Trace elements and melt inclusion in zircon within the Qunji porphyry Cu deposit: Application to the metallogenic potential of the reduced magma-hydrothermal system

Zizhen Zhang; Zhengxi Gao; Yushan Zuo; Lei Zuo; Rui Liu

doi:10.1515/geo-2025-0796

Article Open Access

Trace elements and melt inclusion in zircon within the Qunji porphyry Cu deposit: Application to the metallogenic potential of the reduced magma-hydrothermal system

Zizhen Zhang , Zhengxi Gao , Yushan Zuo , Lei Zuo and Rui Liu

Published/Copyright: April 30, 2025

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From the journal Open Geosciences Volume 17 Issue 1

Abstract

The Qunji porphyry copper (Cu) deposit, located within the Awulale metallogenic belt (AMB) in the western Tianshan orogenic belt, exhibits distinct geochemical and mineralogical characteristics that have not been fully understood. Despite its contribution to our understanding of Cu mineralization mechanisms in reductive metallogenic systems, the oxygen fugacity and ore-forming potential of this deposit are lower than those of typical porphyry Cu deposits. Therefore, there is a need to further investigate the unique features of this deposit. The primary objective of this study was to analyze minerals and trace elements in zircon to quantify the oxidation states of the magma and investigate the presence of reduced porphyry-type magmas and ore-forming fluids in the western AMB. Through this research, we aimed to provide insights into the metallogenic mechanisms and contribute to the understanding of similar deposits in reductive environments. The zircon grains from the Qunji albite porphyry have a Ce⁴⁺/Ce³⁺ ratio of 37.0, indicating that the deposit likely formed in a reduced magmatic–hydrothermal system, which is common in the western Tianshan orogenic belt. Our analytical methods included the use of a cathodoluminescence scanning electron microscope and laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to analyze trace elements in situ. The results revealed a distinct enrichment of heavy rare earth elements and a relative deficit of light rare earth elements, with a positive Eu anomaly. The zircon crystallization environment was determined to be a continental crust environment. Additionally, the Qunji albite porphyry exhibited an A-type granite geochemical affinity and was formed within an extensional environment following tectonic collisions. The oxygen fugacity of the Qunji albite porphyry was notably low, which is a significant characteristic distinguishing it from typical porphyry Cu deposits. Consequently, the Qunji Cu deposit qualifies as a reduced porphyry Cu deposit with relatively low ore-forming potential.

Keywords: zircon; fO 2 ; melt inclusion in zircon; reduced ore system; metallogenic potential

1 Introduction

Zircon is a ubiquitous mineral in nature. For example, it occurs in magmatic, sedimentary, and metamorphic rocks [1,2,3,4,5,6]. Zircon possesses an exceptionally stable crystal structure and can be well preserved in complex geological environments [7,8,9,10]. Furthermore, zircon exhibits high weathering resistance and interference immunity. This property not only allows for the determination of the age of single-grain zircon but also provides insights into the trace element composition of zircon [11,12,13,14,15]. Studies indicate that rare earth elements and trace elements in zircon play a crucial role in reflecting the magmatic formation and properties of zircon [16,17,18].

The Awulale metallogenic belt (AMB) hosts significant copper–gold (Cu–Au) deposits, which are located in the western Tianshan region of China. Geological surveys [19,20] indicate the presence of substantial Paleozoic iron ore deposits in the eastern part of the AMB, as well as significant porphyry Cu deposits in the western segment of the belt [21,22,23]. Accordingly, the Qunji porphyry Cu deposit can be analyzed to investigate the Cu mineralization mechanisms within reductive metallogenic systems.

Aiming to investigate the characteristics of the ore-bearing intrusion associated with the Qunji porphyry Cu deposit in the Western Tianshan Orogenic Belt, minerals and trace elements in zircon were analyzed to quantify the oxidation states of the magma. The primary objective of the present study was to investigate the presence of reduced porphyry-type magmas and ore-forming fluids in the western AMB, originating from an extensional tectonic setting during the late Carboniferous period, and to analyze the variation of the fO ₂ composition during the deposition of sulfides in the reduced ore-forming system.

2 Regional geological background

As illustrated in Figure 1a, the Central Asian orogenic belt is adjacent to the European Plate to the west, the Siberian Plate to the east, and the Tarim and North China Plates to the south [24]. Moreover, Figure 1b reveals that the AMB is situated in the southwestern part of the Central Asian Orogenic Belt and is sandwiched between the Junggar Plate to the north, the Tarim Plate to the south, and the Kazakhstan–Yili Plate to the west. The strata exposed on a large scale in the AMB mainly consist of two sets of Carboniferous–Permian strata, with a sporadic distribution of Mesoproterozoic, Devonian, Triassic, Jurassic strata, and Quaternary sediments.

Figure 1

(a) Geographical location of the Central Asian orogenic belt [52]; and (b) tectonic geographical location map of AMB [56].

Among the previously mentioned sediments, Carboniferous strata, which are rich in Au, iron (Fe), Cu, lead (Pb), and zinc (Zn) deposits, are widely distributed in the Awulal area. The AMB primarily comprises the late Carboniferous sequence and includes the Dahalajunshan (C₁d), Akshak (C₁a), and Yishenjilike (C₂y) formations.

Similarly, the Permian strata are widely distributed in the Awulale area, whereas this stratum is relatively rare in Mount Ishkiri. In the study area, the Permian strata can be categorized into the Wulang Formation (P₁w) and Taerdetao Formation (P₁t) of the Lower Permian, as well as the Xiaoshansayi Formation (P₂x) and Tamuqisayi Formation (P₂t) of the Upper Permian. The main components of each formation are presented in Table 1.

Table 1

The main composition of different formations

Formation	Composition
C₁d	Volcanic-sedimentary rocks, rhyolite, trachyte, trachyandesite, and ignimbrite
C₁a	Purple-colored tuff, andesite, volcanic breccia, silty shale, grayish-green limestone, and grayish-green marl
C₂y	Quartz syenite porphyry felsic volcanic rocks (rhyolite) and rhyolite-intruded minor basalts
P₁w	Continental intermediate-mafic and felsic volcanic rocks such as andesite, dacite, rhyolite, olivine basalt, felsite, volcanic breccia, ignimbrite, and tuff
P₁t	Bimodal volcanic rocks, basalt, and rhyolite, while P₂x contains purplish red and gray thick-bedded conglomerate, pebbly sandstone, sandstone, siltstone, and mudstone
P₂t	Red and gray thick-bedded conglomerate, sandstone, siltstone, and mudstone

The Hamisite Formation is primarily composed of a relatively homogeneous mixture of volcaniclastic sedimentary rocks, including conglomerate, pebbly sandstone, and sandstone. Moreover, the Basiergan Formation is predominantly comprised of red thick-bedded conglomerate and sandstone. As depicted in Figure 2a, the intermediate to felsic pluton (296–306 Ma) is widely distributed in the western AMB. Notably, the AMB exhibits well-developed folds, faults, and dome structures. An E-W-trending tectonic belt formed in the late Early Paleozoic to early Late Paleozoic, which can be considered the earliest stratum compared to others. Figure 2a further illustrates that this stratum is well-developed and forms the axis of the Carboniferous folds. During the Permian, the E-W-trending tectonic belt was transformed by the N-E and N-W-trending tectonic belts, resulting in numerous folds, faults, and dome structures. Considering the influence of regional structures, rocks are mainly oriented parallel to the structure and have a dominant distribution in the intrusive porphyries and mineral deposits. The Changuoer iron deposit is primarily influenced by NW, NWW, and NE fractures [25], and the porphyry Cu ore bodies predominantly form near these structures [26].

Figure 2

Tectonic features and magmatic rock distribution in the Western Amur-More Basin. Detailed map illustrating the tectonics and distribution of magmatic rocks in the western AMB, highlighting key geological formations and relationships [19,20].

The exposed strata comprise the Wulang Formation of the Lower Permian, characterized by basaltic andesite; the Taerdetao Formation of the Lower Permian, which includes basalt and rhyolite; and the Xiaoshansayi Formation of the Upper Permian, exhibiting a conglomerate structure. The primary structure is the Tosba anticline, followed by fault structures, with a stratigraphic trend directed to the north and east, and a dip angle ranging from 50° to 80°. The intrusive rocks primarily consist of alkali-rich acid granite-albite porphyry, with most of the Cu deposits in the study area developed within the intrusive body. The Qunji albite porphyry is oriented in the north–south direction, with the rock mass controlled by a fault in the north that is 1,000 m long and 200 m wide, a narrow fault to the south, and an 80 m wide fault in the middle. Figure 3 illustrates that it intruded into the strata of the Taerdetao Formation of the Lower Permian and established intrusive contact with the basalts of the Taerdetao Formation.

Figure 3

Stratigraphic and albite porphyry distribution map of Qunji copper area [19,20].

The western part of the AMB hosts numerous Cu deposits that share striking similarities with the surrounding rocks, alteration zones, and ore minerals [27]. Accordingly, these deposits are significantly different from typical porphyry Cu deposits. This difference is particularly pronounced in the Qunji Cu deposit. In the western part of AMB, volcanic–subvolcanic hydrothermal Cu deposits are associated with Permian terrestrial intermediate and volcanic rocks, such as the Nulasai and Kezikezang deposits. However, porphyry Cu deposits are found within Late Paleozoic intermediate to acidic intrusive rocks, such as the Yinulasai, Qiongbulake, Qunjisayi, Qunji, and Heishantou deposits [19,20,22,26].

