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Article

The Formation Age and Magma Source of the Xiaonanshan–Tunaobao Cu-Ni-PGE Deposit in the Northern Margin of the North China Craton

by
Guanlin Bai
1,
Jiangang Jiao
1,2,3,*,
Xiaotong Zheng
1,
Yunfei Ma
1 and
Chao Gao
1
1
School of Earth Science and Resources, Chang’an University, Xi’an 710054, China
2
Key Laboratory of Western China’s Mineral Resources and Geological Engineering, Ministry of Education, Xi’an 710054, China
3
Xi’an Key Laboratory for Mineralization and Efficient Utilization of Critical Metals, Xi’an 710054, China
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(7), 733; https://doi.org/10.3390/min14070733 (registering DOI)
Submission received: 11 July 2024 / Revised: 19 July 2024 / Accepted: 19 July 2024 / Published: 22 July 2024
(This article belongs to the Special Issue Mineral Resources in North China Craton)
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Abstract

:
The Xiaonanshan–Tunaobao Cu-Ni-PGE deposit is located in the northern margin of the North China Craton (N-NCC) in central Inner Mongolia. However, the age, magma source, petrogenesis, and sulfide mineralization mechanism of the ore-related Xiaonanshan-Tunaobao pluton remain unclear. Zircon U-Pb dating indicates the Tunaobao pluton formed at 275.9 ± 2.8 Ma (Early Permian), similar to the Xiaonanshan pluton (272.7 ± 2.9 Ma). The ore-related gabbro is enriched in LREE and LILE (e.g., Rb) and depleted in HREE and HFSE (e.g., Nb and Ti). It likely originated from enriched mantle metasomatized by subduction fluids, supported by enriched Hf-Nd isotopes (–34.34 to –6.16 for zircon εHf(t) and –7.24 to –5.92 for whole-rock εNd(t) values) and high Ba/La but low Rb/Y ratios. The δ34S values of the Xiaonanshan sulfides range from 4.5‰ to 11.4‰, indicating a mantle origin with contribution from surrounding rocks. Combining previous recognition with this study, we propose that the Xiaonanshan–Tunaobao pluton formed in a post-collision extensional setting.

1. Introduction

Magmatic Cu-Ni sulfide deposits are mainly formed in ancient continental margin rifts, large igneous provinces, and orogenic belts [1,2,3,4,5]. Most large to giant magmatic Cu-Ni deposits are associated with mantle-derived magmatic activities, such as mantle plume activity, in continental rifts [6,7,8]. For example, the Noril’sk Cu-Ni-PGE deposit in Russia is the largest Cu-Ni-PGE sulfide deposit in the world, and it is a product of Siberian mantle plume activity [9,10]. Furthermore, the scale of Cu-Ni sulfide deposits formed in the continental rifts are usually larger than those produced in the plate convergence margin (e.g., orogenic belt), so the study of the metallogenic mechanism of magmatic Cu-Ni sulfide deposits related to the continental rift environment has always been a research hotspot of deposits.
The central part of Inner Mongolia straddles the southern margin of the Central Asian Orogenic Belt (S-CAOB) and the northern margin of the North China Craton (N-NCC). A large number of mafic-ultramafic plutons, which are distributed in Inner Mongolia, are genetically associated with Cu-Ni sulfide deposits, such as Ebutu, Huanghuatan, Wengeng, Kebu, Wulantaolegai, and Xiaonanshan (Figure 1) [11,12,13,14,15,16]. Discovered in the 20th century, the Xiaonanshan–Tunaobao (XNS-TNB) deposit is an important Cu-Ni-PGE deposit with industrial value discovered in Inner Mongolia, northern China. However, the magma source and evolution process of the XNS-TNB pluton are not clear. In this study, the petrography, petrogeochemistry, geochronology, and isotope geochemistry of the XNS-TNB pluton were studied to explore the formation age, magma source, magmatic evolution process, and tectonic setting.

2. Regional Geology

The XNS-TNB Cu-Ni-PGE deposit discovered in Siziwangqi, Inner Mongolia, is located between the S-CAOB and the N-NCC, bounded by the Solonker-Xar Moron Fault [19,20,21]. The N-NCC has undergone a series of tectonic evolutions, recording multiple geological stages [22,23,24,25,26,27].
The main outcropped strata in the XNS-TNB area are the Dulahala Formation, Jianshan Formation, Halahuogete Formation, and Bilute Formation of the Mesoproterozoic Bayan Obo Group. The Dulahala Formation is mainly composed of gray metamorphic quartz sandstone and feldspar quartz sandstone. The lower part of the Jianshan Formation is a set of gray to dark-gray metamorphic sandstone, and the upper part is a dark-gray silty slate with metamorphic sandstone. The Halahuogete Formation is micrite limestone, and the Bilute Formation is carbonaceous slate [28,29]. In the XNS-TNB Cu-Ni-PGE deposit area, mafic-ultramafic plutons, such as Dajingpo, Xiaonanshan–Tunaobao, and Baiyinaobao are distributed, and all of them intruded into the Bayan Obo Group. But, only the XNS-TNB pluton contains Cu-Ni sulfides, forming an economic magmatic Cu-Ni-PGE deposit.
The fault is the main structure that controls ore-bearing pluton in the XNS-TNB area. There are four fault systems developed in the XNS-TNB Cu-Ni-PGE deposit: EW-, NEE-, NWW-, and NE-striking faults. The predominant NEE- and NWW-striking faults mainly provide space for the emplacement of gabbro pluton that is related to the mineralization of the XNS-TNB Cu-Ni-PGE deposit. The magmatism is extensive in the XNS-TNB area with emplacing ages ranging from the Late Proterozoic to the Paleozoic, and the rock compositions are complex, varying from ultramafic–mafic to intermediate–felsic. The intense magmatic activities in this area mainly occurred in the Hercynian, represented by medium-grained gabbro, diorite, and granite.

