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Article

Origin and Geological Implications of Monzogranites and Rhyolitic Porphyries in the Wunugetu Porphyry Copper–Molybdenum Deposit, Northeast China: Evidence from Zircon U-Pb-Hf Isotopes and Whole-Rock Geochemistry

by
Qingshuang Wang
1,2,
Yanchen Yang
1,*,
Qiulin Fu
3,
Zhongyue Zhang
4,
Xiaodan Guo
5,
Taotao Wu
2,
Lu Chai
2,
Yongheng Zhou
2 and
Yonghai An
5
1
College of Earth Sciences, Jilin University, Changchun 130061, China
2
Shenyang Geological Survey Center of China Geological Survey, Shenyang 110034, China
3
Liaoning Province Institute of Geology and Mineral Resources Co., Ltd., Shenyang 110034, China
4
Liaoning Earthquake Agency, Shenyang 110031, China
5
Liaoning Province Geology and Mineral Group Energy Geology Co., Ltd., Shenyang 110032, China
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(3), 310; https://doi.org/10.3390/min14030310
Submission received: 22 January 2024 / Revised: 13 March 2024 / Accepted: 13 March 2024 / Published: 15 March 2024
(This article belongs to the Special Issue Tectonic–Magmatic Evolution and Mineralization Effect in the Southern Central Asian Orogenic Belt)
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Versions Notes

Abstract

:
The Wunugetu deposit, a large-scale porphyry copper–molybdenum deposit, is located in the southern Erguna block. Its ore bodies are primarily found within monzogranites, granite porphyries, and biotite monzogranites. Additionally, the deposit contains late-stage intrusive dykes of rhyolitic porphyries. This study examined the deposit’s monzogranites and rhyolitic porphyries using lithogeochemistry, zircon U-Pb dating, and Hf isotopic analysis. The main findings include: (1) Zircon U-Pb dating showed that the monzogranites formed around 209.0 ± 1.0 Ma, whereas the rhyolitic porphyries in the northern portion formed around 170.49 ± 0.81 Ma, suggesting magmatic activity in the deposit spanned from the Late Triassic to the Middle Jurassic. (2) The monzogranites exhibited high silicon content (73.16–80.47 wt.%) and relatively low aluminum content (10.98–14.37 wt.%). They are enriched in alkalis (content: 3.42–10.10 wt.%) and deficient in magnesium and sodium, with aluminum saturation indices (A/CNK) ranging from 1.1 to 2.9. In addition, the monzogranites are enriched in large-ion lithophile elements (LILEs) such as Rb, K, and Ba and deficient in high-field-strength elements (HFSEs) like Nb, P, and Ti. (3) The monzogranites have low Zr + Nb + Ce + Y contents of (151.3–298.6 ppm) × 10−6 and 10,000 × Ga/Al ratios varying between 1.20 and 2.33, suggesting that they are characteristic of I-type granites. (4) Positive zircon εHf(t) values ranging from +0.3 to +7.6 in both rhyolitic porphyry and monzogranite samples, increasing with younger emplacement ages, imply that the deposit’s rocks originated from magmatic mixing between mantle-derived mafic magmas and remelts of the juvenile crust. Considering these results and the regional geological evolution, this study proposes that the Wunugetu deposit was formed in an active continental margin setting and was influenced by the Late Triassic–Middle Jurassic southeastward subduction of the Mongol-Okhotsk Ocean.

1. Introduction

The Central Asian Orogenic Belt (CAOB), located between the Siberian Craton and the North China Craton, is recognized as one of the largest Phanerozoic orogenic belts globally. Its extensive geological history features the accretion of continental crust induced by oceanic subduction, the convergence of multiple plates, intracontinental orogeny, and associated multistage tectono-magmatic activity. Hence, the deep magmatic activity and mineralization related to the CAOB’s formation and evolution have garnered significant interest from geologists worldwide [1,2,3,4,5,6,7,8]. Within the CAOB, multiple world-class porphyry copper deposits, such as Oyu Tolgoi, Erdenet, and Aktogai–Aiderly, have been identified, positioning this region as a premier porphyry copper belt on a global scale, also referred to as the Central Asian Metallogenic Belt [9]. This belt, along with the Circum-Pacific and Tethyan metallogenic belts, constitutes one of the three principal global copper metallogenic provinces [10]. Situated in the eastern segment of the CAOB, Northeast China emerged from the amalgamation of various microblocks, including the Erguna, Xing’an, Songnen-Zhangguangcai Range, Jiamusi, and Xingkai blocks [11], highlighting its importance as a notable copper-bearing region in China.
The Wunugetu deposit, situated in the southern Erguna block of Northeast China (Figure 1a), represents a significant porphyry copper–molybdenum deposit within the eastern CAOB. Since its identification, the deposit has garnered considerable attention from the geological community [12,13,14]. Extensive studies of this deposit focus on its geological characteristics, the isotopic geochronology and lithogeochemistry of the ore-hosting surrounding rocks, and ore-forming fluids [12,15,16,17]. However, debates persist regarding the metallogenic periods and geodynamic setting of the Wunugetu deposit. Wang Zhitian’s (1988) initial K-Ar dating of monzogranite porphyry stocks within the deposit yielded an age of 138 Ma [12], leading to the hypothesis of a Late Yanshanian origin. Qin Kezhang (1999), through Rb-Sr dating of the ore-hosting monzogranite porphyries and K-Ar dating of altered sericite, proposed that the deposit formed between 180 and 190 Ma, indicating an Early Jurassic age of this copper–molybdenum deposit [15]. Advancements in analytical methods allowed Tan Gang (2010) to determine a formation age of 177 Ma using Re-Os isotopic dating of the molybdenite [17]. These studies demonstrate that the Wunugetu deposit experienced intense magmatic activity and mineralization events during the Early Jurassic. However, there is limited information on Late Triassic and Middle Jurassic intrusions within the deposit. This study delves into the geological, ore-body, and ore characteristics of the Wunugetu deposit. Employing zircon U-Pb dating, Hf isotope analysis, and whole-rock geochemistry of the ore-hosting porphyritic monzogranites and the late-stage intrusive rhyolitic porphyries, this study aims to constrain the formation periods of ore-forming rock masses and identify the genetic types, source traits, and tectonic setting of the rock masses and late-stage dykes. Additionally, the new data can be used to effectively elucidate the geodynamic context of copper–molybdenum mineralization in the Wunugetu deposit.

2. Geological Setting

2.1. Regional Geological Setting

Located about 24 km southwest of Manzhouli City, the Wunugetu deposit is positioned in the central part of the Erguna block, nestled between the Mongol-Okhotsk suture zone (MOSZ) and the Xiguitu-Tayuan fault (Figure 1a). In the Paleozoic era, the Erguna block, influenced by the evolution of the Paleo-Asian Ocean tectonic system, experienced the complex amalgamation of several microblocks within the CAOB [19,20]. From the Late Paleozoic to the Mesozoic, the block fell under the tectonic influence of the Mongol-Okhotsk Ocean tectonic domain [19,20,21,22,23]. The superposition of multiple tectonic domains has endowed this block with highly developed regional fault structures, primarily including a series of E–W- and NE–NNE-trending faults, as well as secondary faults. The oldest exposed strata within the Erguna block consist mainly of Precambrian strata, overlain by Paleozoic and Mesozoic layers. The Precambrian strata are chiefly made up of a crystalline basement composed mainly of schists, leptites, and quartzites from the Neoproterozoic Jiageda Formation (Ptj). The Paleozoic sequence mainly comprises volcanic and terrigenous clastic rocks from the Middle Devonian Wunu’er Formation, while the Mesozoic strata encompass intermediate-mafic volcanic and pyroclastic rocks from the Middle Jurassic Tamulangou Formation, intermediate-acid volcanic rocks from the Shangkuli Formation, and acidic volcanic and pyroclastic rocks from the Upper Jurassic Manketouebo and Manitu formations. The complex process of tectonic evolution has resulted in frequent regional magmatic activity, with Mesozoic granites being the most extensively developed. The region hosts several significant deposits, including the Badaguan copper–molybdenum deposit, the Wunugetu deposit, the Jiawula and Halasheng lead–zinc–silver deposits, and the Chaganbulagen silver–lead–zinc deposit, all of which are intimately linked to the Mesozoic magmatic activity [15,18,24,25].

