Metallogenic age and hydrothermal evolution of the Huangyangshan graphite deposit in eastern Xinjiang, NW China: constraint from zircon geochronology and geochemistry

The Huangyangshan graphite deposit in the East Junggar region of Xinjiang Province is the world’s first documented graphite deposit hosted within an alkaline granite intrusion. Classified as fluid-deposited graphite deposit, it exhibits features of both magmatic and hydrothermal deposits, thus holding special significance for theoretical research. In this study, we conducted LA-ICP-MS zircon U-Pb dating and trace element analyses on zircons from the Huangyangshan deposit orebodies. And comprehensive analysis has been conducted on the REE geochemical signatures of the youngest fine-grained biotite granite within the Huangyangshan pluton. Based on their textures and element compositions, zircons can be divided into two types. Type I zircons are pale, large-grained, with clear oscillatory zonation, low Th, U, and REE contents, and significant positive Ce and strong negative Eu anomalies, which can be classified as magmatic zircons. Type II zircons exhibit dark coloration, fine grain sizes, poorly developed oscillatory zonation, and elevated contents of Th, U, and REEs. They contain few inclusions and have weak LREE and HREE fractionation, consistent with typical hydrothermal zircon. Zircon U-Pb dating results yield an age of 318.8 ± 4.0 Ma for the magmatic zircons, representing the magmatic crystallization age of the graphite-bearing alkaline granite. Hydrothermal zircons have two age groups: One is 299.9 ± 4.6 Ma, which is close to the age of the fine-grained biotite granite, the latest lithoface associated with graphite mineralization. It might be derived from magmatic hydrothermal fluids, representing the graphite mineralization age. The other is 259.9 ± 3.3Ma, which is obviously later than the age of the Huangyangshan pluton. It possibly related to late regional metamorphic fluids. The fine-grained biotite granite has significantly lower total REEs than other lithofacies of the Huangyangshan pluton, with an M-type tetrad effect in REE distribution. The M-type tetrad effect is the result of intense fluid activity, possibly directly related to hydrothermal graphite mineralization. Therefore, the ∼300 Ma hydrothermal event reflected by the first-stage hydrothermal zircons has a close genetic relationship with the fine-grained biotite granite. The Huangyangshan graphite mineralization has experienced a magmatic hydrothermal process and should be classified as a hydrothermal deposit.

1 Introduction

Due to its superior physical and chemical properties—such as insulation, high-temperature resistance and electrical conductivity—graphite is widely used in both traditional industries and high-tech fields. Based on crystallization degree, natural graphite can be categorized into crystalline graphite and cryptocrystalline graphite. The crystalline graphite, characterized by large flake particle size, good washability and high industrial utilization value, has been an important strategic mineral resource in China (Yan et al., 2018). Globally, the vast majority of crystalline graphite deposits are of regional metamorphic or contact metamorphic type (Wada et al., 1995; Papineau et al., 2010; Manoel and Leite, 2018), while a small number of graphite deposits formed by precipitation from carbon-bearing hydrothermal fluids or magmas are collectively referred to as fluid-deposited type (Luque et al., 1998). Compared with metamorphic graphite deposits, fluid-deposited ones are characterized by broad range of mineralization ages, high graphite grade and crystallization degree, and wide range of carbon sources (Duke and Rumble, 1986; Luque et al., 1998; Luque et al., 2012; Luque et al., 2014; Crespo et al., 2006; Doroshkevich et al., 2007; Huizenga, 2011). However, current research on their formation mechanisms remains limited, and the understanding level is relatively low, thus it holds extremely high research value.

Since 2016, three crystalline graphite mineralization subzones have been discovered in the East Junggar of Xinjiang Province, establishing East Junggar as an important potential graphite metallogenic area in China. The crystalline graphite deposit discovered in the Huangyangshan pluton within Qitai County is the first super-large crystalline graphite deposit related to magmatic rocks in China (Zhang et al., 2017). Preliminary exploration estimates that the graphite resources exceed 70 million tons, showing great mineralization potential. Furthermore, the Huangyangshan graphite deposit also has unique characteristics such as “occurring in alkaline granite”, “the ore having unique spherical structure”, and “graphite closely associated with metal sulfides”. Previous studies have on the Huangyangshan graphite deposit have yielded insights into mineral assemblages and geochemical characteristics, diagenetic age and tectonic setting, as well as magmatic evolution processes (Bai et al., 2018; Shao, 2018; Li et al., 2019; Ai et al., 2020; Sun et al., 2021; Sun et al., 2022; Ren et al., 2022). However, due to the lack of research on hydrothermal indicator minerals, there is still a lack of attention to its magmatic-hydrothermal evolution process.

