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Article

Contrasts in Two-Stage Superimposed Magmatism of the Shizhuzi Magmatic Complex-Mo-Cu-Au System, Liaodong Peninsula, North China Craton

by
Jinjian Wu
1,2,
Jinzhong Yang
1,
Jinhui Yang
2,3 and
Qingdong Zeng
2,3,*
1
China Aero Geophysical Survey and Remote Sensing Center for Natural Resources, Beijing 100083, China
2
State Key Laboratory of Lithospheric and Environmental Coevolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
3
College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
*
Author to whom correspondence should be addressed.
Minerals 2025, 15(6), 631; https://doi.org/10.3390/min15060631
Submission received: 13 May 2025 / Revised: 31 May 2025 / Accepted: 5 June 2025 / Published: 10 June 2025
(This article belongs to the Special Issue Mineralogy of Porphyry Systems: Genesis, Exploration, and Applications)
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Abstract

The North China Craton (NCC) experienced extensive destruction and modification of its subcontinental lithospheric mantle during the Mesozoic, a period marked by intensive tectonism, magmatism, and mineralization. Among the key manifestations of this event are the Shizhuzi magmatic complex (SMC) and related Mo-Cu-Au deposits in the Liaodong Peninsula. This study presents new zircon U-Pb ages and Hf isotope data, along with whole-rock major and trace element geochemical data. Meanwhile, by incorporating published datasets, the magmatism and mineralization of the SMC are discussed. Two-stage magmatic activity is identified in the SMC as follows: (1) Stage I (130–126 Ma) associated with mineralization, and (2) Stage II (121–117 Ma), both corresponding to the peak destruction of the NCC. The mineralized granitoids exhibit I-type affinities and formed in an extension setting. Quartz diorites within this suite were derived from the partial melting of an enriched mantle source, and the high-temperature thermal underplating associated with this process subsequently triggered partial melting of the basaltic lower crust, leading to the generation of granodiorites and monzonitic granites. These rocks experienced limited fractional crystallization (dominated by plagioclase + biotite) and are linked to Mo-Cu-Au mineralization. In contrast, the non-mineralized granitoids are high-K calc-alkaline, peraluminous A-type granites, which developed in an extremely extensional tectonic setting. They were derived from partial melting of ancient lower crust and display characteristics of highly fractionated granites, having undergone extensive crystallization differentiation involving plagioclase + K-feldspar during magmatic evolution. The mineralized and non-mineralized granitoids exhibit distinct differences in lithology, major/trace element characteristics, Hf isotopes, and degree of fractional crystallization. Our proposed two-stage magmatic model—coupled with a mineralization phase—provides significant insights into both magmatic processes and metallogenesis in the Liaodong Peninsula. It further offers key perspectives into the Early Cretaceous decratonization of the NCC in terms of its tectonic–magmatic–mineralization evolution.

1. Introduction

The North China Craton (NCC), the largest and most ancient craton in China (Figure 1a), achieved final cratonization and tectonic stability at approximately 1.85 billion years ago [1,2]. However, during the Mesozoic, the eastern NCC experienced profound modifications in both thickness and composition of its subcontinental lithospheric mantle [3,4,5], which in turn sparked widespread tectonic activity [6,7], intense magmatism [8], and the large-scale mineralization of gold and other metals [9,10,11,12], which can be termed as decratonization or craton destruction [13]. The Early Cretaceous marks the peak period of decratonization for the NCC, a phenomenon widely attributed to the subduction of the Paleo-Pacific plate [13,14]. The Liaodong Peninsula (Figure 1) stands as the most exemplary manifestation of this decratonization process within the NCC.
The Liaodong Peninsula extensively produced magmatic rocks, fault structures, and Au-Pb-Zn deposits during the Mesozoic [15]. Previous studies have indicated that the ore deposits in the Liaodong Peninsula were mainly formed during 130–126 Ma and had a close genetic relationship with the coeval igneous rocks, and so can be regarded as magmatic hydrothermal deposits [15,16,17,18,19,20]. The Shizhuzi magmatic complex represents a newly discovered Mo-Cu-Au system associated with the magmatic complex, featuring both diverse rock types and uncommon mineralization styles within the Liaodong Peninsula [16] (Figure 1b and Figure 2). The Shizhuzi magmatic complex (SMC) consists of a series of intermediate–felsic intrusive rocks, including quartz diorite, granodiorite (Dongbeigou), and monzonitic granite and dioritic porphyrite, which are mineralized granitoids (Figure 2).Ore deposits and occurrences are found within and adjacent to the mineralized granitoids, including the Shawogou Au deposit in the southwest, the Dongbeigou Mo deposit in the northwest, and the Wanbao Mo-Cu deposit in the east. All three types of deposits are predominantly associated with granodiorite. Moreover, the Dongbeigou Mo deposit is related to the monzonitic granite and cryptoexplosion breccia, and the Wanbao Mo-Cu deposit is related to the quartz diorite and banded marble. The Dongbeigou Mo deposit, Shawogou Au deposit, and Wanbao Cu-Mo deposit are all magmatic-hydrothermal in origin and genetically related to the Shizhuzi magmatic complex. The Au deposit is predominantly quartz-vein type, the Mo deposit mainly occurs as disseminated/stockwork veins and cryptoexplosive breccia type, while the Cu mineralization is characterized by skarn-type and quartz-vein assemblages [16,17,18,19]. However, minor late granitoids are not associated with mineralization and occur on the SMC, which are non-mineralized granitoids, such as quartz porphyry, porphyritic granite, and granodiorite (Wanbao). The genesis and evolution of various rock types within the SMC, as well as their genetic associations with the Mo-Cu-Au deposits, are key scientific issues. A more comprehensive investigation of the SMC is essential to better constrain the lithospheric processes and the petrogenesis of the magmatic rocks that contributed to its formation. The geochemical distinction of the mineralized and non-mineralized granitoids is the crucial key to understanding the evolution of the magma and mineralization in decratonization settings.
This study presents new comprehensive data on the petrology, geochronology, major and trace elemental composition, and Hf isotopic geochemistry of quartz porphyry, granodiorite (Wanbao), and porphyritic granite from the SMC. In addition, we incorporated the data on monzonitic granite, quartz diorite, and granodiorite (Dongbeigou) from the SMC published by Wu et al. [16]. These data are utilized to constrain the age, magma source, and evolution of the SMC, thereby elucidating its petrogenesis and its connection to Mo-Cu-Au mineralization. The geochemical characteristics of the mineralized and non-mineralized rocks of the two stages were compared, revealing significant differences between them. Our results provide valuable insights into the magmatism and metallogenesis in the Liaodong Peninsula. Furthermore, they contribute to advancing the understanding of tectonic–magmatic–mineralization evolution for the decratonization of the NCC during the Early Cretaceous.

