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Article

Geochronology and Genesis of the Shuigou Gold Deposit, Qixia-Penglai-Fushan Metallogenic Area, Jiaodong Peninsula, Eastern China: Constraints from SHRIMP U-Pb, 40Ar/39Ar Age, and He-Ar Isotopes

by
Zhenjiang Liu
1,
Shaobo Cheng
2,3,*,
Changrong Liu
4,
Benjie Gu
5 and
Yushan Xue
6
1
School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China
2
International Mining Research Center, China Geological Survey, Beijing 100083, China
3
China Mining News, Beijing 100083, China
4
Shandong Provincial 6th Exploration Institute of Geology and Mineral Resources, Weihai 264200, China
5
School of Earth Resources, China University of Geosciences, Wuhan 430074, China
6
Xi’an Northwest Geological Institute of Nonferrous Metals Co., Ltd., Xi’an 710054, China
*
Author to whom correspondence should be addressed.
Minerals 2025, 15(1), 14; https://doi.org/10.3390/min15010014
Submission received: 3 December 2024 / Revised: 20 December 2024 / Accepted: 25 December 2024 / Published: 26 December 2024
(This article belongs to the Special Issue Rare Metal and Related Deposits: Geology, Geochemistry and Mineralization)
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Abstract

:
The Jiaodong Peninsula is renowned for its significant gold reserves, which exceed 4500 tons. In this study, we conducted zircon SHRIMP U-Pb dating, 40Ar/39Ar geochronology, electron probe microanalysis (EPMA) analysis, and He-Ar isotope analysis on samples from the Shuigou gold deposit located in the Qixia-Penglai-Fushan metallogenic area of central Jiaodong. This quartz vein-type gold deposit is characterized by three mineralization stages: (I) the quartz-pyrite stage, (II) the quartz-polymetallic sulfide stage, and (III) the calcite stage. In stages I and II, gold primarily exists as native gold or electrum. Preliminary analysis suggests that the deposit contains rare critical metals, including bismuth (Bi), tellurium (Te), and antimony (Sb). The Sb is found as pyrargyrite in stage III, while the other critical elements occur as isomorphisms or nanoparticles within host minerals such as pyrite, native gold, and electrum. Geochronology data indicate that the pre-mineralization Guojialing monzogranite formed around 126 ± 1.6 Ma, the syn-mineralization muscovite formed at approximately 125 Ma, and the post-mineralization diorite porphyrite formed at 120.4 ± 1.8 Ma. The 3He/4He ratios of fluid inclusions in the main-stage pyrite range from 0.26 to 1.26 Ra, and the 40Ar/36Ar ratios vary from 383 to 426.6. These findings suggest that the Shuigou gold deposit formed during the destruction of the North China Craton (NCC), similar to other super-large gold deposits in the Jiaodong Mesozoic gold metallogenic province. Gold mineralization has been influenced by mantle, crustal, and meteoric fluids.

1. Introduction

The Jiaodong Peninsula, located in the eastern part of the North China Craton (NCC) (Figure 1a), is the most important gold metallogenetic province in China. Preliminary estimates suggest that proven gold reserves totaling 4500 tons, of which 2700 tons come from deep deposits at depths between 600 and 2000 m [1,2]. Jiaodong is also recognized as the only region in the world where significant gold accumulation occurred billions of years after the host rocks were formed [3]. The gold deposits in this area are primarily found in the Northwest Jiaodong, Qixia-Penglai-Fushan, and Mouping-Rushan Metallogenic Areas (Figure 1b). These deposits exhibit typical characteristics controlled by faults (Figure 1b), mainly influenced by NNE–NE trending faults or interlayer detachment structures, and are classified as “gold-only” type deposits [4]. Recent comprehensive research has confirmed that the critical metals such as Cr, Co, Cd, Rb, Nb, Ta, Hf, W, Sn, REEs, Sb, Bi, and As in the gold deposits exhibit varying degrees of enrichment compared to the average crustal abundances in NCC, with Te, Co, and Cd that can be directly recycled in the Xiadian and Dayingezhuang deposits [5,6].
Precise mica 40Ar/39Ar isotopic dating results indicate that the Jiaodong gold deposits were primarily formed during the Early Cretaceous period. The earliest age recorded in the Dayingezhuang deposit suggests that Mesozoic gold mineralization may have begun around 130 ± 4 Ma [8]. Gold mineralization peaked between 126 and 120 Ma, marked by the formation of gold deposits, including Cangshang (121.3 ± 0.2 Ma) [9], Jiaojia, Xincheng, and Wangershan (121.0 ± 0.4 Ma~119.2 ± 0.2 Ma) [10], as well as Pengjiakuang (120.9 ± 0.4~119.1 ± 0.2 Ma) [11]. The youngest ages of 109.3 ± 0.3 Ma~107.7 ± 0.5 Ma from the Rushan gold deposit indicate that gold mineralization continued until 120~110 Ma [8]. Stable isotope and fluid inclusion studies showed that the low salinity (6~13 wt% NaCl.eqv) and CO2-rich mineralizing fluids are consistent across different regions and depths with δ18OSMOW values of 0.08–8.85‰ and δDSMOW values ranging from −106.48‰ to −48‰ [12,13]. The He-Ar isotope compositions are distributed in the zone between mantle and crust [1]. Various scholars have proposed multiple genetic models to explain the formation of the Jiaodong gold deposits. Fan et al. suggest that the mineralizing fluids originated from magma and are related to the melting of mafic intrusions formed in the Mesozoic-enriched lithospheric mantle [14]. Li et al. propose that the mineralizing fluids were primarily composed of magmatic-hydrothermal fluids from felsic magma mixed with meteoric water, along with mantle-derived fluids [15]. Some scholars have suggested that the Jiaodong gold deposits represent a new type known as “Jiaodong-type” gold deposits [16]. Goldfarb and Santosh argue that the fluids and mineralizing materials of the Jiaodong gold deposits originate from below the crust, possibly from the lithospheric mantle and subducted oceanic crust sediments [3]. This led to the establishment of an oceanic crust subduction model to explain the formation mechanism of the Jiaodong gold deposits. Deng et al. propose a new model for the remobilization of the metasomatized mantle lithosphere in the Jiaodong gold province, suggesting that the upwelling of the asthenosphere triggered the release of gold and sulfur from an enriched and fertilized mantle lithosphere [17]. This process contributed to the formation of auriferous fluids, leading to widespread gold mineralization in the Jiaodong region. Qiu et al. utilized lithium isotopes to demonstrate a strong genetic connection between carbonate metasomatism in the mantle and gold mineralization in the overlying crust in the Jiaodong. While the pre-enrichment of Au in the mantle is essential for the formation of large gold provinces, the oxidation of the lithospheric mantle plays a crucial role in the mobilization of Au [18]. However, most of genetic models are based on data from Northwest Jiaodong, and Mouping-Rushan Metallogenic Areas, with Qixia-Penglai-Fushan Area less considered. More studies of gold deposits in Qixia-Penglai-Fushan Area are needed for the better understanding of gold mineralization in Jiaodong Peninsula, especially when there are other Mesozoic polymetallic mineralization such as tungsten, molybdenum and antimony in the area [19,20].
The Shuigou gold deposit is a quartz vein-type (Linglong-type) gold deposit located in the Daliuhang area of Penglai, within the Qixia-Penglai-Fushan Metallogenic area of central Jiaodong (Figure 1b). This study described the geology and occurrence of gold and critical elements such as Bi, Te, and Sb in the Shuigou gold deposit. Systematic geochronological and geochemical data have been conducted to provide new insights into regional gold mineralization.