Zircon is a common accessory mineral in granitic rocks and is generally one of the first minerals to crystallize (Hoskin, 2005; Yang et al., 2014; Zeng et al., 2017). It can record the magmatic-hydrothermal evolution process and reflect the evolution of melt-fluid compositions (Belousova et al., 2006; Geisler et al., 2007; Xie et al., 2018; Yin et al., 2023). Hydrothermal zircons that crystallize directly from saturated hydrothermal fluids form across a temperature range spanning the high-temperature magmatic stage to the late medium-temperature hydrothermal stage (≈600∼300 °C; Schaltegger, 2007). These zircons are known to survive multistage hydrothermal events, even when host rocks undergo intensive modification (Zhao et al., 2017; Su et al., 2021; Gao et al., 2023). Therefore, hydrothermal zircons can be used to reliably date primary hydrothermal metasomatism or water-rock interaction events, helping to reconstruct the hydrothermal evolution process. This study focuses on zircons from the Huangyangshan graphite orebody, conducting chronological and trace element studies. Combined with previous research results, we discussed zircon genesis and age, as well as the magmatic-hydrothermal evolution process—aiming to provide a theoretical basis for the study of the mineralization process of fluid-deposited graphite deposits.

2 Regional geology

The East Junggar orogenic belt in Xinjiang Province is located in the middle segment of the Central Asian Orogenic Belt. Geographically, it is adjacent to the Junggar Basin to the west, Mongolia to the east, and the Altai and Tianshan orogenic belts to the north and south respectively. Tectonically, it comprises five units from north to south: Durat-Baytag arc, the Aermantai ophiolite belt, the Yemaquan arc, the Kalamaili ophiolite belt, and the Harlik-Dananhu arc. Geochronological data in this region indicate that the Junggar Ocean and the Altai block formed at least in the Early Ordovician and gradually closed in the Late Paleozoic (Xiao et al., 2009; Xiao et al., 2015; Zhang et al., 2013; Xu et al., 2020). The Karamaili ophiolite belt, situated between the Yemaquan arc and the Harlik–Dananhu arc, is considered to be the site where the Junggar Ocean finally disappeared. It extends in NWW direction along the Karamaili Fault (Figure 1; Liu et al., 2017).

Figure 1

Figure 1. Geological sketch map of the Kalamaili area, Eastern Junggar in Xinjiang Province (modified after Sun et al., 2021).

The Kalamaili area, hosting the Huangyangshan graphite deposit, is located south of the Yemaquan arc and north of the Karamaili Fault. During the Carboniferous to Permian, this area experienced a post-collisional extensional tectonic setting, leading to the emplacement of numerous post-collisional alkaline A-type granites such as Laoyaquan, Beilekuduke, and Huangyangshan plutons, which are collectively termed the Kalamaili Granite Belt. These granites all occur in the form of batholiths or stocks, including granodiorite, biotite alkaline granite, hornblende alkaline granite, and riebeckite granite, etc. Previous studies have reported their crystallization ages cluster between 280 and 330 Ma (Table 1), indicating that the alkaline magmatism in the East Junggar lasted for a relatively short period, spanning the Middle-Late Carboniferous to Early Permian. The Huangyangshan pluton is a representative result of magmatism in this granite belt.

Table 1

Table 1. Statistical table of isotopic ages of typical plutons in Kalamaili area.

Structures in the Kalamaili area are dominated by faults, with overall structural lines oriented NW-SE direction and characterized by multi-stage activities. From north to south, the main faults include the southern segment of the Zaheba-Almantai Fault, the Kupu Fault, the Qingshui-Sujiquan Fault, and the Kalamaili Fault. These faults dissect stratigraphic units and control the formation of most intrusive rocks and ore deposits in the area (Figure 1). Polymetallic mineralization dominated by Au, Cu, and Cr is mainly distributed along the Kalamaili fault zone, with faults exhibiting a clear ore-controlling role (Xu, 2010; Sun, 2018). In contrast, graphite and tin mineralization are closely associated with the alkaline granite belt distributed along the northern margin of the Kalamaili Fault, and have close relationship with magmatism (Tang et al., 2007; Chen W. et al., 2018; Ai et al., 2020). The study object of this paper, the Huangyangshan super-large graphite deposit, occurs within the Huangyangshan alkaline intrusion.

3 Deposit geology

The Huangyangshan pluton, which hosts the graphite deposit, is situated on the southeastern side of the Kalamaili granite belt and the northeastern side of the Qingshui-Sujiquan Fault. It exhibits an overall NW-SE trending elliptical shape and intrudes into tuffaceous sandstones and siltstones of the Middle Devonian Beitaishan Formation and Lower Carboniferous Jiangbasitao Formation, characterized by a concentric ring structure (Figure 2a). Based on mineral grain size and types of dark-colored minerals, the pluton is divided into five lithofacies. All lithofacies share characterized of high silica, low aluminum, depleted calcium and magnesium, enriched alkalis, and high differentiation. They all belong to the high-K calc-alkaline series and representing typical alkaline A-type granite (Yang et al., 2009; Guo et al., 2010; Ai et al., 2020). Numerous dark-colored fine-grained intermediate-mafic enclaves are distributed within the pluton, predominantly in riebeckite and amphibole alkaline granites. Petrographic characteristics indicate a magmatic crystallization origin for these enclaves, while mineral geochemical studies reveal that the Huangyangshan pluton experienced significant mixing of mafic mantle-derived magma and felsic crust-derived magma (Yang et al., 2011; Sun et al., 2021). At present, due to the geological characteristics of the Huangyangshan deposit overlapping with two genetic types, its genesis remains debated: One view classifies it as magmatic type (Bai et al., 2018; Ren et al., 2022), and the other as hydrothermal type (Li et al., 2015; Ai et al., 2020).

