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Article

Geochemical and Geochronological Constraints on a Granitoid Containing the Largest Indosinian Tungsten (W) Deposit in South China (SC): Petrogenesis and Implications

by
Jinhua Qin
*,
Denghong Wang
and
Yuchuan Chen
MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China
*
Author to whom correspondence should be addressed.
Minerals 2022, 12(1), 80; https://doi.org/10.3390/min12010080
Submission received: 28 November 2021 / Revised: 24 December 2021 / Accepted: 28 December 2021 / Published: 10 January 2022
(This article belongs to the Special Issue Rare Metal Ore Formations and Rare Metal Metallogeny)
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Abstract

:
Chuankou tungsten (W) ore field, with an estimated WO3 reserve exceeding 300,000 tonnes, is so far the largest Indosinian (Triassic) granite-related W ore field in South China. However, the precise emplacement ages, sources of granitoids, and their relationship with W mineralization are still not well understood. In this research, four main magmatic stages (G-1 to G-4) have been identified in the Chuankou ore field, including G-1 (phase I, biotite monzogranite), G-2 (phase II, two-mica monzogranite), G-3 (phase III, fine-grained granite), and G-4 (phase IV, granite porphyry). LA-ICP-MS U-Pb dating of zircon grains from granitoids of the Chuankou W ore field yields emplacement ages of 230.8 ± 1.6 Ma, 222.1 ± 0.56 Ma, 203.1 ± 1.6 Ma, and 135.5 ± 2.4 Ma, respectively. Granitoids from the Chuankou ore field contain a large amount of peraluminous minerals such as biotite, musvite, garnet and tourmaline. Geochemically, the granitoids have high Si and Al (A/CNK > 1.1) content but low alkali, Fe, Mg, Mn, and Ca content. Moreover, there is enrichment of Rb, Zr, Hf, Th, and U, but depletions of Ba, Sr, P, and Ti. The granitoids have especially low Zr + Nb + Ce + Y and high Rb/Ba ratios, further indicating a highly fractionated S-type granite affinity with a significant crystal fractionation process in regard to K-feldspar, plagioclase, biotite, Ti-bearing minerals (except rutile), zircon, apatite, allanite, and monazite. Whole-rock εNd(t) and TDM2 values are −10.77 and 2090 Ma for G-1, −9.09 to −7.47 and 1764–1684 Ma for G-2, −10.07 to −6.53 and 1669–1471 Ma for G-3, respectively, indicating that the Chuankou granitoids were derived from two episodes of partial melting of the Paleoproterozoic to Mesoproterozoic metamorphic basement. Trace elements within the zircons and whole-rock geochemistry yielded evidence of the close relationship between W mineralization and G-1 and G-2 granitoids of the Chuankou ore field. The batholith of the Chuankou ore field was formed 20–10 Ma later than the peak age of the collisions orogeny and formed in a post-collisional setting.

1. Introduction

South China (SC) is renowned for its extensive magmatism and the giant ore deposit clusters of W, Sn, Mo, Bi, Pb, Zn, Sb, U, Be, Nb, Ta, and REEs in the Yanshanian period [1,2,3,4,5]. These ore deposits host more than 90% of China’s W resources; over 56% of global W resources [1,2,3]. Extensive research has been carried out around Yanshanian W mineralization and related igneous rocks using high-precision geochronological data [2,6,7,8,9,10,11,12,13,14,15,16]. In contrast, the Indosinian igneous rocks and W deposits have been not widely concerned since they are small in size and bear minimal U, Nb, and Ta deposits [17,18,19]. Recently, Sample reports on Indosinian W-Sn mineralization (the Miao’ershan W-Mo deposit, Hehuaping Sn deposit, Xiane’tang Sn deposit, Xitian Sn deposit, Nanyangtian W-Mo deposit, and Qingshan W deposit) have come to the forefront [2,12,20,21,22,23,24] (Figure 1b). Due to the unique spatial and temporal distribution and great metallogenic potential, increasing attention has been given to revealing the ore genesis and related granitoids of Indosinian W deposits [22,24].
Previous research has identified the close genetic relationships between W deposits and granitoids in the South China block (SCB). Numerous studies have shown that W-bearing granitoids generally present S- and/or A-type granitoid affinities and are enriched in SiO2 and volatiles (e.g., Li and F) [25,26]. Recently, Zhang et al. [27] and Jiang et al. [28] confirmed that W-bearing granitoids are highly fractionated I-type granite based on the investigation of Yanshannian W deposits from Jiangxi Province and Guangdong Province. However, Huang et al. [29] proposed that W-bearing granitoids from Indosinian Yuntoujie W deposits are obvious highly fractionated S-type granite affinities. Therefore, further research is needed to solve the issue of whether the W-bearing granitoids are highly fractionated I-type or S-type.
The Chuankou W ore field is situated in the middle of the SCB and has been identified as the largest W ore field of SC with a total W metal content of over 300,000 tonnes (Figure 1a). Moreover, there are 14 important W deposits distributed in the ore field (Table 1). Bai et al. [30] suggested that the host rocks of the Chuankou W deposit were formed 170 to 160 Ma. Peng et al. [31] suggested zircon U-Pb dating of host rocks to around 220 Ma and a molybdenite Re-Os to 221 Ma for the Sanjiaotan W deposit. However, up to now, the precise emplacement ages, sources of granitoids from the Chuankou ore field, and their relationship with W mineralization have been less studied and are still not well understood.
In this study, we present new zircon U-Pb ages, major and trace element characteristics, Sr-Nd isotopic compositions of granitoids from the Chuankou W ore field to constrain the source, magmatic genesis, and their relationships with W deposits.

2. Regional Geology

The Chuankou ore field is situated in the middle-eastern part of Hunan Province, the margin of the Neoproterozoic suture zones between the Yangtze Block and Cathaysia Block—the Qin-Hang suture zone (Figure 1a). The strike of the Qin-hang suture zone yields an NE-SW orientation along the Hangzhou Bay in Zhejiang Province to Qinzhou Bay in Guangxi Province, approximately 2000 km in length and 100–150 km in width [32,33,34]. The Qin-Hang suture zone is also a giant W-Sn-Mo-Bi-Cu-Pb-Zn-g-Au-U polymetallic mineralization zone of the SCB [35] (Figure 1b). During the Neoproterozoic period, this area underwent a collision between the Yangtze Block and Cathaysia Block caused by the closure of the Paleo-South China Sea. The subsequent intracontinental fold orogeny continued to influence the region during the early Paleozoic period. Due to the northward subduction of the Indo-China block and closure of the ancient Tethys Ocean in the late Paleozoic to early Mesozoic, the tectonic regime transitioned to multiplate convergence and caused E-W-trending folded orogenic belts and foreland basins [9,36,37,38,39,40].
Various metal resources are distributed throughout the Chuankou ore field, including W, Sn, Cu, Nb, Ta, Fe, Pb, Zn, and Au (Table 1). The main types of W deposits in the Chuankou ore field are altered granite-type scheelite, quartz vein-type wolframite, and veinlet-disseminated scheelite. The altered granite-type scheelite is mainly developed in the Maowan deposit, Tangjiangyuan deposit, and Baishui deposit. Wolframite and molybdenite grains are disseminated in altered two-mica monzogranites. The quartz vein-type wolframite is mainly developed in the Sanjiaotan deposit, Huanglong deposit, and Nanwan deposit. The main associated metals involve Cu, Bi, Mo, Pb, and Zn. The vein-disseminated scheelite is mainly distributed in the Yanglinao deposit (Figure 2) [41].

3. Ore Deposit Geology

The Proterozoic metamorphic basement exposed in the center of the ore field contains a metamorphic silty slate and an argillaceous slate of the Neoproterozoic Wuqiangxi Formation of Banxi group. These are the most important host rocks of the quartz vein-type wolframite. The Paleozoic strata are exposed in the margin of the ore field and are unconformably covered above the metamorphic basement. It is composed of siliceous sedimentary breccia and shale with of the Devonian Yanglinao Formation (D2y), shale of the Carboniferous Yanguan Formation (C1y), and the diluvial layer of the Quaternary. Among them, the siliceous sedimentary breccia of Yanglinao Formation (D2y) has been confirmed as one of the wall rocks of the vein-type scheelite in the Yanglinao deposit (Figure 2). The Chuankou W ore field is exposed in the core of the Chuankou uplift, which is composed of a series of anticlines. The Chuankou uplift belongs to the eastward extension of the Qiyangshan zigzag-shaped structural ridge axis. Two groups of folds were developed: (1) the early E-W-direction fold belt and (2) the late N-S-direction fold belt. Fault structures in the ore field are oriented mainly in an NNW direction and NEE direction. The ENE-direction fault clusters are early faults that occur near the internal contact zone between the granitoids and surrounding rocks. The NNW-direction fault clusters are deep normal faults, which control the ore body’s occurrences, orientation and enrichment (Figure 2).
Granitoids of the Chuankou ore field are exposed in the core of the Chuankou uplift with an area of 15 km2. According to fieldwork in this research, four main magmatic stages could be observed (Figure 2). The emplacement sequence is biotite monzogranite (G-1) → two-mica monzogranite (G-2) → fine-grained granite (G-3) → granite porphyry (G-4) (Figure 3a–d).
(1) Biotite monzogranites (G-1) are exposed at the Maowan and Baishui deposits. The main minerals assemblage includes quartz (25 to 30 vol.%), plagioclase (40 vol.%), and K-feldspar (25 vol.%). The secondary minerals are biotite (5–10 vol.%) and muscovite (1–5 vol.%). Accessory minerals include magnetite/ilmenite, zircon, apatite, and xenotime. Biotite appears light brown to dark brown with sizes ranging from 200 to 500 μm, whereas the diameters of quartz and feldspar are approximately 2–5 mm (Figure 4e,g).
(2) Two-mica monzogranite (G-2) is the main component, accounting for four out of five exposed areas of the Chuankou granitoids. These monzogranites have a medium- to coarse-grained structure and contain quartz (30%), sodium feldspar (30%), K-feldspar (20%), muscovite (10%), and biotite (5%). Garnet, uraninite, xenotime, and zircon are common accessory minerals with contents of 1–3%. Euhedral to hypidiomorphic crystal molybdenite (1–2 mm), columnar wolframite (~5 mm), and scheelite (0 to 1 mm) occur in the greisen belt, which developed in the shallow part of G-2 (Figure 4a,b,d,h–j).
(3) Fine-grained granite (G-3) is widely exposed at the region and intrudes into the G-2 and metamorphic slate as veins about 30–50 cm in width. G-3 is dark to gray in color and has a fine-grained texture. The minerals assemblage includes quartz, plagioclase, K-feldspar, and muscovite. Generally, the mineral crystals of G-3 are smaller than 0.5 mm. Slight alteration were developed in K-feldspar crystals (Figure 4b,c,l).
(4) Granite porphyry (G-4) is only exposed on the north side of Chishui Village roads. It occurs as a vein and intrudes into G-2 with a width of 15–20 m. G-4 exhibits a large structure and porphyritic texture. The phenocrysts (approximately 30 vol.% of the whole rocks) are 0.5–2 mm in size and composed of quartz (30 vol.% of total phenocrysts), potassium feldspar (60 vol.% of total phenocrysts), and a small amount of plagioclase and muscovite (less than 10 vol.%). The matrix is microgranular, which occupies 70 vol.% of all rocks (Figure 4f,k).

