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Article

Zircon U-Pb and Whole-Rock Geochemistry of the Aolunhua Mo-Associated Granitoid Intrusion, Inner Mongolia, NE China

by
Hao Li
1,2,
Xuguang Li
1,
Jiang Xin
3 and
Yongqiang Yang
1,*
1
State Key Laboratory of Geological and Mineral Resources, China University of Geosciences, Beijing 100083, China
2
No. 5 Geological Party Limited Liability Company of Liaoning Province, Dashiqiao 115100, China
3
Xinjiang Nonferrous Metal Industry (Group) Co., Ltd., Ürümqi 830000, China
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(3), 226; https://doi.org/10.3390/min14030226
Submission received: 30 December 2023 / Revised: 5 February 2024 / Accepted: 19 February 2024 / Published: 23 February 2024
(This article belongs to the Special Issue Mineral Chemistry of Granitoids: Constraints on Crystallization Conditions and Petrological Evolution)
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Abstract

:
The Aolunhua Mo deposit is a typical porphyry deposit, which is located in the middle southern section of the Da Hinggan Range metallogenic belt. Here, we report LA-ICP-MS zircon U-Pb age data from the Mo-associated granitoid, together with the element geochemistry of the zircons, discussing the source material of the ore-forming rock of the deposit. The zircon data constrain the crystallization age of the granite porphyry as 135.0 ± 1.0 Ma, correlating it with the widespread Yanshanian intermediate–felsic magmatic activity. The Th/U ratio of the zircon is greater than 0.1, with a significant positive Ce anomaly (Ce* = 1.72–188.71) and a negative Eu anomaly (Eu* = 0.05–0.57). The zircons show depleted LREE and enriched HREE patterns, as well as low La and Pr contents, suggesting crystallization from crust-derived magmas. Based on the geology of the ore deposit and the age data, in combination with the regional geodynamic evolution, we infer that the Aolunhua Mo deposit was formed near the peak stage of Sn poly-metallic metallogenesis in the Da Hinggan Range region at around 140 Ma, associated with a tectonic setting, characterized by the transition from compression to extension. Based on a comparison with the newly found Mo deposits along the banks of the Xilamulun River, we propose that the Tianshan–Linxi is an important Mo-metallogenic belt. It also suggests an increased likelihood for the occurrence of Mo along the north bank of the Xilamulun River.

Graphical Abstract

1. Introduction

Most of the important Cu, Mo, and Au deposits around the world are associated with porphyry systems [1,2,3,4,5,6,7,8]. A series of porphyry-type Mo deposits include some giant world-class deposits in the Central Asian metallogenic domain (CAMD), notably the Northeast China Mo-Cu metallogenic provinces [9]. In Northeast China, the Da Hinggan Range is an important poly-metallic metallogenic belt, hosting different types of hydrothermal deposits [10,11,12,13,14,15,16,17,18]. A number of ore deposits, such as the Dajin Cu-Ag-Sn-Pb-Zn mineral deposit, the Bairendaba Pb-Zn-Ag ore deposit, the Huanggangliang Fe-Sn ore deposit, and the Baiyinnur Pb-Zn ore deposit [11,12,18,19,20], have been discovered in this region, all of which are large or super-large ore deposits. Several previous investigations have addressed the regional metallogenic series, including the regional metallogenic characteristics, the kinematic background of metallogenesis, and the petrogenesis of the region [11,12,13,21,22,23]. The discovery of the Mo poly-metallic metallogenic belt on the south bank of the Xilamulun River has attracted wide attention [24]. However, there are relatively few studies of metallogenetic rule on the north bank of the Xilamulun River before the Aolunhua porphyry Mo deposit was discovered [25].
The present paper aims to study a rare porphyry type Mo deposit that carries abundant Mo metallogenetic elements, which is located along the north bank of the Xilamulun deep fracture belt. In the following, we present an analysis of mineralogical features, zircon U-Pb geochronology and trace element geochemistry, and the major and trace element geochemistry of the deposit-hosting granite porphyry. Based on these results, we further estimate the age of the ore formation, and interpret the geodynamic setting of the mineralization, both locally and regionally.
Spatially, the Mo-Cu ore deposits are clustered along margin fractures [26], such as the Xilamulun deep fracture belt [27]. The deposits along the south bank can be divided into three stages: a post-collisional orogenic stage at 250–220 Ma; a transitional geodynamic stage at 180–145 Ma; and finally, a stage associated with the large-scale thinning of the lithosphere at 140–120 Ma [28]. However, in the north bank, the ore-forming events occurred mainly around 140–130 Ma, such as the newly found Hashitu porphyry Mo deposit, with an ore-forming age of 148.8 ± 1.6 Ma [17,29], and the newly found Bianjia porphyry Mo-Sn ore deposit, with a quartz porphyry formation age of 140 Ma (see Figure 1). Combined with the geochronological data of the Aolunhua Mo-Cu ore deposit presented in this paper, together with those from the existing literature [30,31], the Tianshan–Linxi porphyry type Mo deposit can be considered as an important metallogenic belt, developed during the peak stage of metallogenesis under an extensional tectonic setting on the north bank of Xilamulun River, and may reinforce the interpretation of a large-scale thinning of the lithosphere during that time.

2. Regional Geological Setting

The middle-south segment of the Da Hinggan Range is located within the collisional suture between the Siberian and North China plates [32] and is a mineral concentration district of the Cu-Sn-Mo poly-metallic metallogenic belt in North China (Figure 1).
The Aolunhua porphyry Cu-Mo deposit is located at the border of Alu-Kerqing Qi and Zarute Qi, with geographic coordinates of E 120°12′00″–120°15′30″; N 44°31′00″–44°34′00″. The Hing-Meng orogen, where the Aolunhua deposit is located, is the eastern elongation of the Central Asian Orogenic Belt, a composite orogen with an extensive history of accretion and terrane amalgamation that spans the Paleozoic and Mesozoic [11,33,34,35,36,37]. The major tectonic features of this region are fault structures. The near E-W trending Xilamulun River fault is a major boundary fault (Figure 1). Magmatism was common throughout the history of the region, including the Caledonian, Variscan, Indosinian, Yanshanian, and Cenozoic events. Among them, the Yanshanian magmatic events were the largest in scale, and were closely related to metallogenesis.