Figure 2

Figure 2. (a) Geological sketch map of the Huangyangshan pluton (modified after Bai et al., 2018). (b) Geological map of the No.1 and 2 ore bodies of the Huangyangshan graphite deposit. (c) Cross-section along line 7–7’ in (b) (modified after Sun et al., 2020).

To date, a total of nine graphite orebodies have been discovered within the Huangyangshan pluton, containing three large or larger scale ones. Orebody ① and ② are hosted at the boundary between medium-to-fine-grained amphibole granite and fine-grained biotite granite, and Orebody ④ occurs within fine-grained biotite granite. All orebodies are lithologically characterized as medium-to-fine-grained graphite-bearing alkaline granite (Figure 3a). Orebody ① is a concealed orebody with weak surface-exposed graphite mineralization. It exhibits a lenticular shape, wide in the middle and narrow in the N-S direction (Figure 2b), and occurs with a gentle dip (Figure 2c). Orebody ② is an outcropping ore body with whole-rock mineralization, extending approximately E-W. It presents a saddle-like shape at the surface (Figure 2b) and transitions to a steep dip at depth (Figure 2c).

Figure 3

Figure 3. (a) Contact boundary between the orebody and country rocks at surface in the Huangyangshan deposit; (b) Spherical and irregular aggregates of graphite; (c) Primary spherical graphite and its internal silicate mineral cores in drill cores; (d) Subhedral-anhedral amphibole in graphite ore (−); (e) Flaky biotite replaced by graphite (−); (f) Sulfides enclosed in spherical graphite ore from drill cores; (g) Anhedral pyrrhotite containing chalcopyrite and pentlandite in graphite ore (−); (h) Flaky graphite associated with albitization (+); (i) Veined graphite and altered biotite within it (−). Gr - Graphite; Amp - Amphibole; Bt - Biotite; Kfs - K-feldspar; Qz - Quartz; Pl - Plagioclase; Ab - Albite; Po - Pyrrhotite; Ccp - Chalcopyrite; Pn - Pentlandite.

The main ore mineral in the orebodies is graphite, mostly occurring as flaky or scaly aggregates forming spherical or irregular masses (Figure 3b). Associated silicate minerals—predominantly feldspar, quartz, amphibole, biotite, and pyroxene—are commonly found within these graphite spheres (Figure 3c). They are closely associated with graphite and cut by it. Amphibole occurs as euhedral-subhedral prismatic grains, with partial chloritization (Figure 3d). Biotite appears as brown flakes (Figure 3e) and is replaced and cut by graphite, suggesting that graphite formed at post-magmatic stage. Symbiotic metal sulfides are predominantly developed in deep ores (Figure 3f), mainly including pyrrhotite, chalcopyrite, pentlandite, and ilmenite. Their distribution shows a positive correlation with graphite (higher graphite content corresponds to higher pyrrhotite content), suggesting a close genetic relationship and graphite forming after pyrrhotite crystallization (Figure 3g). Based on petrographic observation, most flake graphite is closely associated with albitization (Figure 3h), indicating a high-temperature hydrothermal crystallization origin. Furthermore, within spheroidal graphite, veined graphite is observed filling interstices between quartz and feldspar in an anhedral interstitial texture (Figure 3i). Some low-temperature hydrothermal alterations like chloritization and argillization are developed within these veins, suggesting formation during the late hydrothermal evolution stage.

4 Samples and analytical methods

The graphite-bearing alkaline granite sample (ZK701) used for zircon U-Pb dating in this study was collected from the drill core of Orebody ② (Figure 2c), with weak weathering. The sample is mainly composed of graphite (∼10%), quartz (∼40–50%), K-feldspar (∼30–40%), amphibole (∼4–8%), and biotite (<3%), with partial albitization, chloritization and carbonatization alteration.

Zircon separation, mount preparation, and cathodoluminescence (CL) imaging were conducted by Beijing Zircon Age Leading Technology Co., Ltd. Initially, zircon grains with good transparency, high crystallinity, and relatively large grain sizes were handpicked under microscope. These grains were then embedded in epoxy resin, mounted on a circular stub, and polished until their cores were exposed, followed by CL imaging. Based on comparisons of zircon grains in the CL images, those with well-developed crystal forms, high transparency, minimal fractures and inclusions, and distinct zoning were selected for subsequent analysis. The U-Th-Pb isotopies and trace element analysis were performed simultaneously on zircon, using an Agilent 7900 type inductively coupled plasma-mass spectrometry (ICP-MS) equipped with a GeolasPro 193 nm ArF excimer laser ablation (LA) system at the Key Laboratory of Mineral Resources Evaluation in Northeast Asia, Ministry of Natural Resources. Helium (He) was used as the carrier gas for ablated materials, and the synthetic silicate glass standard reference material NIST 610, developed by the National Institute of Standards and Technology (USA), was employed as the reference for element concentrations. The analyses were conducted using a laser repetition rate of 7 Hz, an energy density of 3 J/cm², and a spot size of 32 μm. For dating purposes, the zircon standard 91500—with its U-Th-Pb isotopic ratios referenced from Wiedenbeck et al. (1995)—served as the external isotopic calibrant, analyzed twice every 8–10 sample analyses. For each analysis, time-resolved signals were examined to detect the presence of inclusions or common Pb. Zircon trace element concentrations were calibrated using the glass standard NIST 610 as the external standard, with the theoretical Si content of zircon employed as the internal standard. Data processing was performed using the software ICPMSDataCal (Liu et al., 2008; Liu et al., 2010), and age calculations were carried out using the program Isoplot/Ex v. 3.0 (Ludwig, 2003).

