Petrogenesis of Granitoids from the Waxing Mo Polymetallic Deposit, NE China: Implications for Magma Fertility and Mineralization

Abstract

The Waxing Mo polymetallic deposit is located in the central part of the Lesser Xing’an–Zhangguangcai Range (LXZR), NE China. The Mo (Cu) mineralization in the deposit is dominantly hosted by quartz veinlets and stockworks and is closely related to silicification and potassic alteration, while the W mineralization is most closely related to greisenization. Zircon samples from granodiorite, biotite monzogranite, granodiorite porphyry, and syenogranite in the Waxing deposit yielded U-Pb ages of 172.3 Ma, 172.8 Ma, 173.0 Ma, and 171.4 Ma, respectively. Six molybdenite samples from porphyry Mo ores yielded a Re-Os isochron age of 172.0 ± 1.1 Ma. The granitoids in the ore district are relatively high in total alkali (Na₂O + K₂O), are metaluminous to weakly peraluminous, and are classified as I-type granitoids. The zircon samples from all granitoids showed a relatively consistent Hf isotopic composition, as shown by positive ε_Hf(t) values (3.1–8.3) and young T_DM2 ages (0.69–1.25 Ga). These results, combined with the whole-rock geochemistry, suggest that the magma source of these rocks most likely derived from partial melting of a juvenile middle-lower continental crust, with a minor contribution from the mantle. These granitoids have compositional characteristics of adakites such as relatively high Sr contents (e.g., >400 ppm) and Sr/Y ratios (e.g., >33), as well as weak Eu anomalies (e.g., Eu/Eu* = 0.8–1.1), indicating extensive fractionation crystallization of a hydrous magma. The apatite geochemistry indicates that the ore-related magma in Waxing is F-rich and has a relatively low content of sulfur. The zircon geochemistry reveals that the granodiorite, biotite monzogranite, and granodiorite porphyry have relatively high oxygen fugacity (i.e., ΔFMQ = +1.1~1.3), whereas the fO₂ values of the granite porphyry and syenogranite are relatively low (i.e., ΔFMQ = +0.1~0.5). The whole-rock and mineral geochemistry suggest that the Mo mineralization in Waxing is probably genetically related to granitoids (i.e., granodiorite, biotite monzogranite, and granodiorite porphyry), with higher oxygen fugacity and a high water content, whereas the magmatic S concentration is not the key factor controlling the mineralization. A comparison of the geochemical compositions of ore-forming and barren stocks for porphyry Mo deposits in the LXZR showed that geochemical ratios, including Eu/Eu* (>0.8), 10,000*(Eu/Eu*)/Y (>600), Sr/Y (>33), and V/Sc (>8), could be effective indicators in discriminating fertile granitoids for porphyry Mo deposits from barren ones in the region.

1. Introduction

More than 90% of global molybdenum production is contributed by porphyry Mo and Mo–Cu deposits [1]. China accounts for more than half of the total proven Mo reserve in the world [2]. Nearly 100 porphyry Mo deposits (reserve > 12.2 Mt) have been discovered in NE China, making NE China the most important Mo metallogenic province in China and even in the world [3,4,5].

The Lesser Xing’an–Zhangguangcai Range (LXZR) is located in the eastern segment of NE China, the bulk of which is made up of Phanerozoic granitoids, especially Mesozoic granitoids. In addition to the extensive Mesozoic granitic magmatism, another attractive feature of the LXZR is the large number of giant porphyry Mo deposits discovered throughout this magmatic belt, such as Huojihe, Luming, Fu’anpu, Jidetun, and Daheishan. Unlike the porphyry Mo deposits of North America, which are classified as Climax-type and formed in intraplate rift setting [6,7,8], most of the porphyry Mo deposits in the LXZR magmatic belt have been proposed to have been formed in the setting of the westward subduction of the Paleo-Pacific oceanic plate [4,9].

The genesis of economically important porphyry deposits is believed to be promoted by several factors, including the tectonic setting, metal-rich source region, large volumes of causative magma and fluid, high metal melting point, long-lived magmatic–hydrothermal activity, efficient transport of metals from the magma to the fluid, and localized precipitation of ore minerals [10,11,12,13,14]. However, up to now, it has remained unclear which factors controlled the extensive porphyry Mo mineralization in the LXZR during the Early to Middle Jurassic. The derivation and evolution of the ore-forming magmas is suggested to be an essential control on the formation of the porphyry-type and other magmatic hydrothermal deposits [15,16]. Therefore, a study of the petrogenesis and fertility of ore-related igneous suites of porphyry Mo deposits in the LXZR will provide a critical understanding of the links between magmatism and ore formation in the region.

The Waxing deposit is a newly discovered (in 2022) typical porphyry Mo polymetallic deposit in the LXZR, NE China. In this paper, we present zircon U-Pb and molybdenite Re-Os isotopic data for the ore-associated granitoids and Mo ores in the Waxing deposit to determine their ages. We also report the geochemical composition of whole-rock and accessory minerals of zircon and apatite, as well as the zircon Lu-Hf isotopic results of the ore-related granitoids in the deposit to constrain the petrogenesis and fertility of these rocks. Additionally, based on a comparison of the geochemistry of the granitoids related to representative porphyry Mo deposits and barren ones in the region, we discuss the magmatic factors that control the porphyry Mo fertility and regional mineralization.