3 Petrography and mineralogy

The Qunji albite porphyry is maroon, featuring a fluidal structure and porphyritic texture. As depicted in Figure 4, nearly parallel ore veinlets are developed at the edge of the rock mass. These compositions mainly consist of hydrothermal minerals (such as calcite) or sulfides. The porphyry of the albite porphyry primarily consists of albite (50%), with a high Na₂O content in the whole rock (Table A1). The subsequent alteration is characterized by potassic minerals rather than sodium minerals (Figure 5a), exhibiting a platy structure with highly euhedral crystals, featuring twin crystal development, and showing signs of erosion at the edges (Figure 5b and d), indicating that the albite porphyry is formed by crystal differentiation [28]. The average particle size of albite is 2 mm × 0.2 mm (Figure 5). The matrix primarily consists of feldspar (20%) and quartz (30%), with accessory minerals including zircon, while dark minerals are rare in the rock mass.

Figure 4

Field photos of Qunji albite porphyry [19,20] with a maroon Qunji albite porphyry: (a) development of parallel veins with nearly horizontal pairs at the edge of the albite porphyry, (b) filled vein with hydrothermal minerals, (c) filled vein with sulfide, and (d) albite porphyry with rhyolite structure.

Figure 5

Microscopic characteristics of Qunji albite porphyry: (a) plate-like albite phenocrysts in albite porphyry with cryptic matrix and cross-polarized light; (b) albite phenocrysts in albite porphyry, cross-polarized light; (c) albite double crystals and quartz phenocrysts, cross-polarized light; and (d) albite feldspar in albite porphyry with eroded structure, flowing matrix, cross-polarized light (Ab: albite; Q: quartz).

The Qunji porphyry Cu deposit is located within fault-controlled albite porphyry. The occurrence of the orebody is similar to that of the albite porphyry, featuring veins, lentils, and lenticular shapes that range from 30 to 130 m in length and 5 to 10 m in width. Figure 6 indicates that the orebody near the fault has a Cu grade ranging from 0.2 to 1.5%, which is suitable for industrial applications.

Figure 6

Section map of No. 0 exploration line of Qunji porphyry copper deposit.

As illustrated in Figure 7, the ores can be primarily divided into veinlet and disseminated types located at the edges and within the rock mass, respectively. Sulfide compounds in the disseminated ore are distributed in a spot-like manner throughout the albite porphyry rock mass, while minerals in the vein ore are filled in the fractures of the rock mass in a ribbon-like manner. Since bornite is the most abundant mineral in the area, some veinlets are completely filled with bornite. The alteration observed in the Qunji porphyry Cu deposit is notably weak, with nearly no evident alteration in the disseminated ores. Consequently, only a very narrow potassic feldspathization is developed at the edges of the vein ores.

Figure 7

Field geological characteristics of Qunji porphyry copper deposit under different conditions: (a) no alteration in the contact zone between the ore-body and the surrounding rock; (b) disseminated ore, dark sulfide is distributed in porphyry copper deposits in speckles; (c) parallel veined ores; and (d) vein-like ore, dark sulfide is filled in the vein-like body, and narrow potassiation appears at the edge of the vein-like body.

The main ore minerals of the Qunji porphyry Cu deposit include pyrite, chalcopyrite, bornite, and chalcocite. Figure 8 shows that pyrite is a bright yellow material, which is generally speckled and embedded in other sulfides, with a particle size ranging from 50 to 200 μm. This mineral is mainly distributed in the albite porphyry matrix of disseminated ores and is associated with gangue minerals in vein ores. Moreover, chalcopyrite is distributed in ores and schistose rocks with no obvious crystal structure and is often associated with pyrite. Meanwhile, bornite is flaky, generally exhibits a complete crystal structure, and is often associated with chalcopyrite and pyrite. Since chalcocite forms from hydrothermal alteration in the later stage, it only develops at the edges of bornite, resulting in a very low concentration in the vein. The metasomatic texture of the minerals in the ore is well developed. The pyrite in the infected ore has a cubic euhedral–granular texture and is metasomatized by chalcopyrite along the internal fissures or edges (Figure 8a). Solid solution metasomatism is observed in chalcopyrite, with its replacement by bornite or a combination of chalcopyrite and bornite, while bornite itself is replaced by chalcocite (Figure 8a). The pyrite often occurs paragenetically with chalcopyrite and bornite, but there are also paragenetic combinations of chalcopyrite and bornite (Figure 8b).

Figure 8

(a) and (b) Mineral types and structural characteristics of Qunji porphyry copper deposit (Bo: bornite; Py: pyrite; Cpy: chalcopyrite; Cc: chalcocite).

4 Analytical methods

4.1 Whole-rock major and trace elements

The selected samples were first identified under a light slice microscope, and appropriate rock samples were chosen for pretreatment. Subsequently, some samples were selected for corrosion testing and broken into small pieces. In this regard, the samples were cleaned with MILI-Q ultrapure water, then dried and crushed to less than 200 mesh using an agate mortar in an uncontaminated environment for geochemical analyses. In the present study, elemental geochemical analyses were conducted at ALS Mineral/ALS Chemex Co. Ltd. To this end, X-ray fluorescence spectrometry (Rigaku 100e, Country) was employed to measure the concentration of major oxides, with an analytical accuracy of 2%. Furthermore, trace elements were tested using inductively coupled plasma mass spectrometry (ICP-MS, PE Elan 6000, Los Angeles, USA). The accuracy of this device for rare earth elements and other trace elements is 5% and 5–10%, respectively. Trace elements were measured using an ICP-MS (PE Elan 6000, Los Angeles, USA). The measurement accuracy of the device for rare earth elements and other trace elements was between 5 and 10%, respectively.

4.2 Zircon U–Pb dating and trace elements

The zircon selection process for ore-bearing porphyries in the Qunji Cu deposit includes artificial crushing (60–80 mesh), washing with clean water, separating zircon using conventional gravity and magnetic separation methods, purifying with a binocular microscope, and selecting zircon particles with reasonable transparency and good crystal shape. The zircon particles from the tested samples were placed on a target made of epoxy resin, and the reflected and transmitted light were photographed under the microscope. Subsequently, a cathodoluminescence scanning electron microscope (Chongqing Yujin Technology Co., Tokyo, Japan) was employed to analyze the internal structure of the zircon. LA-ICP-MS zircon U–Pb dating was carried out at the Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, China. The experiments are carried out using a 193 nm ArF-excimer laser system (GeoLas 2005, Göttingen, Germany) with a laser frequency and denudation spot of 6 Hz and 30 μm, respectively. The requirements of 91,500 GJ and NIST610 standards were followed in the test. The ²⁰⁶Pb/²³⁸U ratio was calculated using the GLITTER program (Macquarie University). Meanwhile, the Harvard zircon 91,500 was used as an external reference material to correct instrumental mass bias and depth-dependent elemental and isotopic fractionation [8]. The selection of blank signals for samples, instrument sensitivity drift correction, element content, and U–Th–Pb isotope ratio and age calculations were carried out offline using ICPMSDataCal software [29,30]. The weighted average age diagram and harmonic diagram were completed using Ludwig’s Isoplot3.0 [31].

Concurrent with U–Pb age tests on zircon samples, LA-MC-ICP-MS was used to analyze trace elements in situ. A laser denudation system (GeoLas 2005 of 193 nm ArF-excimer) with a denuded beam diameter of 30 μm and a laser frequency of 6 Hz/s was used in the experiment. Argon was used as the make-up gas and mixed with the carrier gas via a T-connector before entering the ICP [16]. The analysis procedure is according to that described by Yuan et al. [32]. Helium was used as a carrier gas to transport the ablated sample from the laser-ablation cell to the ICP MS torch via a mixing chamber where it was mixed with argon. It should be indicated that NIST SRM 610 was used as a reference material, and ²⁹Si was used as the internal calibrant [24].

4.3 Zircon melt inclusions composition test

Before testing the composition of zircon melt inclusions, its petrography was studied. To this end, the selected zircon samples were observed under the microscope, and relatively complete and more inclusions were selected as the research objects.

The gas phase composition was studied directly by laser Raman spectroscopy (XPLORA PLUS Visible, HORIBA, France) with a light source of 532 nm argon laser and an output power of 44 mV. Furthermore, the size of the laser beam spot was 1 μm, and the spectral resolution was 1 cm⁻¹. The counting time was 10 s, and the spectrum of the whole band from 100 to 400 cm⁻¹ was captured once. Before the test, the laser Raman spectroscopy was calibrated by monocrystalline silicon slices. After calibration, the Raman shifts of the monocrystalline silicon slices corresponded to 520.7 cm⁻¹.

Before analyzing the solid components of the melt inclusions, the inclusions were first exposed and then applied to zircon targets for electron probe analysis using an electron microprobe (JEOL JXA-8230, Tokyo, Japan) with an acceleration voltage of 20 kV, a current of 20 nA, a beam spot diameter of 1 μm, and a detection limit of 100–300 × 10⁻⁶. The standard samples used in the test process are selected according to the different objects tested, and the error of the major element is ±2%.