Alteration and Mineralization

Field observation shows that hydrothermal alteration occurred in the contact zone between the granitoids and Neoproterozoic strata and its adjacent area. The alteration types contain silicification, greisenization, potash feldspathization, tourmalinization, carbonatization, argillization. Greisenization, and silicification as the main high-temperature hydrothermal alterations that are widely developed at the top of the contact zones between the G-2 and Neoproterozoic strata. In addition, greisenization occurred intensely along the margins between barren or fertile quartz veins. The interior of the veins developed potassium feldspar, tourmaline, and calcite.
The mineralization types of the Chuankou ore field include altered granite-type scheelite and molybdenite, quartz vein-type wolframite, and veinlet-disseminated-type scheelite. Among them, the altered granite-type scheelite and molybdenite occur in the top greisenization zone of two-mica monzogranites (Maowan, Hubeichong, and Baishui deposits); generally, low ore grades and limited spatial scales. Quartz vein-type wolframite occurs in the fault zone above the granitoids (Nanwan and Hunaglong deposits). Ore-bearing veins are along the NNE direction, and the angle of inclination is 70° to 80°. Veinlet-disseminated scheelite has economic value only in the Yanglinao deposit, and it occurs in the siliceous breccia belt (D2y) as a mesh vein structure.
(1) Ore minerals assemblage is composed of wolframite, cassiterite, molybdenite, scheelite, chalcopyrite, sphalerite, arsenopyrite, pyrite, molybdenite, and uraninite. Gangue minerals include quartz, calcite, muscovite, tourmaline, fluorite, chlorite, garnet, barite, topaz, and tourmaline. Based on the mineral relationships, characteristics of alteration, and mineralization, four phases and five stages of mineralization processes have been generally identified (Figure 5).
(2) The medium- to high-temperature hydrothermal period is the main metallogenic stage and includes the early stages of the quartz vein–wolframite–molybdenite assemblage and the late stage of the quartz–wolframite–molybdenite (bismuthinite)–scheelite assemblage. During the mineralization process, scheelite and molybdenite crystallized slightly later than wolframite; The tabular wolframite crystals were widely filled by scheelite. Minerals assemblage includes wolframite, molybdenite, scheelite, bismuthinite, and pyrite (less), and a small amount of chalcopyrite (Figure 6b–d,f–h).
(3) The low- to middle-temperature hydrothermal period. The quartz and sulfide stage shows no obvious mineralization of W. The minerals assemblage is composed by chalcopyrite, sphalerite, pyrite, and arsenopyrite. (Figure 6i–l)
(4) Low-temperature hydrothermal period. Low-temperature minerals (fluorite and calcite) and a small amount of sulfide (sphalerite and galena) are the dominant minerals in this period.

4. Sampling and Method

4.1. Sampling

Thirteen samples were collected for the whole-rock geochemical analysis (HNCK1, 2, 3, 10-1, 10-3, 10-5, 10-6, 10-8, 10-9, 10-10, 10-14, 14-1, and HNOH1). Samples HNCK1, 2, 3, 10-6, 10-8, and HNOH1 were collected in the Baishui deposit, HNCK1 and 2 are altered two-mica monzogranite (G-2), and HNCK3 and 10-6 are fresh two-mica monzogranite (G-2). HNCK10-8 and HNOH1 are granite porphyry samples (G-4). HNCK10-1, 10-3, and 10-5 were collected from the Sanjiaotan deposit (HNCK10-1 and 10-3 are altered two-mica monzogranite (G-2), and HNCK10-5 is fine-grained granite (G-3)). HNCK10-9 and 10-10 are fine-grained granite (G-3) from the Nanwan deposit, and HNCK10-14 and 14-1 are biotite monzogranites (G-1) from the Manwan deposit. Four out of thirteen samples were selected carefully for LA-ICP-MS zircon U-Pb analysis (HNCK2, 10-8, 10-10, 10-14), and 6 out of 13 samples were selected for whole-rock Rb-Sr and Sm-Nd isotopic composition analysis (HNCK1, 2, 3, 10-5, 10-9, and 10-14).

4.2. Geochoronology

Zircon grains were separated for U–Pb age dating at the Langfang Regional Geology and Mineral Resources Survey Institute. The bulk samples were crushed to 60–80 mesh size, and zircons were separated using gravity and electromagnetic techniques and hand-picked under a binocular microscope. The samples were then mounted on epoxy resin, smoothed and polished, and finally gold coated. The zircons were examined using transmitted and reflected light and cathodoluminescence (CL) microscopy. Zircon U–Pb dating was performed at the Institute of Mineral Resources, CAGS, Beijing, using a Finnigan Neptune inductively coupled plasma mass spectrometer (MC-ICP-MS) with a new wave UP213 laser-ablation system. Helium was used as the carrier gas, and the beam diameter was 30 μm with a 10 Hz repetition rate and laser power of 2.5 J/cm2. Eight ion counters were used to simultaneously receive the 238U, 235U, 232Th, 208Pb, 207Pb, 206Pb, 204Pb, and 202 Hg signals, whereas data for 208Pb, 232Th, 235U, and 238U were collected on a Faraday cup. Zircon GJ-1 was used as standard, and Plešovice zircon was used to optimize the mass spectrometer. U, Th, and Pb concentrations were calibrated using 29 Si as an internal standard and zircon M127 (U: 923 ppm; Th: 439 ppm; Th/U: 0.4750) as an external standard [42]. 207Pb/206Pb, and 206Pb/238U were calculated using the ICP-MS DataCal 4.3 program. Common Pb was not corrected because of high 206Pb/204Pb. Abnormally high 204Pb data were deleted. The Plešovice zircon was dated as unknown and yielded a weighted mean 206Pb/238U age of 337 ± 2 Ma (2SD, n = 12), which is in good agreement with the recommended 206Pb/238U age of 337.13 ± 0.37 Ma (2SD) [43]. Age calculations were performed, and Concordia diagrams were generated using the Isoplot/Ex 3.0 software [44].

4.3. Geochemistry

Whole-rock major, trace, and rare earth element concentrations were analyzed at the National Geological Experiment Test Center, Beijing. Whole-rock major, trace, and rare earth element concentrations were analyzed at the National Geological Experiment Test Center, Beijing. Whole-rock major elements were analyzed using a plasma spectrometer (PE8300). All results were normalized against the Chinese rock reference standard JY/T015-1996 [45]. The analytical uncertainties were less than ±2%.

4.4. Sr-Nd Isotope

Fresh samples were ground with an agate mill and powders were spiked with mixed isotope tracers, dissolved in Teflon capsules with HF + HNO3 acid, and separated by conventional cation-exchange techniques. The isotopic measurements were performed on a VG-354 mass spectrometer at the Institute of Geology and Geophysics, Chinese Academy of Sciences [46]. The mass fractionation corrections for Sr and Nd isotopic ratios were based on 86Sr/88Sr = 0.1194 and 146Nd/144Nd = 0.7219. Repeat analyses yielded an 87Sr/86Sr ratio of 0.71023 ± 0.00006 for the NBS-987 Sr standard and an 143Nd/144Nd ratio of 0.511845 ± 0.000012 for the La Jolla standard. Detailed descriptions of the analytical techniques can be found elsewhere—in [47] and references therein.

5. Results

5.1. Chronology

(1) G-2: Zircon grains are columnar crystals with sizes from 150 to 200 μm (Figure 7). CL images have shown that zircons have typical oscillatory magmatic zoning. Pb content ranges from 12.1 to 124 ppm, Th content ranges from 67.82 to 219.30 ppm, and U content ranges from 506.25 to 1187.55 ppm (Table 2). Out of 30 analyzed spots of the biotite monzogranites, 14 spots yield 206Pb/238U ages of 215.9 ± 4.54 to 231 ± 2.19 Ma, and the obtained zircons have a concordance age of 222.1 ± 0.56 Ma (MSWD = 2.8) (Figure 8a).
(2) G-1: The length/width ratios of zircons are close to 1–2. The sizes of zircons range from 100 to 150 µm (Figure 7). The U content ranges from 249.1 to 1094.1 ppm, Pb content ranges from 12.1 to 124 ppm, and Th content ranges from 132.1 to 1072 ppm. Th/U ratios are from 0.23 to 1.81, and 206Pb/238U ages are from 206.6 ± 6.3 to 232.9 ± 7.1 Ma. The concordance age of the zircon grains is 230.8 ± 1.6 Ma (MSWD = 0.31).
(3) G-3: Zircons are columnar crystals with grain sizes ranging from 50 to 150 μm, typical of acidic magmatic zircons, with Th/U ratios of 0.12–2.07, Pb content from 17.9 to 265.71 ppm, Th content from 54.46 to 1425.03 ppm, and U content from 295.74 to 12,287.53 ppm. The obtained 206Pb/238U ages reveal two notably different groups: the first group is from 200.5 ± 3.51 to 203.9 ± 3.55 Ma with a concordance age of 203.1 ± 1.6 Ma (MSWD = 7.2). The 206Pb/238U age of the second group ranges from 218.2 ± 4.11 to 226.8 ± 4.05 Ma, and the concordance age is 224.8 ± 1.6 Ma (MSWD = 0.047) (Figure 8d).
(4) G-4: Zircons from granite porphyry have a minimum size ranging from 50 to 100 μm. The oscillating zones are not well developed. Three out of thirty analysis spots have Pb contents ranging from 17.6 to 21.6 ppm, Th contents from 268.1 to 555.5 ppm, and U contents from 495.9 to 810.2 ppm. The Th/U ratios range from 0.54 to 0.77 and obtained 206Pb/238U ages range from 134.2 ± 4.2 to 137.5 ± 4.2 Ma. The concordance age is 135.5 ± 2.4 Ma (MSWD = 1.3) (Figure 8f). Twenty-one out of thirty analyses yield 206Pb/238U ages from 202.4 ± 6.1 to 231.9 ± 7.1 Ma, and the concordance age is 222.9 ± 2.2 Ma (MSWD = 0.13) (Figure 8e), which is consistent with the wallrock two-mica monzogranite (G-2). In addition, the scattered points are 2586.5 Ma, 808.3 Ma, 1068 Ma, and 421 Ma, which may represent the formation ages of inheritable magmatic zircons or xenocrysts.