2. Regional Geology

The Waxing deposit is situated in the Lesser Xing’an–Zhangguangcai Range (LXZR) within NE China (Figure 1a). It forms part of the Central Asian Orogenic Belt, and along with adjacent areas, underwent a complex geological evolution history during the Phanerozoic [17,18]. During the Paleozoic, the Paleo-Asian oceanic plate subducted southward and finally closed along the Solonker–Xilamulun–Changchun suture, resulting in the amalgamation of the micro-continent blocks in this region [9,17]. In the Jurassic to Early Cretaceous, the LXZR was dominantly controlled by the Paleo-Pacific tectonic domain. The development of Early Jurassic calc-alkaline magmatic rocks with arc geochemical characteristics in the eastern part of NE China, North Korea, and Japan, as well as the accretionary complex in the continental margin of Northeast Asia, indicates that the subduction of the Paleo-Pacific plate beneath the Eurasian continent began at this time [18,19]. The subduction resulted in regional lithospheric thickening, NE-trending lithospheric extension, and development of deep faults in back-arc areas [9,20].

The stratigraphic sequence in the region is dominantly by Paleozoic and Mesozoic volcano-sedimentary rocks, as well as Quaternary sediments [4]. The major regional faults are mainly EW-, NE-, and NS-trending. The Solonker–Xilamulun–Changchun suture in the southern part of the LXZR is the main regional EW-trending fault, which marks the closure of the Paleo-Asian Ocean [17] (Figure 1b). The NE-striking strike–slip faults are the results of the subduction of the Paleo-Pacific plate [9,18] (Figure 1b). The Mesozoic subduction–accretionary complexes (e.g., the Heilongjiang complex) along the LXZR–Yanbian arc magmatic belt preserve records of subduction of the Paleo-Pacific Ocean from the Early Jurassic [21,22]. Phanerozoic granitic rocks are widely distributed in the region (Figure 1b) and were emplaced in three main periods: Early Paleozoic, Late Triassic to Middle Jurassic, and Early Cretaceous [9,18]. Numerous porphyry Mo deposits in this region are genetically associated with Early to Middle Jurassic granite magmatism [23,24]. Figure 1

(a) Location of the study area in NE China. (b) Distribution of porphyry Mo deposits in the LXZR (modified from [25]).

[Figure omitted. See PDF]

3. Geology of the Waxing Deposit

The Waxing Mo polymetallic deposit lies in the central part of the LXZR (Figure 1b). The strata exposed in this ore district include the Lower Cretaceous Jianxing Formation, Cenozoic Pliocene–Pleistocene Harbin Formation, and Holocene sediment (Figure 2). The Jianxing Formation is situated northwest of the ore district, which has an outcrop area of about 2 km² in the deposit. This formation is composed dominantly of conglomerate and sandstone. The Harbin Formation is distributed along the margins of the deposit, except the northwest. The formation crops out about 4 km², and is mainly composed of loess-like subclay. The Holocene sediment in the deposit is modern river bed alluvium, which has an exposed area of about 1 km². There are no large regional folds and faults in the ore district. A series of small faults have been identified in the district, with widths ranging from 0.1 m to 1 m. According to a 1:5000 high-precision magnetic survey, it was inferred that 9 major faults were developed in the deposit.

The magmatic rocks in the deposit include granodiorite, biotite monzogranite, granite porphyry, granodiorite porphyry, and syenogranite (Figure 2). The granodiorite consists mainly of quartz (0.5–3 mm, 20–25 vol.%), plagioclase (1–4 mm, 30–40 vol.%, An% = ~30%), K-feldspar (0.5–3 mm, 10–14 vol.%), biotite (0.6–1.5 mm, 8–15 vol.%), and hornblende (0.5–1 mm, 5–10 vol.%), along with titanite, apatite, magnetite, and ilmenite in smaller proportions. The biotite monzogranite (porphyry) shows a granular (–porphyritic) texture and consists mainly of quartz (1–3 mm, 25–30 vol.%), K-feldspar (1–5 mm, 30–35 vol.%), plagioclase (1–4 mm, 25–30 vol.%, An% = ~25%–30%), and biotite (0.5–1.5 mm, 5–10 vol.%). When porphyritic, the phenocrysts of the rock comprise K-feldspar (1–3 cm, 60–70 vol.%), quartz (6–8 mm, 25–30 vol.%), and plagioclase (5–12 mm, 5–10 vol.%). The accessory minerals in the rock are mainly zircon, titanite, and apatite. The granite porphyry is porphyritic with 5–8 vol.% phenocrysts, which are composed of K-feldspar (2–3 mm, 40–50 vol.%), quartz (2–4 mm, ~40 vol.%), plagioclase (1–2.5 mm, 8–10 vol.%), and biotite (0.5–1.2 mm, 3–4 vol.%). The groundmass (0.2–0.6 mm, 90–95 vol.%) contains the same minerals as the phenocrysts. Zircon, apatite, and Fe-Ti oxides (0.5–1 vol.%) are the main accessory minerals in the rock. The granodiorite porphyry contains phenocrysts (10–15 vol.%) of plagioclase (2–4 mm, ~60% vol.%), quartz (1.5-2.5 mm, 20–30 vol.%), and minor K-feldspar and hornblende. The groundmass (0.2–0.5 mm, 85–90 vol.%) comprises plagioclase, quartz, K-feldspar, and hornblende. The accessory minerals include titanite, apatite, zircon, and magnetite. The syenogranite predominantly comprises quartz (0.5–1.5 mm, 30–35 vol.%), K-feldspar (0.6–2 mm, 40–50 vol.%), plagioclase (0.8–1.3 mm, 10–15 vol. %), and biotite (0.3–0.8 mm, 3–5 vol.%), with zircon, apatite, and Fe-Ti oxides (1%–3%) as the main accessory minerals (Figure 3 and Figure 4).