5 Results

5.1 Whole-rock major and trace element compositions

The samples from the Qunji albite porphyritic pluton mainly contains SiO₂ (66.4–76.9 wt%), Na₂O (3.23–7.16 wt%), and total alkali (6.02–9.66 wt%), with small amounts of other compositions such as low MgO (0.13–0.26 wt%), P₂O₅ (0.06–0.08 wt%), and CaO (0.47–1.84 wt%), with an Mg^# concentration of (0.08–0.23 wt%) [22], FeO^T/MgO ratio of 6.01–21.4, and (Na₂O + K₂O)/CaO ratio of 4.61–17.7 (Table A1). The relatively high SiO₂ and total alkali contents indicate a peralkaline signature for these samples. Furthermore, the A/CNK ratio varies in the range of 0.78–1.22, implying that these samples mostly belong to the metaluminous series. Figure 9a shows the evolution of samples from alkaline to the peralkaline field, which is consistent with the characteristics of alkaline rocks. The Al-index map demonstrates that the Qunji albite porphyry falls in the transition region from metaluminous to peraluminous (Figure9b). These samples were slightly enriched in light rare earth elements (LREEs) with negative Eu anomalies (Eu/Eu* = 0.39–0.66). The normalized diagrams of trace elements in the primitive mantle in Figure 10b reveal that Ba, Nb, Ta, Sr, P, and Ti are depleted, while Rb, Th, U, K, Zr, and Hf are relatively enriched and have high Ga/Al ratio and other geochemical characteristics, which are considered as typical characteristics of A-type granites. Figure 11 shows the distribution of studied samples in the A-type granite. Accordingly, it is inferred that the Qunji albite porphyry has an A-type granite geochemical affinity. From a mineralogy perspective, the main mineral combination of A-type granite consists of quartz + dark-colored femic minerals ± alkali feldspar, with little or no potassic feldspar, while Qunji albite porphyry is mainly composed of quartz and albite, similar to A-type granite. In summary, Qunji albite porphyry can be classified as an A-type granite.

Figure 9

Geochemical diagram of Qunji albite porphyry. (a) SiO₂ vs Na₂O + K₂O diagram; (b) A/NK vs A/CNK diagram.

Figure 10

(a) Distribution patterns of normalized rare earth elements in Qunji albite porphyry chondrites and (b) mantle normalized diagrams of trace elements.

Figure 11

Discriminant diagram of the A-type granite of the Qunji albite porphyry. (a) 10000Ga/Al vs Zr; (b) 10000Ga/Al vs Nb; (c) Zr+Nb+Ce+Y vs (K₂O+ Na₂O)/CaO; and (d) Zr+Nb+Ce+Y vs FeOT/MgO.

In this article, 18 points were analyzed for 18 zircons in sample QJ008. The data are shown in Table 2, and the cathodoluminescence (CL) images are shown in Figure 12. It is observed that the prepared zircon grains in Qunji albite porphyry are usually colorless and transparent, and most zircon grains are either long or short columnar with relatively complete and crystal angles. The length of the longer axis of zircon grains is in the range of 50–150 μm. Moreover, the grains have an average length-to-width ratio of 1.2–1.5, a Th/U ratio of 0.7–1.4, and include oscillatory magmatic zoning with few fissures. The majority of these zircons remain unmetamorphosed, which reflects their magmatic origin. In the present study, 18 tests were carried out, and the obtained results in Table 2 and Figure 13 confirm that the mean squared weighted deviation (MSWD) is 1.3 and the age range of ²⁰⁶Pb/²³⁸U are 295–319 Ma with a weighted mean age of 303 ± 3 Ma (2σ; n = 11).

Table 2

LA-ICPMS zircon U-Pb dating data of Qunji albite porphyry

Point	Content (×10⁻⁶)		Th/U	Isotope ratio						Isotope age (Ma)
Point	Th	U	Th/U	²⁰⁷Pb/²⁰⁶Pb	1σ	²⁰⁷Pb/²³⁵U	1σ	²⁰⁶Pb/²³⁸U	1σ	²⁰⁷Pb/²⁰⁶Pb	1σ	²⁰⁷Pb/²³⁵U	1σ	²⁰⁶Pb/²³⁸U	1σ
qj008-1	34.23	46.83	0.73	0.0511	0.0092	0.3410	0.0614	0.0483	0.0037	243	370	298	46	304	23
qj008-2	31.50	47.45	0.66	0.0540	0.0033	0.3485	0.0199	0.0481	0.0010	369	134	304	15	303	6
qj008-3	63.51	68.82	0.92	0.0504	0.0020	0.3338	0.0133	0.0484	0.0008	213	93	292	10	305	5
qj008-4	85.59	86.79	0.99	0.0505	0.0023	0.3383	0.0162	0.0484	0.0008	217	106	296	12	305	5
qj008-5	39.31	52.79	0.74	0.0577	0.0087	0.3859	0.0580	0.0483	0.0030	520	335	331	43	304	19
qj008-6	72.14	74.38	0.97	0.0579	0.0026	0.3837	0.0166	0.0483	0.0007	528	100	330	12	304	5
qj008-7	106.19	108.10	0.98	0.0515	0.0021	0.3472	0.0150	0.0485	0.0009	261	93	303	11	305	5
qj008-8	47.28	58.19	0.81	0.0515	0.0024	0.3360	0.0152	0.0475	0.0008	265	107	294	12	299	5
qj008-9	298.14	321.35	0.93	0.0511	0.0013	0.3439	0.0093	0.0484	0.0005	256	59	300	7	305	3
qj008-10	38.53	51.60	0.75	0.0475	0.0028	0.3177	0.0193	0.0484	0.0009	76	133	280	15	304	6
qj008-11	52.86	77.61	0.68	0.0532	0.0024	0.3550	0.0166	0.0484	0.0008	345	102	308	12	305	5
qj008-12	188.40	175.57	1.07	0.0539	0.0017	0.3498	0.0110	0.0471	0.0006	369	72	305	8	297	4
qj008-13	53.31	63.27	0.84	0.0508	0.0028	0.3352	0.0168	0.0483	0.0009	232	126	294	13	304	5
qj008-14	169.84	161.10	1.05	0.0572	0.0017	0.3690	0.0110	0.0468	0.0007	498	67	319	8	295	4
qj008-15	76.40	94.12	0.81	0.0553	0.0064	0.3669	0.0419	0.0484	0.0024	433	257	317	31	305	15
qj008-16	217.89	155.97	1.40	0.0586	0.0050	0.3953	0.0342	0.0484	0.0018	554	187	338	25	305	11
qj008-17	35.91	49.05	0.73	0.0571	0.0027	0.3906	0.0175	0.0499	0.0010	494	104	335	13	314	6
qj008-18	91.10	114.84	0.79	0.0585	0.0024	0.4107	0.0179	0.0508	0.0008	546	87	349	13	319	5

Figure 12

Typical CL images of zircon from the Qunji albite porphyry.

Figure 13

(a) and (b) LA-ICPMS zircon U-Pb age of Qunji albite porphyry.

The concentration of trace elements and the ratio of Ce⁴⁺/Ce³⁺ in zircon samples were meticulously analyzed, and the results are presented in Table A2. This analysis revealed a distinct enrichment of heavy rare earth elements (HREE) and a relative deficit of LREE, resulting in a positive anomaly, while the element Eu exhibited a negative anomaly (as depicted in Figure 14a). The variation range of the Ce⁴⁺/Ce³⁺ ratio and its average are 16.2–93.0 and 37.0, respectively. Furthermore, the whole-rock Zr-saturation temperature calculated by whole-rock Zr content and whole-rock principal composition is 873–919°C, with an average of 903°C (Figure 14b), the high crystallization temperature is also an important characteristic of A-type granites.

Figure 14

(a) Chondrite normalized rare-earth partitioning diagram of zircons from the Qunji albite porphyry and (b) zirconium saturation temperature diagram of the albite porphyry.

The porphyry composition in porphyry was analyzed, and the results showed that the porphyry was mainly albite, with low content of An and Or components, mainly Ab component (Table A3), and the chemical formula was NaAl_0.9–1.2Si_3.1–3.9O_7.9–10.1. The results of the analysis are shown in Table A3. Trace element analysis was carried out on albite porphyry, and the results of the analysis are shown in Table A4. It is noteworthy that the content of trace elements in the Qunji albite porphyry is relatively low, with notable elements including Rb, Sr, Zr, Sn, Ba, La, Ce, Pb, and Ga.

5.2 Characteristics of melt inclusions in zircon

Figure 15 shows the chemical composition analysis of melt inclusions in zircon. It should be indicated that the gas and solid phase composition analysis was carried out by laser Raman spectroscopy and electron probe, respectively. The test results are shown in Table 3.

Figure 15

(a) Micrograph of zircon inclusions of Qunji albite porphyry. (b–d) Multiphase inclusions in zircon.