5.2. Geochemistry

Thirteen samples from the Chuankou ore field were analyzed and the analysis results are listed in Table 3.
G-1 is characterized by high SiO2 (76.79–76.86 wt.%), ALK (7.06–7.07 wt.%), Fe (FeOT = 1.43–1.44 wt.%), Al (A/CNK = 1.11–1.113, A/NK = 1.307–1.32), and K/Na ratios. G-2 has higher contents of SiO2 (76.08–78.36 wt.%), K2O (3.50–4.27 wt.%), and Al (A/CNK = 1.139–3.335) than G-1. G-3 contains various contents of SiO2 (74.47–77.61%), Al2O3 (12.91–16.47 wt.%) and characterized by low Na2O (0.12–3.54 wt.%) and ALK (3.52–6.91 wt.%) contents. G-4 has the lowest Na2O content (0.08 wt.%), MnO content (0.04 wt.%), and has the highest K2O contents (4.77–4.79 wt.%). In the SiO2 versus ALK diagram, the granitoids plot into the subalkaline granite field (Figure 9a). In the SiO2 vs. K2O diagram and Si vs. ALK-Ca diagram, all the samples plot into the high-K calc-alkaline field (Figure 9b,d). In the A/NK-A/CNK diagram, samples plot into the peraluminous field, implying that the granitoids of the Chuankou ore field belong to the high-K calc-alkaline and peraluminous series (Figure 9c).
G-1 shows a typical light REE-enriched pattern with an obvious negative Eu anomaly (δEu = 0.28 to 0.30) (Figure 10b). The values of LaN/YbN range from 3.92 to 4.18, indicating moderate fractionation between HREEs and LREEs. Zr, Hf, Th, and U are enriched and Ba, Sr, P, and Ti are depleted in Figure 11b. The Rb/Sr ratios range from 7.91 to 7.96, the K/Rb ratios range from 83.51 to 84.19, the Rb/Ba ratios range from 2.60 to 2.65, and the value of Zr + Nb + Y + Ce ranges from 181.03 to 187.43 ppm. The chondrite-normalized REE patterns of G-2 exhibit a strongly negative Eu anomaly (δEu = 0.06~0.23) (Figure 10a). The values of LaN/YbN range from 0.93 to 2.39. Rb, Hf, and U are enriched and Ba, Sr, and Ti are depleted (Figure 11a). Rb/Sr ratios vary from 14.26 to 34.48, K/Rb ratios range from 42.96 to 73.83, and Rb/Ba ratios range from 6.04 to 7.88. The value of Zr + Nb + Y + Ce ranges from 97.9 to 155.75 ppm. The chondrite-normalized REE patterns of G-3 are similar to G-2. The δEu values of G-3 range from 0.02 to 0.45, and the values of LaN/YbN range from 0.75 to 6.87 (Figure 10c). Rb, Hf, and Th are enriched and Ba, Sr, P, and Ti are depleted (Figure 11c). The Rb/Sr ratios vary from 28.6 to 78.58, K/Rb ratios range from 35.32 to 87.73, Rb/Ba ratios range from 4.50 to 17.16, and the values of Zr + Nb + Y + Ce are from 127.5 to 158.69 ppm. G-4 has an obvious negative Eu anomaly with the δEu values ranging from 0.36 to 0.38, and the (La/Yb)N values from 18.91 to 19.02 (Figure 10d). Zr, Hf, Rb, Th, and U are enriched and Ba, Sr, P, and Ti are depleted (Figure 11d). The Rb/Sr ratios vary from 13.06 to 13.20, K/Rb ratios range from 87.19 to 87.83, and Rb/Ba ratios range from 1.32 to 1.34. The values of Zr + Nb + Y + Ce range from 281.59 to 284.42 ppm.

5.3. Zircon Geochemistry and Ce4+/Ce3+ Ratios

The trace element compositions of zircon grains from the granitoids in the Chuankou ore field are shown in Table 4. Most of the Ti, Sr, and Ta contents of zircon grains are much closer to the values range proposed by Hoskin and Schaltegger [49] (Nb: up to 62 ppm; Sr ≤ 3 ppm; Ti: up to 75 ppm), which could be interpreted as normal magmatic zircon with various microscopic mineral inclusions, such as rutile and ferrotapiolite [50]. The ΣREE contents of G-1 range from 787.62 to 2080.54 ppm, those of G-2 range from 935.37 to 11,137.50 ppm, and those of G-3 range from 1387.73 to 4694.70 ppm. The chondrite-normalized REE patterns reveal an obvious enrichment of HREEs and depletion of LREEs but depletion of LREEs and connect with a magmatic origin [51]. All samples commonly show positive Ce anomalies and negative Eu anomalies in the zircons (Figure 12). However, there is an obvious difference in the degree of Ce and Eu anomalies in that G-1 and G-2 contain more negative Eu anomalies and positive Ce anomalies (δEu = 0.03–0.28; δCe = 1.56–189.58) than G-3 (δEu = 0.12–0.47, with a value of 1.41; δCe = 1.04–8.81). Despite this difference, all zircon grains in the study appear to be magmatic in origin and do not show geochemical evidence of metamorphic, hydrothermal overprinting or radiation-induced damage.
Ballard et al. [52] proposed a detailed calculation formula for the Ce4+/Ce3+ ratio:
Ce 4 + / Ce 3 + = ( Ce melt − Ce zircon / D Ce 3 + zircon / melt ) / ( Ce zircon / D Ce 4 + zircon / melt − Ce melt )
The zircon-melt partition coefficients for Ce3+ and Ce4+ were estimated using the model described by Ballard et al. and Zhang et al. [52,53]. The Cemelt value is approximately equal to the Zr content of bulk rocks, and the parameters of D Ce zircon / melt and D Ce 4 + zircon / melt can be deduced from the lattice strain model proposed by Blundy and Wood [54]. Calculated Ce4+/Ce3+ ratios of G-1 range from 3.33 to 93.28, Ce4+/Ce3+ ratios of G-2 range from 2.72 to 36.67, and Ce4+/Ce3+ ratios of G-3 range from 0.33 to 11.52.

5.4. Rb-Sr and Sm-Nd Isotope

Granitoids from the Chuankou ore field contain low Sr contents (varying from 14.16 to 55 ppm) and high 87Rb/86Sr ratios (13.56–152.35) (Table 5). The initial 87Sr/86Sr, TDM2, εNd(t) are calculated using zircon U-Pb ages of 202.9 Ma for G-3, 224 Ma for G-2, and 230 Ma for G-1. The calculated initial 87Sr/86Sr for G-1 is 0.72109, that for G-2 ranges from 0.67995 to 0.70851, and that for G-3 varies from 0.74915 to 0.85226. The 143Nd/144Nd values of G-3 range from 0.512122 to 0.512303, and the calculated εNd(t) values range from −10.07 to −6.53. The calculated TDM2 varies from 1471 to 1669 Ma and the 143Nd/144Nd value of G-1 is 0.512086; the calculated εNd(t) value is −10.77 and the TDM2 value is 2090 Ma. Moreover, the 143Nd/144Nd values of G-2 vary from 0.512161 to 0.512255, calculated εNd(t) values range from −9.09 to −7.47, and TDM2 values range from 1684 to 1764 Ma.

6. Discussion

6.1. Magmatic Stage of the Granitoids from Chuankou Ore Field

Bai et al. [55] proposed the formation age of Chuankou granitoids ranged from 160 to 170 Ma and emphasized that the mineralization of W occurred in the early Middle Jurassic. Conflicting data by Peng et al. and Qin et al. indicate that the ore-forming age varies from 224 to 230 Ma based on Re-Os isotopic chronology data of molybdenite [31,56]. Due to the absence of detailed field observations and efficient constraints on geochronology, the magmatic process and evolution of granitoids from the Chaunkou ore field remain unclear.
In this study, zircon U-Pb geochoronological analysis of the four main phases (G-1–G-4) was carried out. G-1 is exposed at the depth of the Maowan and Tangjiangyuan deposits. The formation age of G-1 is 230.8 ± 1.6 Ma (MSWD = 0.31). G-2 is the dominant part and represents approximately 70% of the granitoids in size. The formation age of G-2 is 222.1 ± 0.56 Ma, which is similar to the results of 223.1–224.6 Ma within the allowed error range [57]. G-3 intruded into G-2 as a dyke, and two groups of concordance ages can be identified. The first group of 224.8 ± 1.6 Ma (MSWD = 0.047) is consistent with G-2 and suggests that the zircons might be xenocrysts. The second group is 203.1 ± 1.6 Ma (MSWD = 7.2), representing the formation age. G-4 intruded into G-2 as larger veins with width from 0.5 to 3 m. The field observations and analysis results confirm the conclusion that G-4 formed at 135.5 ± 2.4 Ma (MSWD = 1.3).
In summary, the Chuankou ore field experienced at least four stages of magmatism. The emplacement sequence is G-1 (phase I), G-2 (phase II), G-3 (phase III), and G-4 (phase IV).

6.2. Genesis and Relationships Between Host Rocks and Tungsten Mineralization

6.2.1. Genesis Type

The granitoids of the Chuankou ore field are peraluminous, reflected in both the major element ratios (A/CNK ranging from 1.110 to 4.238) and the secondary and accessory minerals (spessartine, muscovite, biotite and tourmaline). The granitoids are commonly enriched in Rb, Zr, Hf, Th, and U, whereas they are depleted in Ba, Sr, P, and Ti. In addition, total alkali content ranges from 3.57 to 7.53 ppm, FeOT/MgO ratios range from 2.40 to 13.98, and Zr + Nb + Ce + Y values range from 97.9 to 284.42 ppm. These indexes are significantly lower than the global average of A-type granite (350 ppm) [58]. In the Zr + Nb + Ce + Y vs. ALK and Zr + Nb + Ce + Y vs. FeOT/MgO diagrams, samples plot into the FG field suggesting that the granitoids from the Chuankou ore field have an affinity for fractionated I/S-type granite (Figure 13a,b). Thirdly, in the A (Al-Na-K)-C (Ca)-F (Fe2+ + Mg) ternary diagram, samples plot in the S-type granite field, also indicating an S-type granite affinity (Figure 14).

6.2.2. Origin

In this study, granitoids from the Chuankou ore field are characterized by high 87Rb/86Sr ratios (varying from 13.5591 to 152.3436) and extremely high 87Sr/86Sr ratios (from 0.751712 to 1.292048). The initial 87Sr/86Sr values range from 0.67995 to 0.85226, which is beyond the range of normal continental crust and primitive mantle. Thus, these data cannot be used to trace the source of magma due to the hydrothermal alteration during the W mineralization process.
Conversely, the activities of Sm and Nd and the relevant isotopic composition remain unchanged in the evolution and alteration process. The Sm-Nd isotopic composition could be considered as a reasonable indicator for the source region. In this research, εNd(t) values of granitoids from the Chuankou ore field are −10.77 for G-1, −7.74 to −9.3 for G-2, and −6.53 to −10.07 for G-3. The samples plot in the Cathaysia basement field in the T(Ma) vs. εNd(t) diagram (Figure 15b). The calculated TDM2 and εNd(t) values (2090 Ma for G-1, 1684 to 1764 Ma for G-2, and 1471 to 1669 Ma for G-3) reveal a crustal origin by partial melting. G-1 was derived from the metamorphic basement in the Paleoproterozoic Era, while G-2 and G-3 were of homogeneous origin in the Mesoproterozoic Era. Significantly negative correlations of the formation ages with TDM2 (2090 Ma → 1684 to 1764 Ma → 1471 to 1669 Ma) and εNd(t) (−10.77 → −9.3 to −7.74 → −10.07 to −6.53) indicate that the proportion of crustal components in the source area decreased gradually; however, the composition of the mantle shows an obvious increasing trend. In the AMF vs. CMF diagram, the granitoids plot near the region of metapelitic sources and metagraywackes far from the metamorphic basalt and tonalite field. This indicates that the source rocks of granitoids from the Chuankou ore field are mainly crystal schists and gneisses formed by metamorphic Proterozoic mudstones and metagraywackes (Figure 15a).

6.2.3. Magmatic Process

During the granitic magmatism process, Ti was mainly absorbed in ilmenite, rutile, titanite, biotite and anatase. The separation of Ti-bearing phases at relatively moderate to low temperatures would have led to a significant depletion of Ti, Nb, Ta. Eu, Sr, and Ba which existed stably by substituting into the K+ site in the K-feldspar and/or Ca2+ site in plagioclase. P is the dominant component of apatite. There is significant depletion of Sr, Ba, P, and Ti of granitoids from the Chuankou granitoids, indicating obvious fractional crystallization of feldspar, biotite, Ti-bearing minerals, and apatite in magmatic processes [59]. In addition, the Eu/Eu* ratios, Rb/Sr ratios, Sr, and Ba could be used as markers to identify fractional crystallization. The correlations between Rb/Sr and Sr, Ba and Sr, and Eu/Eu* and Ba suggest that the fractional crystallization of K-feldspar, plagioclase and biotite was the main genetic mechanism (Figure 16a–d). For the REEs (La and Yb), carrier minerals included zircon, apatite, allanite, and monazite. The correlations between between La and La/Yb suggests that the melt was constrained by the fractional crystallization of allanite and monazite (Figure 16e). In addition, there are no obvious xenoliths (metamorphic slate in the Proterozoic) near the stratigraphic contact belt and no significant correlation between SiO2 content and εNd(t) values. This implies that the fractional crystallization process was relatively clear for the felsic melt rather than for the extensive assimilation-fractional crystallization (AFC) process (Figure 16f).
Furthermore, Zr + Nb + Y contents of the Chuankou complex vary from 75.57 to 187.05 ppm, and the Rb/Ba ratios range from 1.33 to 39.41. An obvious negative correlation trend is exhibited on the Zr + Nb + Y versus Rb/Ba diagram, coinciding with the Sandy Cope granite field, indicating the common regulations of highly fractionated granite (Figure 17).