2.2. Geological Setting of the Wunugetu Deposit

The Wunugetu deposit was discovered by the No. 706 Team of the Heilongjiang Nonferrous Metal Geological Survey in 1978. By 2006, the deposit had 1.106 million tons of copper and 0.362 million tons of molybdenum identified, establishing it as the most significant large-scale porphyry copper–molybdenum deposit within the Erguna block [13]. In 2008, the China National Gold Group Co., Ltd. (Beijing, China) acquired the Wunugetu deposit to further its exploration and production endeavors.
The exposed strata in the Wunugetu deposit encompass the Devonian Wunu’er Formation’s andesites and crystalline limestones (southwest), Upper Jurassic volcanic rocks (north), and extensive Quaternary unconsolidated deposits (Figure 1b).
The Wunugetu deposit underwent two distinct magmatic phases. The first phase, during the Late Triassic, produced biotite granites, monzogranites, and granite porphyries, which together cover about 60% of the deposit’s total area. The biotite granites and monzogranites, forming batholiths, extend across the deposit and its vicinity, covering an exposed area of approximately 110 km2. These rocks are crucial as the ore-hosting rock masses and surrounding rocks of the deposit.
The second magmatic phase, in the Early Jurassic, led to the formation of a volcanic edifice. The volcanic rocks mainly consist of andesitic agglomerates, while the lithologic assemblages of intrusions primarily comprise monzogranite porphyries, quartz porphyries, diorite porphyrites, and rhyolitic porphyries. The rhyolitic porphyries, intruding into the mineral-bearing monzogranite porphyries, show no signs of mineralization or alteration zones. The monzogranite porphyries are distributed in the central portion of the deposit. They are disrupted by the late-stage F7 fault, making them a key ore-hosting rock mass. Additionally, the outcrops in the deposit include minor quantities of dacitic breccias, quartz porphyries, and diorite porphyrites.
Fault structures are prominent in the Wunugetu deposit, including NE-, NNW-, and nearly E–W-trending faults, along with ring-shaped faults in volcanic areas. The NE-trending and ring-shaped faults developed during the mineralization period, whereas the NW-oriented F8 fault emerged in the later stages of mineralization. These faults cut through ore bodies, disrupting their continuity. The E–W-trending F7 fault divides the ore bodies into southern and northern segments.

3. Ore Body Characteristics

The ore bodies within the Wunugetu deposit are arranged in a ring-like pattern orienting NWE, with monzogranite porphyries at their core. The area of mineralization spans roughly 2600 m in length and about 1400 m in width. These ore bodies have a strike of 50° and a dip direction of WN. The F7 fault causes a horizontal displacement of approximately 700 m, thereby splitting the ore bodies into two distinct segments: the southern segment spans about 800 m in width, while the northern segment extends approximately 900 m across. Both segments are subjected to hydrothermal alteration within the deposit. The Wunugetu deposit exhibits typical alteration zones of porphyry-type mineralization, covering an area of approximately 5 km2. These zones roughly comprise potassic (Or), quartz-sericite (Qs), and illite-hydromica (IH) alteration zones [15]. The primary alterations observed include silicification, potassic feldspathization, sericitization, illitization, muscovitization, carbonatization, and kaolinization, with chloritization and epidotization being relatively less common (Figure 2).
The potassic zone (Or), centrally located within the deposit, is found predominantly in the monzogranite porphyry rock masses. The alteration minerals characteristic of this zone are mainly K-feldspar and biotite, with sericite present in smaller quantities (Figure 2a). Molybdenite is the principal type of mineralization in this zone, along with notable occurrences of chalcopyrite and pyrite mineralizations.
The quartz-sericite zone (Qs) extends through the biotite granites and their contact zone with the monzogranite porphyries. This zone is rich in alteration minerals such as quartz, sericite (Figure 2b), and carbonate. The ore minerals in this zone include molybdenite, chalcopyrite, malachite, pyrite, and azurite.
The illite-hydromica zone (IH), located within biotite granites on the periphery of the deposit and rhyolites in the northern part, features alteration minerals like illite, hydromuscovite (Figure 2c), carbonate, and kaolinite. This zone also exhibits lead and zinc mineralizations.

4. Sampling and Methodology

4.1. Sampling and Lithofacies Characteristics of Samples

A total of 14 samples were gathered, comprising three monzogranite samples (WNG01, WNG02, and WNG03), four rhyolitic porphyry samples (WNG06, WNG06-1, WNG06-2, and WNG06-3; Figure 3a) from the deposit’s northern area, four monzogranite samples (WNG15-1, WNG15-2, WNG15-3, and WNG15; Figure 3b) from the southern portion, and three additional monzogranite samples (WNG18-1, WNG18-2, and WNG18-3) from the deposit’s periphery. The specific sampling locations are depicted in Figure 1b.

4.2. Zircon U-Pb Dating

Zircon monomineralic separation, target preparation, cathodoluminescence (CL) imaging, and zircon U-Pb dating were performed at the laboratory of Yandu Zhongshi Testing Technology Co., Ltd. (Beijing, China) The procedures utilized a New Wave UP213 laser ablation system and an M90 inductively coupled plasma mass spectrometer (ICP-MS) manufactured by Analytik Jena AG. Zircon reference materials 91500 and Plesovice employed exhibited the values recommended [26,27], as calculated using ZSkits software ver. 1.1.0. The quantification of trace elements in zircon utilized SRM610 and Si as the external and internal standards, respectively [28]. For U-Pb isotopic dating, zircon reference material 91500 was used as an external standard for isotopic fractionation correction. The U-Pb age concordia diagrams and the weighted average ages of the zircon samples were generated using Isoplot/Exver3 [29]. Additionally, the correction of common lead in U-Pb analyses was performed following Andersen’s (2002) method [30].

4.3. In-Situ Lu-Hf Isotopes of Zircon

In-situ zircon Lu-Hf isotopic analyses were performed utilizing a Neptune Plus MC-ICP-MS manufactured by Thermo-Fisher and a New Wave UP213 laser ablation system, with the procedures and calibration methods akin to those proposed by Wu Fuyuan et al. (2007) [31]. Laser ablation was executed for 31 s at a frequency of 8 Hz and an energy density of 16 J/cm2. Considering the exceptionally low 176Lu/177Hf ratios in zircon, typically below 0.002, the isotopic interference of 176Lu on 176Hf was deemed negligible. The isotopic fractionation factor of Yb was calculated using the average 173Yb/172Yb ratios of various test points, followed by removal of the isobaric interference of 176Yb on 176Hf. The 173Yb/172Yb ratio was established at 1.35274.