Table 3

Zircon melt inclusion composition analysis data of Qunji albite porphyry (wt%)

Inclusion type	Glass						Mineral
Sample	QJ008-1	QJ008-1-1	QJ008-13-1	Qj008-3-2	QJ008-19-1	QJ008-16-1	Qj008-08-1	QJ008-05-1	QJ008-05-2
SiO₂	74.14	76.60	74.96	72.81	68.11	56.22	0.06	0.00	1.45
TiO₂	0.03	0.02	0.07	0.04	0.12	0.05	6.74	15.81	90.60
Al₂O₃	12.75	12.74	14.52	14.60	13.20	12.31	1.86	0.25	1.61
FeO	0.56	0.63	0.50	0.54	2.20	0.17	77.27	69.54	1.16
MgO	0.01	0.01	0.00	0.01	0.00	0.00	0.22	2.27	0.01
MnO	0.00	0.00	0.03	0.00	0.03	0.00	0.91	1.81	0.02
K₂O	5.36	3.74	5.38	5.30	4.89	3.53	0.00	0.02	0.00
Na₂O	4.54	0.86	4.30	4.43	5.12	7.38	0.02	0.00	0.00
CaO	0.45	0.43	0.63	0.67	0.58	1.79	0.00	0.00	0.02
P₂O₅	0.03	0.05	0.01	0.05	0.00	4.32	0.00	0.00	0.00
NiO	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00
SO₃	0.01	0.00	0.02	0.05	0.00	0.00	0.00	0.00	0.00
Cl	0.57	0.50	0.55	0.54	0.37	0.35	0.00	0.02	0.00
F	0.00	0.00	0.01	0.00	0.00	0.06	0.00	0.00	0.00
ZrO₂	0.00	3.43	0.30	0.11	4.78	1.76	0.01	0.05	1.90
CuO	0.00	0.03	0.02	0.01	0.00	0.05	0.00	0.06	0.00
Total	98.33	98.93	101.17	99.02	99.32	87.88	87.09	89.81	96.76

As a result, the melt inclusions were not subjected to heating and quenching, and it was assumed that the composition of the melt inclusions accurately represents the composition of the formation melt, in line with previous findings [33]. The obtained results in Figure 16 demonstrate that the Raman spectra of zircon melt inclusions have two peaks at 2,100 and 3,200 cm⁻¹, reflecting the presence of CO, C–H organic matters, and other relatively reduced gases such as CO, and acetylene in the inclusions. Table 3 indicates that the solid glass components of the inclusions are mainly Si, Al, K, and Na, which are similar to those of porphyry. It also shows that the daughter minerals in the inclusions are minerals containing Fe and Ti, which may be Ti-containing magnetite and rutile. Thus, melt inclusions are effective indices to determine the origin of zircon and the physicochemical environment in which it was formed.

Figure 16

Raman diagram of gas composition of zircon melt inclusions of albite porphyry: (a) Peak of zircon inclusions around 2,100 cm⁻¹ and (b) Peaks of zircon inclusions at 2,100 and 3,200 cm⁻¹.

6 Discussion

6.1 Genetic type of zircon

The w(Th)/w(U) value of zircon is often employed as an indicator of its origin, enabling the differentiation between magmatic, metamorphic, and hydrothermal environments, as demonstrated by previous studies [35]. The radius of the Th⁴⁺ ion is very close to that of the Zr⁴⁺ ion, and their electricity valences are the same. As a result, Th⁴⁺ ions can easily penetrate into the zircon structure. Since the neutron radius of U⁴⁺ is smaller than the radius of Th⁴⁺ ions and close to that of Zr⁴⁺, the content of U in zircon is often higher than that of Th [35]. The Th and U contents, along with their zircon ratios, exhibit significant variations across different origins. Generally, the w(Th)/w(U) values of magmatic zircons are >0.4, and the w(Th)/w(U) values of hydrothermal zircons are <0.1 [36,37,38,39]. Combined with the value of w(Th)/w(U) in Table 2, it is inferred that the above 16 kinds of zircons belong to typical magmatic zircons. However, Hidaka et al. [40] found that some typical magmatic zircons have very low w(Th)/w(U) values. Therefore, the host rock types of zircons cannot be distinguished solely based on the w(Th)/w(U) values of zircons. Leng et al. [41] studied the geochemical characteristics of trace elements in zircon and confirmed that the ratio of w(Th)/w(U) mainly reflects the characteristics of the parent or the local chemical environment at the time of formation or even the fluid source region.

Based on (Sm/La)_N–La (Figure 17a) and δ(Ce)–(Sm/La)_N diagrams (Figure 17b), magmatic zircons from hydrothermal zircons can be detected accurately (data in Table A5). Accordingly, it is concluded that zircons of intrusive rocks in the Qunji mining area are mainly magmatic.

Figure 17

(a) (Sm/La)_N–La diagram and (b) δ(Ce)–(Sm/La) _N diagram.

6.2 Magma crystallization environment

The trace elements in zircon reflect the crystallization environment of the host rock. The trace element uranium (U) and rare earth elements in zircon are combined to construct U–Yb and U/Yb–Y diagrams, allowing for the identification of zircon with oceanic crust and continental crust origins. This analytical method aids in determining whether zircon crystals precipitated from magma associated with continental or oceanic crust, thereby elucidating the provenance of zircon within intrusive rocks [21]. As depicted in Figure 18, zircon data from 16 distinct types of intrusive rocks in the Qunji mining area have been superimposed onto the U–Pb and U/Yb–Y diagrams. Figure 18 illustrates that all zircon measurement points from 18 types of intrusive rocks in the Qunji mining area fall within the continental crust area, suggesting that the studied zircon crystallization environment is a continental crust environment.

Figure 18

(a) U/Yb–Y diagram and (b) U–Yb diagram.

6.3 Geological significance of the western AMB

The Qunji albite porphyry has an age of 303 ± 3 Ma and exhibits affinities with A-type granite. On the contrary, other porphyries, including the 109 Pluton, have similar compositions and ages [28]. Consequently, it is inferred that these materials were formed under similar tectonic conditions during the late Carboniferous. Typically, A-type magmatism is associated with extensional settings [42]. As a result, it is reasonable to conclude that these rock plutons formed within an extensional environment following tectonic collisions.

The Paleo-Asian Ocean in the Tianshan area had closed during the Carboniferous (316 ± 3 Ma) and entered the post-collision extensional (extensional) stage [43,44]. The formation environment of bimodal volcanic rocks of the Taerdetao Formation in this area may originate from the post-collision extensional (extensional) stage [45]. The Qunji albite porphyry was formed after the closure of the Paleo-Asian Ocean in the Tianshan area. The field geological relationship shows that the ore-bearing porphyries intruded into the volcanic rocks of the Taerdetao Formation so the Qunji ore-bearing porphyries may be formed in the extensional stage after the collision. These results confirm that A-type granites usually form in an extensional environment.

The obtained results indicate that the Qunji albite porphyry has a geochemical affinity for A-type granite, which is an important rock type within the granite classification. Eby [45] introduced a tectonic environment map (Figure 19) for alkaline (A-type) granite types, using criteria such as Rb/Nb–Y/Nb, Nb-Y-3Ga, and Nb–Y–Ce discrimination maps. These elements are characteristic of alkaline (A-type) granite, marked by the enrichment of Nb, Yb, Y, and Ga. In the above diagram, alkaline (A-type) granite samples are divided into two types: A1 and A2. Type A1 belongs to non-orogenic intraplate granites, which are related to continental rift environments, mantle hot spots, or mantle plumes. On the contrary, Type A2 is associated with post-collision or post-orogenic environments, generally near continental margins. According to the location of data points in the figure, it is concluded that the crystalline environment of Qunji albite porphyry is predominantly a continental crust environment. Figure 19a reveals that most of the data points for albite porphyry are distributed in the Rb/Nb–Y/Nb diagram. Meanwhile, Figure 19b and c show that Nb–Y–3Ga and Nb–Y–Ce fall within the A2-type granite area, indicating that the albite formed during the post-collision extension stage.

Figure 19

Discriminant map of trace element tectonic environment of A-type granite. A₁: Non-orogenic intraslab granite; A₂: Post-collision or post-orogenic environment [45].

Zircon is an abundant mineral in granite and is resistant to the physicochemical reaction of hydrothermal fluids in the later stage [46,47,48]. Therefore, zircon trace elements can be used to reflect the oxygen fugacity of magma [16,17,24,49,50,51]. Compared with Ce³⁺ and Ce⁴⁺, the substitution of Zr⁴⁺ by zircon and the oxidation of Ce³⁺ to Ce⁴⁺ are facilitated under oxidizing conditions. Therefore, the oxygen fugacity of magma can be determined by the Ce⁴⁺/Ce³⁺ ratio in zircon [15,49,52]. Table A2 and Figure 20 show that this parameter in ore-bearing porphyry in the Qunji area is 16.2–55.0, which is lower than that in Chile (>200), but similar to the Ce⁴⁺/Ce³⁺ value of poor ore-bearing porphyry in Chile. Accordingly, it is inferred that the oxygen fugacity of the Qunji ore-bearing porphyry is relatively low.

Figure 20

(a) and (b) Schematic diagram of oxygen fugatism of porphyry in the western section of Auwulale metallogenic (Data from [15,28,34]).

The specific values of saturation temperature and oxygen fugacity (logfO₂) of Ti zircons can be calculated based on the trace elements in the zircon structure [53,54]. The saturation temperature of Ti zircons of ore-bearing porphyry is 743–828°C, and the oxygen fugacity is −14.2 to −16.1. The comparison of these values with those of the buffer reveals that the oxygen fugacity of Qunji ore-bearing porphyry is mostly below the FMQ line, indicating that the oxygen fugacity is less than ΔFMQ. Accordingly, it can be inferred that the source of this porphyry is deep.

