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Article

Early Paleozoic Adakitic Granitoids from the Xingshuping Gold Deposit of East Qinling, China: Petrogenesis and Tectonic Significance

by
Pei Zan
1,
Shouyu Chen
1,2,*,
Jinduo Chen
3 and
Shengli Li
3
1
Faculty of Earth Resources, China University of Geosciences, Wuhan 430074, China
2
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China
3
No. 1 Institute of Geological Exploration, Henan Geology and Exploration Bureau of and Mineral Development, Zhengzhou 450001, China
*
Author to whom correspondence should be addressed.
Minerals 2021, 11(10), 1032; https://doi.org/10.3390/min11101032
Submission received: 28 August 2021 / Revised: 16 September 2021 / Accepted: 20 September 2021 / Published: 23 September 2021
(This article belongs to the Section Mineral Geochemistry and Geochronology)
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Abstract

:
This study discussed the pertrological classification, geochronology, petrogenesis and tectonic evolution of early Paleozoic granites from the Xingshuping gold deposit in the East Qinling orogenic belt. In order to achieve this target, we carried out an integrated study of zircon U–Pb age, whole-rock major and trace elements, as well as Sr–Nd–Hf isotope compositions for the Xingshuping granites (part of the Wuduoshan pluton) from the Erlangping unit. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U–Pb dating constrains the emplacement age of the Xingshuping granites at 446.2 ± 1.2 Ma. The rocks at Xingshuping can be divided into two types: mainly biotite granite and monzonitic granite. The biotite granites are typical adakitic rocks, while the monzonitic granites show characteristics similar to normal arc volcanic rocks. The geochemical compositions reveal that they were derived from a clay-rich, plagioclase-rich and biotite-rich psammitic lower continental crust source, with contributions of mantle-derived magmas. The distinction is that the biotite granites were primarily derived from partial melting in a syn-collision extension setting, whereas the monzonitic granite went through a fractional crystallization process in an intraplate anorogenic setting.

Graphical Abstract

1. Introduction

The East Qinling orogenic belt (EQOB) is part of the Central China orogenic belt (CCOB), where the North China Craton (NCC) is adjacent to the north and South China Craton (SCC) to the south [1,2] (Figure 1A). The EQOB records complex geological and tectonic history, including continental rifting, ocean basins opening and closure along convergent margins, continental growth and recycling, continental collision and intraplate tectonics [3,4,5,6,7]. It is formed by multiple stages (Neoproterozoic, Paleozoic and Mesozoic) of tectonism since Neoproterozoic and finally formed by collision of the NCC and SCC during the Early Mesozoic; most granitoid magmatism or plutons have been intensively studied [8,9,10,11].
This region hosts the largest molybdenum (Mo) belt in the world [14,15] and the second largest orogenic gold province in China [16,17,18]. It is well known that most of the Mo and Au reserves are associated with late Mesozoic (Late Jurassic to Middle Cretaceous) granites at the southern margin of the NCC [16,17,18,19,20], and only a few deposits are located within the neighbor terranes of the EQOB [20,21] or associated with other orogenic processes [13,22]. The unequal distribution of mineralization and their associated granites in the EQOB remains to be explained.
One of these gold deposits is the Xingshuping gold deposit, which is located in the west of Wuduoshan pluton (one of the biggest plutons in the EQOB with an exposed area of about 1420 km2). This gold deposit was discovered in during the recent decade, and previous research only investigated the stratigraphy. There is currently no consensus on the source and evolution of the granitoids in this deposit, and detailed geochronology, geochemical characteristics and isotopic compositions of these granitic rocks are also unclear. In order to clarify these problems and to provide a basis for further study, in this paper, we report the pertrological classification, geochronology and petrogenesis of granites from the Xingshuping gold deposit combined with the amount of geochronological, geochemical and isotopic data that have been obtained for the Wuduoshan pluton in order to systematically study orogeny-related magmatic events and tectonic evolution.