3. Deposit Geology

The outcropped strata in the XNS-TNB area are mainly quartz sandstone of the Halahuogete Formation and carbonaceous slate of the Bilute Formation of the Bayan Obo Group. The NW-striking fault controls the ore-bearing pluton, and two groups of compression–shear faults control the ore-bearing fluid channels. The intrusions in the deposit area are mainly the Xiaonanshan pluton (e.g., gabbro) and the Tunaobao pluton (e.g., gabbro), followed by quartz diorite porphyry, lamprophyre, and granodiorite porphyry.
The Xiaonanshan pluton can be divided into three parts: the Eastern, Central, and Western pluton. The eastern pluton strikes north-east, about 880 m long and 30 m wide; the central pluton strikes northwest and is about 400 m long and 55 m wide, whilst the western pluton is about 100 m long and 20 m wide (Figure 1b). The Xiaonanshan pluton intruded into the Halahuogete Formation of the Bayan Obo Group, and it is oblique to the bedding strike. At present, discovered orebodies are mainly hosted by the lower part of the central pluton and the surrounding rocks, and the pluton has a high degree of mineralization.
The Tunaobao pluton is 2 km away from the Xiaonanshan pluton to the north. It is more than 400 m long and over 100 m wide. The pluton strikes nearly NW and dips westward (Figure 2). The pluton intruded into the Bilute Formation of the Bayan Obo Group, which is mainly slate, and the trend of the pluton is oblique to the bedding strike. The occurrence of the Cu-Ni orebody is hosted in the gabbro with uralite alteration, close to the lower part of pluton. The boundary is unclear between the orebody and the host rock.

4. Petrography

The Xiaonanshan pluton is mainly dark gabbro and has undergone a strong alteration. The Xiaonanshan gabbro is composed of plagioclase (~20%), clinopyroxene (~30%), serpentine (~20%), orthopyroxene (~5%), amphibole (~10%), minor biotite (~5%), and accessory minerals (~10%). The accessory minerals are mainly metallic minerals that are dominantly pyrrhotite, pentlandite, and chalcopyrite, occurring as droplet textures. Other accessory minerals are ilmenite and apatite. Plagioclase is a subhedral platy structure, with grain sizes of 1–2 mm, with sericite alteration. Pyroxene (e.g., clinopyroxene and orthopyroxene) is a euhedral to subhedral columnar formation, with grain sizes of 1–2 mm, and is strongly altered to amphibole and chlorite (Figure 3a–c).
The Tunaobao pluton is located approximately 2 km north of the Xiaonanshan pluton. The main ore-bearing Tunaobao pluton is gabbro with uralite alteration. The main minerals are clinopyroxene (~35%), orthopyroxene (~10%), and plagioclase (~50%), and olivine (~5%). The metallic minerals are pyrite, pentlandite, and chalcopyrite. Plagioclase with saussuritization distributes between pyroxene and olivine. Clinopyroxene and orthopyroxene are euhedral to subhedral granular structures, with grain sizes of 0.5–1 mm, with strong amphibole, talc, and chlorite alterations. Olivine is granular, with grain sizes of 1–2 mm, with a strong serpentine alteration developed along its cracks (Figure 3d–f).

5. Analytical Method

5.1. Zircon U-Pb Dating

Zircon U-Pb geochronology was conducted in the Key Laboratory of Western Mineral Resources and Geological Engineering of Chang’an University, Ministry of Education. The instruments used were an Analyte Excite 193 nm gaseous excimer laser ablation system of Photon Machines and a 7700× inductively coupled plasma pluton spectrometer of Agilent of the United States. 91,500 and NIST610 were used as internal and external standards for zircon U-Pb dating and trace element analysis, respectively. The raw test data were processed offline by ICPMSDataCal [30] and Isoplot 3.00 [31].

5.2. Zircon Lu-Hf Isotope Analyses

Zircon Lu-Hf isotope analyses were performed at the Key Laboratory of Magmatic Metallogenic and Prospecting of Xi’an Geological Survey Center of China Geological Survey. A multi-receiver model inductively coupled plasma mass spectrometer (MC–ICP–MS) and Geolas Pro laser ablation system were used for analyses. Using helium as the carrier gas of the ablation material, the laser beam spot diameter was 44 μm and the laser ablation frequency was 8 Hz. During the analysis, the weighted average of the 176Hf/177Hf test for GJ-1 was 0.282007 ± 0.000025 (σ), and the Lu decay constant used to calculate the initial 176Hf/177Hf was 1.867 × 10−11yr−1 [32]. The zircon εHf(t) value was obtained based on its U-Pb age, and the chondrite 176Lu/177Hf was calculated with a value of 0.0336 and a 176Hf/177Hf value of 0.282785 [33]. Use the 176Hf/177Hf values of the depleted mantle 0.282325 and the 176Hf/177Hf values 0.0384 to calculate the zircon Hf model’s age (TDM1) [34]. The detailed analytical procedures, blank concentrations, and detection limits are presented by Sun et al. [35].

5.3. Whole-Rock Major and Trace Elements

Whole-rock major and trace element compositions were determined by XRF and ICP-MS, respectively, at Chang’an University, China. Rock powders were fused to make glass disks for XRF analysis, and acid was digested in steel-jacketed Teflon “bombs” to produce solutions for ICP-MS analysis. The analytical uncertainties were ~5% for major elements and ~10% for trace elements. The detailed analytical procedures and corresponding method are presented by Wang et al. [36].

5.4. Whole-Rock Sr-Nd Isotopic Compositions

The whole-rock Sr-Nd isotopic analyses were performed by the Wuhan Sample Solution Analytical Technology Co., Ltd., Wuhan, China. Laser ablation multi-receiver inductively coupled plasma pluton spectrometry (LA-MC-ICP-MS) was used. The laser ablation system used was Geolas HD (Coherent, Göttingen, Germany) and MC-ICP-MS was Neptune Plus (Thermo Fisher Scientific, Dreieich, Germany). All analysis data were processed using professional isotope data processing software “Iso-Compass” [37]. The detailed analytical procedures and corresponding method are presented by Thirlwall [38], Xu et al. [39], and Weis et al. [40].