3. Geology of the Ore Deposit

The Aolunhua porphyry Mo deposit is located to the northwest of the Nenjiang faults (Figure 1). The strata around the Aolunhua Mo-ore deposit mainly belong to the Linxi group (P2l) of the upper Permian and the Manketou Obo group (J2 m) of the upper Jurassic, as well as the Quaternary system (Figure 1D). The upper Permian Linxi group is mainly composed of sandstone and hornfels derived from igneous intrusions. The upper Jurassic Manketou Obo group is distributed in the northeast part of the ore area and shows a disconformable contact with the underlying Linxi group. In the ore area, faults and folds are weakly developed. However, the joints and fissures were filled with a hydrothermal solution, forming a stock work of quartz veins [38], which provided enough space to host the ore minerals of the Aolunhua ore deposit, where the strata were influenced by uplift intrusions. The joints developed in the granite porphyry are conspicuously different from those developed in the external contact zones. Due to the influence of the pre-metallogenic faulting and the pre-existing gneissic structure, the joints in the external contact zones are always steep, following the gneissic foliation, while, within the porphyry intrusion, there are networks of quartz veins with many different orientations.
The ore body is hosted within the inner and external contact zones of the Aolunhua granite porphyry intrusion. Mo and Cu are the two major metallogenic elements. The Mo industrial ore bodies enclosed in the porphyry rock body occupy the main part of the total reserve. It is especially enriched at the top of the rock body. The ore bodies are well preserved, occurring as stockworks. A preliminary investigation showed that there are two ore bodies, classified as the “upper” and “lower” bodies. The ore bodies in the external contact zone are mainly ore-bearing quartz veins, which are controlled by joints and fissures. The major mineralizations are molybdenitizations with the minor secondary oxidation enrichment of copper. The variations in Mo-ore grade are rather large.
In the ore body, the major ore minerals are molybdenite, chalcopyrite, pyrite, and arsenopyrite. The minor ore minerals are bornite, sphalerite, and galena. The vein minerals include quartz, feldspar, calcite, chlorite, and kaolinite. The textures of the ore are mainly granular, poikilitic, mosaic, porphyritic, and pseudomorphic. The structures of the ore are mainly impregnation, vein, stock work, and banded [30]. The wall rocks are characterized by potash alteration, silicification, propylitization, phyllite alteration, and argillation. Among the different types of alteration, potash alteration and silicification are most closely related to metallogenesis.

4. Sample Features and Laboratory Studies

4.1. Sample Features

The wall rocks hosting the ore body are generally granite porphyry. Some fine-grained porphyritic granodiorite and minor coarse-grained granites are also present. The transition between different rock types is gradual. Sample AL03 is a porphyritic granodiorite, collected from the quarry of the Aolunhua Mo-ore deposit. The rock is massive (Figure 2a), grayish-white in color, and porphyritic in texture. Under the microscope, the rock is mainly composed of plagioclase (35%–40%), K-feldspar (20%–25%), quartz (20%–25%), amphibole (2%–3%), and biotite (5%–7%). Minerals are homogeneously distributed with 15%–20% phenocrysts, showing a porphyritic texture (Figure 3b) with a granitic groundmass (Figure 2c). The phenocrysts are mainly composed of plagioclase, a few quartz, biotite, and amphibole phenocrysts. Most of the phenocrysts are euhedral with partial irregular fringes. The plagioclase phenocrysts are euhedral and platy, with prominent zoned structures (Figure 2b). The quartz phenocrysts are granular, and the biotite phenocrysts are idiomorphic flakes (Figure 2d), while the amphibole phenocrysts are euhedral and prismatic. The grain size of the phenocrysts ranges from 0.5 to 1.0 mm. In the groundmass, granular textures are common, with the plagioclase showing some euhedral to subhedral forms, but mostly anhedral forms. K-feldspars are anhedral, and quartz grains are anhedral granular, constituting the granitic texture of the rock (Figure 2c). Locally, K-feldspar and quartz intergrowths forming graphic textures can be found. The grain size of the groundmass minerals ranges from 0.2 to 1.0 mm. The biotites distributed in the groundmass form subhedral–anhedral plates, while amphiboles occur as anhedral short prisms.

4.2. Analytical Methods

4.2.1. Zircon U-Pb Geochronology and REE Elements Analyses

Twenty-seven granite samples were selected for zircon U-Pb dating. The zircon grains were separated through standard gravity and magnetic methods, followed by hand picking under the binocular microscope, all following the crushing of the rock sample. The zircon grains were mounted onto epoxy resin discs, and then polished to expose their internal texture. Before U-Pb dating, zircon grains were imaged under transmitted light, reflected light, and cathodoluminescence (CL) in order to allow for the evaluation of their internal textures. The most suitable grains were then selected for U-Pb analyses.
The U-Pb analyses were carried out with a laser ablation inductively coupled plasma mass-spectrometer (LA-ICP-MS), housed at the China University of Geosciences (Beijing, China). The ICP-MS is made by the US Agilent company, and the mass spectrometer is of the 7500a type. The laser apparatus, of type number UP193SS, was made by the New Wave company in the USA. The laser wave length, laser spot diameter, and frequency were 193 nm, 36 μm, and 10 Hz, respectively, while the pre-ablation and ablation times were 5 s and 45 s, respectively. During the experimental process, He-gas was used as the carrier with a flow velocity of 0.8 L/min. The element integration time is 20 ms for U, Th, and Pb, 6 ms for Si and Zr, and 10 ms for the other elements. Raw data were processed using the GLITTER 4.41.1 program to calculate isotopic ratios and 207Pb/206Pb, 206Pb/238U, 207Pb/235U ages, respectively. The age calculation uses standard zircon TEM as the external standard for the correction of the isotope ratio. Standard zircon 91500 [39] and Qinghu were used as monitoring blind samples, the element contents are calculated by using the international standard NIST610 [39] as an external standard, and Si as an internal standard, NIST612 and NIST614 [39] are taken as monitoring blind samples. The correction of 204Pb follows ref. [39]. Each analysis is reported at 1σ uncertainties, and isoplot 3.0 was used to calculate the U-Pb ages, as well as to make the Concordia plots [40].