2. Geologic Setting, Deposit Geology and Samples

2.1. Regional Geology

The EQOB located in Central-Eastern China, is one of the most important collision orogens due to the convergence between the NCC and SCC [1,2]. This orogen is bounded at the north by the Lingbao–Lushan Fault and on the south by the Mianlue–Bashan Fault [23], separated into the southern margin of the NCC (S-NCC), Northern Qinling belt (NQB) and the Southern Qinling belt (SQB) by the Luonan–Luanchuan Fault (LLF) and the Shangnan–Danfeng suture (SDS), respectively [24,25,26,27]. The SDS underwent a Middle Paleozoic subduction collision event and Mesozoic–Cenozoic intraplate strike-slip faulting [8,23,26].
The NQB is predominately composed of three groups: the mid-upper Proterozoic Kuanping group, lower Paleozoic Erlangping group and lower Proterozoic Qinling complex from north to south, with the Waxuezi–Qiaoduan Faults (WQF) and Zhuyangguan–Xiaguan Faults (ZXF) as boundaries [26] (Figure 1A). The Erlangping terrane comprises mainly Neoproterozoic–Early Paleozoic backarc basin volcano-sedimentary successions and associated intrusions [3]. Previous studies have been carried out on most magmatism and each terrane of the NQB, especially on the Paleozoic granites [2,23,26]. The Paleozoic magma evolution is mainly divided into three stages: 505~470 Ma, 450~422 Ma and 415~400 Ma [28].
The Wuduoshan pluton is an Early Paleozoic intrusive in the eastern part of the NQB, with complex granite types and multi-stage emplacement. Most part of the intrusion is located in the basic volcanic rocks of Erlangping group, and the southeast part comprises local intrusions into the Qinling complex above Erlangping group [29] (Figure 1B). The rock types mainly comprise medium fine grain biotite monzogranite, medium fine grain two mica monzogranite and porphyric biotite monzogranite. Available data show that granitoid emplacement of Wuduoshan pluton took place during a long time span from 468.5 ± 4.1 Ma [30] to 414.5 ± 2.3 Ma [31] concentrate mainly in the 441~428 Ma range [13,29,30,32,33]; the crystallization age, petrogenesis and related geodynamic background are still controversial. More than ten Au deposits or orebodies occur in the pluton or the inner-contact and outer-contact zones, most of which are distributed in the western part of the pluton [34] (Figure 1B). The Xingshuping Au deposit is one of the deposits located in the inner-contact zone.

2.2. Deposit Geology and Samples

The Xingshuping deposit is located ~15 km east of Xiaguan town in Southern Henan Province, north of the ZXF. The deposit is still in the exploration stage, and its reserves and grade are unknown. Within the ore district, Au mineralization is closely related to magmatism, and the auriferous quartz veins are hosted mainly in medium fine grain biotite granite, as well as in the contact zone between the biotite granite and quartz-micaceous schist of the Yanlinggou formation, Qinling group. The ore-forming age, origin, genesis, evolution of the magmatic activity and the relationship between the magma and fluids are also unknown.
The stratigraphic sequence in the district mainly comprised the Xiaozhai formation of the lower Paleozoic Erlangping group in the north, Yanlinggou formation of the Paleoproterozoic Qinling group in the central to south and upper Cretaceous Gaogou formation in the south (Figure 2). The Xiaozhai Formation consists of fine-grained metaclastic rocks, quartz-micaceous schist, quartz-biotite schist and phyllosilicate plagioclase schist, with flysch protoliths and interbed marbles [35]. The Yanlinggou formation consists mainly of biotite plagioclase gneiss, dolomitic marble and biotite-quartz schist, with metamorphic overprint greenschist facies [36]. The deposit is controlled strictly by the secondary faults of the NNW-trending ZXF. The exposed magmatic rocks in the mining area include biotite granite and monzonitic granite. The biotite granites are widespread, and monzonitic granites occur more in the drilling cores.
Following detailed field investigations and sample collection, we selected representative biotite granite and monzonitic granite samples from field outcrop and drilled holes for detailed studies, respectively. The biotite granite is yellow/grey and composed of K-feldspar, quartz, biotite and plagioclase (Figure 3) and accessory apatite, zircon, sphene, magnetite and allanite. The biotite monzonitic granite consists of K-feldspar, plagioclase, quartz, biotite, hornblende and a small quantity of accessory apatite, zircon and sphene. The Au orebodies, predominantly the auriferous quartz vein, are hosted in the fractures of the biotite granite intrusion or in the contact area between the biotite granite and the quartz-micaceous schist of the Yanlinggou formation. The ore-bearing wall rocks are mainly dolomitic marble that underwent silicification with pyrite and chlorite.