2. Regional Geology

The Jiaodong Peninsula is located at the southeastern edge of the NCC. It is bordered to the west by the trans-lithospheric Tan–Lu (Tancheng–Lujiang) Fault and to the south by the Yangtze Craton (Figure 1a). It primarily consists of Precambrian metamorphic basement rocks and Mesozoic igneous rocks (Figure 1b), with a minor presence of Mesozoic sedimentary-volcanic deposits [21,22].
The Precambrian metamorphic basement rocks are primarily composed of Archean supracrustal rocks, tonalite–trondhjemite–granodiorite (TTG) gneisses, Paleoproterozoic granitoid intrusions, high-grade metamorphic Fenzishan and Jingshan Groups, low-grade metamorphic Zhifu Group, Neoproterozoic low-grade metamorphic Penglai Group, and various lenses or sheets of metamorphic mafic-ultramafic rocks. The Archean supracrustal rocks mainly consist of biotite-plagioclase gneiss, biotite leptite, leucoleptite, amphibolite, and banded iron formation. TTG gneisses are found from northern Qixia to southern Laixi–Laiyang. These gneisses have protolith ages of approximately 2.9 Ga, 2.7 Ga, and 2.5 Ga, undergoing amphibolite to granulite facies metamorphism around 2.5 Ga and 1.86 Ga [23,24]. The Jingshan Group is made up of Al-rich gneisses and marbles, while the Fenzishan Group primarily includes pelitic schists, fine-grained paragneisses, marbles, and minor amphibolites. The Zhifu Group consists of quartzite and quartz schists containing muscovite and tourmaline. The Penglai Group includes quartzite, slate, and limestone [25]. Paleoproterozoic granitoids are characterized by both deformed and undeformed varieties, including alkali feldspar granite, albite granite, gneisses, syenogranite, and pegmatitic granite. These granitoids can be categorized into two groups: those formed around 2.2 to 2.1 Ga, which are pre-tectonic, and those from ca. 1.8 Ga, which are post-tectonic [26].
Mesozoic sedimentary-volcanic rocks are found in the Jiaolai basin (Figure 1b), which consists of three main groups, listed from bottom to top: the Laiyang Group, the Qingshan Group, and the Wangshi Group. The Laiyang Group consists of a sequence of sandstone, siltstone, shale, and conglomerate, with some rare interlayers of volcanoclastic rocks. The Qingshan Group is characterized by eruptive cycles that include both volcanic and clastic rocks. Lastly, the Wangshi Group is made up of red beds, along with mafic and ultramafic lavas, sandstones, and conglomerates [27].
Mesozoic magmatism in the Jiaodong region is primarily characterized by the presence of granitoids and dykes. The Mesozoic granitoids developed during three episodes: (1) the Linglong-Kunyushan-Wendeng suite, with zircon U–Pb ages ranging from 160 to 150 Ma; (2) the Guojialing suite, which has zircon U–Pb ages between 130 to 126 Ma; (3) the Weideshan suite, with zircon U–Pb ages from 120 to110 Ma [19,28,29]. The dykes include lamprophyre, diorite, diorite porphyry, dolerite, granodiorite/granite, and gabbro, with ages ranging from 127 to 114 Ma [30].