2. Geological Background

2.1. Regional Geological Setting

The NCC occupies a key tectonic position, bounded by the Pacific Rim to the east, the Central Asian Orogenic Belt to the north, and the Yangtze Craton to the south (Figure 1). Evidence derived from xenolith studies indicates that the NCC possessed a lithospheric thickness exceeding 200 km during the Paleozoic, yet this thickness diminished to less than 80 km by the Cenozoic era [3,5,8], indicating significant crustal thinning by >100 km in the Mesozoic. This phase of thinning was accompanied by extensive magmatism, extensional tectonism, and local magmatogenic hydrothermal mineralization, all of which have been referred to as decratonization [4,8,12,21]. The peak of this decratonization was during the Early Cretaceous, contemporaneous with the westward subduction of the Paleo-Pacific plate [22,23,24]. Extensive Au-Mo-Cu-Fe-Pb-Zn ore deposits formed in the NCC during the Mesozoic (Figure 1a), with the Jiaodong Peninsula being the largest Au district (>5800 t) in China [25] and the Liaodong Peninsula hosting a significant Au-Pb-Zn-Mo-Cu polymetallic ore district [15]. Other important ore districts in the NCC include Chifeng-Chaoyang, Qingling-Xiaoqinling, and Yanliao [9,16]. The majority of ore deposits in the NCC formed over a relatively short time span from 140 to 120 Ma [10,16].
The Liaodong Peninsula is located in the northeastern part of the NCC, east of the Tanlu Fault (Figure 1), and hosts numerous magmatic intrusions and NE–NW striking faults (Figure 1b). The Liaodong Peninsula is composed of Archean–Paleoproterozoic basement rocks, Mesoproterozoic–Paleozoic sedimentary cover rocks, and Mesozoic–Cenozoic volcanic and magmatic rocks [26]. The Precambrian basement in the Anshan area formed at 3.8–3.2 Ga, along with late Archean ca. 2.5 Ga gneisses and the Paleoproterozoic Liaohe Group, which was deposited and metamorphosed at 1.9–1.85 Ga [27,28]. These are overlain by thick sequences of Mesoproterozoic, Neoproterozoic, and Paleozoic sedimentary rocks. The youngest events include three periods of magmatism that produced more than −20,000 km2 of igneous rocks, including the following: (1) 231–210 Ma diorite, dolerite, and monzonitic granite with mafic microgranular enclaves [8]; (2) 180–153 Ma diorite, tonalite, and gneissic monzonitic granite [8,29]; and (3) 131–120 Ma diorite, granodiorite, granite, and monzonitic granite [8,30].

2.2. The Shizhuzi Magmatic Complex-Mo-Cu-Au System

The Shizhuzi magmatic complex (SMC), located in the Kuandian area (Dandong) of the Liaodong Peninsula near the Yalu River (Figure 1b and Figure 2), covers approximately 120 km2 and is spatially associated with the intersection of NW- and NE-striking fault systems. Field observations suggest that these structural discontinuities likely controlled the emplacement of the NW–SE elongated complex, which exhibits structural parallelism with the dominant fault zone. The SMC comprises a diverse assemblage of intrusive rocks that can be categorized into the following: mineralized granitoids, including quartz diorite, monzonitic granite, granodiorite (Dongbeigou/DBG), dioritic porphyrite, granite porphyry, and crytoexplosive breccia; and non-mineralized granitoids, represented by quartz porphyry, porphyritic granite, and granodiorite (Wanbao/WB) (Figure 3). Granodiorite constitutes the most voluminous lithology, forming a continuous NW–SE trending body, while quartz diorite predominantly occurs along the eastern margin. The less abundant monzonitic granite and dioritic porphyrite are restricted to the western and central sectors of the complex. The SMC was emplaced into the Paleoproterozoic Liaohe group and Neoproterozoic Qingbaikou groups (mainly gneiss, schist, sandstone, and marlstone), as well as Cambrian–Ordovician strata (mainly limestone and banded marble). The contact relationship between the different intrusive phases is generally diffuse and gradual, and a few mafic enclaves were found in the SMC. The complex hosts several economically significant deposits, including the Shawogou Au deposit, Dongbeigou Mo deposit, and Wanbao Mo-Cu deposit (Table 1) [16].
The Shawogou Au deposit, situated in the southwestern sector of the SMC, occurs at the contact zone between granodiorite (DBG) and metasedimentary rocks of the Gaixian Formation (Liaohe Group). The deposit comprises three principal auriferous veins extending 100 to 1000 m in length and 1 to 14.2 m in width. These subparallel veins predominantly exhibit NW- or SW-dipping orientations and are associated with intense wall-rock silicification. In the central-northwestern SMC, the Dongbeigou Mo deposit (~0.5 km2) is hosted within monzonitic granite and granodiorite. Mineralization occurs as stockwork-disseminated type, with molybdenite primarily concentrated in quartz veinlets (1–20 mm wide), accompanied by subordinate pyrite. The Wanbao Cu deposit represents a skarn-type mineralization formed through contact metasomatism between granodiorite and Cambrian carbonate rock. The orebody displays characteristic layered and lenticular morphologies. These three deposits demonstrate clear spatial and temporal relationships with the SMC. Previous geological and geochemical investigations [16,18,19,20,31,32,33] have consistently established a genetic linkage between the mineralization events and the magmatic evolution of the SMC, suggesting a unified metallogenic system.

3. Sample Descriptions and Analytical Methods

Fresh, unaltered samples of non-mineralized granitoids (including granodiorite [WB], porphyritic granite, and quartz porphyry) were collected for analysis. Zircons were separated from the non-mineralized granitoids for U-Pb dating via laser-ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS). Hf isotope analyses were performed in situ at the same zircon domains previously targeted for U-Pb dating. For comparative purposes, Hf isotopic data from mineralized granitoids (granodiorite [DBG], quartz diorite, and monzonitic granite) were compiled from [16]. Whole-rock geochemical analyses were conducted exclusively on the porphyritic granite and quartz porphyry, while data for the mineralized granitoids were referenced from [16]. Data processing and subsequent calculations were executed using the ICPMSDataCal and Isoplot software packages, relying on formulas sourced from the relevant literature.

3.1. Zircon U-Pb Dating

Zircon grains were separated using standard magnetic separation and heavy liquid techniques, and the grains were mounted in epoxy, before polishing and imaging using cathodoluminescence, transmitted, and reflected light at the Beijing Geoanalysis Technology Co., Ltd., Beijing, China. Zircon U-Pb dating and trace element analyses were conducted by LA-ICP-MS at Wuhan Sample Solution Analytical Technology Co., Ltd., Wuhan, China. Laser sampling was performed with a GeolasPro laser ablation system that consists of a MicroLas optical system and a COMPexPro 102 ArF excimer laser (193 nm wavelength, Coherent Corp., Saxonburg, PA, USA). The ICP-MS instrument (Agilent 7700e) was used to acquire the ion signal intensities. Helium and argon were used as the carrier gas and the make-up gas, respectively. The beam diameter and repetition rate were set to 32 µm and 5 Hz, respectively. The calibration of the zircon U-Pb dating and trace element data was performed through comparison with the zircon standard 91500 and glass NIST610. Each analysis consisted of approximately 20–30 s of background acquisition, followed by 50 s of sample data acquisition. Quantitative calibration, time-drift correction, and integration of background and analyzed signals for U-Pb dating and trace element analysis were performed using ICPMSDataCal software [34]. Isoplot/Ex_ver. 4.15 was used to make Concordia diagrams and weighted mean calculations [35].

3.2. Whole-Rock Element Analyses

All the whole-rock samples were crushed to 200 mesh and analyzed at ALS Chemex, Guangzhou, China. Major element contents were determined using a PANalytical PW2424 X-ray fluorescence (XRF) and Agilent ICP–atomic emission spectrometer (ICP-AES). About 1 g of whole-rock powder was dissolved and mixed with LiNO3 to make glass beads after fusion. According to the standard (GSR-1) measurements, the uncertainties of major element concentrations are <5%. Trace element contents were determined using a Perkin Elmer Elan 9000 ICP-MS. About 0.1 g of crushed whole-rock powder was dissolved using Li2B4O7-LiBO2 mixtures at 1050 °C. After cooling, the solution was extracted and diluted with HF-HNO3-HCl before it was analyzed. During mass spectrometric measurement, external standards G-2 and BHVO-1 were used to monitor drift in mass response. The precision of trace element concentrations was generally better than 10%.