In the Waxing district, two groups of ore body are recognized: (1) ore body group 1 (mineralized zone I) in the west mainly contains copper and tungsten mineralization; (2) ore body group 2 (mineralized zone II) in the east mainly contains molybdenum and tungsten mineralization (Figure 2). In the deposit, the Mo and Cu mineralization is dominantly hosted by quartz veinlets and stockworks and is closely related to silicification and potassic alteration, while the W mineralization is most closely related to greisenization. The W ore mineral is scheelite, coexisting with quartz and muscovite in greisenization. The ore minerals include molybdenite, scheelite, chalcopyrite, pyrite, and rutile. The gangue minerals are mainly quartz, biotite, muscovite, calcite, and K-feldspar (Figure 5). The wall rock alteration types include silicification, potassic alteration, sericitization, chloritization, greisenization, kaolinization, and carbonate alteration.

4. Sampling and Methods

Thirty granitoid samples, including granodiorite, biotite monzogranite, granite porphyry, granodiorite porphyry, and syenogranite, were collected from the drill holes and outcrop in the Waxing ore district. After an initial examination using optical microscopy, twenty unaltered or least-altered samples were selected for zircon U-Pb and Lu-Hf isotopic, whole-rock, and mineral (zircon, apatite) geochemical analyses. Additionally, six molybdenite samples from quartz vein ores were collected from drill holes and used for Re-Os isotopic analyses. A description of the samples and analytical methods is given in Supplementary Materials Files S1 and S2 [26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48] (Table S1).

5. Results

5.1. Geochronology

5.1.1. Zircon U-Pb Ages

Zircon samples from samples of granodiorite, biotite monzogranite, granodiorite porphyry, and syenogranite were selected for U-Pb dating. The results are listed in Supplementary Table S2. The zircon grains from all samples were generally euhedral to subhedral and transparent. Their lengths ranged from 100 to 200 μm, with length/width ratios of 1:1 to 3:1, showing clear oscillatory growth zoning in CL images, which indicates a magmatic origin. The thorium and U contents of the analytical zircon samples were 72–906 ppm and 134–2090 ppm, respectively. The thorium/U ratios of the zircon grains were 0.22–0.77, also indicating a magmatic origin [49]. Therefore, the U-Pb dates may be confidently interpreted as the ages of magmatic intrusion.

The results of the zircon U-Pb dating are illustrated in Figure 6. The ²⁰⁶Pb/²³⁸U ages of 21 zircon grains from the granodiorite sample (ZK1002-1) range from 170 to 174 Ma, and the concordia age is 172.3 ± 0.4 Ma (MSWD = 0.02, Figure 6a). Sixteen analyses of zircon samples from a biotite monzogranite sample (ZK1101-7) yielded ²⁰⁶Pb/²³⁸U ages of 171 to 175 Ma, with a concordia age of 172.8 ± 0.5 Ma (MSWD = 0.05, Figure 6b). The zircon ²⁰⁶Pb/²³⁸U ages of the granodiorite porphyry (ZK1903-16) are in the range of 171 to 180 Ma, with an intercepted age of 173.0 ± 1.3 Ma (n = 26, MSWD = 0.95, Figure 6c). Eleven zircon grains from a syenogranite sample (C-10-1) yielded ²⁰⁶Pb/²³⁸U ages ranging from 166 to 181 Ma, with a concordia age of 171.4 ± 2.1 Ma (MSWD = 1.7, Figure 6d). These results indicate that the granitic intrusion in the Waxing deposit occurred over a narrow time period of 173–171 Ma.

5.1.2. Molybdenite Re-Os Ages

Rhenium and Os isotopic data for six samples of molybdenite are presented in Table S3. The total Re and ¹⁸⁷Os contents are in the ranges of 5608–43,487 ng/g and 9.96–78.04 ng/g, respectively. The analytical samples have Re-Os model ages varying from 169.4 ± 2.2 to 172.3 ± 2.3 Ma and a mean value of 170.9 ± 0.9 Ma. The six samples yield an isochron age of 172.0 ± 1.1 Ma (MSWD = 0.42) (Figure 7). This result is interpreted as the age of Mo mineralization in the Waxing deposit. This age is consistent with that of granitoids in the Waxing deposit and indicate that the Mo mineralization is genetically associated with the granitic magmatism.

5.2. Zircon Lu-Hf Isotope

A portion of the zircon samples that had been U-Pb-dated were chosen for the Lu-Hf isotopic analysis, and the results are shown in Table S4. A total of 40 spot analyses were obtained for zircon samples of 4 granitoid types. The ¹⁷⁶Lu/¹⁷⁷Hf ratios of the zircon samples are low (0.00051–0.00148), showing a low radiogenic Hf accumulation. Generally, the zircon samples from all rock types show a relatively consistent Hf isotopic composition. The ε_Hf(t) values and T_DM2 ages of the zircon samples vary from 3.1 to 8.3 and 0.69 to 1.25 Ga, respectively (except one spot of sample ZK1903-16-5, which yielded a negative ε_Hf(t) value of −0.5). The results show that there is no significant difference in Hf isotopic composition among the different rock types.

5.3. Whole-Rock Geochemistry

The whole-rock elemental compositions of the 20 granitoid samples from the Waxing deposit are given in Table S5. Among these rock types, the syenogranite and granite porphyry samples display higher SiO₂ values (70.2–73.1 wt.%), while the granodiorite and granodiorite porphyry samples have relatively low SiO₂ values (66.1–69.8 wt.%) and the biotite monzogranite samples have SiO₂ values of 68.5–70.6 wt.%. The samples are relatively high in total alkali (Na₂O + K₂O) and plot in the regions of granite and granodiorite in the TAS diagram (Figure 8a). Most of the samples show relatively high K₂O contents and fall in the high-K calc-alkaline series. Two samples of the granodiorite porphyry fall in the low-K calc-alkaline series (Figure 8b), which were probably affected by alteration. All samples have relatively high Al₂O₃ contents of 14.2–16.4 wt.%, with A/CNK values varying from 0.95 to 1.12, showing a metaluminous to weakly peraluminous composition (Figure 8c). The CaO, TiO₂, Na₂O, MgO, TFe₂O₃, and P₂O₅ contents of these rocks shows linear trends for their SiO₂ content (Figure 9), defining a genesis from a common magma source. The samples have MgO contents of 0.4–1.1 wt% and moderate Mg^# values of 30–50.