5 Results

5.1 Zircon petrography and trace element compositions

Based on morphological, color, and cathodoluminescence (CL) texture characteristics, zircons from the graphite-bearing alkaline granite can be divided into two distinct types (Figure 4). Type I zircons are euhedral to subhedral prismatic grains with a relatively light color (white or light gray) and larger grain sizes, with most having a long axis exceeding 100 μm. They display distinct oscillatory zoning (Figure 4a). Some zircons display core-rim textures with dark rims, and certain zircons contain inherited cores and mineral inclusions (Figure 4a), indicating a magmatic origin with subsequent intense hydrothermal alteration. CL image characteristics of Type II zircons significantly differ from those of magmatic zircons. These zircons are dark black in color, mostly occurring as euhedral short prisms or granular grains with relatively small sizes (long axis generally ranging from 70 to 130 μm). They either lack oscillatory zoning or have indistinct zoning, with a small number of inclusions visible internally (Figure 4b).

Figure 4

Figure 4. CL images and analytical spot locations of representative zircons from the graphite-bearing granite in drillhole ZK701. (a) CL images and analytical spot locations of pale magmatic zircons. (b) CL images and analytical spot locations of dark hydrothermal zircons.

The REE compositions of zircons (analyzed by LA-ICPMS) are presented in Table 2. Type I zircons have relatively low Th and U contents, with Th ranging from 34 to 137 ppm (mostly <100 ppm) and U from 101 to 331 ppm (mostly <200 ppm), yielding Th/U ratios of 0.30–0.48. They contain total rare earth elements (∑REE) of 652–1784 ppm, with an average of 963 ppm, characterized by depletion in light rare earth elements (LREE) and enrichment in heavy rare earth elements (HREE). The LREE contents vary from 6 to 75 ppm, whereas the HREE contents range from 611 to 1735 ppm, resulting in LREE/HREE ratios of 0.01–0.1 (Table 2). These zircons exhibit similar chondrite-normalized REE patterns with strong positive Ce anomalies (Ce/Ce* = 7.61–316.24). Additionally, they have extremely low La and Pr contents, showing significant positive Ce anomalies and relatively strong negative Eu anomalies in the chondrite-normalized REE distribution diagram (Figure 5a).

Table 2

Table 2. Zircon rare earth trace element composition of the graphite-bearing granite in drillhole ZK701.

Figure 5

Figure 5. Chondrite-normalized REE patterns for the zircons from the graphite-bearing granite in drillhole ZK701 normalized to the chondrite composition of Sun and McDonough (1989). (a) Chondrite-normalized REE patterns of magmatic zircons. (b) Chondrite-normalized REE patterns of hydrothermal zircons.

Type II zircons exhibit extremely high Th and U contents, with Th ranging from 1149 to 8724 ppm (mostly >3000 ppm) and U from 2124 to 11693 ppm (mostly >4000 ppm), yielding Th/U ratios between 0.53 and 1.01—significantly higher than those of magmatic zircons. Compared to Type I zircons, these zircons generally have higher rare earth element (REE) contents (∑REE = 1192–24533 ppm, averaging 6168 ppm) (Table 2). They display less pronounced fractionation between light and heavy REEs, with LREE contents varying from 76 to 13385 ppm and HREE contents ranging from 995 to 11148 ppm, resulting in LREE/HREE ratios of 0.02–1.2. In the chondrite-normalized REE distribution diagram (Figure 5b), their patterns are relatively flat. Y contents (mostly >1%) are significantly higher than those in Type I zircons (mostly 0.1%–0.2%). Additionally, Type II zircons have high La contents (2.56–1609.66 ppm) and low (Sm/La)_N (0.59–8.19) and Ce/Ce* (1.8–3.96) values, indicating weaker positive Ce anomalies.

5.2 Zircon U-Pb dating

Due to the presence of two zircon types, a total of 45 zircon grains were selected for analysis from sample ZK701, including 18 magmatic zircons and 27 hydrothermal zircons, yielding 43 valid zircon spot ages (Table 3). These spot ages range from 256 ± 6 Ma to 327 ± 9 Ma, all lying on or near the U-Pb concordia line (Figure 6). Based on their zircon types and age distribution characteristics, they can be clearly divided into three groups:

Table 3

Table 3. LA-ICP-MS zircon U-Pb dating data of graphite-bearing granite in drillhole ZK701 (1σ values represent the relative uncertainties).

Figure 6

Figure 6. U–Pb concordia diagrams and weighted mean ages for the magmatic and hydrothermal zircons from the graphite-bearing granite in drillhole ZK701.