3.3. In Situ Zircon Hf Isotope Analyses

In situ zircon Hf isotope analyses were performed at the IGGCAS using a Neptune Plus MC-ICP-MS (Thermo Fisher Scientific, Waltham, MA, USA), equipped with a 193 nm GeoLasPro excimer ArF laser ablation system (Geolas HD, Lambda Physik, Göttingen, Germany). In situ Hf isotopic analyses were carried out on the same zircon grains that had been analyzed for U–Pb dating. Analyses were completed on a spot size of 44 μm, a laser repetition rate of 4 Hz, and a fluence of 4.0 J cm−2. A single analysis consisted of 200 cycles, each with an integration time of 0.131 s. The measured Hf isotope ratios were corrected for mass fractionation using the exponential law of 179Hf/177Hf = 0.7325. The isobaric interference correction of 176Yb to 176Hf is the key to obtaining accurate 176Hf/177Hf values in zircon in situ Hf isotope measurements. The βYb value obtained from the sample spot analysis itself and 176Yb/172Yb ratio of 0.5887 [36] were applied for the Yb correction. The measured 176Hf/177Hf ratio for the standard zircon SA01 was 0.282500 ± 0.000030, identical to the value of 0.282293 ± 7 [37] by a solution method within analytical uncertainty. The decay constant 176Lu of 1.86 × 10−11 year−1 [38] and the measured 176Lu/177Hf and 176Hf/177Hf ratios were used to calculate the initial 176Hf/177Hf ratios. In addition, (176Lu/177Hf)CC = 0.015 for average upper continental crust [39], (176Hf/177Hf)DM = 0.28325 and (176Lu/177Hf)DM = 0.0384 for depleted mantel [39], and (176Hf/177Hf)CHUR,0 = 0.282772 and (176Lu/177Hf)CHUR = 0.0332 for chondritic ratios [40] were taken for the calculation of εHf(t) values and Hf model ages.

4. Results

4.1. Petrography for the SMC Granitoids

Representative hand specimen photographs of the SMC granitoids are shown in Figure 3. The granodiorite (DBG) (Figure 3a) represents the dominant lithology of the SMC, forming its main body, followed by monzonitic granite (Figure 3b) and quartz diorite (Figure 3c). All three rock types exhibit equigranular textures in hand specimens but display variations in mafic mineral content (hornblende and biotite) and feldspar-type proportions (plagioclase vs. K-feldspar). The porphyritic diorite shows a close genetic association with gold mineralization, commonly exhibiting cross-cutting quartz-sulfide veins (Figure 3d). Within the Dongbeigou Mo deposit, pinkish cryptoexplosive breccias (Figure 3e) are observed, characterized by angular clasts predominantly composed of K-feldspar and quartz. At the Wanbao Cu deposit, extensive skarn formations resulting from magmatic-hydrothermal metasomatism of marble are well developed, forming skarn-type polymetallic mineralization. Figure 3f displays typical massive Cu mineralization within the skarn. The non-mineralized granitoids display light coloration, typically appearing white to grayish-white in hand specimens. The quartz porphyry and porphyritic granite exhibit porphyritic textures (Figure 3g,h), with their groundmass consisting of cryptocrystalline quartz and feldspar minerals, respectively. In contrast, the granodiorite (WB) (Figure 3i) shows an equigranular texture in hand specimens.
Representative microphotographs of the SMC granitoids are presented in Figure 4, with Figure 4a–c illustrating hydrothermal alteration features in these granitic rocks. In Figure 4a, the monzonitic granite exhibits silicification and sericitization, with feldspar and mica minerals being significantly altered. Figure 4b displays a phyllic-altered (quartz-sericite-pyrite) granodiorite under cross-polarized light, showing characteristic interference colors. The granodiorite is crosscut by quartz veins with pronounced sericitization along the margins (Figure 4c).
The quartz porphyries display grayish-white to milk-white coloration and exhibit porphyritic texture (Figure 4a,d). The phenocrysts (500 μm to 3 mm in size) are predominantly quartz with minor feldspar, set in a cryptocrystalline matrix. The porphyritic granites (Figure 4b,e) share similar coloration and textural characteristics but differ in mineralogy, containing phenocrysts of plagioclase, alkaline feldspar, microcline, and quartz within a fine-grained quartz–feldspar matrix. The granodiorite (WB) exhibits a grayish-white coloration and displays a hypautomorphic granular texture, as illustrated in Figure 4c,f. The rock’s mineral composition is characterized by plagioclase (~35%), quartz (~25%), alkaline feldspar (~18%), and mica (~17%), accompanied by accessory minerals, including zircon, sphene, and apatite. Notably, plagioclase grains are relatively large (2–3 mm in size) and exhibit a plate-like morphology, with distinct polysynthetic twins (Na-feldspar) observable under microscopic examination. The mica crystals are well-formed (euhedral), while hornblende displays a subhedral to granular habit.

4.2. Zircon U-Pb Ages

The results of the granodiorite (WB), porphyritic granite, and quartz porphyry are listed in Table S1 and shown in Figure 5. Zircon grains are predominantly colorless, transparent, and subhedral to euhedral with elliptical shapes, ranging from 50 to 150 μm in length and showing aspect ratios of 1:1 to 1:3. They exhibit typical igneous oscillatory zoning, and all analytical spots were placed on zircon rims. Thirteen analyses of zircon grains from the granodiorite (WB) cluster showed a tight coherent group on the Concordia diagram, with a Concordia age of 120.9 ± 0.8 Ma (MSWD = 1.3) (Figure 5a) and a weighted mean 206Pb/238U age of 120.9 ± 1.6 Ma (MSWD = 0.59) (Figure 5b). Ten analyses of zircon grains from the porphyritic granite plot near the Concordia curve showed a Concordia age of 118.9 ± 0.3 Ma (MSWD = 1.3) (Figure 5c) and a weighted mean 206Pb/238U age of 118.9 ± 0.6 Ma (MSWD = 0.71) (Figure 5d). Eleven analyses of zircon grains from the quartz porphyry cluster showed a tight coherent group on the Concordia diagram, with a Concordia age of 117.4 ± 0.3 Ma (MSWD = 5.3) (Figure 5e) and a weighted mean 206Pb/238U age of 117.7 ± 0.6 Ma (MSWD = 1.05) (Figure 5f).