All samples exhibit similar patterns of chondrite-normalized REE (e.g., light rare earth element (LREE) enrichment relative to heavy rare earth elements (HREEs)), with (La/Yb)_N ratios ranging from 7.3 to 76.7 (Figure 10a). Among the rock types, the syenogranite samples display moderately negative Eu anomalies (Eu/Eu* = 0.53–0.67), while the other types of samples show weakly negative to positive Eu anomalies (Figure 10a). The rocks have similar primitive mantle-normalized trace element diagrams characterized by large ion lithophile element enrichment and high field-strengthened element depletion (Figure 10b). Additionally, the analyzed granitoid samples also exhibit relatively high Sr contents (224–657 ppm), as well as Sr/Y ratios (33.7–76.9).

5.4. Apatite Major Element Compositions

Because no apatite crystal has been separated from granite porphyry and syenogranite samples using heavy liquid and magnetic techniques, apatite samples from granodiorite (ZK1002-1), biotite monzogranite (ZK1101-7), and granodiorite porphyry (ZK1903-16) in the Waxing deposit were analyzed for their major element compositions. The apatite grains commonly display euhedral and subhedral crystal shapes, measuring 100–160 μm in diameter. The apatite crystals mainly occur in both hornblende and biotite phenocrysts and groundmass. The majority of the apatite grains exhibit homogeneous luminescence, with others showing zoning textures (Figure 11a). The apatite grains analyzed in this study were fluid-inclusion-free and showed primary magmatic origin characteristics; thus, they were believed to have formed under volatile, undersaturated conditions, meaning they can reflect the physicochemical conditions of the host magma.

The apatite major element concentrations are shown in Table S6. The apatite samples are similar in their CaO and P₂O₅ contents. The individual apatite grains in all samples are essentially homogeneous in their halogen (i.e., F and Cl) and SO₃ concentrations, even those with zoned textures in the BSE images. All apatite samples display similar high F (2.61–3.82 wt%) and low Cl contents (0.02–0.16 wt%) and belong to fluorapatite (F-apatite) (Figure 11b). The analytical apatite samples have relatively low SO₃ contents (<0.14 wt%, except one spot of 0.52 wt%, Figure 11c).

The results of the trace element analyses of zircon from the granitoids in the Waxing deposit are shown in Table S7. The result shows that zircon samples from different types of granitoids generally display a negative Eu anomaly and positive Ce anomaly. In this study, we took elements such as La and Ti as indicators to monitor effects on the zircon, such as melt or fluid inclusions and hydrothermal alterations [53,54]. Thus, the data with unreasonably high La or Ti contents were excluded from the temperature and fO₂ estimations.

The formation temperature of zircon can be represented by the titanium-in-zircon temperature according to [46]:

(1)$\log (\mathrm{ppm} \mathrm{Ti}-\mathrm{in}-\mathrm{zircon})=(5.711\pm 0.072)-{\displaystyle \frac{4800\pm 86}{\mathrm{T}\left(\mathrm{K}\right)}}-\log {\alpha }_{{\mathrm{SiO}}_2}+\log {\alpha }_{{\mathrm{TiO}}_2}$

In this study, the values of α_SiO2 and α_TiO2 (activities of silica and titanium) in the above formula are buffered at 1 and 0.7, respectively, because all granitoid rock types in the Waxing deposit contain quartz and titanite [55,56]. Using this method, the estimated average Ti-in-zircon temperatures of the five rock types (i.e., granodiorite, biotite monzogranite, granite porphyry, granodiorite porphyry, and syenogranite) in Waxing are 715 ± 73 °C (n = 51), 707 ± 64 °C (n = 36), 751 ± 85 °C (n = 15), 728 ± 64 °C (n = 57), and 749 ± 81 °C (n = 18), respectively. In general, there is no obvious Ti-in-zircon temperature difference between the zircon samples from different types of granitoids.

The zircon trace element oxybarometer from [48] was used in this study to quantitatively estimate the redox state of the ore-related magma in Waxing. This method has been proven to be reliable in the quantitative estimation of fO₂ in magma [57,58]. The average magmatic ΔFMQ (log fO₂ difference between the sample value and the fayalite–magnetite–quartz mineral buffer) values of the granodiorite, biotite monzogranite, granite porphyry, granodiorite porphyry, and syenogranite were +1.3 ± 0.9, +1.2 ± 0.9, +0.1 ± 1.2, +1.1 ± 0.9, and +0.5 ± 1.3, respectively. Thus, among all types of granitoids in Waxing, the granodiorite, biotite monzogranite, and granodiorite porphyry had relatively high oxygen fugacity levels (i.e., ΔFMQ = +1.1~1.3), whereas the fO₂ values of the granite porphyry and syenogranite were relatively low (i.e., ΔFMQ = +0.1~0.5).

6. Discussion

6.1. Petrogenesis of Granitoids in Waxing Revealed by the Whole-Rock and Mineral Geochemistry

6.1.1. Magmatic Source

All types of granitoids from the Waxing deposit have comparable geochemical compositions, characterized by a metaluminous to weakly peraluminous profile (A/CNK = 0.95–1.12), the enrichment of LREEs, and the depletion of HREEs (Figure 10b). In general, these granitoids do not exhibit a high degree of fractionation; thus, the relatively low A/CNK values (most <1.1) imply that they are more likely I-type [59]. Furthermore, these rocks are absent of aluminum-rich magmatic silicate minerals such as muscovite and cordierite but contain hornblende (especially in granodiorite), which is different from typical S-type granite. Experimental studies indicate that P₂O₅ is negatively correlated with SiO₂ in I-type granites because of the low solubility of apatite in the magmas, while the P₂O₅ of S-type granites is increased or unchanged with the increase in SiO₂ [60]. As shown in Figure 9f, the P₂O₅ of the analyzed samples is negatively correlated with the SiO₂, suggesting that they are I-type granites. Additionally, these granitoids are geochemically comparable with the contemporary granitoids widely distributed in the LXZR and even in NE China, which are proposed to be derived from the juvenile crust that originated in the mantle during the Phanerozoic [61]. Therefore, we propose that the granitoids in Waxing are I-type.