4.2.2. Whole-Rock Geochemical Analyses

Fresh granitoid samples for elemental analyses were first trimmed and chipped, and then powdered in an agate mill to about 200 mesh for analyzing. The analyses of major elements were conducted on the basis of Rock Samples from the United States Geological Survey. The analyses of silicate petrochemistry were conducted by X-ray fluorescence spectrometry. The analysis apparatus is a Phillip X-ray fluorescence spectrometer PW 2014. The analytical precision and accuracy for most major elements measured are generally better than 5%. FeO was analyzed by the titration method, with a standard deviation less than 10 percent. The analyses of trace elements were conducted, according to the general rule of the ICP-MS method; the apparatus used was an HR-ICP-MS (element 1), made by Finigan MAT. Rhodium was used as an internal standard to monitor any signal drift during counting. The analytical error is generally less than 5% for trace elements. The analyses were conducted in the Analytical Center of the Geological Institute of the Ministry of Nuclear Industry. The analytical results are given in Table 1.

5. Results

5.1. Zircon U-Pb Geochronology

The selected zircon grains are colorless, transparent-to-pale yellow, and euhedral, with a typical elongated prismatic shape (Figure 3). The Th/U ratios of the grains are greater than 0.1 (Table 2), indicating a magmatic origin [41]. Their magmatic origin is further supported by their typical magmatic oscillatory zoning under cathodoluminescence (CL) images (Figure 3). The lack of a core-mantle structure and deuteric alteration shells suggests the zircon crystals were originally crystallized from a common magma. Therefore, the age of the zircons could represent the timing of magma crystallization. A total of 27 zircon grains were analyzed from the granite porphyry sample, and the results are given in Table 2. The contents of Th and U are greatly variable, ranging from 18.46–467.96 ppm and 28.96 ppm–768.17 ppm, respectively. On the U-Pb concordia diagram (Figure 4a), all data are plotted along the concordia line or near to it, showing a high degree of concordance, without any loss or addition. The 206Pb/238 U-Pb age of the zircons varies from 131 Ma to 140 Ma (Figure 4a,b). The zircon ages range from ~140 Ma to 130 Ma, documenting the history from the magma emplacement to the crystallization. The large range of zircon ages that reflect the magma evolution history have also been reported in the Adamello Intrusive suite, N. Italy [42], and Acadian deformation and Devonian granites in northern England [43]. The analytical results accurately represent the crystallization age of the granite porphyry. Zircon U-Pb dating results indicate that the granite porphyries, which are closely related with the Aolunhua Mo deposit, are products of Yanshanian early Cretaceous magmatism.

5.2. Zircon Trace Element Geochemistry

Using the method proposed by [6], after eliminating 3 of the granodiorite samples of zircon trace element data, 30 analytical points of trace element data are left for study. The contents of the trace elements in zircon from the Aolunhua granite porphyry are given in Table 3. Their distribution (Figure 5a) indicates that the zircons are enriched in large ion lithospheric elements of Th, Zr, and Hf, and have a strong negative anomaly of La, Nd, and Ti. The chondrite normalized REE distribution patterns of zircon (Figure 5b) show that all of the analytical results are depleted in LREE and enriched in HREE, and the Aolunhua granodiorite zircon samples show a prominent Ce positive anomaly (Ce* = 1.72–188.71) and prominent Eu negative anomaly (Eu* = 0.05–0.57). The zircons are high in ΣREE (299.02 × 10−6–2548.68 × 10−6) and have a high degree of variation, which are characteristic of a magmatic origin [44].

5.3. Whole-Rock Geochemistry

5.3.1. Major Elements

The Aolunhua granite porphyry samples (AL01, AL03, AL05, AL03-01, AL03-02) have SiO2 contents ranging between 70.00%–77.05%, Al2O3 contents of 10.64%–13.30%, K2O contents of 4.04%–4.76%, and Na2O contents of 2.98%–4.37%, indicating that they are acidic and K-rich. The Al saturation index (A/CNK) ranges between 0.838–0.916. On the diagram of A/CNK-A/NK, the Aolunhua samples display a meta-aluminous series, similar to the characteristics of I-type granites. On the R1-R2 diagram, these samples plot in the field of syn–orogenic granites (Figure 6b).

5.3.2. Trace Elements

The trace element content of the Aolunhua granite porphyries (AL01, AL03, AL05, AL03-01, AL 03-02) are given in Table 1. The prominent characteristics of the samples are their enrichment in Rb, Th, etc., with Rb variations in the range of 97.1–125 ppm, and Th variations in the range of 4.12–6.61 ppm. The Hf, Y, and Yb concentrations are low. The Hf content ranges from 1.68–2.66 ppm. Y varies from 8.31 ppm to 9.16 ppm, whereas Yb varies from 0.714 ppm to 0.871 ppm.