6.2.4. Relationships between Host Rocks and Tungsten Mineralization

There are three main substitution mechanisms of scheelite in the concentration of REEs: (1) 2Ca2+ ↔ Na+ + REE3+, (2) Ca2+ + W6+ ↔ REE3+ + Nb5+, and (3) 3Ca2+ ↔ 2REE3+ + □ (□ vacancy) [60,61]. A significant comparative study between REE patterns of G-1/G-2 from the Chuankou ore field and Sch-3 was performed and showed high correlation [54]. In addition, the Sr isotopic composition (Isr) of G-1 (0.72109) is close to the medium composition of Sch-1 and Sch-3, which is derived from magmatic-hydrothermal conditions without significant fluid/rock interactions and fluid mixing. In addition, G-1, G-2, and G-3 are highly fractionated S-type granite and contain W concentrations that are several to ten times higher than average crustal concentrations (1.9 ppm and 0.6 ppm, respectively [62]). This characteristic is very similar to the host rocks of well-known Dahutang superlarge W deposits [63].
To date, the Chuankou W deposit has been identified as the largest Indosinian W deposit in the SCB and contains quartz vein type-, veinlet type-, and altered granite type-W ore bodies. Cai et al. obtained a formation age of 224.6 ± 1.31 Ma for the altered two mica monzogranites [57], which are generally thought to be host rocks of disseminated wolframite and scheelite. The ore formation ages of quartz vein-type mineralization ranged from 224 to 230 Ma [31,56,64]. These data are consistent with the 206Pb/238U ages of G-1 (230.8 ± 1.6 Ma) and G-2 (222–224 Ma). Field observations have also shown the close spatiotemporal relationship between G-1, G-2, and W mineralization. However, the ages of G-3 and G-4 are 203.1 ± 1.6 Ma and 135.5 ± 2.4 Ma (MSWD = 1.3), respectively. Seemingly, these intrusions were emplaced after W mineralization.
Systematic evidence indicates that the host rocks of the Chuankou W ore field were G-1 and G-2. However, how did W separate from the intrusions and become vastly concentrated in a limited spatial area? Generally, rutile was the main W-bearing mineral during the early stage of magmatic activity, while wolframite and scheelite dominated the later stage of magmatic to hydrothermal activity. Because the six-coordination Ti4+ could be substituted by W6+ accompanied by a double substitution of Fe to maintain the charge balance [65], W could be concentrated in large amounts in rutile and was significantly depleted in the residual melt and fluid. However, the granitoids from the Chuankou ore field (G-1 and G-2) contain 0.26–0.35 wt.% MgO and 1.29–1.77 wt.% FeOT and belong to the normal ilmenite-series granite, indicating an obvious absence of rutile in the early crystalline phase [63,66]. In addition, W is a lithophilic element in the bulk silicon earth (BSE), and the multiple stages of partial melting and separation crystallization would have caused a strong concentration of W in the late period of the residual melt phase. Thus, G-1 and G-2 granitoids have significant potential for the mineralization of W.
In addition, with increasing oxygen fugacity, the mineralization series of Sn → W → Mo → Cu (Mo) → Cu (Au) was carried out in succession [67]. The occurrence of W mineralization could be attributed to the reduced granitic magmas that typically belong to the ilmenite series [68,69]. A possible contribution from W4+ may have only been at the very lowest oxygen fugacity accessible to the experimental method in the melt [70,71,72]. Zircon is a common accessory mineral in intermediate-acid igneous rocks and is stable during later hydrothermal alteration and physiochemical processes. Due to its similar ionic radii and electrovalence, Ce4+ is more easily absorbed in zircon crystals than light rare earth metal ions (such as Ce3+) that occupy the site of Zr4+ under oxidizing conditions. Hence, zircon can be invoked as a tracer for the evaluation of relative oxygen fugacity based on its Ce4+/Ce3+ ratios. In this paper, the value of Ce4+/Ce3+ was calculated as 0.33–93.28, which is much lower than the host rocks of well-known, large-scale, porphyry Cu-Au deposits, such as Chuquicamata-El Abra [50], and typical Cu-Au (Mo) deposits from the SCB, such as Dabaoshan porphyry Mo deposits (Ce4+/Ce3+ = 356–1300; Li et al.) [73] and Dexin porphyry Cu deposits (Ce4+/Ce3+ = 495–1922) [53]. In contrast, the Ce4+/Ce3+ ratios were closer to those of W and Sn-bearing granitoids, such as the Guposhan, Qitianling, and Xuehuading granitoids, suggesting a significant metallogenetic potential of W and Sn [69] (Figure 18).
Blevin [75] carried out important work on the granite in the Lachlan fold belt and proposed the parameters to estimate the redox state of granite [75]:
ΔOx1 = Fe2O3/FeO(wt.%)
ΔOx2 = log(Fe2O3/FeO) + 0.3 + 0.03FeOT(wt.%)
The calculated results show that the redox state (ΔOx1) of G-1 ranges from 0.03 to 0.31, that of G-2 ranges from 0.09 to 0.91, that of G-3 ranges from 0.41 to 1.68, and that of G-4 is 0.35. The ΔOx2 of G-1 ranges from −1.19 to −0.16, that of G-2 ranges from −0.70 to 0.32, that of G-3 ranges from −0.06 to 0.56, and that of G-4 is −0.13. Obviously, G-1 and most G-2 had the lowest degree of oxidation. This condition provides an opportunity to remove substantial W from magma to hydrothermal fluids. Indeed, the slightly higher values of ΔOx1 and ΔOx2 in G-3 and G-4 indicate that W would have remained in biotite or muscovite by substitution with the Al3+ and/or Ga3+ site instead of expulsion from the melt. Further investigation is needed for the relationship between G-3, G-4 granitoids, and regional W mineralization.

6.3. Metallogenesis and Geodynamic Implications

During the early Middle Triassic, the intense collision and extensive metamorphism between the Indo-China block and Sibumas-Qingtang block exerted far-reaching effects on the SCB [76,77]. In addition, the southeastward subduction and collision of the North China block (NCB) with the South China block (SCB) overlapped due to the closure of the Paleo-Tethys Ocean. The SCB experienced multidirectional compression and extensive shortening, accompanied by thickening of the continental lithosphere [78,79,80,81,82]. During the late Mesozoic period, due to the tectonic regime transformation from Paleotethys dominant to paleo-Pacific tectonic dominant, the tectonic axis changed from the E-W direction to the NE-SW direction [40,83]. The tectonic regime is characterized by multiple stages of compression and extension, resulting in the formation of extensive magmatism and mineralization [9,39,84,85,86].
Indosinian W deposits are zonal and near the E-W direction, whereas Yanshanian W deposits are distributed in the NE-SW direction. The formation age of Indosinian W-Sn deposits in the SCB reveals that the two stages of W mineralization formed from 231.4 to 225 Ma and 213.3 to 193 Ma [56]. Two peak values of age data from Indosinian igneous rocks have been proposed [87,88,89]; the early stage aged from 243 to 233 Ma, while the late stage is from 222 to 204 Ma. There is a strong coupling relationship between Indosinian W deposits and igneous rocks. In addition, the W deposits in Guangxi Province vary from 214.1 to 211.9 Ma, which is reasonably linked to Miao’ershan and Limu granites (western part). The W deposits in Hunan Province and Jiangxi Province were formed from 230 to 225.4 Ma and 231.4 to 202 Ma, respectively (central part). The W deposits of Yunnan and Fujian Provinces are significantly younger than those from the central part of SC, which formed from 209 to 207 Ma and 226 to 193 Ma (eastern part) (Figure 1b). A possible “V”-shaped distribution model in the region indicates that the central belts of W deposits are relatively older than the others. The western and eastern parts have significantly lower values than those in the central part, which may represent the reactivation of the Proterozoic Qin-Hang tectonic belt under the Indosinian collision orogenetic regime of SC.
Regional Sr-Nd isotopic compositions show that εNd(t) values of Indosinian granitoids range from −14.4 to −8 [17,90]. The two-stage depleted mantle model ages of Indosinian granitoids range from 1.63 to 2.09 [17,90]. In general, the TDM2 values better match the formation ages of the Paleoproterozoic metamorphic basement of the SCB [82]. On the other hand, Yanshanian TDM2 values range from 1.04 to 2.28, especially in Northeast Jiangxi. The Nanling area and coastal zone of Fujian and Zhejiang Provinces show multiple belts of low TDM values (<1.6 Ga) and high εNd(t) values (>−9), which might match the Mesoproterozoic basement [38,91,92,93]. Numerous research data confirm that the main source of Yanshanian W mineralization was the Mesoproterozoic metamorphic basement, such as the Shuangqiaoshan group [81,94,95], which has an abnormal enrichment of W content—ten times more than the concentration of the average crust (11.7 ppm of the Shuangqiaoshan group) [96]. The more ancient basement identified in this study suggests a relatively deeper derivation of Indosinian W mineralization. Many valuable insights have been reported regarding the tectonic mechanism of W mineralization in the SCB, and the consensus suggests that the large Yanshanian W mineralization in the SCB was constrained closely by the paleo-Pacific plate regime, which mainly includes the extension of the Shi-Hang belt [38], a mantle plume [7,97], back-arc extension and lithospheric thinning [98], and slab subduction [99,100]. However, a distinct dynamic mechanism was identified in which Indosinian magmatism and mineralization extended approximately east-west in a zone that formed under the extension of a post-collisional setting, which could have been linked to the closure effects of the ancient Tethys Ocean. This setting reflects a relative “free” extension space of the overall compression regime [40,101].
Studies have recently revealed two dominant mineral assemblages and two stages of tectonic regimes in the Indosinian in SC [48,95]. G-1, G-2, and G-3 formed about 20–10 Ma later than the peak period of orogeny triggered by the collage of the SCB, North China craton, and Indo-China block. This reflects a post-collisional setting, which is parallel to the contemporaneous A-type granite in the SCB. In the late stage of the magmatic processes of G-1 and G-2, fertile magmatic fluid converged on the upper part of the granitoids and filled the internal fissure of the slate with the formation of extensive greisenization and granite-type wolframite (Maowan, Wubeichong, and Baishui) and quartz vein-type wolframite (Huanglong, Nanwan, and Sanjiaotan) interior contact belt. The continuous migration of ore-forming fluid up to the interbedded limestone and shale of the Devonian Yanglinao formation occurred (D2y). Adequate fluid–rock interactions and abundant Ca2+ ion reservoirs from the strata made it possible for large-scale dissemination and veinlet scheelite to form (Figure 19b).