3. Ore Deposit Geology

The Shuigou gold deposit is a quartz vein-type gold deposit with a reserve exceeding 5 tons of gold. It is situated in Daliuhang, to the northeast of Penglai City (Figure 1b and Figure 2a). The gold deposit district is characterized by well-developed fault structures that trend NNE–NE, including the Shuigou fault, F1 fault, and F2 fault. The primary igneous rocks in the area are the Linglong monzogranite and the Guojialing monzogranite (Figure 2a), which are found on both sides of the Shuigou fault. Additionally, late Yanshanian diorite porphyrite and porphyry, which intersect the gold-bearing quartz veins, are also present.
The ore bodies are primarily located within alteration zones characterized by pyrite-sericite-silicified breccia and quartz veins, which are controlled by NNE–NE trending faults (Figure 2). A total of eleven alteration zones have been identified, with the No. 1 and No. 2 zones being the largest (Figure 2b). The No. 1 alteration zone is controlled by the F1 fault. It has a surface outcrop length of 250 m and a current measured length of 650 m in the adit. The zone ranges from 0.5 m to 2.0 m in width, strikes between 10° to 20°, and dips to the southeast at 58° to 84°. This alteration zone is composed of pyrite-sericite-silicified breccia, which locally contains pyrite-quartz veins. Both the hanging wall and footwall of this zone are made up of Guojialing monzogranite. Gold mineralization varies inconsistently but is more prominent in areas abundant with pyrite-quartz veins, where local gold grades can exceed 20 g/t. The No. 2 alteration zone is controlled by the F2 fault, which has a surface outcrop length of 650 m and a width ranging from 0.5 m to 2.0 m. This zone strikes at an angle of 5° to 15° and dips southeast at 65° to 78°. It consists of pyrite-sericite-silicified breccia and locally contains quartz veins. Both the hanging wall and footwall are composed of Guojialing monzogranite. The gold grades in this zone range from 0.05 g/t to 5.59 g/t.
The primary ore minerals found in the Shuigou gold deposit are native gold, electrum, and pyrite, along with minor amounts of pyrrhotite, sphalerite, galena, and chalcopyrite. The gangue minerals primarily consist of quartz, feldspar, sericite, chlorite, and calcite. The main ore textures observed include crushed, euhedral, subhedral-anhedral, replacement-dissolution, inclusion, filling, and colloform textures. Mineralization occurs in three distinct stages: the quartz-pyrite stage (I), the quartz-polymetallic sulfide stage (II), and the calcite stage (III). Gold is mainly precipitated in stages I and II (Figure 3 and Figure 4).

4. Samples and Analytical Methods

All samples in this study were collected from the underground mine of the Shuigou gold deposit. Thin sections of the host rocks and ores were prepared for petrographic and EPMA analyses. Zircons from the Guojialing monzonite granite and post-mineralization diorite porphyrite were separated and prepared for SHRIMP U-Pb dating. Additionally, muscovite and pyrite were separated from samples representing the main mineralization stage for 40Ar/39Ar geochronology and He-Ar isotope analysis, respectively.

4.1. EPMA Analysis

Spot analyses and element mapping of samples were performed using a JEOL JXA-8230 electron probe microanalyzer manufactured by Japan at the Key Laboratory of Metallogeny and Mineral Assessment, Chinese Academy of Geological Sciences, Beijing, China. The operating conditions for chosen mineral samples were 15 kV accelerating voltage and a beam current of 50 nA, with variable counting times between 10 and 100 s and between 5 and 50 s in the peak and background, respectively. The beam diameter ranged from 1 to 5 μm. Elements Se, As, Cr, S, Pb, Bi, Sb, Cu, Fe, Zn, Te, Mo, Ag, Au, Co, and Ni were analyzed. The operating conditions for element mapping were 15 kV accelerating voltage with 100 nA beam current, 0.5 μm step size, and 50 ms dwell time for qualitative element maps; Ag, As, Au, Bi, Cu, Fe, S, and Te distribution data were collected.

4.2. SHRIMP Zircon U-Pb Dating

Zircon U–Pb dating was carried out using SHRIMP II manufactured by Australia at the Beijing SHRIMP Center, Chinese Academy of Geological Sciences, Beijing, China. A primary 20–30 µm O2– ion beam of 3–6 nA was used to bombard the surfaces of the zircons. Five scans were made for each analysis after a raster time of 120–200 s. Standard zircons for elemental abundance calibration included 91,500 (U = 91 ppm), SL13 (U = 238 ppm), and M257 (U = 840 ppm) [31,32]. TEMORA with a 206Pb/238U age of 417 Ma was used for calibration [33] and was analyzed after every three sample analyses. Common Pb corrections were based on the measured 204Pb contents. Uncertainties for individual analyses are quoted at 1σ, whereas errors for weighted mean ages are quoted at the 95% confidence level.

4.3. 40Ar/39Ar Dating

The mineral separate and reference sample ZBH-25 with an age of 132.9 ± 1.3 Ma [34] were irradiated in the high-flux engineering test reactor (HFETR) facility at the Nuclear Power Institute of China. After a cooling period of three months, the 40Ar/39Ar analyses were performed at the Beijing Research Institute of Uranium Geology. The decay constant used for calculation is 5.543 × 10−10 a−1.

4.4. He-Ar Isotopes

He and Ar isotopes were analyzed at the Stable Isotope Laboratory, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing, China. The ratios were measured by Helix SFT. The 4He signal was received by a Faraday cup. The 3He signal was received by ion multiplier under the condition of 4.5 kv source voltage, 1218 µA current, 15.56 v trap voltage, and 450 µA trap current. The 40Ar and 36Ar were received with a Faraday cup. The 38Ar was received with a multiplier. The ion source voltage and current were 4.5 kv and 454 µA. The trap voltage and trap current are 15.02 v and 200 µA. The standard air 3He/4He, 40Ar/36Ar, and 36Ar/38Ar ratios are 1.4 × 10−6, 295.5, and 5.35, respectively.