4.3. Whole-Rock Geochemistry

The whole-rock geochemical data of both the porphyritic granite and quartz porphyry (non-mineralized granitoids), along with complied data for the mineralized granitoids are presented in Table S2 and illustrated in Figure 6, Figure 7, Figure 8, Figure 9 and Figure 10. The porphyritic granite and quartz porphyry display comparable major and trace element characteristics. The porphyritic granite is characterized by SiO2 contents ranging from 78.61 to 78.62 wt.%, total alkali (Na2O + K2O) values of 6.98–7.04 wt.%, and A/NK and A/CNK ratios of 1.44–1.55 and 1.38–1.54, respectively. These compositional features place the samples firmly within the peraluminous, high-K calc-alkaline granite field, as shown in Figure 6. Similarly, the quartz porphyry exhibits SiO2 contents of 76.99–78.6 wt.%, total alkali contents of 4.93–5.92 wt.%, and A/NK and A/CNK ratios ranging from 1.93 to 2.32 and 1.47 to 1.75, respectively, also plotted within the same compositional field shown in Figure 6. Chondrite-normalized rare-earth element (REE) patterns (Figure 7a) reveal significant light REE (LREE) enrichment relative to heavy REEs (HREEs) in both rock types. The porphyritic granite shows LREE/HREE and (La/Yb)N ratios of 5.38–6.08 and 3.39–11.41, respectively, while the quartz porphyry displays corresponding ratios of 5.24–5.90 and 2.74–11.13. Both rock types exhibit pronounced negative Eu anomalies (δEu = 0.07–0.08 for porphyritic granite; 0.16–0.29 for quartz porphyry). The primitive-mantle-normalized trace-element spider diagram (Figure 7b) shows positive anomalies for U and K and negative anomalies for Ba, Nb, Sr, P, Eu, and Ti in the porphyritic granite and quartz porphyry.
The mineralized granitoids display systematic geochemical variations across different rock types, as evidenced in Figure 6 and Figure 7. In the TAS diagram (Figure 6), quartz diorite samples (57.13–58.09 wt.% SiO2) plot consistently within the diorite field, showing metaluminous character (A/CNK = 0.83–0.85) and high-K calc-alkaline affinity (K2O = 1.86–2.51 wt.%). Granodiorite (DBG) samples (66.39–68.03 wt.% SiO2) occupy the granodiorite field with transitional metaluminous to peraluminous signatures (A/CNK = 0.96–1.02), while monzonitic granite samples (69.83–70.97 wt.% SiO2) plot within the granite field, displaying slightly peraluminous features (A/CNK = 1.00–1.12). All three rock types maintain high-K calc-alkaline characteristics, with K2O contents increasing progressively from quartz diorite to granodiorite (3.24–3.74 wt.%) to monzonitic granite (7.10–7.47 wt.%). The corresponding chondrite-normalized REE patterns (Figure 7a) reveal consistent LREE enrichment (La/Yb)N ratios and HREE depletion across all mineralized granitoids. Quartz diorite exhibits a slight Eu anomaly, while granodiorite and monzonitic granite show more pronounced fractionation patterns. Primitive-mantle-normalized trace element diagrams (Figure 7b) demonstrate systematic variations, as follows: quartz diorite displays negative Ba, Nb, P, and Ti anomalies with positive Sr and K anomalies; granodiorite shows similar patterns but with additional negative Pr and positive Er anomalies; and monzonitic granite exhibits the most differentiated signature, with negative Sr, Ba, Nb, P, Ti, and Zr anomalies coupled with positive K and Er anomalies.

4.4. In Situ Zircon Hf Isotopes

In situ Hf isotope analysis of zircon grains was carried out in areas close to, or overlapping with, those spots that had been analyzed for their U-Pb isotopic composition earlier. The Hf isotope data, εHf(t), single-stage model ages (TDM1), and two-stage model ages (TDM2) of the granodiorite (WB) (120.9 Ma), porphyritic granite (118.9 Ma), quartz porphyry (117.4 Ma), and the mineralized granitoids are listed in Table S3 and shown in Figure 11. In situ Hf isotope analysis of 12 zircon grains from the porphyritic diorite yielded initial 176Hf/177Hf ratios of 0.281891 to 0.282527, the corresponding εHf(t) values vary from −28.36 to −6.10, TDM1 ages from 1884 to 1046 Ma, and TDM2 ages from 2972 to 1567 Ma. In situ Hf isotope analysis of 14 zircon grains from the granodiorite (WB) yielded initial 176Hf/177Hf ratios of 0.282274 to 0.282476, the corresponding εHf(t) values vary from −15.07 to −7.95, TDM1 ages from 1392 to 1093 Ma, and TDM2 ages from 2131 to 1680 Ma. In situ Hf isotope analysis of 11 and 10 zircon grains from the porphyritic granite and quartz porphyry, respectively, yielded initial 176Hf/177Hf ratios of 0.282117 to 0.282227 and 0.282110 to 0.282178, the corresponding εHf(t) values are between −20.84 and −16.94 and between −21.07 and −18.69, respectively, their TDM1 ages range is from 1700 to 1537 Ma and 1732 to 1623 Ma, and their TDM2 ages are from 2490 to 2246 Ma and 2506 to 2356 Ma, respectively.
In situ Hf isotope analyses of zircons from the mineralized granitoids reveal consistent isotopic characteristics across different rock types. For quartz diorite (14 zircons), the 176Yb/177Hf and 176Lu/177Hf ratios range from 0.0138 to 0.0440 and 0.0006 to 0.0017, respectively, with initial 176Hf/177Hf ratios of 0.282328–0.282483. The corresponding εHf(t) values vary from −13.0 to −7.4, yielding TDM1 ages of 1297–1085 Ma and TDM2 ages of 2006–1657 Ma. Granodiorite zircons (14 analyses) show slightly lower 176Yb/177Hf (0.0102–0.0235) and 176Lu/177Hf ratios (0.0005–0.0011), with initial 176Hf/177Hf ratios of 0.282331–0.282443. The calculated εHf(t) values range from −12.7 to −8.9, corresponding to TDM1 ages of 1287–1134 Ma and TDM2 ages of 1993–1746 Ma. Monzonitic granite zircons (14 analyses) exhibit the most restricted isotopic ranges, with 176Yb/177Hf ratios of 0.0091–0.0157 and 176Lu/177Hf ratios of 0.0004–0.0007. The initial 176Hf/177Hf ratios (0.282335–0.282447) and εHf(t) values (−12.8 to −8.8) are comparable to those of other rock types, yielding TDM1 ages of 1280–1125 Ma and TDM2 ages of 1990–1739 Ma.