Group 1 consists of 18 magmatic zircons with relatively older ages ranging from 315 ± 9 Ma to 327 ± 9 Ma. The weighted mean age is 318.8 ± 4.0 Ma (MSWD = 0.10), representing the magmatic crystallization age of the graphite-bearing medium-fine-grained alkaline granite. Group 2 comprises 12 hydrothermal zircons with ages concentrated between 297 ± 6 Ma and 303 ± 8 Ma. The weighted mean age is 299.9 ± 4.6 Ma (MSWD = 0.052), slightly younger than the magmatic crystallization age of the graphite-bearing granite and consistent with the crystallization age of the fine-grained biotite alkali-feldspar granite phase (Sun et al., 2021), indicating that the hydrothermal event forming these zircons occurred in the Late Carboniferous. Group 3 includes 13 hydrothermal zircons with ages ranging from 256 ± 6 Ma to 267 ± 7 Ma. The weighted mean age is 259.9 ± 3.3 Ma (MSWD = 0.31), significantly younger than the pluton crystallization age, suggesting a later overprinting hydrothermal event.

6 Discussion

6.1 Genesis of the two types of zircons

During the crystallization differentiation of highly fractionated granites, the crystallization of anhydrous or low-water minerals gradually increases the water content of the system, leading to a magmatic-hydrothermal transitional stage. Zircons can crystallize throughout this process, forming both magmatic and hydrothermal zircons. Notably, magmatic zircons formed in the early magmatic stage may be altered by later exsolved fluids to form hydrothermal zircons, ultimately resulting in the high abundance of hydrothermal zircons in highly evolved granites (Reed et al., 2000; Meng et al., 2024). This phenomenon serves as a direct indicator that the magmatic system has entered the magmatic-hydrothermal evolutionary stage.

According to previous studies, magmatic zircons are characterized by colorless transparency, distinct oscillatory zoning, low Th and U contents, extremely low LREE contents, significant LREE-HREE fractionation, and pronounced positive Ce anomalies and negative Eu anomalies (Hoskin, 2005; Fu et al., 2009; Li et al., 2014). In contrast, hydrothermal zircons typically appear as dark brown or dark translucent crystals with spotty or spongy textures, contain diverse mineral inclusions, exhibit vague or absent oscillatory zoning, have relatively high LREE contents, weak LREE-HREE fractionation, and absent or weak Ce and Eu anomalies (Geisler et al., 2003; Kozlik et al., 2016; Takehara et al., 2018; Jiang et al., 2019). Based on these criteria, Type I zircons in this study can be inferred as magmatic and Type II zircons as hydrothermal (Table 2). This classification is further supported by geochemical diagrams. In the ΣREE vs. ΣLREE and U vs. Th diagrams (Figures 7a,b), Type I zircons (with low element contents) and Type II zircons (with high element contents) plot in the magmatic zircon and hydrothermal zircon fields, respectively. In the La versus (Sm/La)_N and (Sm/La)_N versus Ce/Ce* diagrams (Figures 7c,d), most data points of Type I and Type II zircons fall within or near the fields of magmatic and hydrothermal zircons, respectively. These observations further confirm the presence of two zircon types in the Huangyangshan graphite deposit, indicating intense hydrothermal evolution during the mineralization process.

Figure 7

Figure 7. Discriminant diagrams for the zircons from the graphite-bearing granite in drillhole ZK701. (a) ΣREE vs. ΣLREE diagram; (b) U vs. Th diagram; (c) La vs. (Sm/La)_N and (d) (Sm/La)_N vs. Ce/Ce* diagram (base discrimination diagrams after Hoskin, 2005).

It should be noted that typical hydrothermal zircons usually exhibit irregular crystal forms, well-developed internal pores, and dissolution features—traits that do not fully align with the characteristics of Type II zircons. Instead, Type II zircons have relatively well-formed euhedral forms and few inclusions. Additionally, some Type II zircons contain residual light-colored magmatic zircon cores (Figure 4b), indicating that these hydrothermal zircons did not crystallize directly from Zr-saturated hydrothermal fluids but were likely altered or modified by hydrothermal fluids. This is consistent with the core-rim textures observed in some magmatic zircons (Figure 4a), suggesting that the dark rims formed due to hydrothermal alteration after the crystallization of magmatic zircons. After hydrothermal metasomatism, the Th, U, and LREE contents of the original light-colored magmatic zircons increased, which is the main reason for the darkening of hydrothermal zircon. Type II zircons represent the hydrothermal disturbance events experienced during the late evolutionary stage of magmatic zircon evolution.

6.2 Graphite mineralization age

Previous studies have shown that hydrothermal zircons can either crystallize directly from medium-low temperature hydrothermal fluids or form via alteration along the margins or fractures of primary zircons. This process may reset the U-Pb chronometric system of altered zircons and effectively recording the timing of hydrothermal activity (Rubin et al., 1993; Van Lichtervelde et al., 2009; Xia et al., 2021). Petrographic studies indicate that hydrothermal alterations in the Huangyangshan graphite ores are dominated by high-temperature albitization, greisenization, and low-temperature chloritization and sericitization. Among these, high-temperature hydrothermal alterations such as albitization are paragenetic with graphite ores of the main mineralization stage, whereas low-temperature hydrothermal alterations are mostly distributed in granitic matrices and some light-colored felsic cores, showing a weak genetic relationship with spherical graphite (Sun, 2022). This suggests that graphite mineralization is associated with high-temperature hydrothermal processes.