5.5. Sulfur Isotopic Composition

Experiments were conducted at the State Key Laboratory of Continental Dynamics, Northwest University, Xi’an, China. Sulfur isotopic measurements were performed using a Nu Plasma 1700 MC-ICPMS (Nu Instruments, North Wales, UK). A 193-nm ArF excimer laser ablation system (RESOlution M-50-LR, West Sacramento, CA, USA) was used for in situ analysis. A micro-drill machine was used to sample sulfides from the matrix-effect study and the ore deposit. The excimer laser ablation system was equipped with a two-volume sample cell (Laurin Technic S-155, West Sacramento, CA, USA), in which a holder for randomly shaped flat samples could be embedded. The sensitivity and fractionation for isotope analysis were independent of the sampling position inside the large cell because the extraction of laser-ablated aerosols was performed through the small cell above the sample’s surface. Nu Plasma 1700 MC-ICPMS is equipped with 16 Faraday cups and 3 ion counters. Cup configurations for sulfur isotopes were theH5 cup for 34S, Ax cup for 33S, and L4 cup for 32S. Serious interference from molecular ions, especially the oxygen species, can be completely separated from 32S, 33S, and 34S using a higher resolution mode (resolving power = 18,000). Details of the method are presented by Chen et al. [41].

6. Results

6.1. Zircon U-Pb Geochronology

The LA-ICP-MS zircon U-Pb dating result of gabbro is shown in Table 1. Most of the zircon grains in the gabbro sample have an irregular morphology, euhedral to subhedral, with clear oscillatory zones in CL images (Figure 4). The result shows that the Pb contents of zircon samples are 8.13 ppm–282 ppm, the Th contents are 26.7 ppm–377 ppm, and the U contents are 85.3 ppm–1043 ppm. The Th/U ratios are 0.31–0.71, with an average value of 0.53, showing typical characteristics of magmatic zircons [42,43].
A total of 27 zircons was selected for U-Pb geochronology. The results show that some zircons are older, with a variation range of 2579–1361 Ma, and some zircons have an age variation range of 961–319 Ma. Twelve zircons have 206Pb/238U age variations of 278–273 Ma and present a weighted average age of 275.9 ± 2.8 Ma (MSWD = 0.13) (Figure 5), which can represent the formation age of gabbro in the Tunaobao pluton, indicating that the XNS-TNB pluton formed in the Early Permian.

6.2. Zircon Hf Isotope

The Lu-Hf isotopic compositions of zircons from the Tunaobao gabbro are presented in Table 2. The 176Lu/177Hf and 176Hf/177Hf ratios of eight zircon samples from gabbro are 0.001187–0.002636 and 0.2821–0.2828, respectively. They show εHf(t) values ranging from −34.34 to −6.16, and crustal model ages (TDM1) ranging from 1653 Ma to 516 Ma.

6.3. Whole-Rock Major and Trace Elements

Whole-rock geochemical data of gabbro samples are presented in Table 3. The gabbro samples from XNS-TNB are characterized by an SiO2 of 44.39–50.50 wt% and Al2O3 of 5.56–13.41 wt%. They have lower TiO2 contents (0.48 wt%–1.05 wt%), but high Fe2O3T (12.39 wt%–19.45 wt%) and MgO contents (11.65 wt%–24.44 wt%).
The ΣREE contents of gabbro are 33.79–103 ppm. Most samples have (La/Sm)N ratios ranging from 1.32 to 2.28, (Gd/Lu)N ratios ranging from 1.19 to 2.07, and (La/Yb)N ratios ranging from 2.30 to 5.26, with variable Eu anomalies (δEu = 0.76–1.10). Chondrite-normalized REE patterns of all samples show an enrichment of light rare-earth elements (LREEs) and right-dipping type (Figure 6a). On the primitive mantle-normalized trace element spider diagram (Figure 6b), the samples are enriched in Rb, Th, and Ta, but depleted in Ba, P, Nb, and Ti.

6.4. Sr-Nd Isotopes

The Sr-Nd isotopic compositions of the XNS-TNB pluton (20XNS-5, 20XNS-7, 20XNS-16, 20TNB-3, 20TNB-7, and 20TNB-11) are shown in Table 4. Using 275.5 Ma for the correction, the (87Sr/86Sr)i value is 0.7206–0.7373 and the (143Nd/144Nd)i value is 0.5199–0.5120. The corresponding ɛNd(t) values range from −5.92 to −7.24.

6.5. Sulfur Isotope Geochemistry

The in situ S isotopic compositions of sulfides from the Xiaonanshan Cu-Ni-PGE sulfide deposit are shown in Table 5. The δ34S values of all samples are in the range of 4.5–11.4‰. Among them, the δ34S values of six chalcopyrites are 6.1–10.9‰. The δ34S values of six pyrrhotites and seven pyrites are between 4.6–8.1‰ and 5.4–11.4‰.

7. Discussion

7.1. Age of the XNS-TNB Pluton

Most published zircon U-Pb ages from the XNS-TNB area are mainly 280–273 Ma, such as gabbro in Baiyinaobao (277.2 ± 7.3 Ma) [18], gabbro in Xiaoannshan (272.7 ± 2.9 Ma) [15], and rapakivi granites in Xiaonanshan (280.4 ± 1.0 Ma) [45]. These ages in the XNS-TNB area belong to the Early Permian. However, Zhou et al. [16] obtained a zircon U-Pb age of 1343 Ma and baddeleyite U-Pb age of 1333 Ma for Xiaonanshan pyroxenite. The Bayan Obo Group in the XNS-TNB area has strong ductile deformation, whilst the XNS-TNB pluton has no obvious deformation characteristics in terms of rock appearance or microscopic microstructure. Considering that the XNS-TNB pluton intruded into the strata of the Bayan Obo Group, the formation ages of the pluton may not be Proterozoic.
In this study, the LA-ICP-MS zircon U-Pb age of gabbro is 275.9 ± 2.8 Ma, which is consistent with the abovementioned ages of the Baiyinaobao [18] and Xiaoannshan plutons [15] within the error range. Combined with the study of pluton geology, deposit geology, and zircon U-Pb geochronology, we believe that the XNS-TNB pluton belongs to the contemporaneous Early Permian magmatic event.