4.4. Whole-Rock Major- and Trace-Element Analyses

Complete silicate analysis was performed at the laboratory of Yandu Zhongshi Testing Technology Co., Ltd. Major element analysis utilized the acid dissolution method in conjunction with a Zetium X-ray fluorescence spectrometer (XRF) from PANalytical, with analytical precision errors under 0.1%. Trace element analysis was carried out with an M90 ICP-MS from Analytik Jena AG, with analytical errors maintained below 10%.

5. Results

5.1. Petrography

The rhyolitic porphyries, as stocks, intrude into granite porphyries, characterized by porphyritic textures and blocky structures. Their phenocrysts, making up 10% of the composition, consist of quartz (5%) and feldspar (5%), with particle sizes between 0.4 and 1.4 mm. Their matrix, constituting 90%, is mainly feldspar and quartz. It manifests felsitic textures, with radial or fan-shaped grains scattering locally (Figure 3c,e).
The monzogranites comprise plagioclase (35%), alkali feldspar (30%), and quartz (35%), with consistent mineral grain sizes ranging from 1.6 to 3.0 mm. The plagioclase is hypidiomorphic, tabular, and granular, featuring sericite alterations on their surfaces. In contrast, the alkali feldspar appears as xenomorphic grains (Figure 3d,f).
The monzogranite porphyries are composed of plagioclase (30%), alkali feldspar (30%), quartz (32%) (Figure 3d), sericite (5%), and pyrite (3%). The grains are uniform in size, ranging from 1.6 to 3.0 mm. The plagioclase is subhedral, appearing in tabular and granular shapes, with sericite pseudomorphing its surfaces. The alkali feldspar occurs as xenomorphic grains, comprising perthitic feldspar with irregularly vein-like, spotted, and patchy patterns. It exhibits weak sericitization on surfaces, with sericite replacing along the perthite (Figure 3f). The pyrite occurs mainly as euhedral to anhedral grains distributed among the minerals’ intergranular spaces.

5.2. Zircon U-Pb Ages

The LA-ICP-MS zircon U-Pb dating data are shown in Table 1, partial zircon CL images are illustrated in Figure 4a,b, and the concordia diagrams with weighted average age curves are presented in Figure 5a,b. Zircon grains from rhyolitic porphyry sample WNG06 ranged from idiomorphic to hypidiomorphic columnar shapes, with sizes ranging from 50 to 150 μm. These grains were primarily short columnar, followed by long columnar, with length/width ratios from 1:1 to 2.5:1 and minor fissures occasionally visible. Oscillatory zoning was observed in the CL images of these zircon grains. Their Th/U ratios spanned from 0.74 to 1.34, all above 0.1, indicating a magmatic origin for these grains. Analysis of 22 test points on this sample yielded 206Pb/238U ages between 169 and 173 Ma, corresponding to weighted average ages of 170.49 ± 0.81 Ma (MSWD = 0.68).
Zircon grains from monzogranite sample WNG15 displayed shapes from idiomorphic to hypidiomorphic columnar, with sizes varying between 50 to 200 μm. These grains were predominantly short columnar and secondarily long columnar, with length/width ratios ranging between 1:1 and 3:1. Oscillatory zoning was apparent in the CL images of the zircon grains. The Th/U ratios of the zircons spanned from 0.32 to 0.97, all above the 0.1 threshold, indicating a magmatic origin. Analysis of 18 test points on this sample revealed 206Pb/238U ages between 205 to 218 Ma, with weighted average ages of 209.02 ± 1.0 Ma (MSWD = 0.57).

5.3. In-Situ Lu-Hf Isotopes of Zircon

The in-situ Lu-Hf isotopic analysis results of zircon are summarized in Table 2. The Hf isotopic data were calculated using U-Pb ages obtained from the same zircon test points. Zircon grains from samples WNG06 and WNG15 exhibited 176Hf/177Hf ratios within the ranges of 0.282742–0.282874 and 0.282658–0.282784, respectively, corresponding to εHf(t) values ranging from +2.4 to +10.8 for WNG06 and from +0.3 to +4.6 for WNG15. The derived two-stage model ages (TDM2) for these samples were between 727 to 1058 Ma for WNG06 and 949 to 1227 Ma for WNG15.

5.4. Whole-Rock Major and Trace Element Analyses

The analytical outcomes for major, trace, and rare earth elements (REEs) across 12 rock samples are compiled in Table 3. Regarding major elements, these samples contained 70.16–80.47 wt.% SiO2, 10.98–14.37 wt.% Al2O3 (rhyolite), 0.17–3.77 wt.% Na2O, 2.95–9.36 wt.% K2O, 0.06–0.99 wt.% CaO, 0.14–0.37 wt.% MgO, and 3.42–10.10 wt.% Na2O + K2O, indicating high silicon content and depletion of sodium generally. The total alkali–silica (TAS) diagram shows that most samples fell within the granite field (Figure 6), in line with petrographic results.
Regarding major elements, the monzogranite samples contained 73.16–80.47 wt.% SiO2, 10.98–14.37 wt.% Al2O3, 0.17–3.77 wt.% Na2O, and 2.95–9.36 wt.% K2O. Notably, samples WNG01, WNG02, and WNG15-2 exhibited elevated K2O levels, suggesting the potential influence of potassic feldsparization within the deposit. The CaO varied from 0.06 to 0.99 wt.%, MgO from 0.14 to 0.37 wt.%, and total alkalis (Na2O + K2O) from 3.42 to 10.10 wt.%, indicating high silica and low sodium. All the samples fell within the granite field on the TAS diagram (Figure 6).
The rhyolitic porphyry samples revealed SiO2 between 75.77 wt.% and 77.45 wt.%, Al2O3 from 10.98 to 14.37 wt.%, Na2O at 0.23 wt.%, K2O from 5.00 to 5.91 wt.%, CaO between 0.09 and 0.12 wt.%, MgO from 0.17 to 0.18 wt.%, and Na2O + K2O from 5.23 to 6.14 wt.%, also demonstrating high silica and low sodium traits. These samples fell within the granite field on the TAS diagram (Figure 6).
In the K2O–SiO2 diagram (Figure 7a), the samples fell within the high-K calc-alkaline to shoshonitic series zones, with one point in the calc-alkaline series zone, indicating the rhyolite and monzogranite samples’ classification belongs to these series. All rock samples, with aluminum saturation index (A/CNK) values from 1.1 to 2.9, fell within the peraluminous zone on the A/NK vs. A/CNK diagram (Figure 7b).

5.5. Rare Earth and Trace Elements

The rhyolite samples from the Wunugetu deposit showed total REE (ΣREE) contents ranging from 33.08 ppm to 78.07 ppm, LREE/HREE ratios between 13.70 and 15.96, and (La/Yb)N ratios from 21.48 to 31.23, indicating a general enrichment in light rare earth elements (LREEs) and a relative depletion in heavy rare earth elements (HREEs). Their chondrite-normalized REE patterns were rightward curves, with negative Eu anomalies (Eu/Eu*= 0.58–0.75; Figure 8a; Table 3).
The monzogranite samples from the Wunugetu deposit yielded ΣREE contents from 61.57 ppm to 192.91 ppm, LREE/HREE ratios from 3.39 to 18.51, and (La/Yb)N ratios from 2.67 to 25.01, showing an enrichment in LREEs. Their chondrite-normalized REE patterns were also rightward curves, indicative of negative Eu anomalies (Eu/Eu* = 0.46–0.75; Figure 8a; Table 3).
As revealed by the primitive mantle-normalized profiles, both rhyolitic porphyry and monzogranite samples exhibited similar patterns, both showing significant enrichment in LILEs such as Rb, K, Ba, and elements like Th, U, La, but depletion in HFSEs like Nb, P, and Ti (Figure 8b; Table 3). Both rock types had relatively low Sm/Nd ratios (rhyolitic porphyry: 0.17; monzogranite: 0.14 to 0.19, averaging 0.19), Rb/Sr ratios (rhyolitic porphyry: 1.64 to 2.70, averaging 2.24; monzogranite: 0.90 to 10.53, averaging 2.59), and Rb/Ba ratios (rhyolitic porphyry: 0.13 to 0.54, averaging 0.33; monzogranite: 0.13 to 0.30, averaging 0.20), along with higher K/Rb ratios (rhyolitic porphyry: 363.32 to 778.55, averaging 503.03; monzogranite: 200.48 to 658.60, averaging 353.81).