5. Analytical Results

5.1. Composition of the Major Ore Minerals

The EPMA analysis data are detailed in Supplementary Table S1, as well as Figure 5 and Figure 6. Major ore minerals measured include pyrite, pyrrhotite, sphalerite, native gold, and electrum.
The stage I pyrite (Py1) and pyrrhotite (Pyr1) samples were analyzed. The Py1 samples (n = 13) contain the following compositions: 45.76–46.69 wt% Fe, 53.07–53.65 wt% S, 0–0.42 wt% As, and negligible amounts of Se, Bi, Te, Co, and Ni. The Pyr1 samples (n = 5) are composed of 59.15–61.11 wt% Fe and 37.99–37.58 wt% S. Additionally, the gold mineral present in stage I is primarily native gold, which consists of 80.49–89.71 wt% Au and 7.54–17.27 wt% Ag.
In stage II, the sphalerite (Sp2) samples (n = 4) contain 59.21–64.29 wt% Zn, 33.22–34.01 wt% S and 2.10–7.12 wt% Fe. The gold mineral in stage II is primarily electrum, comprising 58.26–75.15 wt% Au and 23.00–36.73 wt% Ag.

5.2. Zircon SHRIMP U-Pb Geochronology

Zircon U-Pb results are presented in Table 1 and Figure 7.
The zircon grains from sample DLH2 of the Guojialing monzonite granite are subhedral to euhedral. They can be either stubby or elongated, measuring between 250 and 350 μm in length. In cathodoluminescence (CL) images, these grains display magmatic oscillatory zoning patterns (Figure 7a). A total of 16 analyses were conducted on 16 grains. Thirteen analyses on syn-magmatic domains indicate uranium (U) contents ranging from 202 to 381 ppm, with Th/U ratios between 0.31 and 0.77. These analyses yield a weighted mean 206Pb/238U age of 126 ± 1.6 Ma (MSWD = 1.18) (Figure 7b). Additionally, three inherited domains exhibit ages of 134.4 Ma, 150 Ma, and 163.3 Ma (Figure 7a).
Zircon grains from sample DLH5 of diorite porphyrite are subhedral to euhedral in shape, appearing as either stubby or elongated prisms with lengths ranging from 150 to 400 μm. In CL images, these grains display magmatic oscillatory zoning (Figure 7c). A total of 12 analyses were conducted on the syn-magmatic domain across 12 different grains. The results indicate U contents between 193 and 2552 ppm, with Th/U ratios ranging from 0.77 to 2.44. Additionally, the analyses yield a weighted mean 206Pb/238U age of 120.4 ± 1.8 Ma (MSWD = 0.77) (Figure 7d).

5.3. 40Ar/39Ar Geochronology

The two muscovite samples yield well-defined 40Ar/39Ar plateau ages. Sample 13DLH15 has a plateau age of 125.76 ± 0.52 Ma, based on 83.6% of the released 39Ar, while sample 14DLH20 yields a plateau age of 126.8 ± 0.59 Ma based on 84.7% of the released 39Ar. Additionally, the isochron ages for the two samples are 125.55 ± 0.55 Ma and 125.90 ± 0.69 Ma, respectively. These isochron ages are consistent with the plateau ages within the margin of error (Figure 8 and Table 2).

5.4. He-Ar Isotope Compositions

The He-Ar analysis results indicated that the fluid inclusions in pyrite contain 4He levels ranging from 15.02 to 228.31 × 10−8 cm3 g−1 at standard temperature and pressure (STP). The ratios of 3He/4He range from 0.26 to 1.26 Ra. Additionally, the contents of 40Ar varies from 14.69 to 31.62 × 10−8 cm3 STP g−1, with 40Ar/36Ar ratios between 383 and 426.6. All samples demonstrate high F 4He values, ranging from 1459 to 3789 (Table 3) [35].

6. Discussions

6.1. The Timing of Gold Mineralization at the Shuigou Deposit

The formation of gold deposits in the Jiaodong region primarily took place during the Mesozoic period, as mentioned in the introduction. In the Qixia-Penglai-Fushan metallogenic area, most gold deposits are concentrated in the northern Daliuhang ore field and the southern Qixia ore field (Figure 1b). Besides the Shuigou gold deposit analyzed in this paper, over 30 gold deposits have been identified in the Daliuhang area, including Heilangou, Menlou, Ankou, Qijiagou, and Qiangjiagou. Among these, the Heilangou gold deposit is large-scale, while the others are medium to small in scale. The deposits are predominantly of the quartz vein type, with a few classified as alteration rock types. Although the deposits are not large, they feature high ore grades and often contain visible gold [36]. Rb-Sr isotope dating of pyrites from the Penglai gold field indicates an isochron age of 122.3 ± 3.1 Ma for the Hexi deposit and 117.8 ± 6.5 Ma for the Heilangou and Daliuhang deposits [37]. In the southern region, the Qixia gold field generally contains small-scale ore deposits, but recent discoveries include the Hushan large-scale alteration rock-type gold deposit. Monazite U-Pb dating shows that mineralization in this deposit began around 120 Ma [38].
In this study, the 40Ar/39Ar dating of hydrothermal sericite indicates that the Shuigou gold deposit formed around 125 Ma. The mineralization age can be further refined by the chronology of the pre-mineralization Guojialing monzogranite, which is dated at 126 ± 1.6 Ma, and the post-mineralization diorite porphyrite, dated at 120.4 ± 1.8 Ma. When compared to the ages of other large and super-large gold deposits in the Jiaodong region, it can be concluded that the Shuigou gold deposit formed during the regional peak of gold mineralization.
Additionally, based on the crosscutting relationships and ages of ore veins and dykes, a mineralization age between 129.7 Ma and 129.3 Ma has been established for the adjacent Shijia gold deposit, which predates the mineralization observed in this study [39]. We propose that these ages suggest a relatively extended period of mineralization in the Penglai area, which began at ca. 130 Ma, which is similar to the earliest gold event in the Dayingezhuang deposit and continued until the peak mineralization period of the Jiaodong Peninsula.