7. Conclusions

(1) The formation age of G-1 is 230.8 ± 1.6 Ma (MSWD = 0.31), G-2 is 222.1 ± 0.56 Ma, G-3 is 203.1 ± 1.6 Ma (MSWD = 7.2), and G-4 is 135.5 ± 2.4 Ma (MSWD = 1.3). The emplacement sequence is G-1 (phase I), G-2 (phase II), G-3 (phase III), and G-4 (phase IV).
(2) Granitoids from the Chuankou ore field had significantly high contents of Si and Al and low contents of alkali, Fe, Mg, Mn, and Ca. The granites are commonly enriched in Rb, Zr, Hf, Th, and U but depleted in Ba, Sr, P, and Ti, indicating obvious highly fractionated S-type granite affinities. The Chuankou complex was derived from the partial melting of the Cathaysia basement and underwent significant fractionation of K-feldspar, plagioclase, biotite, Ti-bearing minerals (except rutile), zircon, apatite, allanite, and monazite.
(3) G-1 and G-2 showed a more reductive state than G-3 and even typical host rocks of porphyry copper deposits were identified to have an obvious correlation with W mineralization of the Chuankoou ore field.
(4) Indosinian W deposits were formed in a post-collision setting triggered by the collisional orogeny of SC in the late Paleozoic to early Mesozoic. However, the Yanshanian W deposits reflect strengthened crust–mantle interactions which resulted from the multistage extension of the SCB caused by the westward subduction of the paleo-Pacific plate.

Author Contributions

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

Funding

This paper is financed by the China Geological Survey’s projects (DD20190397) and National Natural Science Foundation of China (NSFC 41802082).