3. Analytical Methods

3.1. Whole Rock Major and Trace Element Analyses

Major and trace element analyses of the rocks at Xingshuping were conducted by ALS Chemex (Guangzhou) Co. Ltd. Approximately ~0.9 g of sample was added to ~9.0 g lithium borate flux (50–50% Li2B4O7-LiBO2), mixed well and fused in an autofluxer between 1050 °C and 1100 °C. A flat glass disk was prepared from the resulting melt. This disk was then analyzed by X-ray fluorescence spectrometry (XRF) for major elements, with an analytical precision better than ±1–2%. For trace elements, 0.2 g of sample was added to lithium metaborate flux (~0.9 g), mixed well and fused in a furnace at 1000 °C. The resulting melt was then cooled and dissolved in 100 mL of 4% nitric acid. This solution was analyzed by inductively coupled plasma mass spectrometry (ICP-MS) for trace elements with analytical precision better than ±5% for most trace elements. Two standards (plagioclase amphibolite GSR-15 and granitic gneiss GSR-14) were simultaneously analyzed in order to monitor analytical quality. A loss-on-ignition (LOI) measurement was undertaken on samples of dried rock powder by heating in a preignition silica crucible to 1000 °C for 1 h and recording the percentage weight loss [37]. The major and trace element compositions are reported in Table 1.

3.2. Whole Rock Sr–Nd Isotope Analyses

Whole rock Sr and Nd isotopic compositions were measured on a Triton thermal ionization mass spectrometer (TIMS) and Neptune Plus Multi-Collector (MC)-ICP-MS, respectively, at the State Key Laboratory of Geological Processes and Mineral Resources (GPMR), China University of Geosciences (CUG), Wuhan. The sample powders were digested in Teflon bombs with mixed agents of double distilled HNO3 and HF acids at 190 °C for 48 h. Subsequently, the samples were completely dissolved in 1 mL of 2.5 M HCl solution. Procedural Sr and Nd blanks were <4 ng and <1 ng, respectively [38].
Isotopic ratios of 143Nd/144Nd and 87Sr/86Sr were normalized to 146Nd/144Nd = 0.721900 and 88Sr/86Sr = 8.375209, respectively. Analyses of BCR-2 and GBW04411 standards produced 143Nd/144Nd = 0.512655 ± 4 and 87Sr/86Sr = 0.760035 ± 5 [38]. 147Sm/144Nd and 87Rb/86Sr ratios were calculated from the measured Nd and Sr isotopic compositions and Sm, Nd, Rb and Sr contents [38]. The Sr–Nd compositions are shown in Table 2.

3.3. LA-ICP-MS Zircon U–Pb Dating and Lu–Hf Isotope Analyses

Zircon grains for LA-ICP-MS U–Pb dating were separated using conventional heavy liquid and magnetic separation methods. Representative zircon grains were hand picked under a binocular microscope, mounted on an epoxy resin disk and polished down to nearly half the section to expose their internal structures for LA-ICP-MS analysis. Zircons were documented with transmitted and reflected light micrographs as well as with cathodeluminescence (CL) images to reveal their internal structures, and the mount was vacuum coated with high-purity gold. CL images were then taken with the scanning electron microscope at the State Key Laboratory of Geological Processes and Mineral Resources (GPMR), China University of Geosciences (CUG), Wuhan.
Zircon U–Pb dating was performed by using the laser ablation (LA) inductively coupled plasma mass spectrometry (ICPMS) at GPRM, CUG. A pulse Geolas of 193 nm ArF Excimer laser with 50 mJ/pulse energy at a repetition ratio of 10Hz coupled to an Agilent 7500a quadrupole ICP-MS was used for ablation. The sizes of laser spot were 32 μm in diameter. The detailed analytical procedures used followed those described by Liu et al. [39]. Harvard zircon 91500 was used as an external standard to normalize isotopic fractionation during analysis. Zircon standard GJ-1 was analyzed as a controlled standard for four times each sample. Lead isotopic data, U–Pb ages and trace element contents were processed using the ICPMSDataCal software [40]. The external errors of the standard 91500 were propagated to the ultimate results of each analytical spot [39]. Uncertainties on individual analysis are reported at 1σ level, and the weighted mean ages for pooled U/Pb analyses are quoted at 95% confidence interval [41]. The U–Pb results were conducted with the ISOPLOT program of Ludwig [42]. The results are shown in Table 3.
Trace-element analysis was performed on zircon using the same LA-ICPMS. Oxide production rate was tuned to <0.5% ThO/Th. The NIST610 glass was used as an external standard to calculate the trace element concentrations of unknowns, with working values recommended by Pearce [43]. Mineral inclusions were monitored by 29Si and 49Ti signatures during analysis. A detailed compilation of instrument and data acquisition parameters was given by Liu [39]. The formation temperatures of zircons were calculated by using the Ti-in-zircon thermometer [44,45]. Quartz is present in all the studied samples. Thus, the activity of SiO2 is considered as one for all samples. Due to the absence of rutile in all the samples, but the existence of ilmenite, the activity of TiO2 was set to be 0.7, as suggested by Watson [45].
Zircon Lu–Hf isotope compositions for the samples were determined using a Neptune plus multi-collector (MC)-ICPMS system, in combination with a Geolas 2005 system at the GPMR, CUG. Zircons were ablated by a 193 nm excimer ArF laser-ablation systems with spot size of 44 μm and a laser repetition rate of 10 Hz at 100 mJ/pulse. Measurements of Lu–Hf isotopic compositions were made on the same spot or domain formerly analyzed for U–Pb isotopes. Offline selection and integration of analytical signals and mass bias calibrations were performed by using ICPMSDataCal [37]. During the Hf isotopic analysis, raw count rates for 172Yb, 173Yb, 175Lu, 176(Hf + Yb + Lu), 177Hf, 178Hf, 179Hf, 180Hf and 182W were collected, and isobaric interference corrections for 176Lu and 176Yb on 176Hf were determined precisely. Zircon standards 91500 and GJ-1 were used as references during analysis. 176Lu/177Hf and 176Hf/177Hf ratios of 0.0336 and 0.282785 for the chondritic uniform reservoir (CHUR) and a decay constant of 1.867 × 10−11/year for 176Lu [46] were adopted for calculating the εHf(t) values. Two-stage Hf model ages (TDM2) are calculated by assuming a mean 176Lu/177Hf value of 0.015 for the average continental crust [47]. We adopted TDM2 for all samples, for they were not directly derived from the Depleted Mantle. The notations of εHf(t), ƒLu/Hf, TDM1 and TDM2 are defined as in Wu [48].