5. Discussion

5.1. Two Stages of Magmatism and a Stage of Mineralization

Previous studies have demonstrated that the subcontinental lithospheric mantle (SCLM) of the NCC experienced substantial transformation and thinning during the Mesozoic [13], with the peak of cratonic destruction occurring in the Early Cretaceous [7]. This critical period was marked by intense magmatic activity, widespread tectonic deformation, and large-scale mineralization events [8,9,10,11,21,22,23,24,25]. Notably, Early Cretaceous magmatic activity displayed a distinct eastward migration trend across the NCC, producing predominantly calc-alkaline mafic to felsic rock assemblages. Significant ore deposits associated with these processes are concentrated west of the Tanlu Fault, particularly in the Jiaodong and Liaodong ore districts [10].
The Shizhuzi magmatic complex and Mo-Cu-Au system in the Liaodong Peninsula involved two-stage magmatism and a stage of mineralization, precisely coinciding with the peak period of NCC destruction. The Shizhuzi system hosts three major ore deposits: the Dongbeigou molybdenum deposit, the Wanbao copper deposit, and the Shawogou gold deposit, and previous studies have suggested that these deposits were predominantly formed during 130–126 Ma [18,19,20,31,32,33]. The mineralization ages of the ore deposits within the SMC are comparable to those of other deposits in the Liaodong Peninsula, such as the Wulong Au deposit (127–126 Ma) [47], Baiyun Au deposit (126 Ma) [48], and Huatong Cu–Mo deposit (127.6–126.3 Ma) [19]. The magmatic rocks cover an area of about 100 square kilometers, and the mineralized granitoids primarily consist of monzonitic granite (126.2 Ma), granodiorite (DBG) (129.5 Ma), and quartz diorite (129.8 Ma) [16]. In contrast, the non-mineralized granitoids are mainly composed of granodiorite (WB) with a Concordia age of 120.9 ± 0.8 Ma (Figure 5a) and a weighted mean 206Pb/238U age of 120.9 ± 1.6 Ma (Figure 5b), porphyritic granite with a Concordia age of 118.9 ± 0.3 Ma (Figure 5c) and a weighted mean 206Pb/238U age of 118.9 ± 0.6 Ma (Figure 5d), and the quartz porphyry with a Concordia age of 117.4 ± 0.3 Ma (Figure 5e) and a weighted mean 206Pb/238U age of 117.7 ± 0.6 Ma (Figure 5f). The mineralized granitoids and non-mineralized granitoids in the Shizhuzi magmatic complex were formed during 130–126 Ma and 121–117 Ma, respectively.
Previous studies have systematically compiled geochronological data on various deposits in the NCC [10,23]. The peak Au-Mo mineralization occurred predominantly during the Early Cretaceous, exhibiting a clear spatiotemporal pattern. In the Taihang Mountains and Xiaoqinling regions, gold mineralization was concentrated at 140–120 Ma, while, in the eastern Jiaodong and Liaodong areas, it shifted to 125–115 Ma [9]. Further east, along the cratonic margin in Korea, mineralization ages cluster around ~110 Ma, revealing a progressive younging trend from west to east [10]. Notably, Early Cretaceous magmatic activity follows the same spatial-temporal progression [10,23]. At present, the subduction of the Paleo-Pacific plate is recognized as the most important geodynamic mechanism for the Early Cretaceous decratonization of the NCC [7,8,22]. Feng et al. (2020) [49] documented evidence for a component derived from the subducting plate in the Early Cretaceous volcanic rocks in the Liaodong-Jinan area, providing direct evidence of the Early Cretaceous magmatism and mineralization having been induced by the subduction of the Paleo-Pacific plate in the NCC. During 130–120 Ma, the Paleo-Pacific Plate underwent continuous rollback, triggering intense extensional tectonics in eastern North China [23], which led to the formation of pull-apart basins and widespread metamorphic core complexes. Magmatic activity peaked at ~125 Ma, as evidenced by the emplacement ages of numerous igneous rocks [10]. Furthermore, previous studies combining slab rollback rates with spatiotemporal patterns of mineralization have proposed that the subducting slab began to stagnate in the mantle transition zone beneath the eastern gold belt at ~120 Ma [10,13,14]. This stagnation likely served as the primary driver for the subsequent magmatic flare-up at 120 Ma [24]. The prolonged rollback of the Paleo-Pacific slab and its subsequent stagnation in the mantle transition zone at ~120 Ma not only accounts for the sustained and episodic nature of the North China Craton (NCC) destruction, but also explains the two-stage magmatism observed in the SMC. Notably, only one magmatic phase produced significant mineralization, reflecting fundamental differences in source composition, petrogenesis, and magmatic evolution.

5.2. Petrogenesis of the Mineralized Granitoids

The quartz diorites exhibit high MgO (3.58–3.90 wt.%) and Mg# (51.6–55.5), with relatively low SiO2 (57.1–58.1 wt.%), coupled with elevated Cr and V concentrations (>100 ppm). Zircon crystallization temperatures (826–921 °C) significantly exceed typical crustal melting ranges [50], strongly favoring a mantle-derived basaltic parental magma. This interpretation is reinforced by the following: (1) MORB-like Nb/Ta ratios (15.6–16.3) [51] and (2) characteristic subduction-related trace element patterns featuring LILE/LREE enrichment coupled with marked depletion in HFSEs (Nb, Ta, Ti) (Figure 7), which typifies subduction-related magmatism [52]. Nb/U values (4.9–7.7) approximate continental crustal averages (6.2) [50]. Zircon εHf(t) values (−7.4 to −13.0) resemble those of lithosphere-derived mafic rocks in the Liaodong Peninsula [53] but contrast with depleted mantle sources [54]. Collectively, these features indicate that the quartz diorites originated from an enriched SCLM source with continental crustal contamination.
Granitic rocks are typically classified into distinct genetic types (e.g., I-, S-, and A-types) based on the I-S-A-M classification scheme [54], each exhibiting unique mineralogical and geochemical characteristics due to differences in magma sources and petrogenetic processes. The granodiorites and monzonitic granites in this study display high-K calc-alkaline affinities, as evidenced by their SiO2 vs. K2O relationships (Figure 6b and Figure 9h). In the (Na2O + K2O − CaO) vs. SiO2 diagram (Figure 6b), these rocks plot within the calc-alkaline field, trending toward alkalinity with increasing SiO2. They exhibit low Zr and Zr + Nb + Ce + Y concentrations, along with 10,000 × Ga/Al ratios below 2.6 (Figure 10), consistent with I-type granite characteristics. This interpretation is further supported by their relatively low zircon crystallization temperatures (820–681 °C) and the presence of hornblende [16].
Several genetic models have been proposed to explain the formation of I-type granites, including the following: (a) partial melting of basaltic crust with or without fractional crystallization [55]; (b) extensive fractional crystallization of primitive basaltic magmas [56]; and (c) mixing of crustal- and mantle-derived components [57]. The Shizhuzi granodiorites and monzonitic granites exhibit low MgO, Cr, and V contents, aligning with experimental results from partial melting of basaltic crustal sources [58]. This is reinforced by highly incompatible trace element ratios—such as Nb/Ta (avg. 13.0) and Zr/Hf (avg. 35.7)—which closely match the average crustal values (11.4 and 33, respectively) [59]. Zircon 176Lu/177Hf ratios (0.002) indicate negligible post-crystallization radiogenic Hf modification, confirming that the measured 176Lu/177Hf ratios reflect the magma’s isotopic composition at the time of zircon crystallization. The granodiorites and monzonitic granites exhibit overlapping εHf(t) values (−12.8 to −8.8; Figure 11) and Hf model ages (1.7–2.0 Ga), suggesting derivation from Paleoproterozoic crustal material extracted from a depleted mantle source. These signatures resemble those of Archean to Paleoproterozoic rocks in the northern Liaodong Peninsula [60], potentially indicating an ancient crustal source for the SMC.
However, comparable geochemical signatures may alternatively reflect Cretaceous underplating of enriched mantle-derived basaltic magmas, as inferred from coeval quartz diorites exhibiting similar zircon Hf isotopic compositions. The current data cannot definitively discriminate between these scenarios. Nevertheless, the absence of inherited zircons and the markedly lower εHf(t) values (−20) typical of Archean North China Craton crust [8] favor the underplating model. Thus, the parental magmas of the granodiorites and monzonitic granites were likely derived from partial melting of underplated basaltic rocks, possibly sharing a common source with the coeval quartz diorites. The granodiorites and monzonitic granites exhibit significant variations in major and trace element concentrations, displaying linear trends in Figure 9 and Figure 12, indicative of fractional crystallization processes involving plagioclase + biotite during their formation.