6. Discussion

6.1. The Chronology of Petrogenesis

The accurate determination of the chronology of petrogenesis is important in understanding the genesis of an ore deposit. The zircon isotope system is a reliable method to obtain the age of petrogenesis. Therefore, the results are quite reliable. The present study has found the zircon U-Pb LA-ICP-MS crystallization age to be 135.0 ± 1.0 Ma. As viewed from the perspective of metallogenesis, the ore deposit is directly hosted by the contact zone between the granite porphyry body and its wall rocks, which is closely related in space with the granite porphyry. Therefore, the study of the characteristics of the ore deposit and the metallogenic geochronology suggest that the Aolunhua ore deposit is the product of the Yanshanian intermediate–felsic magmatic hydrothermal activity.
The crystallization age of the Aolunhua ore-bearing granite porphyry, i.e., 135.0 ± 1.0 Ma, as presented in this paper, is nearly identical to the zircon U-Pb SHRIMP age of 134 ± 4 Ma obtained by [30], which suggests that the magmatism originated at about 130 Ma. In addition, the Re-Os isochron age of 131.2 ± 1.9 Ma was obtained for the Aolunhua porphyry Mo deposit [45]. In the Banlashan Mo deposit, 50 km SW of the Aolunhua Mo deposit, the crystalline age of the granite porphyry is dated at 131.1 ± 1.8 Ma [27]. Additionally, the Yangchang Mo deposit provides an isochron age of 138.5 ± 4.5 Ma for two groups of molybdenite [46]. The ages are also close to the petrogenic age of the Aolunhua Mo deposit. It is clear that the deposits are products of the intensive Cretaceous tectono-magmatic activities, which also confirms that the large scale magmatism-fluid-metallogenic events developed in Da Hinggan Range, and even in East China, happened at around 130 Ma [46,47].
Besides the geotectonic situation of the Aolunhua Mo-deposit at the north of the Xilamulun River deep fracture belt, the discovery of the Banlashan and Yangchang Mo-deposit further confirms that the southern section of the Da Hinggan Range not only hosts large scale, mainly Cu, Sn, Pb, and Zn ore deposits, but is also an excellent prospect for further exploration of mainly Mo-metallogenic element deposits in this region.

6.2. The Tracer Significance of Trace Elements in Zircon

The trace element composition in zircon is important for developing a proper understanding of the petrogenesis of zircon and its host rocks. The contents of the trace elements in zircon from the Aolunhua granite porphyry are given in Table 3. The hydrothermal zircons are believed to precipitate from aqueous fluids, in most cases, at relatively low temperatures, rather than from magmas. The Th content of the zircon is 18.96 ppm–710.61 ppm, and the U content is 27.25 ppm–768.7 ppm; thus, the relevant Th/U ratios range from 0.6–0.76 (larger than 0.1), indicating a magmatic origin [44,46]. There are local testing sites higher in U content. Chakoumakos et al. [47] studied zircons from Sri Lanka and found that the metamict domains in zircon had a very high U-content. The average U content is 3000 ppm. After studying different zircon samples from the Adirondack terrain, Valley et al. [48] found that the highly magnetic, high metamictized zircons had higher U contents than those of low magnetism and weak metamictization. All research results show that the metamict domain in zircon is high in U content.
The REE distribution patterns of zircon from Aolunhua granite porphyry are shown in Figure 5b. The ΣREE values are high and the variation is large, ranging from 299.02 × 10−6 to 2548.08 × 10−6. All of the analytical spots show a prominent Ce positive anomaly and an Eu negative anomaly (Figure 5b), with a large variation range: Ce* = 1.72–188.71, Eu* = 0.05–0.57 [49,50], which are within the range of crust-derived zircons [51]. Unlike other REEs that have only +3 valency, Ce and Eu commonly have two oxidation states in terrestrial magmas, and zircon more preferentially incorporates the oxidized cations Ce4+ (0.97 Å) and Eu3+ (1.07 Å) into the Zr4+ (0.84 Å) site of its structure than the reduced Ce3+ (1.14 Å) and Eu2+ (1.25 Å) [49]. Thus, high Ce4+/Ce3+ and Eu/Eu * ratios usually reflect the high oxygen fugacity (ƒO2) of the parental magmas.
In addition, all of the testing spots show the characteristics of enrichment in HREE (Figure 5b). According to [44], if the range of variation of the LREE in recrystallized zircon is clearly larger than that of the HREE, it can be interpreted as the result of the greater instability of LREE in the zircon. It is obvious that during recrystallization, LREE in zircons are easier to drive out of the zircon lattice, leading to a decrease in LREE contents. The low contents of La and Pr and the Ce positive anomaly are characteristic of REE in crust-derived magmatic zircons.