Acknowledgments

This paper is financed by the China Geological Survey’s projects (DD20190397) and National Natural Science Foundation of China (NSFC 41802082). We would like to thank Qin Jin-nin, Cai Fu-cheng, Liu Shan-bao and Wang Cheng-hui, Fan Ming-feng and other geologists for their help during the field investigations and samples analysis.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. (a) Geological block of China and (b) Regional geological map of South China. NC, north China Block, SC, south China Block. The green box is the location of this work.
Figure 1. (a) Geological block of China and (b) Regional geological map of South China. NC, north China Block, SC, south China Block. The green box is the location of this work.
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Figure 2. Geological map of Chuankou tungsten ore field.
Figure 2. Geological map of Chuankou tungsten ore field.
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Figure 3. (a) Geological map of Sanjiatan deposit, (b) Geological map of Wubeichong deposit, (c) Geological section map of Xiazilin ore block in Sanjiatan deposit, (d) Line 12 profile map of Wubeichong deposit.
Figure 3. (a) Geological map of Sanjiatan deposit, (b) Geological map of Wubeichong deposit, (c) Geological section map of Xiazilin ore block in Sanjiatan deposit, (d) Line 12 profile map of Wubeichong deposit.
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Figure 4. Petrographic photographs of intrutions in Chuankou ore field. (a) the wolframite- quartz vein in coarse two-mica monzogranite(G-2), (b) Fine-grained granite (G-3) intrude into coarse two-mica monzogranite, (c) Fine-grained granite (G-3) intrude into shallow metamorphic slate, (d) Disseminated spessartine developed in two-mica monzogranite(G-3), (e,g) Biotite monzogranite(G-1), (f,k) Granite porphyry(G-4), (h–j) Two-mica monzogranite(G-2), (l) Fine-grained granite(G-3). Bi- biotite, Pl- plagioclase, Kfs- K-feldspar, Ms- muscovite, Qtz- quartz, Grt- garnet.
Figure 4. Petrographic photographs of intrutions in Chuankou ore field. (a) the wolframite- quartz vein in coarse two-mica monzogranite(G-2), (b) Fine-grained granite (G-3) intrude into coarse two-mica monzogranite, (c) Fine-grained granite (G-3) intrude into shallow metamorphic slate, (d) Disseminated spessartine developed in two-mica monzogranite(G-3), (e,g) Biotite monzogranite(G-1), (f,k) Granite porphyry(G-4), (h–j) Two-mica monzogranite(G-2), (l) Fine-grained granite(G-3). Bi- biotite, Pl- plagioclase, Kfs- K-feldspar, Ms- muscovite, Qtz- quartz, Grt- garnet.
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Figure 5. The mineral paragenetic sequence of the Chuankou ore field.
Figure 5. The mineral paragenetic sequence of the Chuankou ore field.
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Figure 6. (a–c,f–h) Ore and photomicrograph of quarz-wolframite vein from Chuankou ore field, (d,e) Ore and photomicrograph of alterated granite type wolframite. (a–h), Medium to high temperature hydrothermal mineralization stage, (i–l), Medium to low temperature hydrothermal mineralization stage. Sch- scheelite; Wf- wolframite; Ms- muscovite; Py- pyrite, Cpy- chalcopyrite, Sp- sphalerite, Mo- molybdenite, Qtz- quartz.
Figure 6. (a–c,f–h) Ore and photomicrograph of quarz-wolframite vein from Chuankou ore field, (d,e) Ore and photomicrograph of alterated granite type wolframite. (a–h), Medium to high temperature hydrothermal mineralization stage, (i–l), Medium to low temperature hydrothermal mineralization stage. Sch- scheelite; Wf- wolframite; Ms- muscovite; Py- pyrite, Cpy- chalcopyrite, Sp- sphalerite, Mo- molybdenite, Qtz- quartz.
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Figure 7. Analysis sites and cathodoluminescence (CL) images of typical zircons.
Figure 7. Analysis sites and cathodoluminescence (CL) images of typical zircons.
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Figure 8. The zircon concordance diagrams of granitoids from Chuankou ore field. (a) G-2; (b) G-1; (c,d) G-3, (e,f) G-4.
Figure 8. The zircon concordance diagrams of granitoids from Chuankou ore field. (a) G-2; (b) G-1; (c,d) G-3, (e,f) G-4.
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Figure 9. Major elements diagrams of granitoids from Chuankou ore field. (a) ALK (ALK = Na2O + K2O) versus SiO2 diagrams, (b) K2O versus SiO2 diagrams, (c) A/NK versus A/CNK diagrams, (d) ALK-Ca versus SiO2 diagrams.
Figure 9. Major elements diagrams of granitoids from Chuankou ore field. (a) ALK (ALK = Na2O + K2O) versus SiO2 diagrams, (b) K2O versus SiO2 diagrams, (c) A/NK versus A/CNK diagrams, (d) ALK-Ca versus SiO2 diagrams.
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Figure 10. Chondrite-normalized REE patterns of granitoids in Chuankou ore field (Standardized values from [48]). (a) G-2; (b) G-1; (c) G-3, (d) G-4.
Figure 10. Chondrite-normalized REE patterns of granitoids in Chuankou ore field (Standardized values from [48]). (a) G-2; (b) G-1; (c) G-3, (d) G-4.
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Figure 11. Primitivemantle-normalized trace element patterns of intrusions in Chuankou ore field (Standardized values from [48]). (a) G-1; (b) G-2; (c) G-3, (d) G-4.
Figure 11. Primitivemantle-normalized trace element patterns of intrusions in Chuankou ore field (Standardized values from [48]). (a) G-1; (b) G-2; (c) G-3, (d) G-4.
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Figure 12. Chondrite-normalized REE patterns of zircon grains from igneous rocks in Chuankou ore field (Standardized value from [48]).
Figure 12. Chondrite-normalized REE patterns of zircon grains from igneous rocks in Chuankou ore field (Standardized value from [48]).
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Figure 13. Genetic type discrimination diagram of intrusions in Chuankou ore field, (a) ALK versus Zr + Nb + Ce + Y diagram, (b) FeOT/MgO versus Zr + Nb + Ce + Y diagram (after [58]).
Figure 13. Genetic type discrimination diagram of intrusions in Chuankou ore field, (a) ALK versus Zr + Nb + Ce + Y diagram, (b) FeOT/MgO versus Zr + Nb + Ce + Y diagram (after [58]).
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Figure 14. ACF diagrams of granitoids from Chuankou ore field.
Figure 14. ACF diagrams of granitoids from Chuankou ore field.
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Figure 15. (a) AMF versus CMF diagrams, (b) εNd(t) versus formation age diagrams.
Figure 15. (a) AMF versus CMF diagrams, (b) εNd(t) versus formation age diagrams.
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Figure 16. (a) Rb/Sr versus Sr diagram, (b) Eu/Eu* versus Sr diagram, (c) Ba versus Sr diagram, (d) Ba versus Eu/Eu* diagram, (e) La/Yb versus La diagrams, (f) εNd(t) versus SiO2 diagram; Zr- zircon, Ap- apatite, Mon- monazite, Allan- allanite, Opx- orthopyroxene, Cpx- clinopyroxene, Kf K-felspar, Pl- plagioclase, Bi- biotite, FC- fractional crystallization, AFC- assimilation.
Figure 16. (a) Rb/Sr versus Sr diagram, (b) Eu/Eu* versus Sr diagram, (c) Ba versus Sr diagram, (d) Ba versus Eu/Eu* diagram, (e) La/Yb versus La diagrams, (f) εNd(t) versus SiO2 diagram; Zr- zircon, Ap- apatite, Mon- monazite, Allan- allanite, Opx- orthopyroxene, Cpx- clinopyroxene, Kf K-felspar, Pl- plagioclase, Bi- biotite, FC- fractional crystallization, AFC- assimilation.
Minerals 12 00080 g016
Minerals 12 00080 g017 550
Figure 17. Rb/Ba versus Zr + Nd + Y diagrams of intrusions in Chuankou Tungsten ore field, Sandy Cope and Alckey granite represent highly fractionated granite after [58].
Figure 17. Rb/Ba versus Zr + Nd + Y diagrams of intrusions in Chuankou Tungsten ore field, Sandy Cope and Alckey granite represent highly fractionated granite after [58].
Minerals 12 00080 g017
Minerals 12 00080 g018 550
Figure 18. The Ce4+/Ce3+ versus EuN/EuN* diagram. The data of blue field named Porphyry Cu-Mo-Au are from [49,70] and there in, the orange field are from [74].
Figure 18. The Ce4+/Ce3+ versus EuN/EuN* diagram. The data of blue field named Porphyry Cu-Mo-Au are from [49,70] and there in, the orange field are from [74].
Minerals 12 00080 g018
Minerals 12 00080 g019 550
Figure 19. (a) Model explaining the geodynamic setting for the Indosinian W mineralization in SC and (b) Model explaining the formation of the granitoids and their relationship to tungsten mineralization.
Figure 19. (a) Model explaining the geodynamic setting for the Indosinian W mineralization in SC and (b) Model explaining the formation of the granitoids and their relationship to tungsten mineralization.
Minerals 12 00080 g019
Table
Table 1. The mineralization characteristics of Chuankou ore field.
Table 1. The mineralization characteristics of Chuankou ore field.
DepositMajor MetalsSecondary MetalsMineralization TypeOre Grade/%
ChuankouWCu, Bi, MoQuartz vein-type0.2–1.82
BaishuilingWCu, Bi, MoQuartz vein-type0.01–1.10
SanjiaotanWCu, Bi, MoQuartz vein-type0.45–1.42
HuangnilongWCu, Bi, MoQuartz vein-type1.07–4.88
GaoritangWCu, Bi, MoQuartz vein-type0.3–1.83
AoshangwuWCu, Bi, MoQuartz vein-type0.24–2.24
Liushutang WCu, Bi, MoQuartz vein-type0.62–0.90
TangjiangyuanWCu, MoAltered granite-type0.828
HuanglongWCu, Bi, MoQuartz vein-type0.65
WubeichongWCu, Bi, MoQuartz vein-type0.01–0.44
YanglinaoWCu, Bi, MoQuartz vein-type0.47
MaowanWCu, MoAltered granite-type
Tangjiawan WSnPlacer-type250 g/m3
BaishuilingWCu, Bi, MoQuartz vein-type0.079–0.399
Table
Table 2. The LA-ICP-MS U-Pb analysis results of zircons from granitoids from Chuankou ore field.
Table 2. The LA-ICP-MS U-Pb analysis results of zircons from granitoids from Chuankou ore field.
LithologySpotWB/10−6Common Pb Isotope Ratio (±1σ)Common Pb Isotope Age (Ma) (±1σ)
PbThUTh/U207Pb/206Pb207Pb/235U206Pb/238U207Pb/206Pb207Pb/235U206Pb/238U
Ratio±1σRatio±1σRatio±1σAge±1σAge±1σAge±1σ
G-2HNCK2_1111.67634.03822.29 0.77 0.051870.001070.24370.00520.034530.00036279.646.38221.44.25218.92.23
HNCK2_289.52 344.80 644.70 0.53 0.049640.000950.247340.004880.035310.00035178.243.96224.43.98223.72.2
HNCK2_3219.30 865.55 1673.73 0.52 0.082790.001380.368480.006430.033320.000341264.332.17318.54.77211.32.11
HNCK2_4138.38 338.58 964.59 0.35 0.050470.000850.25180.004360.036480.00035216.538.52283.542312.19
HNCK2_5207.26 722.05 1456.89 0.50 0.051230.000720.254940.003630.036170.00033251.132230.62.93229.12.08
HNCK2_6143.88 370.56 1028.90 0.36 0.050210.000760.248280.003830.035560.00033204.734.81225.23.12225.22.08