5.3. Petrogenesis of the Non-Mineralized Granitoids

In the standard petrogenetic discrimination diagrams (Figure 6), the non-mineralized granitoids (including porphyritic granite and quartz porphyry) consistently cluster within well-defined compositional fields, demonstrating three diagnostic features: (1) pronounced high-K calc-alkaline affinity (Figure 6b), (2) distinct peraluminous composition (Figure 6c), and (3) chemical signatures indicative of highly fractionated granitic melts (Figure 6a,d).
Quartz porphyry typically originates from high-silica (Figure 9), potassium-rich calc-alkaline magmas (high-K calc-alkaline series), belonging to either I-type or A-type granite series, resulting from crustal partial melting or magmatic differentiation [54]. In the 10,000 × Ga/Al vs. Zr/Y/Ce/Nb diagrams (Figure 10), the quartz porphyry samples plot within the I-type granite field in all diagrams, except for the slightly elevated Nb contents in Figure 10d. This geochemical signature suggests a genetic relationship to crustal melting triggered by subducting slab dehydration [61]. In situ Hf isotope analyses of 10 zircon grains from the quartz porphyry yield εHf(t) values ranging from −21.07 to −18.69, with TDM1 and TDM2 model ages of 1732–1623 Ma and 2506–2356 Ma, respectively, indicating derivation from partial melting of ancient crustal sources.
The porphyritic granite exhibits elevated SiO2 and K2O contents but low concentrations of other major elements (Figure 9). In the 10,000 × Ga/Al versus Zr/Y/Ce/Nb diagrams (Figure 10), all samples consistently plot within the A-type granite field. These geochemical characteristics collectively support its classification as an A-type granite. The porphyritic granite exhibits Hf isotopic features similar to those of the quartz porphyry. In situ Hf isotope analysis of 11 zircon grains from the porphyritic granite yields εHf(t) values ranging from −20.84 to −16.94, with TDM1 ages of 1700–1537 Ma and TDM2 ages of 2490–2246 Ma. These results suggest that the non-mineralized granitoids (including the porphyritic granite and quartz porphyry) share a comparable origin and magmatic source, both belonging to A-type granites. The porphyritic granite exhibits Y/Nb, Ce/Nb, and Zr/Nb ratios of 0.69–0.81, 1.23–1.31, and 2.48–2.53, respectively, while the quartz porphyry shows corresponding ratios of 1.93–2.32, 0.44–1.32, and 1.96–2.59. These trace element ratios are all relatively low, indicating that they belong to A2-type granites (where Y/Nb < 1.2, Ce/Nb < 3.5, and Zr/Nb < 10) [62]. Given the extensional tectonic setting of the North China Craton at ~120 Ma [6,7,8,9,10], these rocks are proposed to have formed through partial melting of ancient crustal materials.
The porphyritic granite and quartz porphyry exhibit pronounced depletions in Eu, P, and Ti (Figure 7), indicating that the parental magma underwent extensive fractional crystallization involving plagioclase and K-feldspar. This advanced differentiation process resulted in a residual melt enriched with SiO2 (>70 wt.%) and volatiles (e.g., H2O, F), ultimately generating the characteristic porphyritic texture [63].

5.4. Comparison of the Mineralized and Non-Mineralized Granitoids

The Shizhuzi magmatic complex consists of various lithologies, with granodiorite being predominant, along with granite, quartz diorite, monzogranite, and quartz porphyry. Geochronological results indicate that this complex was formed by two magmatic events at 130–126 Ma and 121–117 Ma, respectively. The first magmatic event is temporally consistent with the mineralization age (129–126 Ma), suggesting a close genetic relationship between the mineralized granitoids and ore formation. In contrast, the second magmatic event occurred about 5 million years later and represents non-mineralized granitoids. The marked contrast in metallogenic potential between the early mineralized and late non-mineralized granitoids may be related to differences in their magmatic sources and evolutionary processes. Their geochemical characteristics are compared to investigate these differences.
Through comprehensive studies including zircon U-Pb dating, zircon Hf isotopes, and whole-rock geochemical analyses, these two types of granitoids have been distinguished. As shown in Figure 7, chondrite-normalized REE patterns and primitive mantle-normalized spider diagrams reveal significant differences. The mineralized granitoids exhibit right-inclined REE patterns with LREE enrichment and HREE depletion, along with weak negative Eu anomalies. In contrast, the non-mineralized granitoids show tetrad effects in their REE patterns, strong negative Eu anomalies, and pronounced negative anomalies for Th, P, and Ti, resembling highly fractionated granites. In Rb-Ba-Sr ternary diagrams (Figure 6d), the non-mineralized granitoids plot within the field of highly fractionated granites, while the mineralized granitoids fall into the field of normally crystallized granites. Harker diagrams serve as powerful tools for elucidating magmatic evolution and petrogenesis. As shown in Figure 9, systematic variations in major element oxides versus SiO2 content reveal fundamental compositional differences between the two granitoid groups. The mineralized granitoids display continuous magmatic evolution trends, while the non-mineralized granitoids clearly separate from them, showing extremely high SiO2 contents and lower concentrations of Al2O3, MgO, TFe2O3, CaO, TiO2, and MnO, indicating an evolutionary trend controlled by high-degree fractional crystallization. These major element characteristics suggest that the mineralized and non-mineralized granitoids originated from different source materials and experienced distinct magmatic evolution pathways.
Specific trace element pairs were selected for comparative studies using bivariate diagrams, which also clearly distinguish between the mineralized and non-mineralized granitoids (Figure 8). Element pairs such as Zr-Hf, Y-Ho, and K-Rb have similar ionic radii, charges, and geochemical behaviors, and are, therefore, considered geochemical twins [64]. Decreasing ratios like Zr/Hf can indicate increasing degrees of fractional crystallization [65]. The non-mineralized granitoids show lower Zr/Hf ratios (17.97–20.33) (Figure 8a), suggesting higher degrees of fractional crystallization. Additionally, Rb/Sr ratios are commonly used as indicators of differentiation degree [66], while Sr/Y ratios may reflect magma source depths [67]. The two granitoid types show significant differences in these trace element ratios. The mineralized granitoids have higher Sr/Y, (La/Yb)N, LREE/HREE, δEu, U/Th, and Zr/Hf ratios (Figure 8), suggesting derivation from deeper melting sources. In contrast, the non-mineralized granitoids exhibit higher Rb/Sr (2.73–8.60) and (K2O + Na2O)/CaO ratios (5.06–173.75), characteristic of highly fractionated granitoids.
Zircon U-Pb dating and Hf isotopes provide crucial constraints on the magma sources of both mineralized and non-mineralized granitoids, further amplifying their differences. As shown in Figure 11, the non-mineralized granitoids have significantly more negative Hf isotope values, similar to other barren granites in the Liaodong region [8]. In contrast, the mineralized granitoids have εHf(t) values mostly >−15, resembling Archean and Paleoproterozoic basement rocks and lithospheric mantle-derived mafic rocks in the Liaodong Peninsula [52,60], but differing from depleted mantle sources [53]. These comprehensive studies demonstrate that the mineralized and non-mineralized granitoids have distinct origins and evolutionary paths. The early mineralized granitoids (quartz diorites) were derived from the partial melting of enriched mantle, whose thermal input induced partial melting of basaltic lower crust to form granodiorites and monzonitic granites. These underwent limited fractional crystallization (plagioclase and biotite) and were associated with Mo-Cu-Au mineralization. In contrast, the non-mineralized granitoids originated from the partial melting of the ancient lower crust, experienced a high degree of fractional crystallization (plagioclase, K-feldspar), and consequently did not generate economic mineralization.