The presence of two peaks in the Raman spectra of zircon melt inclusions indicates the existence of CO, C–H organic matter, and other relatively reduced gases such as CO and acetylene. Meanwhile, the solid glass components in the inclusions are primarily composed of Si, Al, K, and Na, with minerals being Ti-bearing magnetite and rutile. It is worth noting that these materials formed in an environment with low oxygen fugacity, indicating that the ore-bearing porphyry of the Qunji Cu deposit has low oxygen fugacity. Additionally, the term ΔFMQ was estimated following the method proposed by Loucks et al. [50]. The results revealed that ΔFMQ ranges from −0.73 to 3.29 (Table A6). These findings consistently indicate that the oxygen fugacity of Qunji albite porphyry is notably low, which is a significant characteristic for metallogenic potential assessment.

6.4 Zircon characteristics indicate metallogenic potential

In the western AMB, several late Paleozoic porphyritic plutons associated with mineralization can be found, including the Qunjisayi, the 109, the Mosizote plutons, and the Yuntoushan. These plutons have identical alteration and ore assemblages (chalcopyrite–bornite–chalcocite) and lack primary hematite and sulfate minerals [28]. Typically, zircon particles in these plutons display Ce⁴⁺/Ce³⁺ ratios of <200 and fO₂ values around ΔFMQ + 2. It is inferred that reduced ore systems widely occur in the western AMB. Given the post-collision extensional environment of the region, it is possible that the asthenospheric mantle is closer to the surface and more likely to penetrate into the lower crust. The asthenospheric mantle is known for having low oxygen fugacity values, which could contribute to the relatively low oxygen fugacity values observed in the melts generated within the extensional setting [55].

Shen et al. [57] showed that in the Cu tonnage of the CAOB porphyry Cu deposit, the ratio of Ce⁴⁺/Ce³⁺ and Eu/Eu* in individual zircon grains gradually decreases. The performed analyses on Qunji, Qunjisayi, and 109 reveals that the lower the Ce⁴⁺/Ce³⁺ and Eu/Eu* (Figure 21), the lower the reserves of Cu deposits. Consequently, in comparison to typical porphyry Cu deposits, the ore-bearing porphyry of the Qunji porphyry Cu deposit exhibits relatively low oxygen fugacity and a poorer metallogenic potential. Furthermore, the characteristics of zircon can effectively serve as indicators of metallogenic potential.

Figure 21

(a) and (b) Ratios of Ce⁴⁺/Ce³⁺ and Eu/Eu* for individual zircon grains versus the Cu tonnage of porphyry Cu deposits in the CAOB (Data from [57]), Qunji, Qunjisayi, and 109 data points.

7 Conclusions

The conducted analyses reveal that the Qunji albite porphyry, dated at 303 ± 3 Ma, was formed in an extensional environment following the Late Carboniferous collision. It exhibits metaluminous to peraluminous characteristics with an alkaline composition. Furthermore, it demonstrates the typical traits of an A-type granite and is the result of the remelting of the lower crust that is of recent origin. The Ce⁴⁺/Ce³⁺ ratio of zircon is 16.2, which is significantly lower than that of typical porphyry Cu deposits and ore-bearing porphyry (>200). The zircon crystallization of the intrusion rocks in the Qunji mining area primarily originates from the continental crust. Additionally, the mineral assemblages of the Qunji porphyry Cu deposit are mainly reactive minerals that formed under low oxygen fugacity conditions.

Furthermore, the presence of C–H assemblages of reducing organic matter in the zircon inclusions of Qunji albite porphyry suggests a reductive nature of the ore-forming hydrothermal process. Consequently, it can be inferred that the Qunji Cu deposit qualifies as a reduced porphyry Cu deposit. Compared with the ore-bearing porphyries of typical porphyry Cu deposits, the oxygen fugacity of the Qunji porphyry Cu deposit is relatively low, and the mineralization potential is poor. However, porphyry Cu deposit in the western AMB can explain the Cu mineralization mechanism in the reductive metallogenic system.

Based on the performed analyses and the obtained results, it is concluded that the zircon characteristics reflect the metallogenic potential of porphyry Cu deposits, so they can be used as an accurate indicator in metallogenic investigations.

Acknowledgments

The Sinomate Institute of Materials Research (Guangzhou) Co., Ltd. (SIMR) provided assistance with data explanation, which also indirectly supported this research.

Funding information: This study was financially supported by multiple sources. The National Natural Science Foundation of China provided funding under Grant No. 42102076. The Shandong Provincial Natural Science Foundation also contributed to the research with Project No. ZR2021QD037.
Author contributions: Methodology, Zhengxi Gao and Yushan Zuo; Zizhen Zhang, Lei Zuo and Rui Liu, writing–review and editing; Ru Liu, funding acquisition. All authors have read and agreed to the published version of the manuscript.
Conflict of interest: Authors state no conflict of interest.
Data availability statement: The data are available from the corresponding author on reasonable request.

Appendix

Table A1

Data of main content (%) and trace elements (×10⁻⁶) of Qunji albite porphyry (the data labeled and * is referenced from Liu and Chen [22] and Wang et al. [23], respectively)