6.3. The Tectonic Setting of the Formation of Ore-Bearing Intrusive Body

The major ore-hosting igneous rock in Aolunhua is fine-grained porphyritic granodiorite, and chronological studies show that the porphyritic granodiorite zircon dating yields the age of 135.0 ± 1.0 Ma. The petrochemical data indicate that the Aolunhua Mo-deposit porphyritic granodiorites are meta-aluminous. On the R1-R2 discrimination diagram (Figure 6b), they plot into the field of syn-collisional granites. However, for the plots on the (Yb+Nb)-Rb diagram (Figure 7a), the Aolunhua ore-bearing igneous rocks plot on the boundary between the syn-collisional (Syn-COLG) and the volcanic arc granite (VAG) fields. The plots on the Y-Nb diagram (Figure 7b) are within the field of the volcanic arc and the syn-collisional granites (VAG+syn-COLG), while the plots in Y-Sr/Y diagram (Figure 7c) show that they are adakaitic in character.
Previous studies have shown that the southern segment of the Da Hinggan Range experienced partial subduction and continent–continent collision in the Paleo-Asian Ocean, between the North China and Siberian Paleo continents, which formed the Hing-Meng orogenic belt [52]. In recent years, more studies have confirmed that the collision between the Siberian and North China plates likely happened in the mid-late Permian period and continued to the mid Triassic period. By the late Jurassic period (150 Ma), the western segment of the Mongol–Okhotsk ocean had closed, and the continental collision ended [53]. For the Da Hinggan Range in northeastern China, the NNW subduction of the Izanagi plate beneath the Eurasian plate triggered intensive magmatism and a mineralization event in this region, which is the most important tectonic activity in the Mesozoic [28].
After the conclusion of the Da Hinggan Range orogeny, the crust of the southern segment of the Da Hinggan Range gradually experienced a transition to an extensional setting. On the R1-R2 discrimination diagram, the granite porphyries of the Aolunhua Mo deposit mainly plot into the syn-collision field, whereas on the Y-Sr/Y diagram, they plot into the field of adakaite, indicating that the petrogenesis occurred under rather high pressures. Combining this knowledge with the petrogenic age of 135.0 ± 1.0 Ma obtained in this study, these results suggest that the tectonic setting of the magmatic rocks in the ore area was in transition between a compression-orogenic and extensional back-arc regime. Moreover, Wang et al. [54] proposed that block margins and suture zones are preferred settings for large scale metallogenesis. The main metallogenic pulse formed in response to the magmatic activity and minerogenesis, during which an extensional back-arc regime was developed in the Xilamulun area, following accretionary orogenesis and the thickening of the continental crust.
In fact, at this regional, the large-scale porphyry-type Mo mineralization was dominated by a tectonic-magmatic event: slab rollback, accompanied by related lower crust delamination, asthenospheric upwelling, and lithospheric thinning in eastern China during the Cretaceous era (140–90 Ma). Although old crustal material may have been involved in the genesis of Mo-forming magmas, the partial melting of the juvenile lower crust provided significant contributions. In addition, other factors, including high magma oxygen fugacity, the efficient exsolution of metal-bearing fluids from magmas, and the boiling or immiscibility of fluids, may have played a fundamental role in the Mo enrichment and subsequent mineralization [9]. The Mo minera lizations of the Aolunhua deposit, the Banlashan deposit, and the Yangchang deposit occurred within or near the Cretaceous intrusive stocks. The geochronology of the ore-forming and intrusive rocks is consistent. Therefore, there is a close spatial and temporal relationship between the Mo mineralization and Cretaceous intrusive stocks in DHMP. The Mo mineralization took place in Cretaceous regional volcanic-magmatism. It is consistent with the fastigium of lithospheric thinning in North China.

7. Conclusions

(1) The zircon U-Pb LA ICP-MS age of 135.0 ± 1.0 Ma for the granite porphyry of the Aolunhua Mo deposit of Inner Mongolia indicates that the granite porphyry is the product of early Cretaceous magmatic activity.
(2) The Th/U ratio of the zircon from the ore-bearing igneous body of the ore deposit is greater than 0.1, with a prominent Ce positive anomaly (Ce* = 1.72–188.71) and an Eu negative anomaly (Eu* = 0.05–0.57), indicating typical magmatic zircon, with depletion in LREE and enrichment in HREE, and low La and Pr contents. The positive Ce anomaly reveals the characteristics of a crust-derived magmatic zircon.
(3) The Aolunhua ore-deposit is formed within the Cu-Mo metallogenic belt at the northern flank of the Xilamulun River deep fracture, which constitutes the Linxi–Tianshan Cu-Mo ore deposit belt and was formed during the peak stage of metallogeny at 140 Ma, caused by the magmatic activity, developed during the transitional stage between compression-orogeny and back-arc extension.

Author Contributions

H.L.: Conceptualization, Methodology, Validation, Formal analysis, Investigation, Data curation, Writing—original draft. X.L.: Conceptualization, Validation, Formal analysis,. J.X.: Methodology, Validation, Formal analysis. Y.Y.: Conceptualization, Methodology, Validation, Formal analysis, Investigation, Data curation, Writing—original draft, Supervision, Funding acquisition. All authors have read and agreed to the published version of the manuscript.

Funding

The study is supported by the Natural Science Foundation (Grant No. 41272110), China Nuclear Uranium Co., Ltd. in joint with East China University of Technology (Grant No. 2023NRE-LH-06), and the special program from Geological Survey of China (No. 12120113089400, 12120114076801).

Data Availability Statement

Data are contained within the article.

Acknowledgments

We are thankful to Pirajno Franco for his valuable help with the revision of manuscript. The CL image is conducted by Chen Li of the Physics Institute of Peking University, and the field work was assisted by the geologists of the Aolunhua Mo deposit, to whom the authors are deeply indebted.

Conflicts of Interest

Hao Li is an employee of No. 5 Geological Party Limited Liability Company of Liaoning Province. Jiang Xin is an employee of Xinjiang Nonferrous Metal Industry Group Co., Ltd. The paper reflects the views of the scientists and not the companies.