6.2. Occurrence of Gold and Trace Elements

Previous studies have confirmed that most of the gold in the Jiaodong Peninsula is present as discrete native gold and electrum grains, which are largely sited in fractures at all scales in ore or gangue minerals such as pyrite, galena and quartz [40,41]. The microscopic photographs in this study show that the native gold and electrum grains of the Shuigou deposit mainly occur as (1) fissure gold in the fractures of minerals such as pyrite, quartz, and sphalerite (Figure 3f,g); (2) intergranular gold between minerals such as pyrite, sphalerite, and quartz (Figure 3i); and (3) inclusion gold in pyrite, quartz, sericite, and galena (Figure 3h). Further EPMA results show that the major ore minerals such as pyrite, chalcopyrite, galena, pyrrhotite, and sphalerite barely have any gold, which indicates that little gold is lattice bounded (Supplementary Table S1 and Figure 5 and Figure 6). Combined with the microscopic observation and EPMA analysis, it can be concluded that the gold in the Shuigou deposit shares similar occurrence characteristics to other gold deposits in the Jiaodong Peninsula.
As, Bi, and Te minerals like arsenopyrite, calaverite, hessite, joseite, altaite, and aikinite have been documented in other Jiaodong gold deposits in Northwest Jiaodong and the Mouping-Rushan Metallogenic Areas [42,43,44,45], but none were identified in this study.
In contrast, EPMA spot analyses indicate that Py1 and Py2 (n = 14) contain arsenic levels ranging from 0 to 0.417 wt%, Pyr1 (n = 5) shows values between 0.011 and 0.070 wt% As Sp2 (n = 5) demonstrates arsenic content from 0 to 0.034 wt% As (see Supplementary Table S1). These findings suggest that arsenic primarily occurs in pyrite as an isomorphic substitution. Moreover, EPMA mapping of pyrite indicates that As is unevenly distributed within the mineral (Figure 5.). The distribution of Bi and Te aligns closely with that of gold. EPMA mapping reveals that the Bi and Te content increase in areas where native gold and electrum are present (see Figure 5 and Figure 6). The composition of Bi and Te in the gold minerals ranges from 0.249 to 0.628 wt% Bi and from 0 to 0.115 wt% for Te. EPMA analyses indicate that the pyrite, pyrrhotite, and sphalerite from different stages of mineralization contain minimal amounts of Bi and Te (refer to Supplementary Table S1). These findings suggest that Bi and Te may exist as nanoparticles either on the surface or within the fissure of the gold minerals [46].
Au-Sb deposits are typically found in regions where orogenic gold deposits have formed [47]. However, no Sb mineralization has been reported in Northwest Jiaodong and Mouping-Rushan Metallogenic Areas, except for the Chakuang Au-Sb deposit in Yantai. The fault-controlled ore bodies and mineralization age of the Chakuang deposit are consistent with those of other Jiaodong gold deposits, with antimony primarily occurring as stibnite [20]. It is worth noting that the antimony mineral was first confirmed in a gold deposit in the Penglai area. In this study, we confirm the presence of pyrargyrite, which developed in the stage III calcite veins of the Shuigou gold deposit. The observed presence of antimony in both the Chakuang and Shuigou deposits suggests a potential for antimony metallogenesis within the Qixia-Penglai-Fushan area of the central Jiaodong Metallogenic Province.

6.3. Source of Ore-Forming Fluids

Fluid inclusions trapped in pyrite can preserve their noble gas compositions, such as helium (He) and argon (Ar), for up to a hundred million years. This makes them increasingly valuable for tracing ore-forming fluids [48,49,50]. There are three major reservoirs of helium on Earth: (1) the mantle, which has a 3He/4He ratio of 6–9 Ra; (2) the continental crust, with a 3He/4He ratio of 0.01–0.05 Ra; and (3) the atmosphere, where the 3He/4He ratio is 1 Ra.
Due to the continuous escape of atmospheric helium into space, its abundance in the atmosphere is significantly lower than that in the mantle and crust. As a result, the influence of meteoric water on mantle and crust-derived fluids is usually negligible. Notably, the 3He/4He ratios of mantle-derived fluids can be nearly three orders of magnitude higher than those of fluids originating from the crust, making the helium composition a sensitive isotopic indicator of mantle contributions [35].
The high values of F4 helium ranging from 1459 to 3789 observed in this study indicate that the concentrations of 4He in the ore-forming fluids are three orders of magnitude greater than those found in meteoric water. Assuming that the detected 36Ar originates entirely from meteoric water, there would be only approximately 0.02 × 10−8 cm3 STP g−1 of 4He from meteoric water. This suggests that the influence of meteoric water on the ratios of 3He/4He is negligible. The 3He/4He ratios from the Shuigou gold deposit range from 3.64 × 10−7 to 1.76 × 10−6 (0.26–1.26 Ra). These ratios fall within the range between the mantle helium and crustal helium lines when plotted on the 3He vs. 4He and 3He/4He vs. 40Ar/36Ar diagrams (Figure 9a).
The 40Ar/36Ar ratios range from 383.0 to 426.6, which are similar to the meteoric water ratios of 295.5. This suggests the involvement of meteoric water (see Figure 9b). By analyzing the He-Ar isotope compositions of the Shuigou gold deposit, we can conclude that the mineralization event was influenced by contributions from mantle, crustal, and meteoric fluids.
Published isotopic data for He-Ar suggest that most of the gold deposits in the Jiaodong area exhibit 3He/4He ratios typical of mantle-crust mixing, along with 40Ar/36Ar ratios that are equal to or higher than those found in meteoric water [1,51]. Our findings indicate that the He-Ar isotopic compositions are consistent with those of other gold deposits in the Jiaodong Peninsula.