Sample	qj09^†	qj09-1^†	qj12^†	qj13^†	QJ02*	QJ09*	QJ10*	QJ11*	QJ13*	QJ14*	QJ15*	QJ19	QJ20	QJ21	QJ22*	QJ26*	QJ28	QJ32*	QJ008	QJ100*
SiO₂	76.9	76.5	67.9	72.7	76.9	71.0	69.0	71.3	70.8	66.4	65.3	69.5	70.0	70.6	70.6	71.5	69.7	72.3	70.5	71.5
TiO₂	0.41	0.38	0.57	0.42	0.42	0.51	0.53	0.53	0.53	0.61	0.54	0.35	0.35	0.50	0.49	0.51	0.53	0.42	0.52	0.49
Al₂O₃	11.7	11.6	14.4	13.7	9.8	14.7	14.6	13.5	13.0	15.6	14.1	14.0	14.3	14.3	14.2	13.7	13.5	13.2	14.0	14.5
TFe₂O₃	3.13	4.23	3.57	2.51	3.04	3.25	3.01	3.23	3.29	3.81	4.04	3.99	3.19	3.07	2.96	4.03	2.76	3.22	2.22	2.08
Fe₂O₃	2.28	2.90	3.00	2.48	1.09	1.37	0.37	0.32	0.28	0.68	1.31	1.21	1.43	0.97	1.31	1.68	0.79	1.39	0.29	0.77
FeO	1.10	1.65	0.90	0.30	1.04	0.90	1.74	1.94	2.02	1.98	1.53	1.58	0.80	1.18	1.53	1.14	1.14	0.86	1.26	0.68
MgO	0.14	0.12	0.21	0.10	0.13	0.21	0.45	0.21	0.24	0.16	0.19	0.51	0.48	0.22	0.22	0.24	0.10	0.23	0.38	0.26
MnO	0.02	0.03	0.05	0.05	0.11	0.11	0.10	0.10	0.10	0.08	0.09	0.17	0.10	0.11	0.13	0.11	0.09	0.10	0.05	0.03
CaO	0.43	0.39	2.96	1.24	0.72	0.55	0.67	0.57	0.55	0.63	1.84	0.56	0.63	1.18	1.21	0.47	0.91	0.75	0.88	0.58
Na₂O	4.70	4.52	6.68	7.92	3.23	6.66	7.16	5.27	5.37	6.96	5.49	2.99	3.07	5.99	5.33	4.92	5.22	3.98	5.19	5.69
K₂O	2.88	3.05	1.98	0.13	2.79	2.66	0.94	3.02	3.25	2.70	2.99	7.00	6.92	3.43	4.27	3.38	3.24	5.27	2.75	3.72
P₂O₅	0.06	0.05	0.08	0.05	0.06	0.08	0.07	0.06	0.06	0.07	0.06	0.05	0.05	0.07	0.06	0.06	0.07	0.06	0.06	0.06
LOI	0.38	0.37	2.05	1.12	0.95	0.26	1.40	0.25	0.49	0.26	0.77	0.86	1.12	0.39	0.52	0.71	0.77	0.31	1.18	0.90
∑	104	106	104	103	98.2	100	97.9	98.0	97.7	97.4	95.4	100	100	99.8	100	99.7	96.9	99.9	97.8	99.8
Na₂O + K₂O	7.58	7.57	8.66	8.05	6.02	9.32	8.10	8.29	8.62	9.66	8.48	9.99	9.99	9.42	9.60	8.30	8.46	9.25	7.90	9.40
(Na₂O + K₂O)/CaO	17.7	19.3	2.93	6.49	8.36	17.0	12.09	14.5	15.7	15.3	4.61	17.8	15.9	7.98	7.93	17.7	9.30	12.3	9.98	16.2
A/CNK	1.01	1.01	0.78	0.89	1.02	0.99	1.04	1.04	0.97	1.01	0.90	1.03	1.05	0.91	0.91	1.16	1.11	1.08	1.22	1.08
A/NK	1.08	1.08	1.09	1.04	1.18	1.07	1.14	1.13	1.05	1.09	1.15	1.12	1.14	1.05	1.06	8.30	8.46	9.25	7.90	9.40
Mg^#	4.64	3.03	6.16	4.20	4.54	6.70	14.25	6.74	7.50	4.46	4.97	12.44	14.33	7.38	7.63	6.21	3.87	7.35	16.0	12.2
T_Zr(°C)	917	903	873	898	898	895	913	915	912	917	895	908	911	889	891	918	903	885	919	907
F					289	289	343	329	315	374	391	343	329	374	358	265	308	301	343	315
Cl					35.8	48.3	49.7	89.1	28.6	89.1	96.4	61.4	89.1	37.3	29.3	31.0	23.6	50.2	35.8	48.3
CIA	50.2	50.3	43.7	47.1	50.4	49.8	51.0	50.9	49.3	50.2	47.5	50.8	51.1	47.6	47.7	52.0	49.4	49.2	51.7	50.0
Li	6.36	5.84	3.66	4.33	10.10	3.75	8.15	6.08	9.68	3.58	4.41	6.66	6.66	6.64	5.59	7.29	5.18	6.21	11.0	9.82
Be	1.60	1.75	2.98	1.82	2.77	2.75	3.42	2.70	2.53	2.60	2.44	1.60	1.60	1.95	2.35	2.23	4.18	3.35	4.04	3.88
Sc	8.58	7.37	10.20	8.74	5.90	6.80	6.80	7.40	5.30	6.30	7.00	12.50	12.5	12.7	6.5	7.40	5.40	5.40	6.80	6.70
V	15	12.5	28.8	16.7	24.6	36.3	40.1	34.6	30.5	45.5	25.3	16.3	16.3	10.9	31.7	35.6	29.3	29.1	31.2	34.5
Cr	16	22.6	12.1	12.6	27.25	16.6	9.68	7.73	23.6	6.36	11	16.7	16.7	1.93	29.9	5.37	16.5	21.2	0.34	1.47
Co	1.56	2.64	2.58	1.79	2.77	3.12	2.34	1.78	1.62	1.15	1.87	2.88	2.88	2.40	1.85	1.68	2.15	3.04	1.76	1.86
Ni	2.80	7.91	4.36	1.91	2.93	2.65	2.00	2.01	2.28	1.91	1.33	1.70	1.70	0.35	1.88	1.99	1.60	2.48	0.57	0.74
Cu	3,325	2,059	547	1,158	10,087	9.59	18,261	11,479	18,957	15,479	14,609	258.00	258	136	621	3,304	5,913	43.80	6,609	1,565
Zn	13.0	9.83	26.5	11.1	22.7	36.7	43.9	26.8	15.6	19.3	18	53.2	53.2	57.5	14.3	20.2	17.2	47.4	33.3	18.6
Ga	14.2	13.8	21.2	17.6	11.2	17.8	19.7	15.8	15.2	17.7	14.2	17.2	17.2	18	16.4	16.6	15.0	13.9	17.0	16.2
Rb	58.8	62.2	45	2.75	72.9	52.9	26.9	66.1	69.8	57.3	56.9	197	197	192	68.2	71.7	65.8	114	57.2	69.9
Sr	32.3	30.2	74.4	38.2	44.2	71	89.1	60	43.3	41.9	40.4	38.6	38.6	40.3	27.4	35.6	47.0	49.7	61.5	49.7
Y	38.5	33.9	56.5	41.4	91.4	40.8	41.6	21.2	27.4	32.8	40.0	49.9	49.9	47.1	37.8	20.7	32.9	41.8	38.4	36.2
Nb	17.1	15.2	22.6	19.3	57.7	21.3	22.3	23.3	23.5	26.9	25.0	13.9	13.9	13.5	25.1	24.4	23.8	23.6	22.6	24.0
Mo	1.59	2.25	0.94	0.64	1.64	2.21	1.94	2.39	1.54	2.36	0.89	1.31	1.31	1.06	2.65	2.02	1.36	2.10	1.90	1.85
Cd	0.13	0.10	0.04	0.07	0.04	0.02	0.11	0.11	0.23	0.06	0.15	0.03	0.030	0.032	0.038	0.10	0.03	0.06	0.10	0.04
In	0.04	0.03	0.08	0.02	0.04	0.05	0.12	0.05	0.05	0.06	0.10	0.09	0.09	0.16	0.06	0.05	0.06	0.05	0.05	0.04
Sb	0.54	0.86	1.11	0.39	0.54	0.71	0.42	0.41	0.48	0.45	0.50	0.28	0.28	0.21	0.56	0.42	0.42	0.82	0.30	0.38
Cs	0.51	0.51	0.73	0.16	0.83	0.61	0.30	0.43	0.44	0.28	0.43	1.00	1.00	1.02	0.40	0.48	0.38	1.10	0.41	0.51
Ba	245	266	201	16.7	337	261	158	355	316	241	232	557	557	544	241	316	303	523	294	331
La	28.7	24.5	47.7	11.5	33.6	23.0	63.6	20.9	54.0	27.7	16.4	10.8	10.8	21.8	51.7	33.6	15.9	18.6	17.2	31.9
Ce	64.5	55.0	103.0	38.6	68.4	53.2	98.2	42.0	104.0	49.0	40.8	28.3	28.3	57.2	87.3	67.4	41.5	36.7	41.9	72.2
Pr	7.51	6.89	11.80	6.50	11.30	7.01	11.66	5.30	11.5	6.43	5.50	3.15	3.15	6.44	11.0	7.88	6.51	5.26	6.01	9.44
Nd	29.2	24.5	42.6	26.6	50.5	27.9	40.9	19.4	41.1	24.1	22.4	14.6	14.6	26.7	41.3	26.8	28.1	21.8	25.0	36.7
Sm	5.52	4.82	8.29	6.59	12.49	5.61	6.49	4.13	7.04	5.40	4.82	4.92	4.92	6.33	7.34	4.85	6.18	5.08	6.13	7.05
Eu	0.82	0.74	1.34	0.90	2.21	0.86	1.17	0.80	1.29	1.13	0.93	1.10	1.10	0.93	1.53	0.92	1.21	0.65	1.29	1.39
Gd	4.84	4.40	7.32	5.40	11.10	5.28	6.19	3.40	5.99	4.91	4.61	5.70	5.70	6.16	6.61	4.11	5.29	4.91	5.32	6.19
Tb	1.00	0.90	1.58	1.02	2.17	1.01	1.03	0.64	0.91	0.88	0.88	1.20	1.20	1.24	1.09	0.63	0.97	1.00	1.04	1.02
Dy	5.89	5.52	9.79	6.03	14.47	6.72	6.55	4.04	5.23	5.70	5.90	8.46	8.46	8.18	6.71	3.84	6.01	6.85	6.54	6.27
Ho	1.27	1.07	1.80	1.37	3.17	1.41	1.36	0.81	0.95	1.16	1.26	1.76	1.76	1.68	1.29	0.76	1.20	1.46	1.30	1.26
Er	4.35	3.87	6.00	4.89	10.44	4.42	4.37	2.61	2.95	3.68	3.97	5.41	5.41	5.34	4.07	2.53	3.82	4.54	3.97	3.97
Tm	0.79	0.63	0.97	0.89	1.97	0.84	0.80	0.50	0.53	0.73	0.74	0.96	0.96	0.98	0.74	0.51	0.70	0.87	0.75	0.76
Yb	5.33	4.80	6.66	6.42	13.51	5.47	5.34	3.27	3.50	4.93	4.95	6.25	6.25	6.28	4.88	3.53	4.57	5.69	4.88	5.02
Lu	0.84	0.75	0.95	1.00	2.32	0.96	0.94	0.58	0.64	0.90	0.87	1.11	1.11	1.13	0.86	0.66	0.80	1.03	0.84	0.88
Ta	1.28	1.13	1.68	1.50	4.36	1.57	1.62	1.53	1.53	1.82	1.66	1.01	1.01	0.99	1.54	1.63	1.63	1.69	1.54	1.64
W	1.22	1.12	1.16	0.94	1.37	1.31	1.02	0.84	1.13	1.93	1.28	0.85	0.85	1.16	1.67	0.86	0.86	1.31	0.85	1.12
Tl	0.23	0.29	0.18	0.02	0.27	0.23	0.10	0.25	0.26	0.20	0.24	0.39	0.39	0.41	0.24	0.30	0.26	0.43	0.24	0.32
Pb	3.25	3.34	9.58	3.37	4.49	2.96	7.57	1.24	7.30	3.31	4.77	4.74	4.74	3.21	4.45	1.54	1.69	5.83	9.95	1.94
Bi	0.34	0.24	0.15	0.32	0.70	0.05	0.91	0.08	0.50	1.25	0.94	0.12	0.12	0.18	0.04	0.10	0.05	0.09	0.19	0.02
Th	14.40	12.90	16.60	18.40	14.40	12.30	8.30	6.70	7.53	9.67	8.25	12.60	12.6	14.5	10.9	6.46	10.00	20.30	20.30	7.78
U	5.91	3.95	5.37	3.30	4.23	2.63	1.88	1.35	1.40	1.92	1.47	2.63	2.63	4.65	1.69	1.54	1.66	5.39	3.82	1.51
Zr	602	532	693	651	468	559	621	609	640	707	653	589	589	598	592	591	588	495	614	604
Hf	14.8	12.9	17.6	16.9	13.7	15.0	17.6	16.9	17.8	18.9	18.1	16.1	16.1	16.4	16.0	16.1	16.1	13.4	16.9	16.3
ΣREE	161	138	250	118	238	144	249	108	240	137	114	93.7	16.4	16.0	16.4	158	123	114	122	184
(La/Yb)_N	3.63	3.43	4.83	1.21	1.67	2.84	8.01	4.33	15.9	22.4	22.5	28.4	150.4	226	207	16.0	20.8	25.9	22.2	22.8
10000Ga/Al	2.28	2.25	2.78	2.42	2.15	2.28	2.55	2.22	2.21	2.14	1.90	2.33	28.50	22.20	22.0	2.29	2.11	1.99	2.29	2.11
Zr + Nb + Ce + Y	722	636	875	750	686	674	783	695	795	816	759	681	716	742	745	704	686	597	717	736

Note: A/CNK = Al₂O₃/(CaO + Na₂O + K₂O); A/NK = Al₂O₃/(Na₂O + K₂O); Mg^# = 100MgO/(MgO + FeO); (La/Yb)_N is chondrite normalized values (Sun and Mcdonough, 1989); T_Zr is zircon Hf saturation temperature5.2 Zircon U–Pb ages.