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Figure 1. Simplified tectonic map of the southern Da Hinggan Range and its adjacent areas. Legend: 1—major fault; 2—boundary between countries; 3—fault numbers; 4—porphyry type ore deposits. ① Deep fracture of the north margin of the North China plate. ② Fault of the Xilamulun River. ③ Erenhot – Hegenshan deep fault. ④ Onor–Elunchun fault. ⑤ Derburgan fault. ⑥ Da Hinggan Range Major Fault. ⑦ Nenjiang fault. (A) Location of reginal tectonic of study area; (B) Location in Central Asian Orogenic Belt; (C) Geological map of the Da Hinggan Range; (D) Aolunhua area geological map.
Figure 1. Simplified tectonic map of the southern Da Hinggan Range and its adjacent areas. Legend: 1—major fault; 2—boundary between countries; 3—fault numbers; 4—porphyry type ore deposits. ① Deep fracture of the north margin of the North China plate. ② Fault of the Xilamulun River. ③ Erenhot – Hegenshan deep fault. ④ Onor–Elunchun fault. ⑤ Derburgan fault. ⑥ Da Hinggan Range Major Fault. ⑦ Nenjiang fault. (A) Location of reginal tectonic of study area; (B) Location in Central Asian Orogenic Belt; (C) Geological map of the Da Hinggan Range; (D) Aolunhua area geological map.
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Figure 2. Occurrence and mineral composition of granite porphyry in the Aolunhua deposit Mineral abbreviations: Qtz—quartz, Kfs—K feldspar, Pl—plagioclase, Bi—biotite. (a) Granite porphyry occurrence sample; (b) Photo under orthogonal polarization of granite showing Pl, Qtz; (c) Photo under orthogonal polarization of granite showing Kfs, Qtz; (d) Photo under orthogonal polarization of granite showing Bt, Pl, Qtz.
Figure 2. Occurrence and mineral composition of granite porphyry in the Aolunhua deposit Mineral abbreviations: Qtz—quartz, Kfs—K feldspar, Pl—plagioclase, Bi—biotite. (a) Granite porphyry occurrence sample; (b) Photo under orthogonal polarization of granite showing Pl, Qtz; (c) Photo under orthogonal polarization of granite showing Kfs, Qtz; (d) Photo under orthogonal polarization of granite showing Bt, Pl, Qtz.
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Figure 3. Cathodo-luminescence (CL) image of the representative zircons of the granite porphyries from the Aolunhua Mo deposit. (a) no band; (b) crystalline band; (c) no band; (d) oscillatory band; (e) no band; (f) oscillatory band.
Figure 3. Cathodo-luminescence (CL) image of the representative zircons of the granite porphyries from the Aolunhua Mo deposit. (a) no band; (b) crystalline band; (c) no band; (d) oscillatory band; (e) no band; (f) oscillatory band.
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Figure 4. LA-ICP-MS U-Pb age concordia (a) and the weighted mean age histogram (b) of zircons from fine-grain porphyritic granodiorite (sample AL 03).
Figure 4. LA-ICP-MS U-Pb age concordia (a) and the weighted mean age histogram (b) of zircons from fine-grain porphyritic granodiorite (sample AL 03).
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Figure 5. Primitive mantle normalized trace element spider diagrams (a) and the chondrite normalized REE patterns (b) for zircon grains from the Aolunhua granodiorite.
Figure 5. Primitive mantle normalized trace element spider diagrams (a) and the chondrite normalized REE patterns (b) for zircon grains from the Aolunhua granodiorite.
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Figure 6. The A/CNK-A/NK (a) and R1-R2 (b) diagrams for rock samples from the Aolunhua deposit. In (b): 1—mantle differentiation; 2—pre-collisional; 3—post collisional uplift; 4—late orogenic; 5—non-orogenic; 6—syn-collisional; 7—post orogenic.
Figure 6. The A/CNK-A/NK (a) and R1-R2 (b) diagrams for rock samples from the Aolunhua deposit. In (b): 1—mantle differentiation; 2—pre-collisional; 3—post collisional uplift; 4—late orogenic; 5—non-orogenic; 6—syn-collisional; 7—post orogenic.
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Figure 7. The (Yb+Nb)-Rb (a), Y-Nb (b) and Y-Sr/Y (c) diagrams for rock samples from the Aolunhua deposit.
Figure 7. The (Yb+Nb)-Rb (a), Y-Nb (b) and Y-Sr/Y (c) diagrams for rock samples from the Aolunhua deposit.
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Table 1. The component of macro-elements (wt.%) and trace elements (10−6) of granites from Aolunhua deposit.
Table 1. The component of macro-elements (wt.%) and trace elements (10−6) of granites from Aolunhua deposit.
Rock TypesGraniteFine-Grained Granodiorite GraniteFine-Grained GranodioriteFine-Grained GranodioriteRock TypesGraniteFine-Grained GranodioriteGraniteFine-Grained GranodioriteFine-Grained Granodiorite
Sample Numbers AL-01AL-03AL-05AL-03-1AL-03-2Sample NumbersAL-01AL-03AL-05AL-03-1AL-03-2
Al2O312.8713.3012.9310.6412.21Rb11697.1125113115
SiO273.0371.0470.0077.0574.41Sr466431233409453