6. Discussion

6.1. Diagenetic and Metallogenic Epochs

Mao Jingwen et al. (2005) proposed that metallization in eastern China predominantly occurred during the periods of 180–188 Ma, 135–144 Ma, 115–127 Ma, and 94–105 Ma [37]. Drawing from extensive isotopic dating data, Xu Wenliang et al. (2013) identified six distinct phases of mineralization-related volcanic activity in Northeast China: 220–280 Ma, 173–190 Ma, 158–166 Ma, 138–145 Ma, 106–133 Ma, and 88–97 Ma [38]. In the eastern Xing’an-Mongolia orogenic belt, principal metallization events are dated to 165–195 Ma and 110–115 Ma [39]. The Erguna block, a critical segment of the eastern CAOB, underwent notably intense Mesozoic magmatic episodes, categorized into seven stages: ~246 Ma (Late Permian to early Middle Triassic), ~225 Ma (late Middle Triassic to early Late Triassic), ~205 Ma (late Late Triassic to early Early Jurassic), ~185 Ma (Early Jurassic), ~155 Ma (Late Jurassic), ~137 Ma (early Early Cretaceous), and ~125 Ma (late Early Cretaceous) [40]. This block has revealed considerable porphyry copper mineralization, with several copper–molybdenum deposits like Badaguan, Taipingchuan, Wunugetu, and Naomingte in Mongolia being uncovered. Specifically, the Badaguan deposit’s quartz porphyries and granodiorite porphyries exhibit weighted average zircon U-Pb ages of 217.6 ± 2.6 Ma and 206.5 ± 1.6 Ma, respectively, while its molybdenite shows Re-Os ages of 222.4 ± 3.3 Ma [41,42]. The Taipingchuan deposit’s ore-forming granodiorite porphyries have average zircon U-Pb ages of 202.0 ± 5.7 Ma, with molybdenite revealing an average Re-Os age of 203 Ma [43]. In Mongolia’s Naomingte deposit, the ore-hosting granodiorites demonstrate a diagenetic age of 166 Ma. These findings suggest that the porphyry copper mineralization in the Erguna block primarily occurred from the Late Triassic to the Middle Jurassic, consistent with the Mesozoic magmatic activity timelines proposed by the aforementioned researchers.
The ore bodies in the Wunugetu deposit are primarily found within granite porphyries, monzogranites, quartz monzogranite porphyries, and biotite monzogranites, indicating a strong linkage with these rock types. Prior studies, leveraging isotopic geochronology, have suggested that the ore bodies and their encompassing rock masses share similar formation periods, highlighting Early Jurassic diagenesis and mineralization processes [13,15,44]. Contrarily, this study reveals that an ore-hosting monzogranite sample, WNG15, produced LA-ICP-MS zircon U-Pb ages of 209.0 ± 1.0 Ma, pointing to a late Late Triassic formation. Additionally, rhyolitic porphyries located in the northern part of the deposit, which intrude into the ore bodies without causing mineralization or alteration, implying that they are dykes intruding in the late mineralization stage. These rhyolitic porphyries have shown LA-ICP-MS zircon U-Pb ages of 170.49 ± 0.81 Ma, indicating their formation during the early Middle Jurassic. The diverse ore features within the Wunugetu deposit imply a multi-stage mineralization process. Molybdenum mineralization predominantly occurs in joints and fissures, with the Re content in molybdenite being influenced by various factors such as lithology, paragenetic minerals, and temperature conditions [44,45]. Consequently, the molybdenite age may not precisely reflect the copper mineralization epoch. Considering the petrogenetic ages of monzogranite and rhyolitic porphyry in the deposit, along with chronological testing data on these rock masses obtained by previous researchers, the authors propose that the magmatic activity at Wunugetu Mountain spanned from 209.0 Ma to 170.5 Ma. When combined with the petrogenetic age range from 180 to 188 Ma for the ore-hosting monzogranitic porphyry in the deposit [15,17] and isochron ages of 177.4 to 179.8 Ma for the deposit’s molybdenite [17,44], it can be inferred that the ore-bearing rock-bodies in the Wunugetu region were formed from the Late Triassic to the Early Jurassic, with the mineralization process predominantly occurring during the Early Jurassic.