All samples in this study were collected from drill cores rich in graphite of the main mineralization stage, and the hydrothermal fluid alteration features of Type II hydrothermal zircons are consistent with the aforementioned alteration scenario. Therefore, hydrothermal activity is closely related to graphite mineralization, and the ages of hydrothermal zircons can reflect the crystallization age of graphite. Additionally, hydrothermal zircons mostly form under medium-low temperature conditions (<450 °C) and only zircons subjected to thorough hydrothermal alteration can be used for micro-area dating (Zhu and Song, 2006; Li, 2009). However, graphite in the Huangyangshan deposit formed during an earlier high-temperature hydrothermal stage, so the measured ages of hydrothermal zircons might be slightly younger than the actual crystallization age of graphite.

Due to the lack of suitable dating minerals, previous studies on the Huangyangshan graphite deposit primarily relied on zircon U-Pb dating of the ore-forming pluton to indirectly constrain the mineralization age (Ai et al., 2020; Bai, 2021). The authors previously conducted Re-Os isotopic dating on Huangyangshan graphite, yielding an isochron age of 332 ± 53 Ma with a large error range (Sun et al., 2021)—this can only serve as a reference for corroborating the mineralization age. In this study, three groups of zircon ages were obtained, each with distinct geological chronological significance: (1) Magmatic zircon age (318.8 ± 4.0 Ma). As the only magmatic zircon age group in the graphite ores, it represents the magmatic crystallization age of the graphite-bearing alkaline granite. This age is consistent with that of the medium-fine-grained amphibole granite surrounding Orebodies ① and ② (318.3 ± 4.0 Ma; Sun, 2022), indicating that the graphite-bearing alkaline granite and the country rocks formed contemporaneously as products of the same magmatic event, both emplaced during the early Late Carboniferous. (2) Earlier hydrothermal zircon ages (299.9 ± 4.6 Ma). Slightly younger than the magmatic crystallization age but close to the crystallization age of the fine-grained biotite granite (301.1 ± 3.6 Ma)—a lithofacies closely associated with graphite orebodies—suggesting that the formation of this lithofacies may relate to this hydrothermal event. Flaky graphite aggregates cut through silicate minerals and are closely paragenetic with high-temperature hydrothermal alterations such as albitization (Figures 3d,e). Thus, the graphite formed during the high-temperature hydrothermal stage (not long after magmatic crystallization). In addition, the temperature of fluid inclusions developed in the main graphite metallogenic period is above 450 °C, and their H-O isotope results are projected near the magmatic water area, indicating a magmatic hydrothermal origin (Ai et al., 2020). Thus, this hydrothermal event most likely originated from magmatic fluids exsolved during late magmatic evolution stage, sharing a genetic link with graphite formation, and effectively constrains the lower limit of the main mineralization stage for graphite. (3) Later hydrothermal zircon ages (259.9 ± 3.3 Ma). Significantly different from the crystallization age of the Huangyangshan pluton but consistent with the mineralization ages of regional hydrothermal deposits such as the Shuangquan and Kubusu gold deposits (Xu, 2010; Han, 2014)—indicating a regional hydrothermal event of sufficient scale to affect the Huangyangshan pluton. Previous studies suggest these gold deposits along the Kalamaili Fault are typical orogenic gold deposits, with fluid sources dominated by metamorphic water mixed with minor magmatic or meteoric water (Xu et al., 2010). Therefore, this hydrothermal event in the Huangyangshan graphite orebodies may also relate to metamorphic fluids transported by the Kalamaili Fault and its secondary fractures, though its genetic relationship with graphite requires further investigation.

The Re-Os isotopic dating result for graphite is approximately 330 Ma, but no ∼330 Ma geological bodies have been found in the Huangyangshan pluton to date—the oldest crystallization age of the medium-fine grained riebeckite granite is only 322.7 ± 4.5 Ma (Sun, 2022). Although magmatic metallic sulfides and phenocrysts of silicate minerals such as pyroxene and plagioclase in graphite ores formed during early magmatic evolution, mineral paragenetic relationships indicate that graphite mineralization was significantly later than these early-stage minerals, suggesting graphite’s crystallization age is much younger than 330 Ma.