CaO1.552.242.721.081.54Zr66.472.863.056.165.8
K2O4.374.194.044.764.48Nb4.205.325.494.845.34
TiO20.300.420.420.260.34Hf2.212.662.431.682.02
Fe2O32.302.953.231.051.47Ta0.4020.4380.4160.3610.401
MgO0.610.810.780.510.69W25.13.1015.812.411.4
Na2O3.924.373.042.983.56Re0.0430.0181.950.5780.187
MnO0.0310.0380.0320.0280.022Tl0.6720.5260.8840.5960.504
P2O50.180.180.160.090.12Pb37.322936.521.09.74
FeO0.902.101.900.651.20Th5.466.615.344.124.61
LOI0.580.242.321.230.91Bi1.331.1919.72.531.04
Total100.641101.878101.572100.328100.952
Li9.9313.221.78.479.01U0.9907.151.582.281.73
Be2.221.901.281.992.03Dy1.661.661.871.561.48
Sc7.147.254.422.593.17Ho0.2960.2960.3110.2490.273
V29.633.032.626.734.8Er0.8160.8800.8550.6850.762
Cr4.194.565.898.368.17Tm0.1350.1290.1350.1180.136
Co3.544.067.271.632.48Yb0.8150.8710.8390.7240.714
Ni2.4629.63.100.9281.30Lu0.1410.1310.1350.1060.111
Cu27570692852142221Y9.008.739.168.408.31
Zn114533921252.331.3B2.401.274.392.062.26
Ga17.618.717.616.517.1
Table 2. The dating results of U-Pb isotopes for single zircon in sample AL03 of Aolunhua.
Table 2. The dating results of U-Pb isotopes for single zircon in sample AL03 of Aolunhua.
Sample NumbersContents/(μg/g)RatiosAge/MaTh/U
206Pb207Pb208Pb232Th238U207Pb/206Pb1σ207Pb/235U1σ206Pb/238U1σ208Pb/232Th207Pb/206Pb1σ206Pb/238U1σ207Pb/235U1σ208Pb/232Th
AL03-0129.491.6201.831149.73346.530.048620.003320.144820.010160.021070.000370.00697188119134213791400.43
AL03-0230.561.6042.191177.31357.540.048730.003180.138980.009200.021160.000300.0070581116135213281420.50
AL03-0335.751.922.640211.88418.380.047290.001450.141840.004160.021160.000390.0071212944135213541430.51
AL03-0439.412.1403.060258.55463.670.052300.002990.142860.009120.021050.000360.00677158105134213681360.56
AL03-0524.901.3391.292106.04289.120.048960.002010.143520.006040.021330.000350.0069613867136213641400.37
AL03-0634.341.8413.880313.88406.580.048830.002420.140330.007400.020930.000390.0070513084134213361420.77
AL03-0730.081.6162.086164.92351.590.048850.002970.142470.009080.02120.000400.007221351061352135121450.47
AL03-0837.761.9691.412113.42442.430.048780.002680.137950.008210.021150.000370.007116495135213161430.26
AL03-0947.402.7904.440364.70569.440.048950.002050.149620.006300.020740.000330.0069229970132214291390.64
AL03-1030.251.6331.833149.59351.610.049710.002650.143990.004290.021320.000430.00700146451363137101410.43
AL03-1118.911.0281.39386.78190.360.048990.001470.144210.007530.021410.000360.00777140861372137101560.46
AL03-1250.452.7204.110333.74579.630.048580.001400.145410.004090.021580.000380.0070414142138213851420.57
AL03-1332.051.7242.079169.46377.090.047200.002060.141800.006560.021080.000390.0070113773134213571410.45
AL03-1523.661.2940.55146.05290.510.047340.002580.145540.013480.021230.000350.00702181140135213871410.16
AL03-1645.952.4704.860415.08555.050.048520.003320.138920.007880.020560.000420.0066714770131313251340.75
AL03-1749.492.6003.810319.27595.900.048630.002000.139850.005890.020880.000340.006561281271332133141320.53
AL03-1862.733.2805.610467.96768.170.049630.005140.133790.009980.020550.000310.0066559611312127121340.61
AL03-2044.422.3608.480710.61542.180.049380.002120.134660.008320.020630.000390.006776696132212891360.76
AL03-212.490.1330.22618.4628.960.048520.005140.142900.006240.021360.000380.0070012593136213651410.64
AL03-2218.430.9941.616124.12204.180.048590.002360.147660.011850.022020.000310.00733130132140214061480.61
AL03-2329.891.6373.410249.50340.750.048590.001460.149140.011020.021790.000300.00782178136139214171570.73
AL03-2420.961.1192.221179.22253.510.048880.002580.138450.011850.020600.000340.00696135143131213281400.71
AL03-2636.541.9602.850232.71425.820.048620.001430.142750.015610.021330.000370.00703125144136213581420.55
AL03-2741.412.2202.550204.12486.420.048730.003880.141810.007530.021160.000390.00718128136135213541450.42
AL03-2830.191.6202.122166.71343.070.047290.003320.146620.009060.021880.000360.00730128151140213961470.49
AL03-2910.180.5490.72555.00117.340.052300.001880.145420.015610.021570.000370.00757142127138213871520.47
AL03-3047.222.5204.700399.45560.760.048960.003320.139330.001250.020940.000300.00676111132134313681470.71
Table 3. Trace element analyses of zircons from fine-grain porphyritic granite of Aolunhua deposit (90Zr, 178Hf wt%, others 10−6).
Table 3. Trace element analyses of zircons from fine-grain porphyritic granite of Aolunhua deposit (90Zr, 178Hf wt%, others 10−6).
AL03-1AL03-2AL03-3AL03-4AL03-5AL03-6AL03-7AL03-8AL03-9AL03-10AL03-11AL03-12AL03-13AL03-14AL03-15
49Ti3.032.873.322.422.152.607.322.492.822.7410.912.942.736.953.63
89Y1100.391328.411134.301165.77796.491541.331431.76471.551038.421136.441020.771436.961058.421277.40373.79
90Zr491,255.6482,274.2492,333.3481,478.9475,668.9479,458.5469,524.2476,759.6479,104.1471,036.4475,740.5460,816.8472,844.2475,096.9469,188.0