6.4. Ore Genesis

Based on the geological, geochronological, and isotopic data from this study, it is suggested that the Shuigou gold deposit, along with other gold deposits in the Jiaodong Peninsula, formed in a similar tectonic environment marked by significant crust–mantle interaction [1]. It is generally accepted that the NCC underwent craton destruction during the Mesozoic era [21]. This process resulted in the removal or replacement of over 100 km of lithosphere mantle, leading to intensive magmatism and ductile deformation within the crust [52,53].
The subduction of the Paleo-Pacific (Izanagi) Plate is considered the main tectonic driver behind the Mesozoic geodynamics of the eastern NCC [54]. The onset of this subduction likely began in the Early to Middle Jurassic period, resulting in the metasomatism of the upper NCC subcontinental lithospheric mantle (SCLM) [55]. The rollback of the Paleo-Pacific (Izanagi) Plate is believed to have triggered craton destruction around 140 Ma. An upwelling of the asthenospheric mantle initially caused the thinning of the lithosphere, which was subsequently heated, generating mafic and felsic magmatism [56].
The craton destruction in the Jiaodong Peninsula reached its peak between 130 and 120 Ma, characterized by intense arc-like dykes, volcanic rocks, and the mixing of mafic and felsic granodiorite [19,57,58]. This period was also marked by the replacement of the metasomatized NCC SCLM with the juvenile lithospheric mantle. The ore fluids from this enriched lithospheric mantle ascended along favorable NE- to NNE-trending faults, leading to the formation of the Shuigou gold deposit [59].

7. Conclusions

(1)
The Shuigou gold deposit was formed at ca. 125 Ma, aligning with the peak period of gold mineralization in the Jiaodong region.
(2)
The He-Ar analysis of fluid inclusions in the main-stage pyrite indicates that the fluids involved in the gold mineralization event originated from the mantle, the crust, and meteoric sources.
(3)
The formation of the Shuigou gold deposit occurred in the context of the destruction of the North China Craton (NCC).

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min15010014/s1, Table S1: EMPA results of significant ore minerals from the Shuigou gold deposit.

Author Contributions

Methodology, S.C.; software, B.G.; validation, Y.X.; formal analysis, S.C. and Z.L.; investigation, Z.L., S.C., C.L. and Y.X.; writing—original draft preparation, S.C. and B.G.; writing—review and editing, Z.L. and S.C.; visualization, Y.X.; supervision, Z.L.; project administration, Z.L.; funding acquisition, Z.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was jointly funded by the National Natural Science Foundation of China (Grant No. 92062219) and the China Geological Survey project (grant No. DD20230568).

Data Availability Statement

The original contributions presented in the study are included in the article/Supplementary Materials.

Acknowledgments

We thank the chief editor and the anonymous reviewers for their constructive reviews, which have greatly improved our manuscript.