In this study, zircons extracted from graphite ores exhibit a dichotomous characteristic in both age and genesis—distinctly different from previous studies, where only pale-colored magmatic zircons were found in graphite-free plutons (Ai et al., 2020; Sun et al., 2021). Magmatic zircons in the pluton show consistent morphology, age, and trace element characteristics, with rare captured zircons. This indicates low interference from ancient zircons. For a super-large deposit like the Huangyangshan deposit, the large scale of the ore-forming pluton and the relatively long duration of magmatic-hydrothermal processes are also key factors contributing to this age dichotomy. Based on the ages of magmatic and hydrothermal zircons in graphite ores, as well as the crystallization age of the fine-grained biotite granite that is closely related to graphite, the orebody’s magmatic crystallization age is 318.8 ± 4.0 Ma, the age of the hydrothermal event associated with graphite mineralization is 299.9 ± 4.6 Ma, and the fine-grained biotite granite’s age is 301.1 ± 3.6 Ma (Sun, 2022). These ages constrain that the graphite crystallized in the early high-temperature hydrothermal stage is no older than the magmatic crystallization age and no younger than the crystallization age of hydrothermal zircons.

Therefore, this study proposes that the Huangyangshan graphite deposit formed ∼ 300 Ma, contemporaneous with the late-stage biotite granite in the Huangyangshan pluton. This age is consistent with the Rb-Sr age of the Ganliangzi tin deposit (305 ± 25 Ma, Chen et al., 1999) and the molybdenite Re-Os age of the Sareshike tin deposit (307 ± 11 Ma, Tang et al., 2007)—both related to alkaline granites in this region. Therfore, the Huangyangshan graphite deposit formed in the late Late Carboniferous.

6.3 Hydrothermal processes in the Huangyangshan graphite deposit

Based on the characteristics of zircons in graphite-bearing granite, the Huangyangshan graphite deposit underwent an evolutionary process from magmatism to hydrothermal activity—findings that hold great significance for resolving the dispute over the genesis of the Huangyangshan deposit. In terms of whole-rock compositions (Sun et al., 2021), the four earlier-crystallized lithofacies of the Huangyangshan pluton are characterized by significant LREE enrichment and relatively high positive εHf(T) and εNd(T) values. This suggests they were primarily derived from juvenile crustal materials at the base of the lower crust and experienced extensive magma mixing and fractional crystallization. However, compared with other lithofacies, the youngest fine-grained biotite granite—whose age is close to that of the first group of hydrothermal zircons—exhibits similar major element characteristics but distinctly different REE distribution patterns. This indicates that while sharing a common magmatic source, these lithofacies underwent distinct late-stage evolutionary processes.

Despite having a relatively low total REE content, the fine-grained biotite granite displays an M-type tetrad effect in its REE distribution patterns (Figure 8). The “tetrad effect” of REE is a unique REE pattern in granites, where REEs are divided into four groups (La-Ce-Pr-Nd, Pm-Sm-Eu-Gd, Gd-Tb-Dy-Ho, and Er-Tm-Yb-Lu) using Nd/Pm, Gd, and Ho/Er as boundaries. These groups form four convex or concave curves, termed M-type and W-type REE tetrad effects, respectively (Masuda et al., 1987). This phenomenon is commonly observed in REE-rich alkaline granites and is generally associated with highly evolved magmatic systems, magma interactions with volatile-rich fluids, and fluid (including hydrothermal) activities (Zhao et al., 1999; Zhao et al., 2010). Calculations of REE tetrad effect parameters for the fine-grained biotite granite (Table 4) show that the central element parameters of the first subgroup (Ce_N/Ce*, Pr_N/Pr*) and third subgroup (Tb_N/Tb*, Dy_N/Dy*) are all greater than 1, exhibiting a distinct M-type. The central element parameters of the fourth subgroup (Tm_N/Tm*, Yb_N/Yb*) are approximately 1, indicating an insignificant tetrad effect. The second subgroup deviates from the convex curve due to a strong negative Eu anomaly (Figure 8). Compared with other highly fractionated granites with REE tetrad effects in China, the Huangyangshan fine-grained biotite granite has smaller parameters such as Ce_N/Ce* and Pr_N/Pr* but a more significant negative Eu anomaly, with REE distribution patterns similar to those of the Qianlishan and Baerzhe plutons (Zhao et al., 1999).

Figure 8

Figure 8. Chondrite-normalized REE patterns for different granite phases of the Huangyangshan pluton (data from Sun et al., 2021).

Table 4

Table 4. REE tetrad effect parameters of the fine-grained biotite granite (data from Sun et al., 2021).

Currently, two main viewpoints explain the origin of the REE tetrad effect in granites: (1) Highly fractional crystallization of granitic magma and the crystallization of REE-rich accessory minerals such as monazite, xenotime, and apatite can cause residual melts to exhibit the tetrad effect (Yurimoto et al., 1990; Seward and Barnes, 1997); (2) Intense melts-fluids interactions can induce the tetrad effect in rocks (Bau, 1996; Kawabe, 1999). As mentioned above, while the Huangyangshan pluton underwent significant fractional crystallization during its overall evolution, other lithofacies do not exhibit the REE tetrad effect—suggesting fractional crystallization is not the primary driver of this phenomenon. Additionally, the fine-grained biotite granite lacks typical REE minerals. In contrast, hydrothermal Sn deposits occur in the riebeckite granite phase in the northern part of the pluton, further indicating that REE minerals is not the main cause of the REE tetrad effect.