Based on petrographic observations, no alkaline mafic mineral was found in the granitoids in Waxing, and all granitoid samples in this study displayed relatively low zirconium saturation temperatures (i.e., 771–807 °C, average = 793 °C; Table S5), lower than those of typical A-type granites (>900 °C, [62]). Furthermore, Figure 12a,b show that the samples of granitoids are plotted in the field of unfractionated I/S-type granite, although close to the A-type field. Therefore, these rocks are classified as I-type granitoids. Previous studies have shown that the causative stocks of porphyry Mo deposits in the LXZR are dominantly I-type granitoids [23,24]. In contrast to S-type felsic magmas, metaluminous I-type magmas are more conducive to the development of porphyry Mo deposits because the sources of S-type magmas are predominantly weathered sediments and are depleted in Mo [63].

The zircon Lu-Hf isotopic composition (ε_Hf(t) = −0.5–+8.3, T_DM2 = 689 Ma−1246 Ma) indicates that the magmas of the granitoids from the Waxing deposit were most likely derived from a depleted juvenile crust or a mixed source with some mantle magmas. These rocks have low to moderate MgO contents (0.4–1.1 wt%) and Mg^# values (30–50), suggesting a middle-lower continental crust, with some mantle material probably involved. Figure 12c indicates that the ore-related magma in Waxing is geochemically comparable to that derived from the melting of amphibolite to greywacke.

The granitoids (except syenogranite) in the Waxing deposit display characteristics of adakite (Figure 12d,e), such as high Sr contents (>400 ppm) and Sr/Y ratios but low concentrations of Y (<18 ppm) and Yb (<1.9 ppm) [67,68]. Considering the regional tectonic setting in the Jurassic, the adakitic characteristics of these granitoids could have resulted from the partial melting of a thickened lower crust or partial melting of a subducted oceanic crust [67,69]. At the end of the Paleozoic, the closure of the Paleo-Asian Ocean and extensive crust–mantle interaction led to the formation of a thickened juvenile crust [17]. During the Jurassic, the westward subduction of the Paleo-Pacific plate could have induced partial melting of the thickened middle-lower crust [18], resulting in the formation of ore-bearing magma for the Waxing deposit. Furthermore, the granitoids in the Waxing deposit are characterized by high SiO₂ contents and relatively rich in potassium, implying that the magma was more likely to come from partial melting of the thickened crust than partial melting of the subducted oceanic crust. During this process, some materials (such as oxidized materials and fluids) from the subducted oceanic crust may be added to the magma, increasing the water content and oxygen fugacity of the magma [70,71]. Figure 12f suggests that the magma source was influenced by fluids.

6.1.2. Fractionation Crystallization Process of the Magma

Based on petrographic observations, as well as whole-rock and mineral geochemical characteristics, no evidence of extensive magmatic mixing was identified in Waxing. The compositional variation trends of the samples of granitoids from the Waxing deposit in the Harker diagrams (Figure 9) imply that they were mainly formed from the same parental magma with various degrees of crystal fractionation. The obvious negative correlations between the MgO, TiO₂, TFe₂O₃, P₂O₅, and SiO₂ contents can be attributed to the fractionation of minerals of hornblende, biotite, titanite, magnetite, and apatite.

The granitoid samples from the Waxing deposit are characterized by weak to moderate enrichment of LREEs ([La/Sm]_N = 1.3–6.1), as well as weak MREE enrichment relative to HREEs ([Dy/Yb]_N = 1.3–2.2). This implies that the fractionation of REEs in the causative magma was dominantly controlled by hornblende and titanite, which have a strong affinity for MREEs [72,73]. A small amount of garnet fractionation could have occurred during the magma’s evolution because garnet preferentially partitions HREEs. On the diagram of the (La/Yb)_N vs. Yb_N (Figure 12d), the samples plot between amphibolite and amphibolite + 10% garnet evolution trends, which also indicates that the evolution of the magma was mainly controlled by the fractionation of hornblende, with an additional minor contribution from garnet.

In calc-alkaline intermediate to felsic magmas (e.g., andesite and dacite), Sr tends to get into plagioclase because of the relatively high partition coefficient (~3–5) between the plagioclase and the melt [74]. In contrast, Y has a partition coefficient range of 2–6 between the hornblende and melt, with andesite to dacite compositions, and would enter the mineral [75,76,77,78]. Thus, the high contents of Sr (mostly >400 ppm) and Sr/Y ratios (>33) of these granitoids samples (Figure 12e) from the Waxing deposit are explained by the crystallization of hornblende but not plagioclase in the magma [73,77].