4. Results

4.1. Zircon U–Pb Ages

Figure 4 shows the CL images of representative zircon grains from biotite granite (XSP17-12 sample), along with 206Pb/238U ages and εHf(t) values. Figure 5 shows the zircon U–Pb concordia diagrams and the zircon chondrite-normalized Rare Earth Elements (REE).
The zircon grains from sample XSP17-12 are euhedral to subhedral, transparent and pale yellow to dark grey in color. Their lengths range from 40 to 150 μm with ratios of 1:1–4:1. They exhibited clear core structure and dark oscillatory zoned rims in CL and BSE images (Figure 4), suggesting magmatic crystallization.
Nineteen spot analyses were performed on 19 zircon grains from sample XSP17-12. They yielded a weighted mean 206Pb/238U age of 445.46 ± 0.96 Ma (MSWD = 0.59) (Figure 5A). One of them has a low Th/U ratio of 0.09 (<0.1), others have Th/U ratios of 0.16 to 1.05, which also suggests that these zircons have a magmatic origin [50].
Zircon REE chondrite-normalized diagrams for the biotite granite are shown on Figure 5B. The zircons invariably exhibit significant Eu negative anomalies and characteristic heavy REE (HREE) enrichment with low δEu values of 0.01–0.08 (mean, 0.025), ∑REE contents of 530–1611 ppm and chondrite-normalized REE patterns that are characterized by heavy REE (HREE) enrichments and significantly positive Ce anomalies (Ce/Ce* = 5.2–160, av. 49) (Table 4; Figure 5B), indicating that they are magmatic zircons [51]. They have low Ti contents of 3.8 to 11.3 ppm, and the crystallization temperatures of zircon from the biotite granite are estimated to be 662–757 °C (mean = 714.2 °C), using the approach of Hayden and Watson [52] with SiO2 and TiO2 activities of 1.0 and 0.6, respectively.

4.2. Zircon Lu–Hf Isotopic Compositions

Zircon grains from samples XSP17-12 were analyzed for Lu–Hf isotopes on the same dated spots or morphologically similar domains; the results are listed in Table 5. The initial 176Hf/177Hf ratios denoted by εHf(t) values and Hf model ages for the zircons were by calculated using the U–Pb crystallization ages (t = 446.2 Ma). Histograms of the εHf(t) values for these samples are shown in Figure 6. Ten zircon grains from sample XSP17-12 display initial 176Hf/177Hf ratios varying from 0.282356 to 0.282481. Their corresponding εHf (t) values vary within a narrow range from −5.2 to −0.7, with a weighted mean of −3.7 (Figure 6A). Correspondingly, their single-stage Hf model ages vary from 1.09 to 1.26 Ga, and their two-stage Hf model ages (TDM2) are 1.34–1.59 Ga (mean 1.51 Ga) (Figure 6B, Table 5).