6.2. Origins of Rocks and Source Characteristics

The genetic types of magmatic rocks are pivotal for interpreting the tectonic setting related to their origin and the characteristics of their magma sources. By examining mineral compositions and elemental geochemical traits, alongside considerations such as geotectonic context, variances in magma sources, and magma evolution, it is well-recognized that granitic rocks can be categorized into M, I, S, and A types [31,46,47]. In the case of the Wunugetu deposit under study, a microscopic analysis of monzogranite samples reveals the absence of key aluminous indicator minerals like cordierite, garnet, and muscovite, ruling out their classification as S-type granites [48]. The granitic rocks within the deposit and its vicinity are characterized by high silicon levels, potassium enrichment, and relatively high Th content. M-type granites, known to result from the remelting of the oceanic crust under island arcs, typically have mantle-derived magma sources, thus featuring low K2O and Th contents [49,50], a stark contrast to the Late Triassic to Middle Jurassic rocks found in the Wunugetu deposit. Additionally, no contemporaneous M-type granites have been identified in the study area, indicating that the Mesozoic volcanic and magmatic rocks of the Wunugetu deposit are not M-type magmatic rocks. On the discrimination diagrams for magma origin (Figure 9a–c), the samples predominantly cluster around the I- and S-type granite zones, with only a couple aligning with the A-type granite category. Nonetheless, highly differentiated I- and S-type granitic samples with SiO2 content exceeding 72% share similar geochemical characteristics to A-type magmatic rocks [47,51].
The monzogranites within the Wunugetu deposit are characterized by high silicon content (73.16–80.47 wt.%), relatively low aluminum content (10.98–14.37 wt.%), enrichment in alkalis (3.42–10.10 wt.%), and depletion in magnesium and sodium, with A/CNK ratios (Al2O3/(CaO + Na2O + K2O) ranging from 1.1 to 2.9. On the A/NK–A/CNK diagram, the major element composition classifies these monzogranites as peraluminous to quasi-aluminous rocks. Additionally, these rocks, with low FeOT, MgO, and CaO contents, are enriched in Rb and Th and depleted in Ba, P, and Ti (Figure 8b), indicative of significant crystallization and differentiation from primitive magmas [52,53]. The monzogranites also display low Zr + Nb + Ce + Y content (151.3 ppm–298.6 ppm, average: 198.6 ppm) and 10,000 × Ga/Al ratios (1.20–2.33, average: 2.07), sharply contrasting with the typical characteristics of A-type granitic magmatic rocks (Zr + Nb + Ce + Y content: >400 ppm; 10,000 × Ga/Al ratios: >2.6). As illustrated in the Zr + Nb + Ce + Y–FeOT/MgO diagram (Figure 9c), most samples fell into the highly differentiated magma zone, indirectly confirming that the Wunugetu deposit’s granitic rocks are highly differentiated magmatic rocks. Despite A/CNK ratios from 1.1 to 2.9 suggesting peraluminous to quasi-aluminous nature in the A/NK–A/CNK diagram, previous studies have substantiated that I-type magmatic rocks can exhibit peraluminous and even strongly peraluminous features [54,55]. As revealed by experiments, apatite exhibits low solubility and is prone to saturate undergoing fractional crystallization during magma evolution in I-type felsic magmas, with the P2O5 content diminishing with an increase in the SiO2 content in rocks. Conversely, S-type granites have high apatite solubility, with P2O5 content increasing with the SiO2 content [56]. Thus, the correlation between SiO2 and P2O5 contents serves as a critical indicator for determining the type of granitic magma. As shown in the SiO2–P2O5 diagram (Figure 10a), the magmatic rock samples from the Wunugetu deposit exhibited low P2O5 content (0.04%–0.09%) and a negative P2O5–SiO2 correlation, classifying them as I-type granites. For S-type felsic magmas, Th and Y contents inversely correlate with Rb content, but in I-type magmas, they increase with Rb content [57]. Therefore, the evolutionary trends of Th and Y in magmas can be used to distinguish between S- and I-type granites. The positive correlation of the Th and Y contents with Rb content in the Rb-Y (Figure 10b) and Rb-Th (Figure 10c) diagrams indicates that the deposit’s magmatic rocks are characteristic of I-type granites. The aforementioned microscopic observations reveal the absence of aluminum-rich silicate minerals like muscovite, cordierite, and garnet in monzogranites. All these lead to the conclusion that the Late Triassic magmatic rocks of the Wunugetu deposit are highly differentiated I-type rocks.
The Middle Jurassic rhyolitic porphyry samples from the deposit all fell into the I- and S-type granite zones in the 10,000 × Ga/Al vs. Na2O + K2O, 10,000 × Ga/Al vs. Y, and Zr + Nb + Ce + Y vs. FeOT/MgO diagrams. The Rb-Y (Figure 10b) and Rb-Th (Figure 10c) diagrams, where Th and Y contents show a positive correlation with the Rb content, suggest that the rhyolite porphyries also have the geochemical characteristics of I-type granites.
These Middle Jurassic rhyolitic porphyries are characterized by high silica (75.77–77.45 wt.%), elevated potassium (5.005.91 wt.%), and an A/CNK ratio of 1.85 to 2.14, all above the 1.1 threshold. Their chondrite-normalized REE patterns exhibit pronounced HREE depletion, hinting at the potential residual effects of garnet. Positioned within the I- and S-type granite zones in geochemical diagrams like (10,000 × Ga/Al) vs. (Na2O + K2O), (10,000 × Ga/Al) vs. Y, and (Zr + Nb + Ce + Y) vs. (FeOT/MgO) (Figure 10b,c), the samples also displayed an increase in P2O5 with SiO2 in the SiO2 vs. P2O5 diagram (Figure 10a), indicating that the rhyolite porphyries in the study area exhibit geochemical traits of S-type granites.
In-situ Lu-Hf isotopic analysis of zircon from these samples revealed εHf(t) values between +2.4 and +7.6. Moreover, all these samples fell within the zone of the εHf(t) range for CAOB’s felsic rocks as shown in the t vs. εHf(t) diagram (Figure 11a). Their TDM2 ages ranged from 727 to 1058 Ma, suggesting the rhyolitic porphyries’ primitive magmas originated from the partial melting of the Meso- to Neoproterozoic accreted lower crust.
The Late Triassic monzogranite samples from the Wunugetu deposit yielded zircon εHf(t) values ranging from +0.3 to +4.6. On the t-εHf(t) diagram (Figure 11a), these samples clustered around the chondrite zone, displaying εHf(t) values aligned with those of CAOB’s felsic rocks. This suggests that the study area is a part of the CAOB. The TDM2 ages of these samples spanned 949 to 1227 Ma, indicating that the original magma of the rhyolite porphyries in the Wunugetu deposit is derived from partial melting of the Meso- to Neoproterozoic accreted lower crust.
In summary, both the Late Triassic I-type granites and the Early Jurassic rhyolitic porphyries from the Wunugetu deposit demonstrate positive zircon εHf(t) values. These values show an increasing trend with a decrease in the emplacement age, suggesting that the magmatic source for the study area’s monzogranites is derived from the partial melting of the Mesoproterozoic accreted lower crust.

6.3. Diagenetic and Metallogenic Tectonic Settings

The Wunugetu deposit, nestled within the eastern CAOB and the central MOSZ), is distinguished as the largest porphyry deposit in the Kherlen (Mongolia)-Erguna (China) block. Delving into the tectonic setting of rocks within this deposit is crucial for deepening our understanding of the MOSZ’s tectonic evolution and contributes to the exploration of the regional geological settings of porphyry copper mineralization and the tectonic evolution of the eastern CAOB. Previous studies on the evolution of the Mongol-Okhotsk Ocean generally indicate that this ocean evolved from the Eopaleozoic to the Mesozoic [59], undergoing bidirectional subduction toward the north and the south [22,60].
All samples of the Late Triassic magmatic rocks from the Wunugetu deposit fell within the volcanic arc-syn-collisional granite zone on the Y vs. Nb tectonic discrimination diagram (Figure 12a), with a majority situated within the volcanic arc granite zone on the Y + Nb − Rb diagram (Figure 12b). These Late Triassic magmatic rocks display the characteristics of I-type granites. It is believed that the highly differentiated I-type granites were formed in a subduction environment [61] or during the post-orogenic phase [62]. Considering their geochemical similarities with coeval magmatic rocks exposed in the northern Erguna block [40], this study posits that the study area was in an active continental margin environment subjected to subduction during the Late Triassic. This is associated with the southward subduction of the Mongol-Okhotsk Ocean sandwiched between the Neopaleozoic Siberian and Sino-Korean-Mongolian plates.
As illustrated by the Y-Nb tectonic discrimination diagram (Figure 12a), all samples of the Middle Jurassic rhyolitic porphyries from the Wunugetu deposit fall within the volcanic arc-syn-collisional granite zone. As shown in the Y + Nb vs. Rb (Figure 12b) and tectonic discrimination diagrams, these samples occupied the volcanic arc granite zone. Recent studies have unveiled a suite of Middle Jurassic (168 Ma) muscovite granites in the Sunwu area, adjacent to the study area. These granites originated from the partial melting of the thickened continental crust, resulting from the continent-continent collision during the closure of the Mongol-Okhotsk Ocean [64]. Additionally, the geochemical traits of the S-type granitic rhyolitic porphyry within the deposit suggest their formation in a continent-continent collisional context.
In summary, the geochemical characteristics of the monzogranites and rhyolitic porphyries in the Wunugetu deposit suggest that the Mongol-Okhotsk Ocean was still subjected to subduction during the Late Triassic. By the Middle Jurassic, following the ocean’s closure, the ocean transitioned to a syn-collisional tectonic setting (Figure 13).