Table A2

Trace element analysis of zircon in long porphyry of Qunji albite porphyry (×10⁻⁶)

Sample	QJ008-1	QJ008-2	QJ008-3	QJ008-4	QJ008-5	QJ008-6	QJ008-7	QJ008-8	QJ008-9	QJ008-10	QJ008-11	QJ008-12	QJ008-13	QJ008-14	QJ008-15	QJ008-16
ZrO₂(%)	54.17	54.43	55.81	55.58	54.23	53.95	57.62	54.20	54.95	56.66	55.26	53.49	55.77	56.95	57.10	57.45
P	256.65	301.43	1188.21	393.30	318.15	780.39	305.21	300.54	399.90	273.23	398.06	1379.55	300.33	1687.28	256.98	1214.71
Ti	17.22	21.13	24.41	17.86	18.63	20.73	15.14	18.35	10.23	19.39	24.82	13.79	17.28	19.96	20.81	13.04
Y	663.74	655.03	1127.78	1383.65	623.78	1187.25	1393.14	898.01	1935.20	698.37	1002.99	2085.46	1012.60	1826.83	538.96	1277.09
Nb	0.73	0.73	1.00	0.84	0.68	0.98	0.85	0.79	2.08	0.68	1.41	1.81	0.79	1.66	0.67	1.25
La	0.01	0.03	10.74	1.15	0.01	3.77	0.06	0.00	0.03	0.04	0.08	13.86	0.04	22.95	0.21	4.90
Ce	7.71	7.44	35.13	13.85	8.70	19.91	12.68	8.43	21.13	8.31	9.93	48.58	8.94	71.18	8.72	24.20
Pr	0.06	0.06	3.25	0.64	0.06	1.26	0.28	0.13	0.27	0.10	0.13	4.61	0.19	7.21	0.09	1.74
Nd	1.34	1.41	17.19	6.03	1.18	8.36	4.67	2.39	4.40	1.60	2.07	24.25	3.04	35.33	1.02	9.14
Sm	2.58	2.38	7.18	7.40	2.18	6.30	7.48	4.34	7.82	2.94	3.61	13.56	5.08	14.18	1.79	6.51
Eu	0.75	0.78	2.17	1.99	0.74	2.05	1.78	1.17	1.02	0.85	1.18	2.61	1.41	2.18	0.56	1.29
Gd	13.74	14.07	26.76	33.78	12.30	29.25	34.60	21.12	41.10	14.97	18.91	52.52	23.47	49.67	10.54	28.74
Tb	4.65	4.67	8.35	10.98	4.44	9.39	11.35	7.20	14.33	4.99	6.59	17.12	7.87	15.28	3.62	9.59
Dy	56.65	56.39	97.13	127.05	53.63	107.53	128.88	80.41	171.45	60.63	81.68	194.68	90.64	173.24	45.53	115.07
Ho	22.42	21.90	38.31	48.30	20.92	41.07	48.56	30.88	66.37	23.50	33.42	73.36	34.99	64.21	18.02	44.14
Er	102.74	102.96	175.22	212.12	97.18	181.68	216.05	139.51	301.16	109.20	160.29	322.41	156.00	282.61	85.32	202.54
Tm	22.32	22.28	36.88	43.54	21.01	37.34	44.15	29.12	63.03	23.31	35.06	66.88	32.49	57.71	18.56	42.84
Yb	208.21	213.48	341.65	391.59	198.61	340.68	398.40	268.27	575.51	216.07	333.76	599.91	299.00	512.63	176.99	397.32
Lu	45.22	46.56	74.28	81.58	42.75	72.00	81.95	57.51	119.62	46.51	74.29	123.82	63.41	106.68	37.98	83.68
Hf	6964.84	6813.70	6491.04	7051.36	6979.46	6485.51	7533.66	6736.71	8275.99	7233.43	6635.32	6732.54	7085.85	7398.15	7692.35	7836.33
Ta	0.31	0.35	0.38	0.39	0.29	0.36	0.38	0.35	0.90	0.31	0.46	0.58	0.38	0.57	0.29	0.52
Th	34.23	31.50	63.51	85.59	39.31	72.14	106.19	47.28	298.14	38.53	52.86	188.40	53.31	169.84	35.91	91.10
Eu/Eu*	0.31	0.32	0.42	0.32	0.34	0.38	0.28	0.31	0.14	0.32	0.35	0.26	0.33	0.23	0.31	0.24
Ce⁴⁺/Ce³⁺	47.32	55.00	47.85	18.17	70.16	32.71	16.23	22.92	36.77	40.32	51.48	30.02	19.44	35.38	24.21	43.72
log(ƒO₂) (zircon)	−8.94	−11.10	−22.95	−20.59	−7.84	−22.07	−14.50	−8.32	−12.95	−12.29	−12.38	−25.41	−13.54	−24.12	−14.64	−24.49
T_Ti	791.20	811.36	826.07	794.74	798.88	809.45	778.89	797.40	743.07	802.79	827.81	770.08	791.50	805.69	809.82	764.92

Table A3

Chemical composition of phenocryst of the Qunji albite porphyry (wt%)

Sample	QJ13-1	QJ13-2	QJ13-3	QJ13-4	QJ13-5	QJ13-6	QI15-1	QJ15-2	QJ15-3	QJ15-6	QJ15-9	QJ15-10	QJ15-11	QJ15-12	QJ15-13	QJ26-1	QJ26-2	QJ26-3	QJ26-4	Matrix
SiO₂	69.02	68.62	69.30	69.90	69.82	69.80	67.46	68.92	69.07	69.22	68.69	98.63	68.33	68.73	69.20	68.64	68.95	69.70	69.64	64.77
TiO₂	0.00	0.00	0.00	0.01	0.01	0.00	0.00	0.00	0.01	0.00	0.00	0.00	0.00	0.00	0.00	0.02	0.01	0.00	0.01	0.01
Al₂O₃	20.30	19.78	20.07	19.84	20.27	20.10	20.08	20.16	20.28	20.21	20.17	0.58	20.03	20.07	20.15	20.10	20.03	19.82	20.17	17.83
FeO	0.30	1.06	0.30	0.21	0.06	0.17	0.00	0.01	0.24	0.48	0.00	0.02	0.02	0.14	0.10	0.41	0.60	0.05	0.08	0.44
MgO	0.01	0.03	0.00	0.01	0.00	0.01	0.00	0.00	0.01	0.00	0.00	0.00	0.00	0.00	0.00	0.01	0.03	0.00	0.00	0.02
MnO	0.01	0.00	0.01	0.00	0.02	0.01	0.01	0.00	0.01	0.02	0.01	0.01	0.01	0.01	0.04	0.01	0.02	0.01	0.02	0.00
CaO	0.13	0.07	0.12	0.05	0.09	0.09	0.03	0.01	0.07	0.04	0.04	0.07	0.09	0.04	0.02	0.12	0.08	0.04	0.12	0.02
Na₂O	8.51	9.27	9.96	9.08	9.37	9.46	11.73	11.56	9.12	9.84	11.92	0.02	11.51	11.67	11.36	8.50	9.37	10.31	9.21	0.22
K₂O	0.07	0.10	0.10	0.21	0.15	0.14	0.04	0.03	0.06	0.03	0.05	0.05	0.00	0.04	0.01	0.23	0.11	0.07	0.07	16.10
P₂O₅	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00
Total	98.35	98.93	99.86	99.31	99.78	99.78	99.35	100.69	98.87	99.84	100.88	99.37	99.99	100.70	100.88	98.04	99.19	99.99	99.32	99.40
Si	12.10	12.05	12.04	12.15	12.09	12.10	11.87	11.94	12.07	12.03	11.90	15.91	11.93	11.93	11.96	12.09	12.05	12.09	12.10
Ti	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00
Al	4.19	4.09	4.11	4.07	4.14	4.11	4.16	4.12	4.18	4.14	4.12	0.11	4.12	4.10	4.10	4.17	4.13	4.05	4.13
Fe²⁺	0.04	0.16	0.04	0.03	0.01	0.03	0.00	0.00	0.03	0.07	0.00	0.00	0.00	0.02	0.02	0.06	0.09	0.01	0.01
Mg	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00
Mn	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00
Ca	0.02	0.01	0.02	0.01	0.02	0.02	0.01	0.00	0.01	0.01	0.01	0.01	0.02	0.01	0.00	0.02	0.01	0.01	0.02
Na	2.89	3.15	3.36	3.06	3.15	3.18	4.00	3.88	3.09	3.32	4.00	0.01	3.89	3.92	3.80	2.90	3.17	3.46	3.10
K	0.01	0.02	0.02	0.05	0.03	0.03	0.01	0.01	0.01	0.01	0.01	0.01	0.00	0.01	0.00	0.05	0.02	0.02	0.02
Total	19.25	19.48	19.59	19.37	19.44	19.47	20.05	19.95	19.39	19.58	20.04	16.05	19.96	19.99	19.89	19.29	19.47	19.64	19.38
An	0.85	0.42	0.63	0.32	0.50	0.51	0.15	0.05	0.39	0.24	0.20	41.36	0.41	0.20	0.09	0.78	0.47	0.21	0.72
Ab	99.48	99.24	99.33	98.47	98.99	99.04	99.80	99.85	99.54	99.80	99.75	38.96	100.00	99.80	99.93	98.20	99.20	99.54	99.48
Or	0.08	0.11	0.12	0.24	0.16	0.16	0.04	0.03	0.07	0.03	0.05	0.06	0.00	0.04	0.01	0.27	0.12	0.08	0.08