7.2. Petrogenesis

On the SiO2-(K2O + NaO2) diagram (Figure 7a), gabbro samples fall in the field of the sub-alkaline series. The K2O concentrations and corresponding K2O/Na2O ratios of these gabbro samples range from 0.06 wt% to 1.84 wt% and 0.15 to 3.87, respectively, showing a calc-alkaline affinity on the SiO2 vs. K2O diagram (Figure 7b).
The gabbro of XNS-TNB has higher LOI values and shows alteration features under the microscope. Therefore, it is essential to discuss the relationship between the geochemical data and the mobile elements. Zirconium is one of the least mobile elements. It thus presents an alteration-independent index of geochemical variation [48]. In Figure 8, Zr shows positive correlations with other elements for the XNS-TNB pluton, indicating that these elements (e.g., SiO2, TiO2, Al2O3, Na2O, K2O, CaO, Ni, and Cr) are stable and can be used to discuss petrogenesis.
The Harker diagrams (Figure 9) show the variety of geochemical elements with increasing MgO contents for the XNS-TNB pluton. Fe2O3T increases slightly with increasing MgO, reflecting higher olivine, pyroxene, sulfide, and magnetite abundances compared with mafic rocks. The Al2O3, K2O + Na2O, and TiO2 contents generally decrease with increasing MgO content, reflecting a decrease in plagioclase and ilmenite abundances. There are negative correlations between MgO and CaO contents, indicating the fractional crystallization of clinopyroxene or plagioclase. Nickel slightly increases and Cr shows a generally positive trend with MgO content, indicating that these elements are preferentially incorporated into Mg-rich minerals, such as olivine and pyroxene, during the early stages of magmatic differentiation.
It is generally believed that crustal contamination will lead to an increase in Si, La, Th, and (87Sr/86Sr)i contents or ratios, resulting in a decrease in Mg, Nb, Ta, and εNd(t) values [49,50,51]. The samples of the Xiaonanshan–Tunaobao pluton have high La/Ta (8.54–21.39) ratios and (87Sr/86Sr)i values (0.7206–0.7373), but low εNd(t) values (–7.24 to –5.92). These characteristics indicate that there is obvious crustal contamination in the process of magmatic evolution. The mantle-derived magma mixed with continental crustal materials will increase the abundance of SiO2, K2O, large ionic lithophile elements (LILEs, such as Cs, Rb, and Ba), and high field strength elements (Zr and Hf) in magma, whilst the ratios of La/Nb and Zr/Nb will increase, and the ratios of Ti/Yb and Ce/Pb will decrease. Ce and Pb have the same total partition coefficient, and the Ce/Pb ratio is relatively constant during partial melting and magmatic differentiation, with a typical mantle with a Ce/Pb value of 25 ± 5 and a crustal Ce/Pb of less than 15 [52]. The Ce/Pb ratios of the samples are 0.76–5.91, which is much lower than the mantle value, within the range of the crustal value, indicating that there may be crustal mixing. Some elemental ratios are unaffected by fractionation and thus used to suggest that crustal contamination is present. The Nb/La (0.31–0.71), Y/Nb (2.16–6.13), and Zr/Nb (9.85–23.33) ratios of the XNS-TNB pluton are mainly between the ratios of mantle- and crustal-derived magma, showing the mixing of crustal materials in the magma. On the (Th/Ta)PM-(La/Nb)PM discriminant diagram (Figure 10a), most samples fall between the upper crust and the lithospheric mantle, indicating that the magma mixed with upper crustal materials during the magma’s ascent. In this study, the enriched mantle and the average continental crustal composition [53] were selected as the magma source and mixing unit to calculate the crustal mixing. The results show that the degree of mixing of crustal materials is in the range of 10–20% (Figure 10b).
The εHf(t) values of zircons from the Tunaobao pluton are negative and the variation range is from −34.34 to −6.16, accompanied by a wide range of model ages (2373–657 Ma). Such low εHf(t) values with a wide range (Figure 11a) probably indicate the Tunaobao gabbro was sourced from enriched mantle and the assimilation of crustal materials. Studies have shown the Xiaonanshan–Tunaobao pluton has a high Rb/Sr ratio, and the (87Sr/86Sr)i values are significantly different from those of large Cu-Ni sulfide deposits, such as Kalatongke and Hongqiling in the CAOB [55,56]. On the εNd(t) vs. (87Sr/86Sr)i diagram (Figure 11b), samples of the Xiaonanshan–Tunaobao pluton show high (87Sr/86Sr)i values, but low εNd(t) values (−7.24 to −5.92). Although the (87Sr/86Sr)i values of the Xiaonanshan–Tunaobao gabbro are much higher than the enriched mantle (0.705 to 0.710; Figure 11b), which may have resulted from hydrothermal alteration (e.g., amphibole alteration in gabbro) and cannot be used to trace the magma source, the relatively homogenous and low εNd(t) values further suggest an enriched mantle source, consistent with the conclusion from zircon εHf(t) values.
The ratios of some mobile trace elements can be used to judge the metasomatism of the subducted slab fluid [58] and subduction components [59,60,61]. On the Nb/Y vs. La/Yb diagram (Figure 12a), the XNS-TNB samples are plotted in the field of fluid-induced metasomatism. A number of features of the high Ba/La arcs is critical to their interpretation, thought to be related to the participation of hydrous fluids [60]. On the Ba/La vs. Th/Yb diagram (Figure 12b), the samples show a trend related to slab-derived fluids.
Therefore, we believe that, in the early subduction process, fluids and metasomatized mantle wedges at the base of the lithosphere, resulting from mantle convection or gravity subsidence, released some water during heating, making the asthenosphere mantle enriched in water and fluid, leading to magma melting to form the Xiaonanshan–Tunaobao pluton.
In summary, we propose that the magmatic source of the Xiaonanshan–Tunaobao pluton may be from the EM II lithospheric mantle metasomatized by subducted slab fluid and contaminated by crustal materials.