The rather weak Eu anomalies in the Waxing granitoids (except syenogranite) could be caused by following reasons: (1) the diminished formation of plagioclase under water-rich conditions and pressure levels of 0.6–1.2 GPa [78]; (2) Eu in the magma mainly occurs as Eu³⁺ and tends not to enter the plagioclase during fractionation at a high oxidation state [79,80]; or (3) the co-crystallization of minerals including hornblende, titanite, and apatite because the coefficients of Eu of these minerals are lower than neighboring REEs and the fractionation of these minerals would cause an increase in Eu/Eu* in the magma [81,82,83]. All of these mechanisms are reasonable because the minerals mentioned above have been widely observed in the ore-related granitoids in Waxing, suggesting that the causative magma could be hydrous and oxidized [84]. However, compared to other rock types in the Waxing deposit, the syenogranite samples show relatively low Sr concentrations (224–257 ppm) and moderate negative Eu anomalies (Eu/Eu* = 0.5–0.7), which suggests that the plagioclase fractionation crystallization could have occurred during the magma’s evolution and implies that it has undergone a different magmatic evolution process than other granitoids in Waxing and likely has no directly genetic relationship with Mo mineralization in the deposit, although its age is consistent with that of the Mo mineralization.

6.2. Volatile Characteristics and Redox State of the Magma and Fertility Implications

6.2.1. Volatile Characteristics of the Ore-Related Magma

A relatively high content of water (>4 wt.%) in the causative magma is critical to generate a considerable volume of ore-forming fluids and to form economic porphyry deposits [14,78]. When the intermediate felsic magma contains >4 wt.% H₂O, fractional crystallization of the hornblende could be facilitated at relatively low pressures [78,84,85]. Under water-rich conditions, the fractional crystallization of the hornblende from the magma can make the igneous rock have distinct geochemical characteristics. As mentioned earlier, the granitoids in Waxing have a relatively high Sr/Y ratio (>33), lack obviously negative anomalies of Eu (except syenogranite), and display slightly concave HREE patterns. These results reveal that hornblende accumulated in the magma without the extensive segregation of plagioclase before the emplacement of the magma in the crust, as discussed above. The development of granodiorites in the Waxing ore district and many other porphyry Mo deposits in the LXZR and the presence of abundant hornblende deposits in these stocks suggest that the H₂O contents in the ore-forming magmas were more than 4 wt% during the emplacement.

The composition of magmatic apatite (e.g., SO₃ contents) can be used when evaluating the sulfur contents of magmas based on the S concentrations of apatite in conjunction with the sulfur partition coefficients between the apatite and melt DSapatite/melt [86,87]. The apatite S concentration is dominantly controlled by the magmatic S concentration and redox state [87,88,89]. Sulfur predominantly occurs as S⁶⁺ in apatite; thus, when magmas have the same contents of sulfur, apatite crystallized from the magma with higher oxygen fugacity would have a higher sulfur content [90].

As mentioned earlier, the apatite deposits in the samples of granodiorite, biotite monzogranite, and granodiorite porphyry had relatively low SO₃ contents (mostly <0.14). This result is comparable to those in other Mo-related granitoids in the LXZR and other Mo belts [91,92,93,94]. Given that these three granitoid types have relatively high oxygen fugacity levels according to their zircon geochemistry, this implies that the magmas of granite porphyry and syenogranite have comparable or even lower S concentrations than that of granodiorite, biotite monzogranite, and granodiorite porphyry. This also suggests that the ore-related magmas in Waxing have relatively low contents of S. Additionally, the determination of the sulfur contents in melt inclusions of ore-forming stocks using LA-ICP-MS analyses in previous studies also showed that the sulfur content in magma is not directly related to the scale and grade of porphyry Mo deposits [95,96]. Therefore, the above lines of evidence indicate that the sulfur concentration in causative magma is not a key factor that controls the potential for the formation of porphyry Mo deposits.

The ore-related granitoids in the Waxing deposit display crustal-derived characteristics, including the development of apatite samples with high F contents but very low contents of Cl and ratios of Cl/F, indicating that the magma is a F-rich system [97]. Generally, the apatite samples from the granodiorite had higher Cl concentrations but with some overlap with those from the biotite monzogranite and granodiorite porphyry.

6.2.2. Redox State of the Ore-Related Magma

It is well known that porphyry Mo deposits are genetically related to relatively oxidized magmas. According to one estimation, among the different types of granitoids in the Waxing ore district, granodiorite, biotite monzogranite, and granodiorite porphyry show relatively high oxygen fugacity levels (e.g., ΔFMQ = +1.1~1.3). These results are consistent with the redox state (e.g., fO₂ = FMQ+1 to FMQ+2) of the magmas related to the porphyry deposits, in which the dominant sulfur species would change from S²⁻ to S⁶⁺ [98]. In contrast, the fO₂ values of the granite porphyry and syenogranite are relatively low (e.g., ΔFMQ = +0.1~0.5). The low oxygen fugacity combined with the low water content of the magmas reveals that the granite porphyry and syenogranite have little genetic relationship with Mo mineralization in the deposit. Thus, the ore formation in Waxing was probably related to granitoids with higher oxygen fugacity and a high content of water in the deposit (i.e., granodiorite, biotite monzogranite, and granodiorite porphyry).

6.3. Implications for Regional Mineralization and Exploration

It is controversial whether the magma source for the late Mesozoic large-scale porphyry Mo mineralization in NE China is Mo-rich [3,99,100]. Studies have shown that the causative granitoids of these Mo deposits display a largely varied Hf, Sr, and Nd isotopic compositions, and there is no direct relationship between the isotopic compositions and the Mo tonnages of the deposits [5,101]. Figure 13 shows the relationship between the zircon U-Pb ages and ε_Hf(t) values of fertile suites from the representative porphyry Mo deposits and barren granitoids with ages of 200–160 Ma in the LXZR. As shown in Figure 13b, both the zircon samples from the fertile and barren suites display positive ε_Hf(t) values. In comparison, the zircon samples from the causative granitoids in the Huojihe and Luming deposits (~1–4) have lower ε_Hf(t) values than those of the Fu’anpu and Daheishan deposits (~6–9). The range of zircon ε_Hf(t) values of the granitoids from the Waxing deposit is generally between and also overlaps with the above two groups (Figure 13b). Additionally, the LA-ICP-MS compositional analysis results for the melt inclusions from the ore-associated intrusions in porphyry Mo deposits in NE China reveal that the fertile intrusions have similar Mo concentrations as the barren ones [101]. Therefore, the development of these Mo deposits does not require an extremely Mo-rich source or Mo-bearing magma.