7. Conclusions

(1)
The formation age of the monzogranites in the Wunugetu deposit is established at 209.02 ± 1.0 Ma, while the rhyolitic porphyries are dated at 170.49 ± 0.81 Ma. This indicates that the deposit’s magmatic activity primarily spanned from the Late Triassic to the Middle Jurassic, with the major ore-bearing intrusions dating from the Late Triassic to the Early Jurassic.
(2)
The Triassic monzogranites from the Wunugetu deposit exhibit the geochemical characteristics of I-type granites, including high silica and alkali content, enrichment in Rb and Th, and depletion in Ba, P, and Ti. The rhyolitic porphyries are characterized by high silica and potassium content, with trace elements exhibiting enrichment in LREEs and depletion in HREEs, aligning with the geochemical traits of S-type granites. Both the monzogranites and rhyolitic porphyries within the deposit exhibit positive zircon εHf(t) values, indicating their source regions underwent the partial melting of juvenile crustal materials.
(3)
The Wunugetu porphyry copper–molybdenum deposit was formed within an active continental margin context, influenced by the southeastward subduction of the Mongol-Okhotsk Ocean from the Late Triassic to the Early Jurassic. Following the Mongol-Okhotsk Ocean’s closure during the Middle Jurassic, the Wunugetu region transitioned to a syn-collisional tectonic setting.

Author Contributions

Conceptualization, Q.W. and Y.Y.; methodology, Q.W.; validation, Y.Y., Q.F. and Z.Z.; formal analysis, Q.W., Q.F., Z.Z. and X.G.; investigation, Z.Z., X.G., T.W., L.C. and Y.Z.; data curation, Q.W.; writing—original draft preparation, Q.W.; writing—review and editing, Y.A.; supervision, Y.Y.; project administration, Q.F.; funding acquisition, Y.Y. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Investigation and Evaluation of Copper and Lithium Resources in Mongolia (No. DD20230586) from the China Geological Survey, the Northeast Geological Science and Technology Innovation Center Regional Innovation Fund (No. QCJJ2022-38).

Data Availability Statement

The data presented in this study are available in Table 1, Table 2 and Table 3.

Acknowledgments

The authors express their deep gratitude towards the two anonymous reviewers and the academic editor for their insightful and invaluable suggestions.

Conflicts of Interest

Qiulin Fu is an employee of Liaoning Province Institute of Geology and Mineral Resources Co., Ltd. and Xiaodan Guo is an employee of Liaoning Province Geology and Mineral Group Energy Geology Co., Ltd. We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled.