7.3. Source of Sulfur

The sulfur isotope is widely used in the study of the genesis and formation process of various sulfide deposits [63,64,65,66,67], because it can provide information on the source of sulfur [68]. It is generally believed that there are three main sources of sulfur: (1) mantle-derived sulfur (δ34S = –3‰ to 3‰) [69], (2) modern seawater sulfur (δ34S = about 20‰), and (3) the presence of reduced sulfur in sediments, which is usually characterized by large, negative values [70].
The mean δ34S values of sulfides from the Xiaonanshan Cu-Ni-PGE deposit are as follows: chalcopyrite δ34S (8.4‰) > pyrite δ34S (7.9‰) > pyrrhotite δ34S (6.3‰). This enrichment order does not support an equilibrium state during sulfide formation in the Xiaonanshan Cu-Ni-PGE deposit, but probably reflects rapid sulfide precipitation during the mineralization process [71]. The main metal minerals in the Xiaonanshan Cu-Ni-PGE deposit are pyrite, chalcopyrite, pyrrhotite, pentlandite, and ilmenite, without other observed sulfates, so the δ34S∑S composition is roughly equivalent to the δ34S value of sulfides. Two peaks of δ34S∑S concentrated on 11.4‰ and 6.3‰ in the Xiaonanshan Cu-Ni-PGE deposit are obtained, which is significantly higher but lower than mantle source sulfur and seawater, respectively (Figure 13). In the Xiaonanshan area, the outcropped strata are mainly the Dulahala Formation of the Bayan Obo Group represented by a set of clastic and metamorphic rocks, such as conglomerate, sand-conglomerate, conglomerate-bearing feldspar quartz sandstone, quartzite, and slate, showing the characteristics of a large terrigenous clastic influence and marine sedimentation. The sulfur isotope of the Xiaonanshan ore is significantly higher than that of mantle-derived sulfur, and the surrounding rocks have the characteristics of marine sediments, indicating that the source of sulfur in the Xiaonanshan Cu-Ni-PGE deposit is sourced from mantle and the addition of sulfur from surrounding rock, probably residual seawater.

7.4. Tectonic Setting

Different types of intrusive complexes developed in the central part of Inner Mongolia during the Permian. The magmatic events concentrated at 281–258 Ma. A large number of chronological studies hss been performed on plutons in the region, such as Wengeng anorthosite (285 Ma) [17] and gabbro (269 Ma) [79], Kebu diorite (267.5 ± 1.8 Ma) [13], Wuertagaolemiao granite (271–256 Ma) [80], and Wuliangsitai granite (277 Ma) [81]. The extensive outcrops of Permian granite in the N-NCC indicates that large-scale magmatic activity occurred during this period, and there are different views on whether these plutons are related to the subduction of the Paleo-Asian Ocean or the post-collisional extension.
Combined with previous studies, the formation of Early Permian granodiorite (275 ± 3 Ma) and norite gabbro (270 ± 4 Ma) may be related to the subduction setting [81]. Liu et al. [80] studied hornblende syenite (271 ± 1.8 Ma), and the geochemical results show the rock belongs to alkaline A-type granite. They thought A-type granites found in the area were the westward extension of the A-type granite belt in the Solonker–Hegenshan area, indicating the collision in the central part of Inner Mongolia in the N-NCC occurred earlier than 270 Ma. Xilinhot K-feldspar granite with post-orogenic A-type granite characteristics indicates that the region represents a post-orogenic extension stage [82].
The analysis of the geochemical characteristics of Kuaziliang granite porphyry showed that the plutons were strongly peraluminous and had the characteristics of post-collision granite [83]. Bimodal volcanic rocks and A-type granites developed on the north and south sides of the Solonker–Hegenshan area [84,85,86,87,88,89,90], and the presence of large-scale acidic magmatic plutons in the central part of Inner Mongolia and macroscopic mafic-ultramafic rocks [91] do not support the existence of oceanic crustal subduction in the Permian. In addition, many other studies also suggest a post-collisional environment for the northern NCC in the early Permian. Early–middle Permian Cathaysian flora in Dongwuqi, Inner Mongolia, was identified [92]. These fossils are comparable with those coeval floras in the NCC, indicating that the Paleo-Asian Ocean was closed before the early Permian. It is reported that the paleolatitudes of the Devonian–Permian formations in central Inner Mongolia were consistent with those of the NCC, exhibiting that the Paleo-Asian Ocean was closed prior to the Permian [93].
In the northern NCC, the large-scale magmatic event during the post-collision period could be related to the underplating of mantle-derived melts [81,94]. As discussed above, the source regions of the pluton have involved both slightly depleted mantle and ancient crust, and the emplacement age of the XNS-TNB pluton is the same as other rocks in the N-NCC, suggesting that they might be the results of mafic magmatism underplating during the Permian. The plutons with high εNd(t) values in the XNS-TNB area support the asthenosphere upwelling and melting of the juvenile crust.
In summary, we propose that the tectonic environment of the N-NCC (eastern part of 106° E) during the early Permian was characterized by a post-collisional setting. After the collision, the detachment of the subduction slab induced significant asthenosphere upwelling. This subsequently resulted in lithospheric extension and the partial melting of the juvenile crust. Furthermore, the ascending magma was contaminated with crustal materials and modified to form the XNS-TNB pluton in the post-collision extensional background.

8. Conclusions

(1) The LA-ICP-MS zircon U-Pb age of the Tunaobao gabbro is 275.9 ± 2.8 Ma, consistent with the previous published data, indicating the Xiaonanshan–Tunaobao pluton formed in the Early Permian during a post-collisional extension stage after the closure of the middle segment of the Paleo-Asian Ocean.
(2) Gabbro is a sub-alkaline rock with an evolutionary trend in the tholeiitic series, originating from enriched mantle metasomatized by subduction fluids.
(3) Sulfur isotopic analyses suggest that the source of sulfur in the Xiaonanshan Cu-Ni-PGE deposit is sourced from mantle and the addition of sulfur from surrounding rock, probably residual seawater.

Author Contributions

Conceptualization, J.J.; methodology, J.J.; software, G.B.; validation, G.B. and X.Z.; formal analysis, G.B.; investigation, Y.M.; resources, C.G.; data curation, G.B., X.Z. and Y.M.; writing—original draft preparation, G.B.; writing—review and editing, J.J. and X.Z.; visualization, G.B.; supervision, J.J.; project administration, J.J. and Y.M.; funding acquisition, J.J. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China grant number [92162213] and the project from the Inner Mongolia exploration funds [2020-KY05].