93Nb4.0304.8305.3305.7202.5003.0902.6101.2104.6002.7902.6007.0302.7101.0000.954
139La0.77800.04474.20000.11900.03330.02180.04690.01202.16000.29700.03200.12900.29500.97901.2500
140Ce26.4433.1143.6231.8619.0948.3316.2313.4241.9521.6619.3038.2823.807.375.90
141Pr0.18400.099701.57000.08000.034700.15400.28500.04600.67200.17400.06100.10200.16100.62800.5160
146Nd1.7201.9008.6001.2300.6844.1305.7200.4364.9001.6201.5801.6101.9506.6702.900
147Sm3.165.595.113.902.039.7613.411.084.993.984.114.733.949.553.07
153Eu0.8771.3801.3271.2750.7312.8803.5900.6081.3841.1001.1471.2981.2351.8300.399
157Gd18.6127.0520.6024.1313.0648.9952.296.8721.4021.7120.1627.6621.2040.9113.90
159Tb7.249.887.778.755.1215.6916.392.677.418.347.4710.737.9013.034.65
163Dy97.01122.36100.91109.6765.72168.49170.1535.1692.18106.9293.12136.3398.45146.3845.11
165Ho37.6945.9638.6141.4126.8254.4852.2614.0734.5840.5934.9250.6537.4649.1912.19
166Er172.27203.10176.73184.69124.45214.97194.7369.62161.81180.72155.47218.66164.39194.6446.24
166Tm45.1351.8845.9746.7933.3351.1043.9920.2441.6745.4440.3855.4742.1145.0610.90
172Yb535.18617.11551.00547.79422.97581.25475.64283.62512.19528.58477.09637.11492.08485.27128.23
175Lu100.05114.43102.37101.9684.01105.8678.2465.12101.3695.4888.44117.6790.6387.8023.77
178Hf9334.119017.0310056.969951.029356.059261.378263.119917.209748.668998.797946.2210054.139209.086019.058618.70
181Ta1.1081.2111.5001.6100.7340.6740.7980.3971.2500.9260.7621.7400.8770.4240.480
232Th149.73177.31211.88258.55106.04313.88164.92113.42364.70149.5986.78333.74169.4667.5946.05
238U346.53357.54418.38463.67289.12406.58351.59442.43569.44351.61190.36579.63377.09139.77290.51
Ce*16.0481.343.9973.43116.0185.1215.3275.958.1621.8175.6773.0725.192.111.72
Eu*0.280.290.350.310.380.330.370.520.350.290.320.270.330.240.16
AL03-16AL03-17AL03-18AL03-19AL03-20AL03-21AL03-22AL03-23AL03-24AL03-25AL03-26AL03-27AL03-28AL03-29AL03-30
49Ti3.723.833.3212.427.0511.0111.402.632.032.333.883.572.906.133.92
89Y1420.711651.601985.24808.603286.52721.151569.56934.91570.981084.911359.211516.20980.03973.571396.37
90Zr465,131.3460,473.9462,432.5467,410.5463,055.8476,714.8469,992.5466,770.8463,436.1462,163.6478,752.2468,543.7482,700.4486,641.548,9760.7
93Nb5.2508.4609.9500.6774.2600.8313.1003.7402.2404.2905.5507.8003.5102.6305.980
139La1.49000.27000.11701.13000.07600.01740.54100.05220.07200.01110.03900.02281.37000.01950.8830
140Ce41.1041.1855.619.5167.415.9922.1630.1823.3812.3439.9435.9732.6612.0541.58
141Pr0.31900.14500.11000.63800.82600.08200.28500.03800.03610.06330.06700.04600.37000.06700.2730
146Nd3.241.972.305.6815.061.403.241.180.7991.321.560.972.261.512.84
147Sm6.105.477.577.8330.493.427.153.212.303.874.863.903.044.465.26
153Eu1.9201.6102.3602.8008.1601.5902.6001.2690.8820.1991.6301.2051.1240.9531.590
157Gd32.3034.5043.9729.60115.0215.5436.7417.3613.0122.4428.3323.4017.4921.2828.99
159Tb11.3812.8916.558.6435.215.6413.346.404.448.5610.379.966.698.0310.59
163Dy138.56163.86202.5290.63371.4968.59157.2082.5553.64110.33129.74132.8085.1796.29130.07
165Ho50.4059.3773.1430.23118.3125.6656.1931.5220.0441.3847.6351.9232.9435.8048.71
166Er216.57254.55303.76119.21449.70113.19233.53142.8688.65176.82208.86240.48151.89155.34215.35
166Tm54.0563.2773.9628.1999.1428.3656.4237.6122.5742.2751.6962.6241.2437.7254.59
172Yb644.15708.51817.84313.021065.86327.56622.93465.45281.64468.54602.31747.83509.66426.10637.30
175Lu118.93121.39136.3457.87171.9361.99111.3391.3653.0381.36107.05139.08103.8277.49119.44
178Hf9204.889583.049201.586589.127582.626711.387167.539346.739878.159320.669328.829310.729502.138372.769474.74
181Ta1.1602.3502.5500.1500.9750.1870.7360.8450.6841.5001.5501.9500.7950.6731.490
232Th415.08319.27467.9635.43710.6118.46124.12249.5179.22107.43232.71204.12166.7155.00399.45
238U555.05595.90768.1727.25542.1828.96204.18340.75253.51279.21425.82486.42343.07117.34560.76
Ce*13.5248.0891.942.5722.5319.3313.06150.50106.5552.26140.08188.7110.6646.3519.84
Eu*0.340.280.310.500.370.570.400.420.390.050.340.300.370.250.32
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Li, H.; Li, X.; Xin, J.; Yang, Y. Zircon U-Pb and Whole-Rock Geochemistry of the Aolunhua Mo-Associated Granitoid Intrusion, Inner Mongolia, NE China. Minerals 2024, 14, 226. https://doi.org/10.3390/min14030226

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Li H, Li X, Xin J, Yang Y. Zircon U-Pb and Whole-Rock Geochemistry of the Aolunhua Mo-Associated Granitoid Intrusion, Inner Mongolia, NE China. Minerals. 2024; 14(3):226. https://doi.org/10.3390/min14030226

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Li, Hao, Xuguang Li, Jiang Xin, and Yongqiang Yang. 2024. "Zircon U-Pb and Whole-Rock Geochemistry of the Aolunhua Mo-Associated Granitoid Intrusion, Inner Mongolia, NE China" Minerals 14, no. 3: 226. https://doi.org/10.3390/min14030226

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