HNCK2_7119.68 563.72 842.52 0.67 0.051630.000850.254730.004290.036120.00035269.137.18230.43.47228.72.16
HNCK2_8101.97 626.79 735.73 0.85 0.05130.001640.247970.008370.035240.00045254.171.84224.96.81223.22.82
HNCK2_9166.85 528.06 1187.55 0.44 0.053040.001040.251860.005120.035720.00037330.443.65228.14.15226.32.27
HNCK2_10102.06 716.95 760.66 0.94 0.054870.002630.245420.012470.034110.0006407.1103.55222.910.16216.23.72
HNCK2_11142.53 520.13 966.33 0.54 0.051880.001720.262230.009230.03750.000528073.86236.57.42237.33.09
HNCK2_11142.53 520.13 966.33 0.54 0.051880.001720.262230.009230.03750.000528073.86236.57.42237.33.09
HNCK2_1369.90 396.22 489.87 0.81 0.052790.001480.259120.007670.036270.00044319.662.552346.18229.72.71
HNCK2_1484.02 538.83 598.67 0.90 0.05170.001010.254110.005150.035680.00036272.344.27229.94.172262.25
HNCK2_15101.63 335.55 741.11 0.45 0.050710.001090.247080.005510.034860.00037227.848.78224.24.49220.92.28
HNCK2_16343.28 558.99 2405.11 0.23 0.048710.00120.25090.006550.036280.0004133.957.1227.35.32229.72.52
HNCK2_17149.38 840.17 1097.67 0.77 0.052170.002370.242380.011670.034590.00057293.1100.38220.49.54219.23.57
HNCK2_18154.13 482.91 1137.57 0.42 0.052630.001270.243630.006150.034440.00038312.853.81221.45.02218.32.4
HNCK2_19126.26 487.82 897.52 0.54 0.056530.001870.254930.008910.035760.00048472.672.28230.67.21226.53.02
HNCK2_20168.89 430.85 1238.93 0.35 0.052740.001740.247290.008650.034650.00046317.673.4224.47.04219.62.87
HNCK2_2167.82 212.21 506.25 0.42 0.048790.003150.239940.016480.034050.00073137.8145.22218.413.49215.94.54
HNCK2_2297.03 330.68 698.64 0.47 0.050490.001270.250450.006610.03530.0004217.457.16226.95.37223.62.47
HNCK2_23120.40 382.15 873.04 0.44 0.05310.002460.248780.012270.035050.00059333.2101.69225.69.98222.13.69
HNCK2_24142.21 252.36 1031.23 0.24 0.053320.002060.239830.009790.035050.00052342.584.94218.38.02222.13.23
HNCK2_25154.89 490.49 1134.71 0.43 0.051390.001740.245160.008810.034690.00047258.376.15222.67.19219.82.91
G-3HNCK10-10_142.76 600.88 698.24 0.86 0.052580.001270.257680.005640.035540.00064310.554.15232.84.56225.14
HNCK10-10_217.91 245.77 295.74 0.83 0.053090.002770.261110.012890.035670.00081332.6113.95235.610.38225.95.06
HNCK10-10_3243.65 1330.68 11437.47 0.12 0.050370.001130.248080.004990.035720.00064211.951.392254.06226.23.97
HNCK10-10_4255.31 1425.03 12287.54 0.12 0.050240.001130.24690.004950.035640.00063205.951.36224.14.03225.83.95
HNCK10-10_560.08 691.19 1489.53 0.46 0.053930.001390.266330.006240.035810.00065367.957.16239.85226.84.05
HNCK10-10_626.78 350.62 302.75 1.16 0.051670.001530.252170.006870.035390.00066270.766.56228.35.57224.24.11
HNCK10-10_722.17 242.09 672.73 0.36 0.049490.002030.219260.008440.032130.0006517192.98201.37.03203.94.08
HNCK10-10_843.42 616.93 658.15 0.94 0.052040.001490.255320.006660.035580.00066287.263.89230.95.39225.44.09
HNCK10-10_998.45 1376.99 1277.03 1.08 0.059040.001920.280270.008390.034420.00066568.769.2250.96.65218.24.11
HNCK10-10_1039.09 564.16 453.26 1.24 0.050810.001430.248460.006360.035460.00065232.463.56225.35.17224.64.05
HNCK10-10_1169.24 1035.35 969.17 1.07 0.063050.001820.307680.008060.035390.00066709.860.22272.46.26224.24.08
HNCK10-10_12127.14 1253.68 3790.46 0.33 0.05110.001160.251080.005030.035630.00063245.351.65227.44.08225.73.9
HNCK10-10_1356.35 534.15 2092.28 0.26 0.051360.001220.227570.00480.032130.00057256.953.89208.23.97203.93.55
HNCK10-10_1483.56 626.12 2985.15 0.21 0.05090.001260.221740.00490.03160.00056236.156.25203.44.07200.53.51
HNCK10-10_1557.28 516.40 1802.74 0.29 0.050830.00120.223730.004650.031920.0005623353.572053.86202.63.51
HNCK10-10_1678.82 822.01 1698.14 0.48 0.051520.001450.227420.005790.032010.00058264.363.34208.14.79203.13.63
HNCK10-10_1733.63 318.40 842.75 0.38 0.052670.002120.253690.009530.034940.0007314.489.21229.67.72221.44.37
HNCK10-10_1891.12 1238.66 597.63 2.07 0.145750.004630.784740.022030.039050.000792296.653.66588.212.53246.94.91
HNCK10-10_1992.73 1071.44 1094.50 0.98 0.077410.001950.341750.007630.032020.000571131.749.48298.55.77203.23.57
HNCK10-10_20104.05 1162.69 1090.86 1.07 0.089920.002210.436070.009430.035170.000621423.846.3367.56.67222.83.89
HNCK10-10_2176.24 637.11 1117.42 0.57 0.09750.002240.48070.009570.035760.000621576.942.46398.66.56226.53.86
HNCK10-10_22271.11 428.32 416.13 1.03 0.509910.011595.832550.114170.082970.001444270.133.051951.316.97513.88.55
HNCK10-10_2383.12 987.53 897.08 1.10 0.103080.002470.507790.010580.035740.000631680.343.694177.12226.33.9
HNCK10-10_24125.72 1038.20 1054.02 0.98 0.145940.003450.707670.014450.035180.000622298.940.12543.48.59222.93.83
HNCK10-10_25104.20 252.93 965.27 0.26 0.192570.004860.941520.020450.035470.000642764.240.83673.710.7224.74
HNCK10-10_26265.71 375.74 1953.79 0.19 0.186610.004251.234520.024080.047990.000822712.537.03816.410.94302.25.07
HNCK10-10_2736.95 54.46 429.53 0.13 0.094210.002170.942170.018610.072550.001251512.342.826749.73451.57.5
G-4HNCK10-8_121.6 555.5 721.1 0.77 0.0502 0.0017 0.1461 0.0058 0.0211 0.0007 205.3 74.8 138.5 5.2 134.6 4.2
HNCK10-8_219.1 209.9 401.4 0.52 0.0510 0.0018 0.2482 0.0104 0.0353 0.0011 241.3 80.1 225.1 8.5 223.6 6.9
HNCK10-8_328.2 352.4 528.8 0.67 0.0508 0.0025 0.2392 0.0125 0.0341 0.0011 232.4 107.7 217.8 10.2 216.4 7.1
HNCK10-8_416.4 173.6 343.0 0.51 0.0524 0.0031 0.2514 0.0156 0.0348 0.0012 301.7 129.8 227.7 12.6 220.6 7.5
HNCK10-8_575.9 929.0 1278.2 0.73 0.0522 0.0013 0.2501 0.0084 0.0347 0.0011 295.1 54.1 226.7 6.8 220.1 6.6
HNCK10-8_633.0 356.7 653.3 0.55 0.0521 0.0013 0.2509 0.0087 0.0349 0.0011 289.8 57.6 227.3 7.0 221.3 6.7
HNCK10-8_731.9 430.2 773.8 0.56 0.0520 0.0013 0.2512 0.0087 0.0350 0.0011 285.2 57.8 227.5 7.0 222.0 6.7
HNCK10-8_810.9 155.8 112.5 1.39 0.0511 0.0023 0.2493 0.0124 0.0354 0.0012 245.3 100.8 226.0 10.1 224.1 7.2
HNCK10-8_9101.3 52.7 159.4 0.33 0.1793 0.0038 12.2054 0.3856 0.4937 0.0151 2646.4 35.1 2620.3 29.7 2586.5 65.1
HNCK10-8_1021.3 211.5 537.6 0.39 0.0507 0.0013 0.2469 0.0085 0.0353 0.0011 226.6 58.3 224.1 6.9 223.8 6.8
HNCK10-8_1127.2 414.5 424.7 0.98 0.0503 0.0016 0.2437 0.0095 0.0351 0.0011 210.2 72.8 221.4 7.8 222.5 6.8
HNCK10-8_1279.9 814.2 2356.1 0.35 0.0506 0.0011 0.2451 0.0079 0.0351 0.0011 223.3 51.1 222.6 6.4 222.5 6.7
HNCK10-8_1317.6 268.1 495.9 0.54 0.0497 0.0018 0.1478 0.0063 0.0216 0.0007 182.0 82.8 140.0 5.6 137.5 4.2
HNCK10-8_1425.7 314.2 660.4 0.48 0.0503 0.0015 0.2494 0.0092 0.0360 0.0011 209.2 66.3 226.1 7.5 227.7 6.9
HNCK10-8_1512.7 138.5 371.7 0.37 0.0517 0.0021 0.2395 0.0108 0.0336 0.0011 269.8 89.1 218.0 8.9 213.2 6.7
HNCK10-8_1617.6 454.9 810.2 0.56 0.0486 0.0019 0.1411 0.0064 0.0210 0.0007 129.6 90.4 134.0 5.7 134.2 4.2
HNCK10-8_1725.7 341.6 431.3 0.79 0.0522 0.0024 0.2556 0.0128 0.0355 0.0012 294.5 101.8 231.1 10.4 224.9 7.2
HNCK10-8_1828.7 476.5 659.4 0.72 0.0522 0.0021 0.1786 0.0080 0.0248 0.0008 293.9 87.4 166.8 6.9 158.0 5.0
HNCK10-8_1921.5 301.6 311.5 0.97 0.0511 0.0020 0.2391 0.0108 0.0340 0.0011 243.6 89.6 217.7 8.9 215.3 6.7
HNCK10-8_2032.5 356.3 803.7 0.44 0.0509 0.0013 0.2453 0.0083 0.0350 0.0011 234.0 57.1 222.8 6.8 221.7 6.7
HNCK10-8_2228.8 477.0 748.4 0.64 0.0510 0.0019 0.1998 0.0085 0.0284 0.0009 238.6 82.4 185.0 7.2 180.8 5.6
HNCK10-8_2250.1 114.4 407.6 0.28 0.0667 0.0019 1.2282 0.0442 0.1336 0.0041 827.5 57.8 813.5 20.1 808.3 23.5
HNCK10-8_2335.8 393.7 717.2 0.55 0.0523 0.0013 0.2517 0.0084 0.0349 0.0011 299.2 54.9 228.0 6.8 221.1 6.6
HNCK10-8_2451.2 679.0 752.9 0.90 0.0501 0.0013 0.2434 0.0085 0.0353 0.0011 198.2 60.7 221.2 6.9 223.3 6.7
HNCK10-8_2559.8 811.2 825.3 0.98 0.0498 0.0016 0.2412 0.0093 0.0352 0.0011 184.0 71.6 219.4 7.6 222.7 6.8
HNCK10-8_2626.6 280.5 770.5 0.36 0.0498 0.0015 0.2191 0.0082 0.0319 0.0010 186.8 67.9 201.2 6.8 202.4 6.1
HNCK10-8_2746.4 635.0 472.6 1.34 0.0506 0.0017 0.2454 0.0097 0.0352 0.0011 220.7 74.0 222.9 7.9 223.0 6.8
HNCK10-8_2818.5 265.8 264.0 1.01 0.0516 0.0026 0.2493 0.0133 0.0350 0.0012 268.9 110.4 226.0 10.8 221.8 7.1
HNCK10-8_2940.7 57.5 252.5 0.23 0.0742 0.0022 1.8441 0.0674 0.1802 0.0056 1047.2 57.7 1061.3 24.1 1068.0 30.6
HNCK10-8_3020.0 277.2 288.4 0.96 0.0526 0.0022 0.2528 0.0117 0.0348 0.0011 312.7 91.8 228.9 9.5 220.8 6.9
G-1HNCK10-14_127.8 346.2 335.6 1.03 0.0516 0.0016 0.2591 0.0097 0.0364 0.0011 268.6 67.3 234.0 7.8 230.5 7.0
HNCK10-14_222.3 253.8 411.7 0.62 0.0513 0.0016 0.2581 0.0098 0.0365 0.0011 252.1 69.5 233.1 7.9 231.2 7.0
HNCK10-14_316.2 169.1 378.6 0.45 0.0499 0.0017 0.2531 0.0102 0.0368 0.0011 190.1 76.9 229.1 8.3 232.9 7.1
HNCK10-14_412.1 132.1 249.1 0.53 0.0516 0.0018 0.2587 0.0105 0.0364 0.0011 267.5 76.7 233.6 8.5 230.2 7.0
HNCK10-14_549.0 263.9 639.9 0.41 0.0553 0.0013 0.5142 0.0168 0.0675 0.0020 422.4 51.2 421.3 11.3 421.0 12.3
HNCK10-14_645.9 608.4 346.4 1.76 0.0526 0.0052 0.2628 0.0255 0.0362 0.0015 310.4 209.4 236.9 20.5 229.5 9.3
HNCK10-14_715.9 182.4 288.9 0.63 0.0508 0.0016 0.2548 0.0097 0.0363 0.0011 233.6 70.7 230.5 7.9 230.1 7.0
HNCK10-14_822.6 244.3 549.7 0.44 0.0507 0.0015 0.2555 0.0095 0.0365 0.0011 227.5 68.1 231.1 7.7 231.4 7.0
HNCK10-14_915.8 153.7 396.2 0.39 0.0520 0.0019 0.2587 0.0109 0.0361 0.0011 284.9 80.7 233.6 8.8 228.5 7.0
HNCK10-14_1067.0 970.4 766.9 1.27 0.0512 0.0016 0.2562 0.0097 0.0363 0.0011 247.6 69.1 231.6 7.8 230.0 6.9
HNCK10-14_1169.5 1072.0 592.8 1.81 0.0509 0.0016 0.2556 0.0098 0.0364 0.0011 236.4 70.9 231.1 7.9 230.5 6.9
HNCK10-14_1223.6 311.3 300.2 1.04 0.0518 0.0021 0.2584 0.0117 0.0362 0.0011 276.4 89.1 233.4 9.4 229.1 7.1
HNCK10-14_1327.6 278.7 648.5 0.43 0.0514 0.0015 0.2592 0.0093 0.0366 0.0011 259.1 64.0 234.0 7.5 231.5 6.9
HNCK10-14_14124.0 1694.3 1462.9 1.16 0.0509 0.0017 0.2284 0.0091 0.0326 0.0010 234.2 75.5 208.9 7.5 206.6 6.3
HNCK10-14_1525.8 250.6 667.0 0.38 0.0519 0.0014 0.2603 0.0090 0.0364 0.0011 280.8 59.4 234.9 7.3 230.3 6.8
HNCK10-14_1638.5 364.2 943.7 0.39 0.0507 0.0012 0.2549 0.0083 0.0365 0.0011 227.5 53.7 230.6 6.7 230.8 6.8
HNCK10-14_1729.9 219.9 944.7 0.23 0.0519 0.0014 0.2599 0.0090 0.0363 0.0011 279.5 59.6 234.6 7.3 230.1 6.8
HNCK10-14_1830.3 290.7 676.2 0.43 0.0514 0.0023 0.2589 0.0127 0.0365 0.0012 258.5 99.7 233.8 10.2 231.3 7.3
HNCK10-14_1938.6 355.7 1094.1 0.33 0.0497 0.0012 0.2514 0.0082 0.0367 0.0011 179.3 53.8 227.7 6.6 232.4 6.9
HNCK10-14_2022.7 231.7 502.5 0.46 0.0516 0.0015 0.2603 0.0093 0.0366 0.0011 268.9 63.3 234.9 7.5 231.5 6.9
Table
Table 3. The geochemical analysis results of samples of granitoids from Chuankou ore field.
Table 3. The geochemical analysis results of samples of granitoids from Chuankou ore field.
