaodaizhanggouLD58-1Siderite−6.813−17.4[9]
LD77-1Siderite−5.512.3−18.1
LD78-1Siderite−6.312.5−17.9
LD80-1Siderite−6.512.2−18.1
LD82Siderite−6.512.1−18.3
LD83-1Siderite−6.312.4−18.0
LD10Ankerite−8.113.5−16.9
LD11-1Ankerite−7.814.2−16.2
LD14Ankerite−8.013.9−16.5
LD20Ankerite−7.513.5−16.9
LD77-2Ankerite−3.913.3−17.1
LD78-2Ankerite−5.813.0−17.4
LD80-2Ankerite−7.413.6−16.8
LD83-2Ankerite−9.113.4−17.0
LD09Calcite−6.915.6−14.9
LD11-2Calcite−5.812.2−18.2
LD58-2Calcite−7.414.9−15.5
LD61Calcite−7.614.8−15.6
LD70Calcite−7.914.9−15.6
SanyuangouSY07Calcite−7.6214.2−16.21[53]
SY08-1Ankerite−4.3716.61−13.87
SY08-2Calcite−7.0412.46−17.9
Table 4. Sulfur isotopic compositions of ore sulfides from the Laoliwan Ag-Pb-Zn deposit.
Table 4. Sulfur isotopic compositions of ore sulfides from the Laoliwan Ag-Pb-Zn deposit.
Sample No.Mineralsδ34S (‰)Data Resources
LLWKSD-7Pyrite2.0This study
LLWKSD-12Pyrite4.9
LLW310-6Pyrite4.8
LLW707-2Pyrite3.1
LLW707-1Sphalerite4.7
LLW360-3-2Chalcopyrite5.5
LLW360-1-1Pyrite2.3
LLW360-3-1Galena3.2
LLW360-3-4Sphalerite5.2
LLW310-5-1Galena4.0
LLW310-5-3Sphalerite5.8
LLW310-7Galena3.2
LLW28Galena4.9[47]
LLW114Pyrite3.3
LLW115Pyrite2.4
LLW124Pyrite3.3
LLW127Pyrite3.3
LLW32Galena1.9
LLW136Sphalerite4.0
LLW138Galena2.0
LLW35Sphalerite5.9
LLW40Sphalerite4.1
LLW139Sphalerite3.7
LLW151Galena2.7
Table 5. Lead isotopic compositions of sulfides from the Laoliwan Ag-Pb-Zn deposit.
Table 5. Lead isotopic compositions of sulfides from the Laoliwan Ag-Pb-Zn deposit.
Sample No.Minerals208Pb/204Pb2σ207Pb/204Pb2σ206Pb/204Pb2σ
LLWKSD-7Pyrite37.9530.00615.5600.00217.8920.003
LLWKSD-12Pyrite37.9040.00615.5160.00217.4050.003
LLW310-6Pyrite37.9250.00615.5230.00317.4020.003
LLW707-2Pyrite37.9430.00415.5340.00217.4110.002
LLW707-1Sphalerite37.8730.00415.4980.00217.3010.002
LLW360-1-1Pyrite37.8840.00915.5070.00317.3430.003
LLW360-3-1Galena37.9920.00515.5410.00217.4060.003
LLW360-3-4Sphalerite37.9160.00615.5200.00217.3920.003
LLW310-5-1Galena38.0290.00415.5480.00217.3930.002
LLW310-5-3Sphalerite37.9300.00515.5180.00217.3640.003
LLW310-7Galena37.9980.00515.5400.00217.3860.002
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Xue, J.; Pang, Z.; Chen, H.; Ding, P.; Jia, R.; Tao, W.; Shen, R.; Zhang, B.; Mou, N.; Yang, Y. Genesis of the Laoliwan Ag-Pb-Zn Deposit, Southern Margin of the North China Craton, China: Constrained by C-H-O-S-Pb Isotopes and Sulfide Rb-Sr Geochronology. Minerals 2025, 15, 1122. https://doi.org/10.3390/min15111122

AMA Style

Xue J, Pang Z, Chen H, Ding P, Jia R, Tao W, Shen R, Zhang B, Mou N, Yang Y. Genesis of the Laoliwan Ag-Pb-Zn Deposit, Southern Margin of the North China Craton, China: Constrained by C-H-O-S-Pb Isotopes and Sulfide Rb-Sr Geochronology. Minerals. 2025; 15(11):1122. https://doi.org/10.3390/min15111122

Chicago/Turabian Style

Xue, Jianling, Zhenshan Pang, Hui Chen, Peichao Ding, Ruya Jia, Wen Tao, Ruifeng Shen, Banglu Zhang, Nini Mou, and Yan Yang. 2025. "Genesis of the Laoliwan Ag-Pb-Zn Deposit, Southern Margin of the North China Craton, China: Constrained by C-H-O-S-Pb Isotopes and Sulfide Rb-Sr Geochronology" Minerals 15, no. 11: 1122. https://doi.org/10.3390/min15111122

APA Style

Xue, J., Pang, Z., Chen, H., Ding, P., Jia, R., Tao, W., Shen, R., Zhang, B., Mou, N., & Yang, Y. (2025). Genesis of the Laoliwan Ag-Pb-Zn Deposit, Southern Margin of the North China Craton, China: Constrained by C-H-O-S-Pb Isotopes and Sulfide Rb-Sr Geochronology. Minerals, 15(11), 1122. https://doi.org/10.3390/min15111122

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