5.5. Magmatic Evolution Model

The NCC experienced intense lithospheric destruction during the Mesozoic, triggering widespread magmatic, tectonic, and thermal events, accompanied by the formation of gold and other metal deposits [23]. This cratonic destruction reached its climax during the Early Cretaceous (130–120 Ma), a phenomenon widely interpreted as resulting from the westward subduction and rollback of the Paleo-Pacific Plate [13]. The geodynamic evolution was characterized by a progressive transition from compressional to extensional regimes, ultimately establishing a pure extensional tectonic setting by the peak destruction phase [24]. Within this context, the SMC comprises two stages of magmatic rocks with distinct petrogenetic affinities and one stage of polymetallic mineralization, representing a typical product of continuous formation and evolution during the peak destruction of the NCC (Figure 13).
Within 130–126 Ma: The main body of the SMC formed during this period. The lithologies primarily consist of granodiorite-DBG (129.5 Ma), quartz diorite (129.8 Ma), monzonitic granites (126.2 Ma), diorite porphyry, and cryptoexplosive breccia. Banded marble associated with skarn-type mineralization is also observed in the periphery of the magmatic complex. Mineralization types include the Shawogou Au deposit, Dongbeigou Mo deposit, and Wanbao Cu deposit (130–126 Ma). The diverse magmatic rocks and deposits exhibit close spatial-temporal and genetic relationships. The principal magmatic-mineralization event in the SMC occurred at 130–126 Ma, characterized by the emplacement of mineralized granitoids and the formation of Mo-Cu-Au deposits. The quartz diorite within the mineralized granitoids was derived from the partial melting of an enriched mantle source. Its high-temperature thermal underplating promoted the partial melting of basaltic lower crust, generating the granodiorite and monzogranite. These I-type granitoids underwent moderate fractional crystallization, involving plagioclase + biotite, accompanied by Mo-Cu-Au mineralization.
Within 121–117 Ma: The SMC generated only minor magmatic activity during this interval, dominated by quartz porphyry (117.7 Ma), porphyritic granite (118.9 Ma), and granodiorite-WB (120.9 Ma). This stage was characterized by limited magma production and the absence of associated metal mineralization. The non-mineralized granitoids (including porphyritic granite and quartz porphyry) are high-K calc-alkaline, peraluminous A2-type granites. They were derived from the partial melting of the ancient lower crust and underwent a high degree of fractional crystallization, involving plagioclase + K-feldspar.

6. Conclusions

(1)
The Shizhuzi magmatic complex records two distinct magmatic stages: an early mineralizing stage (130–126 Ma) forming Mo-Cu-Au deposits; and a late magmatic stage (121–117 Ma), representing a typical product of the peak destruction period of the North China Craton.
(2)
The mineralized granitoids exhibit I-type affinities and formed in an extension setting. The quartz diorite was derived from the partial melting of an enriched mantle source, whose subsequent high-temperature thermal underplating triggered partial melting of basaltic lower crust to generate the granodiorite and monzonitic granites. These rocks underwent limited fractional crystallization (plagioclase + biotite) and are associated with Mo-Cu-Au mineralization.
(3)
The non-mineralized granitoids are high-K calc-alkaline, peraluminous A2-type granites formed in an extremely extensional tectonic setting. They were derived from the partial melting of the ancient lower crust and display characteristics of highly fractionated granites, having undergone extensive crystallization differentiation involving plagioclase + K-feldspar during magmatic evolution.
(4)
Significant contrasts exist between mineralized and non-mineralized granitoids in terms of petrology, geochemistry (major/trace elements and Hf isotopes), and the degree of fractional crystallization. A model of two-stage of superimposed magmatism was developed for the Shizhuzi magmatic complex-Mo-Cu-Au system.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min15060631/s1, Table S1: Zircon U-Pb data for the non-mineralized granitoids from the Shizhuzi magmatic rocks; Table S2: Whole-rock major and trace element data of the Shizhuzi magmatic rocks; Table S3: Hf isotopic compositions of zircons from the Shizhuzi magmatic rocks.

Author Contributions

Investigation, J.W.; Writing—original draft, J.W.; Writing—review & editing, J.W. and Q.Z.; Supervision, J.Y. (Jinzhong Yang); Project administration, Q.Z.; Funding acquisition, J.Y. (Jinhui Yang). All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the “Deep Earth Probe and Mineral Resources Exploration–National Science and Technology Major Project”, grant number “2024ZD1001301”.

Data Availability Statement

The data presented in this study are openly available.