Data Availability Statement

Data is contained within the article.

Acknowledgments

We appreciate the Editor and two anonymous reviewers for their constructive comments that greatly improved the quality of this manuscript. We also thank the Xi’an Geological Survey Center of China Geological Survey, the Wuhan Sample Solution Analytical Technology Company, and the State Key Laboratory of Continental Dynamics for their assistance with the Sr-Nd, Lu-Hf, and S isotope analyses.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Division of geological tectonic units in the central part of Inner Mongolia [10,11,13,15,17] (a) [13] and geological sketch map for the XNS-TNB area (b) [18].
Figure 1. Division of geological tectonic units in the central part of Inner Mongolia [10,11,13,15,17] (a) [13] and geological sketch map for the XNS-TNB area (b) [18].
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Figure 2. Geological exploration line for the Xiaonanshan–Tunaobao deposit [18]. (a) Geological sketch map of the Xiaonanshan deposit; (b) geological sketch map of the Tunaobao deposit; (c) exploration line for the Xiaonanshan deposit; (d) exploration line for the Tunaobao deposit.
Figure 2. Geological exploration line for the Xiaonanshan–Tunaobao deposit [18]. (a) Geological sketch map of the Xiaonanshan deposit; (b) geological sketch map of the Tunaobao deposit; (c) exploration line for the Xiaonanshan deposit; (d) exploration line for the Tunaobao deposit.
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Figure 3. Representative photographs and photomicrographs showing major mineral assemblages and sulfide mineralization in the Xiaonanshan (a–c) and Tunaobao gabbro (d–f). Abbreviations: Ccp—chalcopyrite; Cpx—clinopyroxene; Ilm—ilmenite; Opx—orthopyroxene; Pn—pentlandite; Po—pyrrhotite; Py—pyrite; Srp—serpentine.
Figure 3. Representative photographs and photomicrographs showing major mineral assemblages and sulfide mineralization in the Xiaonanshan (a–c) and Tunaobao gabbro (d–f). Abbreviations: Ccp—chalcopyrite; Cpx—clinopyroxene; Ilm—ilmenite; Opx—orthopyroxene; Pn—pentlandite; Po—pyrrhotite; Py—pyrite; Srp—serpentine.
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Figure 4. Cathode luminescence photos of zircon grains from the Tunaobao pluton.
Figure 4. Cathode luminescence photos of zircon grains from the Tunaobao pluton.
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Figure 5. Concordia (a) and weighted mean (b) diagrams of zircon U-Pb dating of the Tunaobao pluton.
Figure 5. Concordia (a) and weighted mean (b) diagrams of zircon U-Pb dating of the Tunaobao pluton.
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Figure 6. Chondrite-normalized REE patterns (a) and primitive mantle-normalized trace elements spider diagrams (b) of XNS-TNB gabbro. The data of chondrite and primitive mantle are from [44].
Figure 6. Chondrite-normalized REE patterns (a) and primitive mantle-normalized trace elements spider diagrams (b) of XNS-TNB gabbro. The data of chondrite and primitive mantle are from [44].
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Figure 7. Na2O + K2O vs. SiO2 diagram (a) [46] and SiO2 vs. K2O diagram (b) [47] of the XNS-TNB gabbro.
Figure 7. Na2O + K2O vs. SiO2 diagram (a) [46] and SiO2 vs. K2O diagram (b) [47] of the XNS-TNB gabbro.
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Figure 8. Heatmap of immobile elements and geochemical data.
Figure 8. Heatmap of immobile elements and geochemical data.
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Figure 9. Harker diagrams for the Xiaonanshan–Tunaobao plutons.
Figure 9. Harker diagrams for the Xiaonanshan–Tunaobao plutons.
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Figure 10. (Th/Ta)PM vs. (La/Nb)PM diagram (a) and (Ta/Th)PM vs. (Th/Yb)PM diagram (b) of the Xiaonanshan–Tunaobao pluton [15,54].
Figure 10. (Th/Ta)PM vs. (La/Nb)PM diagram (a) and (Ta/Th)PM vs. (Th/Yb)PM diagram (b) of the Xiaonanshan–Tunaobao pluton [15,54].
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Figure 11. εHf(t) vs. t diagram of Tunaobao pluton (a) and εNd(t) vs. (87Sr/86Sr)i diagram of the Xiaonanshan–Tunaobao pluton (b) [57].
Figure 11. εHf(t) vs. t diagram of Tunaobao pluton (a) and εNd(t) vs. (87Sr/86Sr)i diagram of the Xiaonanshan–Tunaobao pluton (b) [57].
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Figure 12. Nb/Y vs. La/Yb diagram (a) and Ba/La vs. Th/Yb diagram (b) of the Xiaonanshan–Tunaobao pluton [60,62].
Figure 12. Nb/Y vs. La/Yb diagram (a) and Ba/La vs. Th/Yb diagram (b) of the Xiaonanshan–Tunaobao pluton [60,62].