Rare earth elements are generally considered stable, immobile elements in magmas. However, existing studies have shown that REE mobility increases significantly with the risng proportion of hydrothermal fluids in melts or rocks (Alderton et al., 1980; Veksler et al., 2005). Compared with other lithofacies, the fine-grained biotite granite has a significantly lower total REE content (ΣREE = 40.54–43.16 ppm), with a particularly marked decrease in LREEs (La_N/Yb_N = 0.64–0.85) (Sun et al., 2021), indicating extensive REE precipitation during this magmatic stage. The intensity of the REE tetrad effect can be expressed by the parameter TE₁ [=(Ce/Ce* × Pr/Pr*)^0.5]. The K/Rb and La/Yb ratios of melts reflect the degree of magmatic fractional crystallization, while the Zr/Hf and Y/Ho ratios of rocks indicate melt-fluid interactions. Lower Zr/Hf ratios and higher Y/Ho ratios imply stronger non-CHARAC trace element behavior in melts and more significant fluid activity (Bau, 1996; Chen Y. F. et al., 2018). Plots of TE₁ against these elemental ratios (Figures 9a,b) reveal a clear correlation between TE₁ and Zr/Hf and Y/Ho ratios, indicating a higher degree of REE tetrad effect corresponds to stronger non-CHARAC behavior in melts and more significant fluid influence. In contrast, no obvious correlation exists between TE₁ and K/Rb or La/Yb ratios (Figures 9c,d), suggesting no direct link between the degree of magmatic fractional crystallization and the intensity of the REE tetrad effect. Melt-fluid interactions induced REE fractionation (manifested as the tetrad effect) and disrupted the stability of the magmatic environment, causing significant system decompression and cooling. This conclusion is further corroborated by the low-temperature crystallization stage experienced by Mg-biotite and ferrohornblende formed via hydrothermal alteration in the orebody (Sun et al., 2022). Cooling is the most effective mechanism for graphite precipitation (Luque and Rodas, 1999; Luque et al., 2012) and the dominate factor driving graphite precipitation in the Huangyangshan deposit (Sun, 2022). Consequently, carbonaceous materials precipitated and crystallized to form graphite during the fluid-melt interaction process. This indicates that the melt-fluid metasomatism responsible for the REE tetrad effect in the Huangyangshan fine-grained biotite granite may be directly related to the hydrothermal activity within the graphite orebody.

Figure 9

Figure 9. TE1 vs. Zr/Hf (a), Y/Ho (b), K/Rb (c) and La/Yb (d) diagrams of the Huangyangshan fine-grained biotite granite (data from Sun et al., 2021). Note that the K/Rb and La/Yb ratios reflect the degree of magmatic fractional crystallization, while the Zr/Hf and Y/Ho ratios indicate melt-fluid interactions. The correlation between TE1 and those ratios can reflect the connection of REE tetrad effect and above factors.

The tetrad effect of fine-grained biotite granite indicates its evolution is related to fluid-melt interaction. Meanwhile, hydrothermal zircons in the graphite-bearing alkaline granite confirm the pluton underwent a significant post-magmatic hydrothermal evolution process. Moreover, the zircon U-Pb ages are consistent within error. Therefore, the formation of the fine-grained biotite granite is closely related to the hydrothermal event around 300 Ma recorded by the first stage of hydrothermal zircons and the formation of graphite orebodies. This confirms that hydrothermal events related to graphite mineralization existed during the late magmatic evolution stage of the Huangyangshan graphite deposit.

7 Conclusion

1. Both magmatic zircons and hydrothermal zircons are present in the ores of the Huangyangshan graphite deposit. These hydrothermal zircons have been altered or modified by hydrothermal fluids, indicating that the Huangyangshan graphite deposit has undergone intense hydrothermal evolution, and the mineralization process may be related to hydrothermal activity.

2. The zircon U-Pb ages can be divided into three groups: magmatic zircon age (318.8 ± 4.0 Ma), early hydrothermal zircon ages (299.9 ± 4.6 Ma), and late hydrothermal zircon ages (259.9 ± 3.3 Ma). They represent the magmatic crystallization age of the orebody, the graphite mineralization age, and a later hydrothermal event related to regional metamorphic fluids, respectively.

3. The M-type REE tetrad effect in the fine-grained biotite granite, driven by strong fluid-melt interaction, lead to significant decompression and cooling, providing a necessary condition for graphite precipitation. This hydrothermal activity around 300 Ma might be closely related to the graphite mineralization.

Data availability statement

The raw data supporting the conclusions of this article will be made available by the authors, without undue reservation.

Author contributions

XS: Conceptualization, Data curation, Formal Analysis, Investigation, Writing – original draft, Writing – review and editing. YR: Funding acquisition, Investigation, Project administration, Supervision, Writing – review and editing. ZS: Formal Analysis, Investigation, Methodology, Writing – original draft. JL: Data curation, Investigation, Methodology, Writing – original draft. MH: Data curation, Funding acquisition, Visualization, Writing – review and editing.

Funding

The author(s) declared that financial support was received for this work and/or its publication. This work was financially supported by the National Natural Science Foundation of China (42472138).

Acknowledgments

We sincerely appreciate the geologists from the Xinjiang Branch of China National Geological Exploration Center of Building Materials Industry for their support of our fieldwork.

Conflict of interest

The author(s) declared that this work was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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