Conflicts of Interest

Author Yushan Xue were employed by the Xi’an Northwest Geological Institute of Nonferrous Metals 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. (a) Tectonic location of the Jiaodong Peninsula; (b) Simplified geological map of the Jiaodong Peninsula, showing the distribution of major tectonic units, Mesozoic igneous rocks, faults, and Au deposits (modified from [7]). The division of the Northwest Jiaodong, Qixia-Penglai-Fushan, and Mouping-Rushan Metallogenic Areas is based on [2].
Figure 1. (a) Tectonic location of the Jiaodong Peninsula; (b) Simplified geological map of the Jiaodong Peninsula, showing the distribution of major tectonic units, Mesozoic igneous rocks, faults, and Au deposits (modified from [7]). The division of the Northwest Jiaodong, Qixia-Penglai-Fushan, and Mouping-Rushan Metallogenic Areas is based on [2].
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Figure 2. (a) Geological sketch map of the Shuigou gold deposit; (b) cross-section of Exploration Line No. 0 in the Shuigou gold deposit.
Figure 2. (a) Geological sketch map of the Shuigou gold deposit; (b) cross-section of Exploration Line No. 0 in the Shuigou gold deposit.
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Figure 3. Mine shaft outcrop, hand specimen and microscopic photographs showing the ore texture and structure of the Shuigou Au deposit. (a) Gold-bearing quartz vein cutting the beresite and Guojialing monzogranite. (b) Hand specimens of Guojialing monzogranite. (c) Hand specimens of beresite. (d,e) Hand specimens of stages I and II. (f–h) Photomicrograph of a polished thin section of stage I. (i,j) Photomicrograph of a polished thin section of stage II. (k) Photomicrograph of a polished thin section of stage III. (l) Photomicrograph of a polished thin section of stage I epigenetic oxidized ore. Abbreviations: Arn—argentite, Au—native gold or electrum, Ccp—chalcopyrite, Cv—covellite, Gn—galena, Py—pyrite, Po—pyrrhotite, Pyr—pyrargyrite, Q—quartz, Ser—sericite, and Sp—sphalerite. The diameter of the coin is 19 mm.
Figure 3. Mine shaft outcrop, hand specimen and microscopic photographs showing the ore texture and structure of the Shuigou Au deposit. (a) Gold-bearing quartz vein cutting the beresite and Guojialing monzogranite. (b) Hand specimens of Guojialing monzogranite. (c) Hand specimens of beresite. (d,e) Hand specimens of stages I and II. (f–h) Photomicrograph of a polished thin section of stage I. (i,j) Photomicrograph of a polished thin section of stage II. (k) Photomicrograph of a polished thin section of stage III. (l) Photomicrograph of a polished thin section of stage I epigenetic oxidized ore. Abbreviations: Arn—argentite, Au—native gold or electrum, Ccp—chalcopyrite, Cv—covellite, Gn—galena, Py—pyrite, Po—pyrrhotite, Pyr—pyrargyrite, Q—quartz, Ser—sericite, and Sp—sphalerite. The diameter of the coin is 19 mm.
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Figure 4. Mineralization stages and paragenetic sequence of the Shuigou gold deposit.
Figure 4. Mineralization stages and paragenetic sequence of the Shuigou gold deposit.
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Figure 5. EPMA maps of ore minerals from mineralization stage I. The mapped area is pyrite with gold minerals and chalcopyrite.
Figure 5. EPMA maps of ore minerals from mineralization stage I. The mapped area is pyrite with gold minerals and chalcopyrite.
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Figure 6. EPMA maps of ore minerals from mineralization stage II. The main mineral is sphalerite with chalcopyrite blebs and pyrite. Gold minerals are isolated or in sphalerite.
Figure 6. EPMA maps of ore minerals from mineralization stage II. The main mineral is sphalerite with chalcopyrite blebs and pyrite. Gold minerals are isolated or in sphalerite.
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Figure 7. Representative CL images (a,c)and concordia diagrams (b,d) of zircon grains from the Shuigou gold deposit. The dashed-line ellipses labeled 12, 13, and 16 are inherited zircons.
Figure 7. Representative CL images (a,c)and concordia diagrams (b,d) of zircon grains from the Shuigou gold deposit. The dashed-line ellipses labeled 12, 13, and 16 are inherited zircons.
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Figure 8. 40Ar/39Ar plateau and isochron ages for muscovite from the Shuigou gold deposit.
Figure 8. 40Ar/39Ar plateau and isochron ages for muscovite from the Shuigou gold deposit.
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Figure 9. (a) Diagrams of 3He vs. 4He and (b) 3He/4He vs. 40Ar/36Ar for fluid inclusions in the main-stage pyrites from the Shuigou gold deposit.
Figure 9. (a) Diagrams of 3He vs. 4He and (b) 3He/4He vs. 40Ar/36Ar for fluid inclusions in the main-stage pyrites from the Shuigou gold deposit.
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Table 1. SHRIMP U-Pb data for zircons from the Shuigou gold deposit.
Table 1. SHRIMP U-Pb data for zircons from the Shuigou gold deposit.
SpotU
(ppm)		Th
(ppm)		Th/U206Pb *
(ppm)		207Pb */206Pb *±%207Pb */235U *±%206Pb */238U *±%206Pb/238U Age
DLH2
DLH2-12641140.454.570.050020.00.138021.00.01992.4126.8 ± 3.0
DLH2-23812540.696.490.030037.00.078037.00.01902.3121.4 ± 2.8
DLH2-32311730.774.090.048034.00.134034.00.02012.9128.2 ± 3.6
DLH2-42521030.424.280.054030.00.145030.00.01942.9124.1 ± 3.5
DLH2-52921300.465.280.043027.00.121027.00.02042.3130.4 ± 3.0
DLH2-6202610.313.430.052818.00.142018.00.01952.4124.5 ± 2.9
DLH2-73791560.426.400.05388.10.14408.30.01941.9124.1 ± 2.4
DLH2-82621120.444.660.049021.00.137021.00.02012.5128.3 ± 3.2
DLH2-102911170.425.120.033037.00.090037.00.01982.7126.4 ± 3.4
DLH2-112941100.395.020.040820.00.109020.00.01932.2123.3 ± 2.7
DLH2-143341110.345.400.06537.60.17107.80.01902.0121.2 ± 2.4
DLH2-17245870.374.350.045024.00.124025.00.02022.3128.7 ± 3.0
DLH2-182631130.444.700.044621.00.125021.00.02032.3129.6 ± 2.9
DLH2-12 16,61211360.07343.000.05162.50.16773.10.02361.7 150 ± 2.6
DLH2-13 152640.443.440.062023.00.219023.00.02572.9 163.3 ± 4.6
DLH2-16 2691270.494.920.04849.10.14109.40.02112.0 134.4 ± 2.7
DLH5
DLH5-1255232621.3239.800.04671.80.11673.10.01812.5115.7 ± 2.9
DLH5-23753450.956.010.046210.00.118010.00.01862.7118.5 ± 3.1
DLH5-31933822.043.240.04774.80.12845.50.01952.7124.6 ± 3.3
DLH5-5125712020.9920.100.04763.50.12244.30.01862.6119.1 ± 3.0
DLH5-73023281.125.230.047620.00.125020.00.01912.9121.9 ± 3.5
DLH5-84193900.966.970.04803.90.12724.70.01922.6122.8 ± 3.2
DLH5-34046231.596.580.04704.60.12205.30.01882.6120.2 ± 3.1
DLH5-103944701.236.660.04893.30.13284.20.01972.6125.7 ± 3.2
DLH5-122792620.975.120.096052.00.250052.00.01923.2122.3 ± 3.9
DLH5-133572680.775.770.04985.20.12925.80.01882.6120.1 ± 3.2
DLH5-143324481.395.300.05234.00.13394.90.01862.8118.5 ± 3.3
DLH5-155194280.858.400.04733.40.12254.30.01882.6119.9 ± 3.1
Note: (1) common lead corrected using 204Pb; (2) 206Pb * is radiogenic lead; (4) age in Ma.
Table 2. 40Ar-39Ar step-heating geochronology data for muscovite from the Shuigou gold deposit.
Table 2. 40Ar-39Ar step-heating geochronology data for muscovite from the Shuigou gold deposit.
Heating StepT (°C)(40Ar/39Ar)m(36Ar/39Ar)m(37Ar/39Ar)m40Ar(%)F (40Ar*/39Ar)39Ar (×10−14 mol)39Ar (Cum.) (%)Age ± 1σ (Ma)
Sample: 14DLH20, weight = 20.4 mg, J = 0.004130
170022.03300.02711.119764.0814.13220.491.07103.3 ± 1.3
280022.19640.02010.250073.3816.29133.858.48118.6 ± 1.0
385018.20240.00400.299693.5917.03915.0311.09123.8 ± 0.63
490017.67570.00180.305697.1217.17047.0715.59124.7 ± 0.61
595017.58760.00120.230398.0117.24049.0920.05125.2 ± 0.61
6100017.64950.00110.281298.2017.33578.9619.77125.9 ± 0.62
7105017.51980.00120.251398.0117.17536.8915.20124.8 ± 0.61
8110019.20770.00280.142795.6818.38041.373.02133.2 ± 0.66
9120020.94900.00440.389193.9619.68932.605.73142.4 ± 0.72
Sample: 13DLH15, weight = 20.3 mg, J = 0.004198
170014.19790.00562.797690.0512.81521.382.4895.4 ± 0.59
280018.79680.00930.686485.6416.10777.1412.87119.1 ± 0.71
385017.03250.00010.020299.9017.01617.2713.11125.6 ± 0.61
490016.99520.00010.031199.8716.973913.2423.86125.3 ± 0.61
595016.98680.00010.021599.8616.96269.0816.37125.3 ± 0.61
6100017.03210.00010.048199.9117.01792.835.10125.6 ± 0.61
7110017.18570.00060.070298.9417.004611.1620.13125.6 ± 0.61
8115017.50680.00100.142698.4217.23252.785.02127.2 ± 0.62
9120019.15140.00332.380595.9418.41140.591.06135.6 ± 0.77
Table 3. The He-Ar compositions of pyrites from the Shuigou gold deposit.
Table 3. The He-Ar compositions of pyrites from the Shuigou gold deposit.
Sample4He
(10−8 cm3 STP/g)		3He/4He
(Ra)		40Ar
(10−8 cm3 STP/g)		40Ar/36Ar40Ar *
(10−8 cm3 STP/g)		40Ar */4HeF 4He
DLH1128.310.2616.57383.03.790.133789
DLH1315.020.9714.69408.74.070.272420
DLH1818.671.2631.62426.69.720.521459
Note: (1) 1 Ra = 1.4 × 10−6. (2) 40Ar * is radiogenic 40Ar given all of the Ar come from the fluid inclusions; 40Ar * = 40Ar−295.5 × 36Ar. (3) F 4He = (4He/36Ar sample/(4He/36Ar) air, (4He/36Ar)air = 0.1727.
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Liu, Z.; Cheng, S.; Liu, C.; Gu, B.; Xue, Y. Geochronology and Genesis of the Shuigou Gold Deposit, Qixia-Penglai-Fushan Metallogenic Area, Jiaodong Peninsula, Eastern China: Constraints from SHRIMP U-Pb, 40Ar/39Ar Age, and He-Ar Isotopes. Minerals 2025, 15, 14. https://doi.org/10.3390/min15010014