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Figure 1. (a) Tectonic location map of the Wunugetu porphyry copper–molybdenum deposit; (b) Geological map of the Wunugetu deposit showing the main lithologies and faults with a volcanic edifice [18].
Figure 1. (a) Tectonic location map of the Wunugetu porphyry copper–molybdenum deposit; (b) Geological map of the Wunugetu deposit showing the main lithologies and faults with a volcanic edifice [18].
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Figure 2. Northwest–southeast section (620 line) through the Wunugetu deposit showing the relationship of host monzogranitic porphyry, alteration, and mineralization [24]. Micrographs of potassium feldspathization (a), quartz-sericitization (b), and illite-hydromica (c). Bt—biotite, Qz—quartz, Pl—plagioclase, Kfs—feldspar, Srt—sericite, Ms—Muscovite.
Figure 2. Northwest–southeast section (620 line) through the Wunugetu deposit showing the relationship of host monzogranitic porphyry, alteration, and mineralization [24]. Micrographs of potassium feldspathization (a), quartz-sericitization (b), and illite-hydromica (c). Bt—biotite, Qz—quartz, Pl—plagioclase, Kfs—feldspar, Srt—sericite, Ms—Muscovite.
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Figure 3. Field outcrops, hand specimens, and microscopic photos of the monzogranites and rhyolitic porphyries in the Wunugetu deposit. Qz—quartz, Pl—plagioclase, Kfs—feldspar, Srt—sericite. (a) Field outcrops and sampling locations of rhyolitic porphyries; (b) Sampling location of monzogranite, with fine veins of pyrite and chalcopyrite; (c) Monzogranite hand specimens; (d) Rhyolitic porphyry hand specimen; (e) Microscopic photos of rhyolitic porphyry; (f) Microscopic photos of monzogranites.
Figure 3. Field outcrops, hand specimens, and microscopic photos of the monzogranites and rhyolitic porphyries in the Wunugetu deposit. Qz—quartz, Pl—plagioclase, Kfs—feldspar, Srt—sericite. (a) Field outcrops and sampling locations of rhyolitic porphyries; (b) Sampling location of monzogranite, with fine veins of pyrite and chalcopyrite; (c) Monzogranite hand specimens; (d) Rhyolitic porphyry hand specimen; (e) Microscopic photos of rhyolitic porphyry; (f) Microscopic photos of monzogranites.
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Figure 4. Cathodoluminescence images of zircons in the Wunugetu deposit. (a) Rhyolite Porphyry; (b) Monzogranite.
Figure 4. Cathodoluminescence images of zircons in the Wunugetu deposit. (a) Rhyolite Porphyry; (b) Monzogranite.
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Figure 5. Zircon LA-ICP-MS U-Pb concordia diagrams from Wunugetu copper–gold deposit. (a) Rhyolitic porphyries; (b) Monzogranite.
Figure 5. Zircon LA-ICP-MS U-Pb concordia diagrams from Wunugetu copper–gold deposit. (a) Rhyolitic porphyries; (b) Monzogranite.
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Figure 6. TAS discrimination diagram of igneous rocks in the Wunugetu deposit. Ir—Irvine boundary [32]; above is alkaline, below is subalkaline. 1—Peridotgabbro; 2a—Alkali Gabbro; 2b—Subalkaline Gabbro; 3—Gabbroic Diorite; 4—Diorite; 5—Granodiorite; 6—Granite; 7—Quartzolite; 8—Monzogabbro; 9—Monzodiorite; 10—Monzosyenite; 11—Quartz Monzonite; 12—Syenite; 13—Foid Gabbro; 14—Foid Monzodiorite; 15—Foid Monzosyenite; 16—Foidolite Syenite; 17—Foidolite; 18—Tawite/Urtite/Italite.
Figure 6. TAS discrimination diagram of igneous rocks in the Wunugetu deposit. Ir—Irvine boundary [32]; above is alkaline, below is subalkaline. 1—Peridotgabbro; 2a—Alkali Gabbro; 2b—Subalkaline Gabbro; 3—Gabbroic Diorite; 4—Diorite; 5—Granodiorite; 6—Granite; 7—Quartzolite; 8—Monzogabbro; 9—Monzodiorite; 10—Monzosyenite; 11—Quartz Monzonite; 12—Syenite; 13—Foid Gabbro; 14—Foid Monzodiorite; 15—Foid Monzosyenite; 16—Foidolite Syenite; 17—Foidolite; 18—Tawite/Urtite/Italite.
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Figure 7. SiO2–K2O (a) [33] and A/CNK–A/NK (b) [34] diagrams of monzogranites and rhyolitic porphyries in the Wunugetu deposit.
Figure 7. SiO2–K2O (a) [33] and A/CNK–A/NK (b) [34] diagrams of monzogranites and rhyolitic porphyries in the Wunugetu deposit.
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Figure 8. Chondrite-normalized REE patterns (a) [35] and spidergram of primitive mantle-normalized REEs (b) [36] of monzogranite and rhyolitic porphyries in the Wunugetu deposit.
Figure 8. Chondrite-normalized REE patterns (a) [35] and spidergram of primitive mantle-normalized REEs (b) [36] of monzogranite and rhyolitic porphyries in the Wunugetu deposit.
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Figure 9. Identification of genetic types of monzogranites and rhyolitic porphyries in the Wunugetu deposit [47]. (a) K2O + N2O–Ga/Al diagram; (b) Y–Ga/Al diagram; (c) FeOT/MgO–Zr + Nb + Ce + Y diagram.
Figure 9. Identification of genetic types of monzogranites and rhyolitic porphyries in the Wunugetu deposit [47]. (a) K2O + N2O–Ga/Al diagram; (b) Y–Ga/Al diagram; (c) FeOT/MgO–Zr + Nb + Ce + Y diagram.
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Figure 10. Diagrams of (a) SiO2-P2O3, (b) of Rb-Y, (c) and Rb-Th of monzogranites and rhyolitic porphyries in the Wunugetu deposit [57].
Figure 10. Diagrams of (a) SiO2-P2O3, (b) of Rb-Y, (c) and Rb-Th of monzogranites and rhyolitic porphyries in the Wunugetu deposit [57].
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Figure 11. Hf isotopic characteristics (a), after Yang et al., 2006 [58] and εHf(t) vs. U-Pb ages for zircons (b) of monzonites and rhyolitic porphyries from the Wunugetu deposit.
Figure 11. Hf isotopic characteristics (a), after Yang et al., 2006 [58] and εHf(t) vs. U-Pb ages for zircons (b) of monzonites and rhyolitic porphyries from the Wunugetu deposit.
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Figure 12. Diagrams of monzonites and rhyolitic porphyries from the Wunugetu deposit. (a) Y vs. Nb; (b) Y + Nb vs. Rb [63].
Figure 12. Diagrams of monzonites and rhyolitic porphyries from the Wunugetu deposit. (a) Y vs. Nb; (b) Y + Nb vs. Rb [63].
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Figure 13. Diagram showing the evolutionary model of mineralization in the Mongolian-Okhotsk Ocean [65].
Figure 13. Diagram showing the evolutionary model of mineralization in the Mongolian-Okhotsk Ocean [65].
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Table 1. LA-ICP-MS zircon U-Pb dating data of Wunugetu rhyolite porphyry and monzogranites.
Table 1. LA-ICP-MS zircon U-Pb dating data of Wunugetu rhyolite porphyry and monzogranites.
Test Point NumberThUTh/UIsotope Atomic RatioIsotopic Age (Ma)
(×10−6)(×10−6)207Pb/206Pb1σ207Pb/235U1σ206Pb/238U1σ208Pb/232Th1σ207Pb/206Pb1σ207Pb/235U1σ206Pb/238U1σ208Pb/232Th1σ
Sample WNG06
WNG06-088017241.110.050120.000970.182070.003590.026360.000230.008120.0001320045170316811633
WNG06-2610079321.080.049590.001070.180350.004130.026380.000290.008080.0002217651168416821634
WNG06-215166180.830.050380.001260.184520.005110.026530.000360.008520.0003821358172416921718
WNG06-236146890.890.049590.001200.181070.004530.026540.000320.007950.0003117657169416921606
WNG06-137227830.920.049720.001480.183260.006150.026630.000350.008260.0002418269171516921665
WNG06-209978211.220.050740.001370.186360.004690.026640.000300.008240.0003822962174416921668
WNG06-306306920.910.049250.000950.180370.003330.026650.000320.008670.0002816045168317021756
WNG06-016076240.970.050270.001170.185900.003980.026780.000260.008550.0001820854173317021724
WNG06-224756020.790.049810.001400.184580.005910.026790.000400.008740.0004218665172517031768
WNG06-257157270.980.048870.001100.180150.004030.026800.000320.008600.0003114253168317021736
WNG06-278268231.000.049110.001000.181650.004090.026820.000310.008130.0002015348169417121644
WNG06-165615980.940.050700.001200.187920.004630.026820.000260.008610.0002622755175417121735
WNG06-144575700.800.049170.001550.180740.005740.026820.000330.008590.0002615674169517121735
WNG06-155025700.880.050590.001320.186670.004750.026830.000330.008050.0002522261174417121625
WNG06-093414580.740.050010.001720.185650.006560.026860.000340.008310.0002119580173617121674
WNG06-296647010.950.049420.001240.183960.005110.027020.000450.008800.0002616859171417231775