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Figure 13. δ34S of sulfides from the Xiaonanshan Cu-Ni-PGE deposit. δ34S of sulfides of other deposits are from the data published in previous studies [35,72,73,74,75,76,77,78].
Figure 13. δ34S of sulfides from the Xiaonanshan Cu-Ni-PGE deposit. δ34S of sulfides of other deposits are from the data published in previous studies [35,72,73,74,75,76,77,78].
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Table 1. LA-ICP-MS zircon U-Pb isotope data of the gabbro from the Tunaobao intrusion.
Table 1. LA-ICP-MS zircon U-Pb isotope data of the gabbro from the Tunaobao intrusion.
SamplePb (ppm)Th (ppm)U (ppm)Th/U207Pb/206Pb±1σ207Pb/235U±1σ206Pb/238U±1σ207Pb/235U±1σ206Pb/238U±1σ
22TNB-1-127.47210.3572.70.370.05770.00240.34580.01490.04330.0007301.611.27273.04.08
22TNB-1-29.63100.1196.50.510.05220.00310.3140.01970.04360.0009277.215.25275.35.44
22TNB-1-38.31128.5223.90.570.05690.00430.24130.01610.03170.0006219.513.19201.33.53
22TNB-1-511.80102.6243.10.420.05130.00260.3120.01680.04410.0008275.713.00278.15.02
22TNB-1-652.8257.685.350.670.16380.004411.070.29250.49210.009252924.62258038.77
22TNB-1-7278.2284.3583.40.490.13050.00317.4560.20330.41260.0072216824.42222732.64
22TNB-1-830.34304.7604.20.500.05620.00210.34350.01390.04410.0007299.810.52278.04.39
22TNB-1-929.22307607.70.510.05540.00230.32750.01350.04350.0009287.710.33274.25.27
22TNB-1-1089.63125.9166.80.750.15370.00478.9250.27550.41990.0065233028.19226029.6
22TNB-1-1134.06197.1400.70.490.06010.00250.630.02680.07590.0013496.116.67471.47.56
22TNB-1-1245.8487.56259.20.340.0790.00241.7610.05810.16080.0029103121.36961.415.88
22TNB-1-1334.01202.6412.30.490.05750.00230.58020.02310.07290.0011464.614.85453.86.42
22TNB-1-1567.92154.9141.91.090.12040.00315.9850.1560.35930.0048197422.68197922.98
22TNB-1-1654.32211.5276.10.770.07080.00221.6490.05630.16810.0028989.121.58100215.46
22TNB-1-1712.05159244.70.650.05180.00320.31880.02760.04380.00128121.26276.56.15
22TNB-1-19189.3337.7380.70.890.13140.00347.170.20350.39420.0073213325.29214233.7
22TNB-1-2110.63122.9257.90.480.05360.00290.27080.01420.03690.0006243.411.37233.73.97
22TNB-1-24282.426.75803.10.030.11820.00305.4820.14450.33560.0055189822.65186526.78
22TNB-1-268.1389.75163.70.550.05450.00440.32270.02590.04360.000928419.89275.15.32
22TNB-1-2711.96103.9241.40.430.05760.00370.34660.02160.04410.0008302.216.29278.24.98
22TNB-1-2812.57138.5246.90.560.05560.0030.33330.01770.04380.0008292.113.48276.25.23
22TNB-1-29268.2290.41042.90.280.08320.0022.6990.070.23510.0031132819.22136116.17
22TNB-1-3112.23170.8232.10.740.05390.0030.3220.01770.04370.0008283.513.63275.64.74
22TNB-1-3534.4376.7681.50.550.05410.00210.32890.0140.04390.0008288.710.71276.94.74
22TNB-1-3710.33203.5143.71.420.05830.00350.40990.02590.05080.0009348.818.68319.35.68
22TNB-1-3847.42327.8596.40.550.05560.00240.52590.02290.06840.0012429.115.21426.57.35
22TNB-1-3912.79160.4245.30.650.04870.00280.29520.0180.04350.0008262.614.08274.84.98
22TNB-1-4028.46327.4313.21.050.05590.0030.52970.02730.06850.001431.618.11427.16.13
Table 2. Zircon Hf isotope data of the gabbro from the Tunaobao intrusion.
Table 2. Zircon Hf isotope data of the gabbro from the Tunaobao intrusion.
SitenumberT(Ma)176Yb/177Hf176Lu/177Hf176Hf/177Hf±2σTDM1(Ga)εHf(t)DM
TNB-172760.076580.0011870.28290.0000220.52−6.16
TNB-22750.11180.0017870.28270.0000260.82−13.74
TNB-262750.11870.0020040.28270.0000320.83−13.83
TNB-272780.12040.0019400.28270.0000350.79−12.84
TNB-312750.12800.0021940.28280.0000360.59−7.83
TNB-392750.15830.0026360.28210.0000331.65−34.34
TNB-52780.097560.0016120.28260.0000230.92−16.44
TNB-82780.15130.0022660.28280.0000270.61−8.20
Table 3. Whole-rock major (wt%) and trace (ppm) element data of the Xiaonanshan–Tunaobao intrusion.
Table 3. Whole-rock major (wt%) and trace (ppm) element data of the Xiaonanshan–Tunaobao intrusion.
Sample20XNS-1320XNS-320XNS-1020XNS-1720XNS-620TNB-1020TNB-220TNB-920TNB-520XNS-1120TNB-622TNB-1
RockGabbroAltered GabbroGabbroGabbroGabbroGabbroGabbroGabbroGabbroGabbroGabbroAltered Gabbro
SiO248.5744.3946.9847.3145.9650.5047.8147.3448.6050.2349.1745.39
TiO20.800.480.850.790.700.950.980.971.050.960.780.64
Al2O311.068.179.5610.129.0910.069.129.569.9013.419.285.56
Fe2O315.8819.4518.0217.8319.0614.6518.4519.0816.7412.3914.5217.20
MnO0.160.180.180.170.170.180.200.180.190.140.160.16
MgO12.4320.1514.1313.7915.2113.0015.1112.6012.6511.6515.5324.44
CaO8.256.988.297.668.098.216.328.248.857.278.875.81
Na2O0.920.090.861.121.021.350.421.091.182.241.110.38
K2O1.840.061.051.130.621.001.490.840.721.620.510.35