AMA Style

Liu Z, Cheng S, Liu C, Gu B, Xue Y. Geochronology and Genesis of the Shuigou Gold Deposit, Qixia-Penglai-Fushan Metallogenic Area, Jiaodong Peninsula, Eastern China: Constraints from SHRIMP U-Pb, 40Ar/39Ar Age, and He-Ar Isotopes. Minerals. 2025; 15(1):14. https://doi.org/10.3390/min15010014

Chicago/Turabian Style

Liu, Zhenjiang, Shaobo Cheng, Changrong Liu, Benjie Gu, and Yushan Xue. 2025. "Geochronology and Genesis of the Shuigou Gold Deposit, Qixia-Penglai-Fushan Metallogenic Area, Jiaodong Peninsula, Eastern China: Constraints from SHRIMP U-Pb, 40Ar/39Ar Age, and He-Ar Isotopes" Minerals 15, no. 1: 14. https://doi.org/10.3390/min15010014

APA Style

Liu, Z., Cheng, S., Liu, C., Gu, B., & Xue, Y. (2025). Geochronology and Genesis of the Shuigou Gold Deposit, Qixia-Penglai-Fushan Metallogenic Area, Jiaodong Peninsula, Eastern China: Constraints from SHRIMP U-Pb, 40Ar/39Ar Age, and He-Ar Isotopes. Minerals, 15(1), 14. https://doi.org/10.3390/min15010014

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