WNG06-035896510.900.050330.001050.187680.004230.027060.000290.008890.0001521048175417221793
WNG06-058657481.160.050590.000940.188640.003650.027080.000290.008680.0001322243175317221753
WNG06-283044110.740.048840.001550.181650.005580.027090.000350.008570.0002614074169517221725
WNG06-107897651.030.050710.001140.189900.004190.027120.000250.009020.0002722852177417221815
WNG06-02209915661.340.049530.001180.185850.004640.027170.000310.008640.0001317356173417321743
WNG06-128047401.090.049000.001580.183210.006010.027200.000400.009170.0003314876171517331847
Sample WNG15
WNG15-106679590.630.052520.002940.238920.012950.032990.000460.010350.000123081312181120932082
WNG15-27113723090.470.052200.002870.236800.012760.032900.000350.010330.000102941282161020922082
WNG15-0456911210.480.051980.002000.236670.008780.033020.000330.010370.0000928590216720922092
WNG15-11912360.360.051540.001350.233410.006530.032800.000430.011360.0003526540213520832287
WNG15-182014230.450.051380.001480.229780.006750.032390.000400.010020.0003525845210620522027
WNG15-193135860.490.051290.001570.231140.007990.032560.000520.009720.0004125450211720731968
WNG15-302094620.420.051120.000900.231180.004560.032840.000340.010270.0002324627211420822075
WNG15-2956512610.430.050900.000750.231560.004210.032900.000300.010240.0002623625211320922065
WNG15-08145322660.600.050840.000730.232510.003650.033080.000410.010700.0002923317212321032156
WNG15-142332590.850.050740.001440.229220.006900.032770.000400.010440.0002122947210620822104
WNG15-172745440.460.050760.001130.232670.005600.033160.000390.010800.0003823034212521022178
WNG15-28161125230.600.050570.000870.232000.004870.033110.000430.010460.0004622126212421032109
WNG15-052506410.370.050540.000920.231530.005110.033090.000320.010650.0004122033211421022148
WNG15-1244310480.390.050500.001370.230970.005830.033130.000380.010920.0003721837211521022207
WNG15-2442512340.320.050480.001140.232520.005090.033320.000390.010150.0004721730212421122049
WNG15-16104117840.560.050280.000680.228450.003760.032880.000320.010020.0003120821209320922026
WNG15-09227422160.970.049590.003990.223410.017580.032670.000550.010320.000151761832051520732083
WNG15-063394810.670.049500.000860.228570.004600.033400.000270.010130.0002717132209421222045
Table 2. Zircon Hf isotope analysis results of Wunugetu rhyolite porphyry and monzogranites.
Table 2. Zircon Hf isotope analysis results of Wunugetu rhyolite porphyry and monzogranites.
SampleAge (Ma)176Yb/177Hf2σ176Lu/177Hf2σ176Hf/177Hf2σεHf (0)εHf (t)TDM1 (Ma)TDM2 (Ma)fLu/Hf
WNG06-0021730.0927510.0009750.0027810.0000290.2828360.0000232.35.7620850−0.92
WNG06-0031720.0973050.0014270.0027020.0000470.2828470.0000252.76.1601823−0.92
WNG06-0051720.0844280.0003220.0024410.0000320.2827420.000026−1.12.47511058−0.93
WNG06-0081680.0872120.0011470.0024160.0000460.2827820.0000210.43.8691970−0.93
WNG06-0091710.0810930.0013960.0023980.0000480.2828650.0000253.36.8569781−0.93
WNG06-0101720.0731250.0003710.0020320.0000280.2828550.0000203.06.5578800−0.94
WNG06-0121730.0995450.0009030.0028320.0000460.2828580.0000273.06.5587800−0.91
WNG06-0131690.0932240.0004300.0027510.0000270.2827880.0000270.64.0690959−0.92
WNG06-0141710.0776290.0006280.0022410.0000180.2828890.0000274.17.6532727−0.93
WNG06-0151710.0837560.0009530.0025400.0000470.2828740.0000283.67.1558762−0.92
WNG15-0052100.0628870.0013530.0020380.0000490.2826840.000023−3.11.28281166−0.94
WNG15-0062120.0818180.0020850.0025460.0000500.2826580.000020−4.00.38771227−0.92
WNG15-0082100.1103160.0005820.0035130.0000640.2826730.000028−3.50.68781202−0.89
WNG15-0112080.0475100.0031410.0015090.0001170.2827320.000023−1.43.07461053−0.95
WNG15-0122100.0971430.0017170.0030260.0000810.2827740.0000220.14.3716972−0.91
WNG15-0142080.0924120.0023860.0029850.0000460.2827840.0000200.44.6700949−0.91
WNG15-0162090.0640280.0011030.0019710.0000370.2827510.000016−0.73.67291015−0.94
WNG15-0172100.0854130.0008150.0025330.0000180.2827360.000019−1.33.07621052−0.92
WNG15-0182050.0768440.0008130.0023620.0000230.2827470.000015−0.93.37421028−0.93
WNG15-0192070.0703430.0008180.0022120.0000250.2827400.000019−1.13.17501043−0.93
Table 3. Analysis results of major elements (wt.%), rare earth elements, and trace elements (ppm) in Wunugetu rhyolite porphyry and monzogranites.
Table 3. Analysis results of major elements (wt.%), rare earth elements, and trace elements (ppm) in Wunugetu rhyolite porphyry and monzogranites.
No.3W06-1W06-2W06-3W01W02W03W15-1W15-2W15-3W18-1W18-2W18-3
Rock TypePorphyry RhyoliteMonzogranites
Major element (wt.%)
SiO276.3575.7777.4573.4473.1680.4775.3676.6977.7174.4075.1374.92
Al2O312.8612.8712.7214.2514.3711.3813.0112.8910.9813.5213.2412.81
Na2O0.230.230.230.740.740.170.220.301.593.773.553.73
K2O5.915.335.009.368.243.255.057.155.093.944.142.95
CaO0.090.120.090.070.110.060.060.070.150.990.930.57
P2O50.040.040.040.090.080.050.050.060.050.090.080.07
TiO20.050.050.050.170.170.070.100.090.160.210.180.22
MgO0.170.180.170.170.260.340.340.140.370.270.250.23
MnO0.190.280.110.030.020.030.040.030.040.040.040.03
TFe2O31.291.931.030.540.841.442.290.511.341.431.322.89
LOI2.342.822.490.771.382.112.891.461.910.730.741.39
TOTAL99.5199.6399.3899.6399.3699.3799.4099.3899.3899.3999.5899.81
Trace element (ppm)
Rb62.98121.78113.08117.95113.4877.48146.83138.72171.18158.50166.50122.31
Ba203.79225.28839.21757.42606.85303.08696.061041.381112.03604.78551.03916.73
Th2.776.095.9315.3820.6213.0219.0323.9711.0013.1710.2320.39
U0.250.800.582.492.3814.724.127.381.622.702.843.21
Ta0.270.510.511.931.882.311.651.000.761.291.080.82
Nb4.058.347.9219.0117.7813.7114.1813.2012.2218.7814.9812.12
Sr23.3050.7068.98130.77109.447.3628.3580.05126.96167.97157.60214.75
Zr24.9356.6953.11109.4092.3581.5695.83148.81162.3889.83114.23201.24
Hf1.332.562.484.193.503.633.884.744.593.383.935.30
La7.2115.2516.2523.0632.0729.8736.4246.2737.1210.7410.8854.28
Ce15.2132.3834.4446.7464.0960.4269.6182.4670.7320.5620.2174.95
Pr1.774.104.445.477.296.928.009.158.632.933.287.93
Nd5.7613.8615.3117.9923.3322.6626.1432.6632.2910.5111.6323.94
Sm0.992.392.633.474.183.914.135.195.832.652.873.26
Eu0.180.410.560.650.670.740.740.941.120.570.570.78
Gd0.781.951.993.564.664.104.045.075.532.982.813.09
Tb0.100.240.210.590.790.700.560.660.830.530.480.35
Dy0.461.160.923.685.034.543.013.624.793.522.951.74
Ho0.090.230.190.801.151.030.650.770.970.800.640.39
Er0.280.690.582.543.593.301.992.462.982.522.021.30
Tm0.040.100.080.430.600.590.350.410.500.450.360.22
Yb0.170.510.402.774.304.332.412.753.302.892.461.56
Lu0.040.100.090.490.630.670.420.490.530.490.410.28
Y2.506.255.1221.3530.4829.6718.1421.4826.1522.1817.8110.26
ΣREE33.0873.3878.07112.24152.37143.79158.48192.91175.1462.1361.57174.06
LREE31.1368.3973.6397.39131.62124.53145.03176.67155.7147.9649.44165.14
HREE1.954.994.4414.8520.7619.2713.4516.2419.4314.1612.138.92
LREE/HREE15.9613.7016.596.566.346.4610.7810.888.013.394.0818.51
LaN/YbN31.2321.4829.375.975.354.9510.8212.078.072.673.1725.01
δEu0.640.580.750.570.460.570.550.560.600.620.620.75
δCe1.051.000.991.021.031.031.000.980.970.900.830.89
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Wang, Q.; Yang, Y.; Fu, Q.; Zhang, Z.; Guo, X.; Wu, T.; Chai, L.; Zhou, Y.; An, Y. Origin and Geological Implications of Monzogranites and Rhyolitic Porphyries in the Wunugetu Porphyry Copper–Molybdenum Deposit, Northeast China: Evidence from Zircon U-Pb-Hf Isotopes and Whole-Rock Geochemistry. Minerals 2024, 14, 310. https://doi.org/10.3390/min14030310

AMA Style

Wang Q, Yang Y, Fu Q, Zhang Z, Guo X, Wu T, Chai L, Zhou Y, An Y. Origin and Geological Implications of Monzogranites and Rhyolitic Porphyries in the Wunugetu Porphyry Copper–Molybdenum Deposit, Northeast China: Evidence from Zircon U-Pb-Hf Isotopes and Whole-Rock Geochemistry. Minerals. 2024; 14(3):310. https://doi.org/10.3390/min14030310

Chicago/Turabian Style

Wang, Qingshuang, Yanchen Yang, Qiulin Fu, Zhongyue Zhang, Xiaodan Guo, Taotao Wu, Lu Chai, Yongheng Zhou, and Yonghai An. 2024. "Origin and Geological Implications of Monzogranites and Rhyolitic Porphyries in the Wunugetu Porphyry Copper–Molybdenum Deposit, Northeast China: Evidence from Zircon U-Pb-Hf Isotopes and Whole-Rock Geochemistry" Minerals 14, no. 3: 310. https://doi.org/10.3390/min14030310

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