Acknowledgments

We thank Yongbing Wang, Yunpeng Guo, Peiwen Chen, and Ruiliang Wang for their help during our field work. We thank Hartwig E. Frimmel, M. Santosh, and Pete Hollings for the discussion. We also thank the editor and reviewers for the constructive reviews, who greatly improved the manuscript.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. (a) A simplified map showing the major tectonic divisions of China (modified after [9]); (b) a tectonic map of the North China Craton and distribution of Early Cretaceous granitoids and deposits (modified after [10]); (c) a geological map of the Liaodong Peninsula (modified after [15]).
Figure 1. (a) A simplified map showing the major tectonic divisions of China (modified after [9]); (b) a tectonic map of the North China Craton and distribution of Early Cretaceous granitoids and deposits (modified after [10]); (c) a geological map of the Liaodong Peninsula (modified after [15]).
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Figure 2. Geological map of the Shizhuzi magmatic complex and ore deposits (modified after [16]).
Figure 2. Geological map of the Shizhuzi magmatic complex and ore deposits (modified after [16]).
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Figure 3. Representative photographs of hand specimens for the SMC granitoids: (a) granodiorite (Dongbeigou); (b) monzonitic granite; (c) quartz diorite; (d) porphyritic diorite intruded with quartz-pyrite veins; (e) cryptoexplosive breccia; (f) skarn hosting massive sulfide mineralization; (g) quartz porphyry; (h) porphyritic granite; and (i) granodiorite (Wanbao).
Figure 3. Representative photographs of hand specimens for the SMC granitoids: (a) granodiorite (Dongbeigou); (b) monzonitic granite; (c) quartz diorite; (d) porphyritic diorite intruded with quartz-pyrite veins; (e) cryptoexplosive breccia; (f) skarn hosting massive sulfide mineralization; (g) quartz porphyry; (h) porphyritic granite; and (i) granodiorite (Wanbao).
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Figure 4. Representative microphotographs of hydrothermally altered (mineralized) and non-mineralized SMC granitoids: (a) monzonitic granite with pervasive sericite-quartz alteration; (b) sericitized granodiorite with pyrite; (c) sericitized granodiorite with a quartz vein, showing typical phyllic alteration; (d) porphyritic diorite; (e) cryptoexplosive breccia; (f) skarn; (g) quartz porphyry; (h) porphyritic granite; (i) granodiorite (Wanbao). Symbols: Chl = chlorite; Di = diopside; Ep = epidote; Hbl = hornblende; Mc = microcline; Mo = molybdenite; Ms = muscovite; Pl = plagioclase; Py = pyrite; Q = quartz; Ser = sericite; Silica = silicification; Wo = wollastonite.
Figure 4. Representative microphotographs of hydrothermally altered (mineralized) and non-mineralized SMC granitoids: (a) monzonitic granite with pervasive sericite-quartz alteration; (b) sericitized granodiorite with pyrite; (c) sericitized granodiorite with a quartz vein, showing typical phyllic alteration; (d) porphyritic diorite; (e) cryptoexplosive breccia; (f) skarn; (g) quartz porphyry; (h) porphyritic granite; (i) granodiorite (Wanbao). Symbols: Chl = chlorite; Di = diopside; Ep = epidote; Hbl = hornblende; Mc = microcline; Mo = molybdenite; Ms = muscovite; Pl = plagioclase; Py = pyrite; Q = quartz; Ser = sericite; Silica = silicification; Wo = wollastonite.
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Figure 5. Zircon U-Pb ages for the non-mineralized granitoids from the Shizhuzi magmatic complex: (a,b) granodiorite (WB); (c,d) porphyritic granite; (e,f) quartz porphyry.
Figure 5. Zircon U-Pb ages for the non-mineralized granitoids from the Shizhuzi magmatic complex: (a,b) granodiorite (WB); (c,d) porphyritic granite; (e,f) quartz porphyry.
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Figure 6. Classification diagrams of the whole-rock geochemistry data of the Shizhuzi magmatic complex: (a) TAS diagram [41]; (b) K2O vs. SiO2 [42]; (c) A/NK vs. A/CNK diagram [43]; (d) Rb-Ba-Sr diagram [44].
Figure 6. Classification diagrams of the whole-rock geochemistry data of the Shizhuzi magmatic complex: (a) TAS diagram [41]; (b) K2O vs. SiO2 [42]; (c) A/NK vs. A/CNK diagram [43]; (d) Rb-Ba-Sr diagram [44].
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Figure 7. Chondrite-normalized REE patterns (a) and primitive mantle-normalized trace element spider diagrams (b) for Shizhuzi magmatic complex. The normalizing values of chondrite and primitive mantle are from [45].
Figure 7. Chondrite-normalized REE patterns (a) and primitive mantle-normalized trace element spider diagrams (b) for Shizhuzi magmatic complex. The normalizing values of chondrite and primitive mantle are from [45].
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Figure 8. (a) Zr/Hf versus Rb/Sr diagram; (b) (La/Yb)N versus δEu diagram; (c) LREE/HREE versus δEu diagram; (d) U/Th versus Rb/Sr diagram; (e) Sr/Y versus Y diagram; (f) (Na2O + K2O)/CaO versus Nb + Zr + Ce + Y diagram.
Figure 8. (a) Zr/Hf versus Rb/Sr diagram; (b) (La/Yb)N versus δEu diagram; (c) LREE/HREE versus δEu diagram; (d) U/Th versus Rb/Sr diagram; (e) Sr/Y versus Y diagram; (f) (Na2O + K2O)/CaO versus Nb + Zr + Ce + Y diagram.
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Figure 9. Harker diagrams of different rocks from the Shizhuzi magmatic complex: (a) Al2O3 versus SiO2 diagram; (b) MgO versus SiO2 diagram; (c) TFe2O3 versus SiO2 diagram; (d) CaO versus SiO2 diagram; (e) Na2O versus SiO2 diagram; (f) TiO2 versus SiO2 diagram; (g) P2O5 versus SiO2 diagram; (h) K2O versus SiO2 diagram; (i) MnO2 versus SiO2 diagram.
Figure 9. Harker diagrams of different rocks from the Shizhuzi magmatic complex: (a) Al2O3 versus SiO2 diagram; (b) MgO versus SiO2 diagram; (c) TFe2O3 versus SiO2 diagram; (d) CaO versus SiO2 diagram; (e) Na2O versus SiO2 diagram; (f) TiO2 versus SiO2 diagram; (g) P2O5 versus SiO2 diagram; (h) K2O versus SiO2 diagram; (i) MnO2 versus SiO2 diagram.
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Figure 10. Discriminant diagrams of (a) Zr versus 10,000 Ga/Al; (b) Y versus 10,000 Ga/Al; (c) Ce versus 10,000 Ga/Al; (d) Nb versus 10,000 Ga/Al [46].
Figure 10. Discriminant diagrams of (a) Zr versus 10,000 Ga/Al; (b) Y versus 10,000 Ga/Al; (c) Ce versus 10,000 Ga/Al; (d) Nb versus 10,000 Ga/Al [46].
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Figure 11. Diagrams of initial εHf values (a) vs. the U–Pb ages of the zircons (b). Abbreviations: ECAOB, East Central Asian Orogenic Belt; NCC, North China Craton.
Figure 11. Diagrams of initial εHf values (a) vs. the U–Pb ages of the zircons (b). Abbreviations: ECAOB, East Central Asian Orogenic Belt; NCC, North China Craton.
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Figure 12. Results of Rayleigh fractional crystallization modeling in terms of the variations of (a) Rb versus Sr diagram; (b) Ba versus Sr diagram; (c) Rb/Sr versus Sr diagram; (d) δEu versus Sr diagram. Abbreviations are as follows: Pl = plagioclase; Kfs = potassium feldspar; Bt = biotite.
Figure 12. Results of Rayleigh fractional crystallization modeling in terms of the variations of (a) Rb versus Sr diagram; (b) Ba versus Sr diagram; (c) Rb/Sr versus Sr diagram; (d) δEu versus Sr diagram. Abbreviations are as follows: Pl = plagioclase; Kfs = potassium feldspar; Bt = biotite.
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Figure 13. Magmatic evolution model of the Shizhuzi system in the NCC.
Figure 13. Magmatic evolution model of the Shizhuzi system in the NCC.
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Table 1. Geological characteristics of the Shizhuzi Mo-Cu-Au deposits.
Table 1. Geological characteristics of the Shizhuzi Mo-Cu-Au deposits.
Dongbeigou Mo DepositShawogou Au DepositWanbao Cu-Mo Deposit
Position in the SMCCentral to northwesternSouthwesternEastern
Mineralization typeStockwork-disseminated type, Quartz-vein type, Cryptobreccia typeQuartz-vein typeSkarn type, Quartz-vein type
Associated granitoids and country rockGranodiorite, Monzonitic granite, Cryptoexplosive brecciaGranodiorite, Porphyritic diorite, Gaixian Formation Granodiorite, Quartz diorite, Skarn, Marble
AlterationPotassic, Propylitic alteration, Sericitization, CarbonatizationSilicification, Pyritic sericitization, Chloritization, CarbonatizationSkarnization, Sericitization
Scale>100 kt Mo/0.11%>3 t Au/3.12–6.20 g/t>35 kt Mo/0.095%; >996 t Cu/0.72%
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Wu, J.; Yang, J.; Yang, J.; Zeng, Q. Contrasts in Two-Stage Superimposed Magmatism of the Shizhuzi Magmatic Complex-Mo-Cu-Au System, Liaodong Peninsula, North China Craton. Minerals 2025, 15, 631. https://doi.org/10.3390/min15060631

AMA Style

Wu J, Yang J, Yang J, Zeng Q. Contrasts in Two-Stage Superimposed Magmatism of the Shizhuzi Magmatic Complex-Mo-Cu-Au System, Liaodong Peninsula, North China Craton. Minerals. 2025; 15(6):631. https://doi.org/10.3390/min15060631

Chicago/Turabian Style

Wu, Jinjian, Jinzhong Yang, Jinhui Yang, and Qingdong Zeng. 2025. "Contrasts in Two-Stage Superimposed Magmatism of the Shizhuzi Magmatic Complex-Mo-Cu-Au System, Liaodong Peninsula, North China Craton" Minerals 15, no. 6: 631. https://doi.org/10.3390/min15060631

APA Style

Wu, J., Yang, J., Yang, J., & Zeng, Q. (2025). Contrasts in Two-Stage Superimposed Magmatism of the Shizhuzi Magmatic Complex-Mo-Cu-Au System, Liaodong Peninsula, North China Craton. Minerals, 15(6), 631. https://doi.org/10.3390/min15060631

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