Previous studies revealed that NE China was in the Circum-Pacific tectonic regime after the Late Triassic [109,110]. The late Mesozoic porphyry Mo mineralization history in the LXZR is from ~190 to 166 Ma, and the causative magmas of these Mo deposits are parts of extensive late Mesozoic magmatism in the region [5,23,25]. Therefore, the Mesozoic magmatism and associated metallogenesis in the eastern part of NE China was mostly developed in a continental arc setting and was related to the subduction of the Pacific plate [4,9,23], which resulted in the development of extensive granitic magmatism in the LXZR and generation of a series of important ore deposits.

When water-rich oceanic sediments of the Paleo-Pacific plate subducted into the Eurasian mantle wedge, hydroweakening of the continental lithosphere was caused during the interaction of fluids and the overlying lithosphere [21], leading to the generation of arc magmas characterized by high water contents and oxygen fugacity, which is critical for magma fertility in porphyry deposits [111,112]. As discussed above, the high contents of Sr (>400), Sr/Y ratios (>33), and relatively high Eu/Eu* ratios (>0.8) of ore-related granitoids in the Waxing deposit indicate that the ore-forming magma is water-rich and probably oxidized, facilitating the fractionation of hornblende but diminishes the fractionation of plagioclase. A comparison of the geochemistry of the Mo-mineralized and barren granitoids in the LXZR was conducted (Figure 14). As shown in the figure, the ore-related granitoids from the Waxing and other representative porphyry Mo deposits (Huojihe, Luming, Fu’anpu, and Daheishan) in the LXZR show similarly higher whole-rock Sr contents, Eu/Eu* ratios, and 10,000*(Eu/Eu*)/Y values than those of barren suites in the region (Figure 14a–c). These geochemical characteristics all together reflect the high water content or oxygen fugacity of the magmas and can be fertility indicators for the porphyry Mo deposit [113,114,115]. Additionally, the granitoids of a fertile suite plot are in the region of the adakite on the Sr/Y vs. Y diagram, whereas those of the barren suite are mainly plotted in the normal arc magmatic rock region (Figure 14d). This indicates that although the granitoids of both fertile and barren suites have comparable ages and formed in an arc setting during the subduction of the Pacific plate, differences in magmatic composition (e.g., water-rich vs. water-poor) make these granitoids exhibit different geochemical characteristics (i.e., adakite vs. normal arc magmatic rock; Figure 14d). The whole rock V/Sc ratio is a reliable proxy for the redox state of the magma [116,117]. It was documented that mid-oceanic ridge basalts, for which the ΔFMQ values are close to 0, have V/Sc ratios of 6.74 ± 1.11 [116]. Furthermore, oxidized causative magmas for porphyry deposits have been proposed to have V/Sc values > (32.5 − 0.385 × SiO₂ wt%) [78,117]. As shown in Figure 14e, the fertile suites of porphyry Mo deposits in the LXZR have elevated V/Sc ratios (>8), which are systematically higher than those of barren suites, indicating that the fertile magmas have higher oxygen fugacity. Notably, some granodiorite samples from the barren suites display comparable Sr contents and Eu/Eu* ratios to those of the fertile suites, suggesting that the magma must be both oxidized and water-rich to have metallogenic potential.

To sum up, the magma fertility of porphyry Mo deposits in the LXZR is highly dependent on the content of water and redox state. Our study shows that whole-rock fertility indicators such as the Eu/Eu* (>0.8), 10,000*(Eu/Eu*)/Y (>600), Sr/Y (>33), and V/Sc (>8) ratios could be effective in discriminating porphyry Mo granitoids from barren ones in the LXZR (Figure 14).

Figure 14

Trace element concentrations and ratio plots for the fertile and barren suites for porphyry Mo deposits in the LXZR: (a) Sr vs. SiO₂; (b) Eu/Eu* vs. SiO₂; (c) 10,000*(Eu/Eu*)/Y vs. SiO₂; (d) Sr/Y vs. Y (after [67]); (e) V/Sc vs. SiO₂. The data for fertile suites are from [103,104,105,118]. The data for barren suites are from [106,107,108].

[Figure omitted. See PDF]

7. Conclusions

Based on the analytical results of zircon U-Pb and molybdenite Re–Os dating, as well as whole-rock and mineral geochemical and isotopic data of granitoids from the Waxing Mo polymetallic deposit, we draw the following conclusions.

In the Waxing deposit, the Mo (Cu) mineralization is dominantly porphyry-type and is closely related to silicification and potassic alteration, while the W mineralization is most closely related to greisenization. The granitoids in the deposit, including granodiorite, biotite monzogranite, granite porphyry, granodiorite porphyry, and syenogranite, formed in a relatively narrow range of ~173–171 Ma. The molybdenite Re-Os dating confirms that the Mo mineralization formed in the Middle Jurassic with an age of 172.0 ± 1.1 Ma, which is consistent with the granitic magmatism.

The granitoids in Waxing are classified as I-type, and the magmas were mainly derived from juvenile the middle-lower continental crust. The Mo mineralization in Waxing was probably related to granitoids (i.e., granodiorite, biotite monzogranite, and granodiorite porphyry) with higher oxygen fugacity (i.e., ΔFMQ = +1.1~1.3), as well as a high water content (e.g., >4%). The evolution of the causative magma in the Waxing deposit was dominantly controlled by the fractionation of hornblende.

Geochemical fertility indicators such as the Eu/Eu* (>0.8), 10,000*(Eu/Eu*)/Y (>600), Sr/Y (>33), and V/Sc (>8) ratios reflect the high water content and oxygen fugacity of magmas and could be effective in discriminating fertile granitoids for porphyry Mo deposits from barren ones in the LXZR.