Table A4

Trace element analysis data of albite in Qunji albite porphyry (×10⁻⁶)

Sample	AQJ-1	AQJ-2	AQJ-3	AQJ-4	AQJ-5	AQJ-6	AQJ-7	AQJ-8	AQJ-9	AQJ-10
Ba	93.03	36.78	42.50	55.49	35.84	61.13	36.92	47.12	33.00	39.74
Sn	2.63	2.10	2.57	2.72	2.75	1.83	2.08	2.51	1.32	4.79
Rb	15.71	13.72	11.22	6.40	12.85	16.79	8.79	22.10	10.41	15.87
Sr	90.86	63.82	100.90	76.07	64.12	96.60	60.65	82.68	73.41	54.27
Ga	18.51	20.85	17.19	18.85	16.91	18.05	17.34	19.17	16.67	18.24
P	209.63	142.06	0.00	0.00	1114.05	129.82	37.48	67.42	36.94	29.46
Cr	12.36	8.59	2.36	2.14	5.37	8.70	0.79	0.69	1.25	0.41
Mn	90.95	62.83	64.85	117.61	82.36	54.54	82.53	63.67	61.65	71.33
Fe	4832.14	2381.70	2518.65	1160.65	1573.09	1682.12	2396.95	2148.96	1327.22	1923.36
Ge	0.77	0.51	0.51	0.00	0.54	0.85	1.07	0.30	0.21	0.49
Ti	92.95	60.30	84.30	240.42	346.22	28.43	204.40	79.67	32.59	2405.51
V	2.51	1.49	0.91	0.33	0.72	0.58	1.58	1.46	0.46	7.43
Y	0.48	0.38	0.23	0.38	5.47	0.06	0.25	0.08	0.05	2.43
Zr	6.07	5.39	4.17	1.24	2.80	2.72	1.87	4.11	1.00	6.21
Nb	0.10	0.05	0.05	0.06	0.07	0.04	0.06	0.02	0.01	1.15
Sb	0.25	0.08	0.00	0.36	0.30	0.20	0.34	0.41	0.08	0.18
Cs	0.96	0.74	0.42	0.39	0.70	1.00	0.45	1.98	0.64	0.36
La	1.53	1.36	0.53	1.42	13.32	0.40	1.09	0.28	0.16	0.44
Ce	1.56	1.33	0.53	1.20	21.71	0.63	0.59	0.28	0.20	1.23
Pr	0.14	0.11	0.02	0.10	2.62	0.05	0.04	0.04	0.02	0.21
Nd	0.48	0.60	0.21	0.20	13.06	0.18	0.11	0.15	0.11	1.03
Sm	0.09	0.00	0.04	0.15	3.19	0.00	0.05	0.05	0.04	0.63
Eu	0.15	0.08	0.05	0.19	6.90	0.07	0.02	0.08	0.03	0.88
Gd	0.04	0.02	0.03	0.04	2.63	0.00	0.00	0.05	0.01	0.63
Tb	0.03	0.01	0.00	0.01	0.29	0.00	0.00	0.00	0.00	0.11
Dy	0.13	0.13	0.08	0.05	1.31	0.03	0.06	0.06	0.00	0.55
Ho	0.01	0.03	0.00	0.01	0.17	0.01	0.02	0.01	0.00	0.12
Er	0.04	0.09	0.04	0.08	0.24	0.00	0.08	0.00	0.01	0.33
Tm	0.01	0.01	0.00	0.01	0.05	0.01	0.01	0.00	0.01	0.06
Yb	0.11	0.08	0.07	0.07	0.35	0.03	0.07	0.02	0.00	0.28
Lu	0.02	0.02	0.01	0.02	0.02	0.01	0.02	0.00	0.01	0.03
Hf	0.30	0.23	0.23	0.07	0.13	0.23	0.12	0.29	0.01	0.47
Ta	0.01	0.00	0.02	0.01	0.01	0.01	0.00	0.00	0.00	0.03
Pb	11.51	4.46	3.26	7.45	31.43	1.41	4.36	1.86	1.57	2.02
Th	0.74	0.27	0.26	0.20	0.26	0.20	0.09	0.12	0.03	0.25
U	0.14	0.05	0.03	0.14	0.76	0.03	0.38	0.03	0.02	0.67

Table A5

Element content normalized values of chondrite and Ce and Eu outliers [12]

Sample	(Ce)_N	(Eu)_N	(Sm)_N	(Gd)_N	(La)_N	(Pr)_N	(Lu)_N	Ce*	Eu*	(Sm/La) _N	(Lu/Gd) _N
qj008-1	12.60	12.93	16.86	66.86	0.04	0.63	1780.31	37.40	0.31	399.65	26.63
qj008-2	12.16	13.45	15.56	68.47	0.13	0.63	1833.07	32.07	0.32	122.89	26.77
qj008-3	57.40	37.41	46.93	130.22	45.32	34.21	2924.41	1.44	0.42	1.04	22.46
qj008-4	22.63	34.31	48.37	164.38	4.85	6.74	3211.81	3.91	0.32	9.97	19.54
qj008-5	14.22	12.76	14.25	59.85	0.04	0.63	1683.07	42.20	0.34	337.69	28.12
qj008-6	32.53	35.34	41.18	142.34	15.91	13.26	2834.65	2.23	0.39	2.59	19.92
qj008-7	20.72	30.69	48.89	168.37	0.25	2.95	3226.38	12.95	0.28	193.11	19.16
qj008-9	34.53	17.59	51.11	200.00	0.13	2.84	4709.45	23.26	0.14	403.78	23.55
qj008-10	13.58	14.66	19.22	72.85	0.17	1.05	1831.10	22.23	0.32	113.85	25.14
qj008-11	16.23	20.34	23.59	92.02	0.34	1.37	2924.80	19.02	0.35	69.90	31.78
qj008-12	79.38	45.00	88.63	255.57	58.48	48.53	4874.80	1.48	0.26	1.52	19.07
qj008-13	14.61	24.31	33.20	114.21	0.17	2.00	2496.46	13.47	0.33	196.73	21.86
qj008-14	116.31	37.59	92.68	241.70	96.84	75.89	4200.00	1.35	0.22	0.96	17.38
qj008-15	14.25	9.66	11.70	51.29	0.89	0.95	1495.28	15.54	0.31	13.20	29.15
qj008-16	39.54	22.24	42.55	139.85	20.68	18.32	3294.49	2.03	0.24	2.06	23.56

Table A6

Zircon composition calculation ΔFMQ [50]

Sample	Ce	Ti	U	ΔFMQ
qj008-1	7.71	17.22	46.83	−0.31
qj008-2	7.44	21.13	47.45	−0.73
qj008-3	35.13	24.41	68.82	1.71
qj008-4	13.85	17.86	86.79	0.64
qj008-5	8.70	18.63	52.79	−0.24
qj008-6	19.91	20.73	74.38	1.01
qj008-7	12.68	15.14	108.10	0.77
qj008-9	21.13	10.23	321.35	2.34
qj008-10	8.31	19.39	51.60	−0.39
qj008-11	9.93	24.82	77.61	−0.51
qj008-12	48.58	13.79	175.57	3.27
qj008-13	8.94	17.28	63.27	−0.06
qj008-14	71.18	19.96	161.10	3.29
qj008-15	8.72	20.81	94.12	−0.43
qj008-16	24.20	13.04	155.97	2.15

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Received: 2024-10-20

Revised: 2025-02-14

Accepted: 2025-03-26

Published Online: 2025-04-30

This work is licensed under the Creative Commons Attribution 4.0 International License.

Articles in the same Issue

https://doi.org/10.1515/geo-2025-0796

Keywords for this article

zircon; fO 2; melt inclusion in zircon; reduced ore system; metallogenic potential

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