P2O50.090.050.090.080.080.100.100.100.120.080.060.06
TOTAL100.00100.00100.00100.00100.00100.00100.00100.00100.00100.00100.00100.00
LOI3.015.123.123.023.061.124.523.241.653.762.304.49
Mg#37.6744.4337.7037.3838.1140.6438.7433.7736.8342.0745.2252.31
Li442549565624382224421410
Be0.41.30.50.50.40.60.90.60.70.50.50.4
Sc272428292928242728182220
V172140165179174181145167176266283225
Cr80113339811029112673787880581382713782655
Co1481791632032149820122514265142162
Ni2563328329953771413532043513653174526115881618
Cu21741657288316252652231119220121044106614724
Zn798793899790131929110095109
Ga151214151418141517181310
Rb987668351581204037772921
Sr113126972521369110111411112067
Y141014141317231517161513
Zr744168645977717276696254
Nb3.41.73.13.02.87.83.73.74.24.03.72.9
Mo0.30.30.30.40.40.30.40.90.40.80.70.4
Cd0.50.30.70.50.70.31.60.70.50.10.30.2
In0.10.10.10.10.10.10.10.10.10.10.10.1
Cs5.31.65.07.15.69.824.18.66.61.55.44.9
Ba3142120619412318710213513720710173
La7.63.27.97.27.011.011.88.89.56.37.97.0
Ce17717161523281922161715
Pr2.41.02.52.32.23.23.92.83.11.92.01.8
Nd1041010913161213898
Sm2.81.63.02.82.63.64.43.13.62.32.32.0
Eu1.00.40.90.90.81.11.00.91.10.80.70.6
Gd2.51.52.72.52.43.13.92.83.22.82.62.3
Tb0.50.30.50.50.50.60.80.60.60.50.40.4
Dy3.02.13.23.13.03.74.53.43.82.72.52.1
Ho0.60.40.60.60.60.70.90.60.70.50.50.4
Er1.61.11.61.61.51.92.31.81.91.41.31.1
Tm0.30.20.30.30.20.30.40.30.30.20.20.2
Yb1.61.01.61.51.51.92.11.71.81.21.10.9
Lu0.20.20.20.20.20.30.30.30.30.20.20.1
Hf2.51.52.52.52.42.72.12.42.61.81.61.4
Ta0.50.30.40.60.41.30.60.80.70.40.60.4
Pb6.03.26.57.112.826.229.925.424.52.711.25.9
Bi1.91.52.32.62.90.45.43.81.70.41.00.5
Th2.31.42.32.22.24.23.12.83.21.62.41.8
U0.40.20.50.40.50.70.60.60.70.50.40.4
ΣREE64.9633.7967.0163.3460.2884.99103.2673.2981.3960.8162.6054.88
(La/Yb)N3.472.303.483.533.454.244.013.673.703.844.965.26
(La/Sm)N1.751.321.711.631.742.001.751.801.701.752.282.28
(Gd/Lu)N1.351.191.381.291.361.261.421.311.332.071.942.04
δEu1.100.760.981.040.951.000.760.940.980.910.910.82
Table 4. Whole-rock Sr-Nd isotopic composition of the Xiaonanshan–Tunaobao intrusion.
Table 4. Whole-rock Sr-Nd isotopic composition of the Xiaonanshan–Tunaobao intrusion.
SampleRb (ppm)Sr (ppm)87Rb/86Sr(87Sr/86Sr)±2σT(Ma)(87Sr/86Sr)iSm (ppm)Nd (ppm)147Sm/144Nd143Nd/144Nd(143Nd/144Nd)iεNd(t)TDM(Ga)εSr(t)
20XNS-548.76130.21.0830.73560.000007275.50.73143.1010.720.17470.51230.5120−6.043.34386.3
20XNS-760.2979.932.1820.74580.000006275.50.73733.3512.350.16410.51220.5119−6.822.81469.7
20XNS-1646.8181.591.6600.74200.000006275.50.73553.0410.320.17800.51230.5119−6.913.80444.5
20TNB-357.0790.521.8240.73210.000007275.50.72492.8210.630.16040.51230.5120−5.922.51294.9
20TNB-728.93104.20.80350.72380.000007275.50.72062.618.950.17630.51220.5119−7.033.68233.2
20TNB-1130.83101.20.88150.72460.000009275.50.72112.749.930.16680.51220.5119−7.243.02240.6
Table 5. Sulfur isotopic data of sulfide minerals from the Xiaonanshan Cu-Ni deposit.
Table 5. Sulfur isotopic data of sulfide minerals from the Xiaonanshan Cu-Ni deposit.
SampleSulfide Mineralδ33Sv-CDTδ34Sv-CDTΔ33S
20XNS-1#1Chalcopyrite4.910.5−0.5481
20XNS-1#1Pyrrhotite3.77.6−0.2143
20XNS-1#1Pyrrhotite4.28.10.0291
20XNS-1#2Chalcopyrite5.410.9−0.1835
20XNS-1#2Chalcopyrite5.410.20.1364
20XNS-1#2Pyrrhotite2.47.8−1.682
20XNS-1#2Pyrite5.310.8−0.2571
20XNS-1#2Pyrite5.911.40.03385
20XNS-1#2Pyrite5.511.2−0.2735
20XNS-10#1Pyrrhotite0.94.9−1.603
20XNS-10#1Pyrrhotite1.14.9−1.414
20XNS-10#1Pyrite2.95.6−0.024
20XNS-10#1Pyrite3.15.80.05875
20XNS-10#2Chalcopyrite4.96.31.716
20XNS-10#2Chalcopyrite4.16.20.8764
20XNS-10#2Chalcopyrite3.86.20.6625
20XNS-10#2Pyrrhotite1.34.6−1.058
20XNS-10#2Pyrite3.15.60.2157
20XNS-10#2Pyrite2.85.40.019
Δ33 S = δ33 S − 1000 × [(1 + δ34 S/1000) 0.515 − 1]
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Bai, G.; Jiao, J.; Zheng, X.; Ma, Y.; Gao, C. The Formation Age and Magma Source of the Xiaonanshan–Tunaobao Cu-Ni-PGE Deposit in the Northern Margin of the North China Craton. Minerals 2024, 14, 733. https://doi.org/10.3390/min14070733

AMA Style

Bai G, Jiao J, Zheng X, Ma Y, Gao C. The Formation Age and Magma Source of the Xiaonanshan–Tunaobao Cu-Ni-PGE Deposit in the Northern Margin of the North China Craton. Minerals. 2024; 14(7):733. https://doi.org/10.3390/min14070733

Chicago/Turabian Style

Bai, Guanlin, Jiangang Jiao, Xiaotong Zheng, Yunfei Ma, and Chao Gao. 2024. "The Formation Age and Magma Source of the Xiaonanshan–Tunaobao Cu-Ni-PGE Deposit in the Northern Margin of the North China Craton" Minerals 14, no. 7: 733. https://doi.org/10.3390/min14070733

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