SampleHNCK10-1HNCK10-3HNCK1HNCK2HNCK10-14-1HNCK10-14HNCK10-6HNCK3HNCK10-10HNCK10-9HNCK10-5HNCK10-8HNOH1
LithologyGreisenization G-2G-1G-2G-3G-4
wt.%
SiO283.6484.0782.5384.6576.8676.7976.0878.3677.3674.4777.6175.5275.53
TiO20.050.040.050.050.140.150.10.040.030.020.030.260.26
Al2O39.819.569.999.3212.2612.3712.7213.7413.5416.4712.9114.7714.77
Fe2O30.240.291.820.940.040.080.11.140.280.630.280.220.23
FeO0.680.731.130.61.411.361.120.760.390.380.680.630.63
MnO0.070.230.120.070.090.090.10.130.040.040.260.040.04
MgO0.150.140.240.380.340.350.260.330.070.070.270.350.33
CaO0.150.240.050.040.980.960.740.160.170.140.680.140.17
Na2O2.270.070.010.013.073.083.170.013.540.140.120.080.08
K2O1.722.712.621.5243.984.273.53.373.383.444.774.79
P2O50.060.040.010.010.060.060.060.070.020.020.040.040.04
LOI1.11.661.662.260.610.520.822.640.864.093.512.792.74
SUM99.9399.78100.2399.8599.8699.7799.52100.8899.6699.8499.8499.6199.6
ppm
Ni1.481.242.061.7343.722.871.781.3227.581.62.032.31
Pb6.5717.0213.317.145.3743.6348.8423.729.7420.425.6851.8252.49
Rb508.82292.23469236394.43395.14479.56676791.82744.72682.86453.74452.3
Sb0.4575.3514.916.20.820.420.436.33.890.84.151.781.81
Sn22.0951.3538.39.3710.0510.0113.1535.853.137.9344.6312.7213.21
Sr4.028.035550.449.5649.9133.6219.610.9114.1623.8734.3734.63
Ta11.194.186.964.035.475.174.038.730.5548.2733.483.272.93
Th6.647.656.786.2318.3517.5314.9414.85.636.66.6531.7232.33
Tl2.261.221.921.22.412.282.752.783.73.013.342.522.49
U23.830.923.21.8620.6319.9920.0344.612.763.7123.379.069.03
V3.935.664.983.0313.8913.5781.643.253.593.1913.1513.36
W7.6238.260.3252.812.094.3412.211.5211.979.597.317.79
Zn21.3851.2128.713.737.8238.234.6826.219.9227.132.8711.9614.86
Zr24.6143.0728.927.979.9578.0163.1741.421.2524.0423.23150.11147.78
La2.45.322.625.524.7622.6315.33.4916.187.094.2947.6750.33
Ce6.9911.775.728.9251.3347.8534.4610.736.156.3814.3194.54100
Pr1.121.630.771.316.86.344.611.45.082.042.5613.5214.43
Nd3.595.272.774.3922.7220.8215.355.1317.546.659.444649.82
Sm1.51.60.91.224.94.623.862.146.441.984.258.959.82
Eu0.030.0700.090.420.430.270.050.240.240.020.981.03
Gd1.131.280.891.144.013.983.341.753.941.132.616.416.96
Tb0.40.390.230.2610.990.960.421.080.270.791.161.23
Dy2.632.491.641.816.236.316.322.635.61.254.235.025.31
Ho0.450.490.320.341.351.331.370.460.910.170.690.780.83
Er1.451.621.091.144.354.294.341.442.70.462.142.082.17
Tm0.350.350.230.210.790.780.820.320.590.090.470.290.3
Yb2.862.751.741.694.254.144.62.74.50.753.251.81.91
Lu0.460.450.280.250.840.830.870.40.720.120.590.280.29
Y13.9213.669.1510.537.8237.1838.221429.73522.6119.2919.95
Table
Table 4. Trace element composition (ppm) of zircons of granitoids from Chuankou ore field.
Table 4. Trace element composition (ppm) of zircons of granitoids from Chuankou ore field.
SampleHNCK-2-01HNCK-2-02HNCK-2-03HNCK-2-04HNCK-2-05HNCK-2-06HNCK-2-07HNCK-2-08HNCK-2-09HNCK-2-10HNCK-2-11HNCK-2-12HNCK-2-13HNCK-2-14HNCK-2-15
G-2
La0.90 0.02 1.17 0.06 7.56 0.17 0.88 2.73 2.62 17.13 0.00 0.63 2.96 0.15 1.41
Ce25.29 12.40 96.62 9.68 273.32 17.91 47.45 25.89 106.06 601.34 4.04 16.28 21.47 11.88 44.03
Pr0.47 0.29 0.73 0.00 8.10 0.17 1.27 1.12 2.89 25.23 0.06 0.35 1.33 0.00 1.13
Nd6.10 1.52 6.01 1.56 63.79 4.47 8.15 8.71 20.54 183.58 3.71 6.33 6.68 0.87 10.12
Sm11.37 5.50 11.35 3.30 72.62 7.66 12.39 8.34 30.36 248.71 8.31 11.60 5.85 2.93 16.63
Eu1.33 0.32 0.56 0.84 5.62 0.69 1.42 0.60 2.65 17.20 0.54 1.30 1.03 0.27 0.50
Gd43.64 23.00 34.51 18.37 131.27 26.92 34.30 31.75 68.74 381.70 24.91 35.33 33.02 15.35 43.81
Tb18.07 13.11 15.08 9.24 57.49 13.31 12.61 13.04 32.12 170.15 13.92 17.00 12.09 7.30 17.34
Dy213.53 138.20 178.97 107.65 521.08 137.97 170.44 154.84 375.47 1638.95 190.06 207.54 213.79 95.04 220.01
Ho84.31 54.48 59.35 44.01 135.41 57.93 55.60 61.58 112.44 428.51 72.73 69.98 54.12 38.57 81.74
Er371.80 236.53 273.48 196.59 567.00 251.59 244.81 262.17 384.47 1588.06 304.01 304.97 232.52 174.72 336.47
Tm91.57 58.63 70.25 54.92 145.73 58.21 60.87 66.32 110.18 413.87 93.74 73.19 57.93 46.50 91.92
Yb933.18 737.00 764.00 606.80 1719.15 650.12 671.90 776.50 1353.13 4850.35 1309.38 809.60 617.41 477.71 1077.43
Lu126.35 87.38 93.20 83.53 190.45 88.06 93.70 104.75 145.25 572.73 173.69 104.92 85.85 64.08 142.00
Ta2.56 1.83 4.58 3.59 8.22 1.78 3.87 4.39 8.92 14.89 14.54 1.53 1.93 2.19 6.70
Nb3.86 3.40 5.70 4.75 36.24 3.24 4.71 5.96 15.91 111.73 10.06 2.75 2.21 2.58 7.51
W3.43 0.87 20.75 2.39 224.53 0.08 22.22 1.20 64.24 744.07 4.01 0.26 1.32 0.00 71.64
Sn1.22 0.70 1.60 1.27 0.00 0.25 1.35 0.49 0.97 2.36 10.68 0.60 1.30 0.50 0.00
Ce4+/Ce3+8.56 18.23 32.64 18.92 4.69 8.62 11.12 7.50 7.80 2.97 2.72 4.51 7.75 36.67 8.92
δEu0.16 0.08 0.08 0.26 0.17 0.13 0.20 0.10 0.17 0.17 0.11 0.18 0.18 0.10 0.05
(Ce/Ce*)D22.52 45.35 78.89 46.97 13.34 22.69 28.54 20.03 20.70 9.27 8.77 13.00 20.62 88.82 23.36
SampleHNCK10-14-01HNCK10-14-02HNCK10-14-03HNCK10-14-04HNCK10-14-05HNCK10-14-06HNCK10-14-07HNCK10-14-08HNCK10-14-09HNCK10-14-10HNCK10-14-11HNCK10-14-12HNCK10-14-13HNCK10-14-14HNCK10-14-15
G-1
La0.52 0.03 0.24 1.57 0.40 7.64 0.04 2.68 2.25 0.00 0.00 0.27 2.21 0.00 0.98
Ce10.67 10.97 26.27 32.82 9.57 26.02 19.43 28.54 21.44 21.54 13.73 13.84 16.58 19.18 16.27
Pr0.28 0.13 0.24 1.66 0.00 2.06 0.11 2.03 0.97 0.03 0.15 0.00 0.61 0.00 0.31
Nd2.62 0.44 4.80 10.94 0.51 9.37 3.64 13.88 9.27 2.37 2.25 2.65 4.17 2.00 3.00
Sm2.05 2.69 5.51 15.05 1.03 4.01 6.62 23.31 9.44 3.90 4.25 1.95 3.86 2.45 4.65
Eu0.35 0.09 1.80 2.23 0.27 0.25 0.89 2.83 0.95 0.81 0.11 0.15 0.90 0.77 0.62
Gd10.09 16.25 23.16 57.96 9.22 19.40 24.23 38.13 33.10 27.64 19.85 18.41 17.91 20.05 13.61
Tb6.72 9.30 9.99 19.55 3.71 7.68 11.09 17.58 13.44 14.88 10.38 7.89 8.84 8.93 6.11
Dy92.16 117.29 135.00 242.08 62.09 122.91 144.72 225.49 155.97 190.67 141.33 103.92 108.16 109.14 80.57
Ho37.02 44.25 53.61 87.34 27.26 51.60 55.36 72.33 58.82 76.74 49.81 40.12 44.33 41.55 31.92
Er163.62 189.23 218.28 313.63 140.60 225.78 227.03 344.23 242.08 375.28 237.95 172.02 230.55 193.13 152.35
Tm43.16 48.75 53.37 74.80 37.36 58.04 57.97 93.31 52.15 91.49 62.76 47.36 61.25 52.23 34.55
Yb513.31 589.04 611.02 811.23 440.76 601.55 697.92 1084.79 595.18 980.66 667.68 539.34 686.35 534.13 385.14
Lu69.75 82.74 88.76 107.07 63.68 84.37 88.60 131.40 80.08 128.82 87.25 68.95 93.77 69.17 57.53
Ta2.35 2.89 2.60 2.02 2.24 3.26 2.65 6.76 1.23 5.00 3.12 2.62 3.45 2.66 2.27
Nb2.74 2.88 4.33 4.33 2.80 4.62 4.12 9.16 1.13 6.58 3.21 3.05 4.16 3.08 3.58
W208.89 3.06 0.29 1113.80 1.34 2929.50 0.08 826.84 0.00 43.12 6.10 0.45 53.45 0.31 259.16
Sn4.54 2.00 1.44 1.04 2.44 0.00 1.31 0.83 1.23 0.00 0.82 4.83 4.57 2.19 2.44
Ce4+/Ce3+19.12 64.88 15.50 4.50 93.28 11.58 12.96 3.33 4.17 33.24 18.09 21.44 15.45 32.84 13.82
δEu0.19 0.03 0.42 0.20 0.18 0.07 0.19 0.29 0.15 0.17 0.03 0.05 0.28 0.23 0.22
(Ce/Ce*)D47.44 155.33 38.87 12.96 222.34 29.65 32.91 10.21 12.19 80.72 45.01 52.91 38.77 79.76 34.94
SampleHNCK10-10a-1HNCK10-10a-2HNCK10-10a-3HNCK10-10a-4HNCK10-10a-5HNCK10-10a-6HNCK10-10a-10HNCK10-10a-11HNCK10-10a-12HNCK10-10a-13HNCK10-10a-14HNCK10-10a-15
G-3
La1.58 23.77 1.03 5.54 2.02 1.20 2.21 0.92 5.27 12.01 1.99 2.09
Ce22.73 50.62 15.88 38.46 15.11 22.28 8.16 12.11 23.80 36.39 22.83 19.39
Pr0.59 5.47 0.83 2.13 0.78 0.29 0.25 0.59 1.29 3.88 2.76 0.75
Nd11.71 38.38 4.42 19.55 5.27 5.05 4.58 6.23 8.03 16.72 52.38 7.18
Sm14.88 30.11 7.00 25.58 10.06 12.59 5.63 11.89 9.91 9.72 13.36 12.98
Eu2.64 5.20 0.95 4.47 1.03 1.44 0.55 1.20 1.48 8.13 3.86 2.29
Gd49.57 64.22 27.11 76.35 31.97 49.87 25.61 48.36 27.80 27.79 40.47 48.53
Tb22.61 22.02 11.71 31.17 17.52 22.23 11.07 29.72 13.43 17.08 16.11 20.53
Dy279.87 291.96 172.42 354.28 315.86 269.62 147.22 399.42 183.43 249.03 200.44 223.72
Ho100.58 102.80 74.13 125.47 125.25 107.39 54.88 162.62 73.58 118.46 74.50 80.77
Er429.13 424.07 327.38 476.88 565.61 432.73 244.54 798.37 273.39 486.20 295.84 352.58
Tm108.85 100.56 80.92 96.75 173.30 104.45 66.14 223.92 76.40 139.04 64.09 88.51
Yb1114.37 1209.43 903.11 1061.55 1977.23 1101.13 724.86 2630.70 843.59 1380.64 749.70 901.04
Lu148.83 136.98 133.65 133.95 292.72 167.34 92.04 368.63 133.89 189.78 107.65 122.48
Ta1.49 5.47 3.02 1.41 7.61 2.76 2.25 15.80 2.99 7.23 0.78 3.11
Nb3.85 14.32 4.10 5.84 7.22 3.36 3.02 8.24 4.29 22.01 2.04 3.16
W21.48 5517.37 793.71 335.84 77.92 503.39 332.05 47.46 637.48 2347.57 53.20 165.03
Sn11.94 10.89 0.17 39.41 36.37 13.69 1.00 2.46 9.40 20.39 1.43 41.27
Ce4+/Ce3+3.73 1.73 10.83 2.27 11.52 -0.23 4.49 7.03 7.74 9.39 0.33 4.58
δEu0.27 0.35 0.18 0.29 0.16 1.34 0.12 0.13 0.26 1.41 0.47 0.25
(Ce/Ce*)D11.15 6.44 27.89 7.70 29.51 1.83 12.96 18.95 20.60 24.48 3.14 13.16
Table
Table 5. The Sr-Nd isotopic composition of samples of granitoids from Chuankou ore field.
Table 5. The Sr-Nd isotopic composition of samples of granitoids from Chuankou ore field.
SampleLithologyAge
(Ma)		Rb
(ppm)		Sr
(ppm)		87Rb
86Sr		87Sr
86Sr		ISrεSr(t)
HNCK10-9G-3203744.7214.155152.34641.2920480.852262101.5
HNCK10-5G-3203682.8623.8782.83780.988280.74915637.4
HNCK10-14G-1230395.1449.9122.92520.7960910.72109239.4
HNCK1G-22244695524.69220.7843040.7056419.9
HNCK222423650.413.55910.7517120.7085160.7
HNCK322467619.699.87110.9981220.67995−344.9
Sm
(ppm)		Nd
(ppm)		147Sm
144Nd		143Nd
144Nd		INdTDM2εNd(0)εNd(t)fSm/Nd
4.61720.820.13410.5121220.5119441669−10.07−8.44−0.32
1.9786.6490.17990.5123030.5120641471−6.53−6.1−0.09
4.2489.4420.2720.5120860.5116772090−10.77−12.980.38
0.92.770.19640.5121730.5118851705−9.07−9.070
1.224.390.1680.5121610.5119151684−9.3−8.48−0.15
2.145.130.25220.5122550.5118851764−7.47−9.070.28
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Qin, J.; Wang, D.; Chen, Y. Geochemical and Geochronological Constraints on a Granitoid Containing the Largest Indosinian Tungsten (W) Deposit in South China (SC): Petrogenesis and Implications. Minerals 2022, 12, 80. https://doi.org/10.3390/min12010080

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Qin J, Wang D, Chen Y. Geochemical and Geochronological Constraints on a Granitoid Containing the Largest Indosinian Tungsten (W) Deposit in South China (SC): Petrogenesis and Implications. Minerals. 2022; 12(1):80. https://doi.org/10.3390/min12010080

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Qin, Jinhua, Denghong Wang, and Yuchuan Chen. 2022. "Geochemical and Geochronological Constraints on a Granitoid Containing the Largest Indosinian Tungsten (W) Deposit in South China (SC): Petrogenesis and Implications" Minerals 12, no. 1: 80. https://doi.org/10.3390/min12010080

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