Author Contributions

Y.L.: writing—original draft, editing, funding acquisition. D.-Y.S.: conceptualization, methodology, writing—reviewing, supervision. Y.G.: conceptualization, methodology, writing—reviewing, supervision. H.-C.W.: project administration, resources. Y.-X.M.: project administration, resources. J.X.: methodology, resources. X.-T.L.: resources. All authors have read and agreed to the published version of the manuscript.

Data Availability Statement

The experimental data used to support the conclusions of this study are included within the article and Supplementary Materials.

Acknowledgments

We wish to thank the reviewers and editors for their insightful comments.

Conflicts of Interest

Hong-Chao Wang and Yu-Xin Ma are employed by The Fifth Geological Exploration Institute, Heilongjiang Bureau of Geology and Mineral Resources. The paper reflects the views of the scientists and not the company.

Footnotes

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Figures

Figure 2. Geological map of the Waxing ore district.

Figure 3. Representative photographs of the granitoids from the Waxing deposit: (a) granodiorite; (b) granodiorite porphyry; (c,d) biotite monzogranite (porphyry); (e) granite porphyry; (f) syenogranite. Abbreviations: Qz—quartz; Kfs—K-feldspar; Pl—plagioclase; Bt—biotite.

Figure 4. Representative photomicrographs of the granitoids from the Waxing deposit. (a) granodiorite; (b) plagioclase with growth zoning in granodiorite; (c) biotite monzogranite; (d) granodiorite porphyry; (e) granite porphyry; (f) syenogranite. Abbreviations: Qz—quartz; Kfs—K-feldspar; Pl—plagioclase; Bt—biotite; Hbl—hornblende.

Figure 5. Photographs of alteration and mineralization features in the Waxing deposit: (a,b) biotite monzogranite cut by quartz–molybdenite vein with silicification and potassification; (c) greisenization in granodiorite; (d) sericitization for plagioclase and K-feldspar and chloritization for biotite in granodiorite; (e) carbonate alteration for plagioclase phenocryst in granodiorite porphyry; (f) molybdenite in quartz–molybdenite vein; (g) pyrite and chalcopyrite in ore vein; (h) scheelite coexists with Qz and Ms in greisenization; (i) rutile is replaced by pyrite and chalcopyrite. Abbreviations: Qz—quartz; Kfs—K-feldspar; Pl—plagioclase; Bt—biotite; Mo—molybdenite; Py—pyrite; Ccp—chalcopyrite; Sch—scheelite; Rt—rutile; Ms—muscovite; Cal—calcite.

Figure 6. LA-ICPMS zircon U-Pb Concordia diagrams for (a) granodiorite, (b) biotite monzogranite, (c) granodiorite porphyry, and (d) syenogranite in the Waxing deposit.

Figure 7. Isochron Re-Os age (a) and weighted mean age (b) for molybdenite from the Waxing deposit.

Figure 8. Diagrams of (a) (Na2O + K2O) vs. SiO2 (after [50]), (b) K2O vs. SiO2 (after [51]), and (c) A/NK vs. A/CNK for the granitoids in the Waxing deposit. A/NK = Al/(Na + K) (molar ratio); A/CNK = Al/(Ca + Na + K) (molar ratio).

Figure 9. Harker diagrams of ore-related granitoids in the Waxing deposit. (a) TiO2 vs. SiO2; (b) Al2O3 vs. SiO2; (c) TFe2O3 vs. SiO2; (d) MgO vs. SiO2; (e) CaO vs. SiO2; (f) P2O5 vs. SiO2. The symbols explanation are the same as in Figure 8.

Figure 10. Chondrite-normalized REE patterns (a) and primitive mantle (PM)-normalized trace element diagrams (b) for the ore-related granitoids in the Waxing deposit. The chondrite and PM values are from [52].

Figure 11. (a) Representative BSE images of apatite, with the analyzed spots and numbers of EPMA. (b) Triangular plots of molar proportions of OH, Cl, and F in the apatite. (c) Cl vs. SO3 contents of apatite from the granitoids in the Waxing deposit. The symbols explanation are the same as in Figure 8.

Figure 12. Plots of (a) (Na2O + K2O)/CaO vs. Zr + Nb + Ce + Y (after [64]), (b) Zr vs. 10,000 Ga/Al (after [64], the evolution trend line is after [65]), (c) (Na2O + K2O)/(TFeO + MgO + TiO2) vs. Na2O + K2O + TFeO + MgO + TiO2 (after [66]), (d) (La/Yb)N vs. YbN (after [67]), (e) Sr/Y vs. Y (after [67]), and (f) Rb/Y vs. Nb/Y for the granitoids in the Waxing deposit. The symbols explanation are the same as in Figure 8.

Figure 13. (a) Hf isotopic characteristics of zircon samples of granitoids from the Waxing deposit. (b) Comparison of Hf isotopic compositions of the fertile and barren suites of porphyry Mo deposits in the LXZR. The data for the fertile suites are from [102,103,104,105]. The data for the barren suites are from [106,107,108].

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/min14111104/s1: Table S1. A general description of the analytical samples from the Waxing deposit. Table S2. Zircon U-Pb dating results of the granitoids in the Waxing deposit. Table S3. Re-Os isotopic data of molybdenite samples from the Waxing deposit. Table S4. Zircon Lu-Hf isotopic data of the granitoids in the Waxing deposit. Table S5. Whole-rock major (wt%) and trace element (ppm) compositions of the granitoids in the Waxing deposit. Table S6. Apatite major (wt%) element compositions of the granitoids in the Waxing deposit. Table S7. Zircon trace (ppm) element data of the granitoids in the Waxing deposit.

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