4.3. Whole-Rock Major and Trace Elements

The six biotite granite samples plotted in the granite field, two monzonitic granite samples are plotted in syenite and quartz monzonite granite field, respectively, in the SiO2 vs. Na2O + K2O (TAS) diagram (Figure 7A). Previously available data with respect to the Wuduoshan pluton are also shown in Figure 7 for comparison.
The biotite granites have high SiO2 (70.65–80.72 wt%), K2O (3.22–5.77 wt%) and Na2O (1.8–4.86 wt%) contents but variable CaO contents (0.31–1.8 wt%) and total alkalis (Na2O + K2O) ranging from 5.02 to 9.16 wt%, with K2O/Na2O ratios from 0.84 to 2.12. Thus, they fit within the high-K Calc-alkaline series to shoshonitic series in the SiO2 vs. K2O classification diagram (Figure 7B). They have variable contents of Al2O3 (10.17–15.36 wt%) and, thus, exhibit A/CNK value of 0.98 to 1.45 (Figure 7C), dominantly showing slightly peraluminous chemical features. They have low MgO contents (0.07–0.49 wt%), TFe2O3 (0.88–2.33), with low Mg# values (13.6 to 29.6) (Figure 7D). They exhibit high (Na2O + K2O)/CaO and Ce + Nb + Zr + Y, dominantly plotting in the field of A-type granites (Figure 7G). The content of major elements and their trends with increasing SiO2 are shown in Figure 8. The biotite granite rocks are characterized by enrichment in large-ion lithophile elements (LILE) such as Rb, Th, U and K and the light rare earth elements (LREE); and significant depletions in high-field-strength elements (HFSE) such Nb, Ta, Zr, Hf, P and Ti (Figure 9A). They are LREE enriched and HREE depleted and show right dipping profiles with strong negative Eu anomalies (δEu = Eu/Eu* values from 0.09 to 0.38) typical of highly fractionated granites (Figure 9B), indicating the removal of feldspar or mica by fractional crystallization during magma evolution.
The two monzonitic granite samples have low SiO2 contents (60.22–65.21 wt%), variable K2O (4.82–9.44 wt%) and Na2O (1.2–2.48 wt%). On the TAS diagram, they plot in the syenite granite and quartz monzonite granite field (Figure 7A), respectively, and shoshonitic series (Figure 7B). They have high Al2O3 (13.44–16.33 wt%), with total alkalis (Na2O + K2O) 7.3 to 10.64 wt% and relatively high K2O/Na2O ratios from 1.94 to 7.87, thus exhibiting different A/CNK values from 0.89 to 1.27 and fall within metaluminous and strong peraluminous (Figure 7C), respectively. They have CaO (0.36–3.2 wt%), MgO (0.98–1.59 wt%), TFe2O3(4.9–8.2) and Mg# values (27.8–28.4) (Figure 7D). They exhibit different (Na2O + K2O)/CaO (2.28 to 29.56) and Ce + Nb + Zr + Y, thus plotting in the different fields of fractionated granites and non-fractionated granites (Figure 7G), respectively, indicating that they have went through different evolutionary processes. In chondrite-normalized REE patterns, they are characterized by slight enrichment in LREE and also slight depletion in HREE, which is different with the biotite granites, showing typically “V” shaped pattern curve with significant negative Eu anomalies (δEu = Eu/Eu* values from 0.22 to 0.29) (Figure 9B). In the primitive mantle normalized trace element diagram, they are enriched in LILEs (Rb, Th, U and K) (Figure 9A) and significantly depleted in HFSEs (Nb, Ta, P, Zr, Hf and Ti), indicating that a large number of plagioclase and mica were removed by fractional crystallization during magma evolution.

4.4. Whole-Rock Sr–Nd Isotopes

Initial Sr isotope ratios and εNd (t) values are calculated at t = 446 Ma. The five biotite granite samples exhibit low initial Sr isotopic ratios of 0.701201 to 0.709437 and negative εNd (t) values of −7.12 to −4.31, two monzonitic granite samples show similar initial Sr isotopic ratios of 0.707542 to 0.708316 and negative εNd (t) values of −11.17 to −12.92, (Table 5). The biotite granites have two-stage Nd model ages (TMD2) vary between 1.37 Ga and 1.56 Ga, which are comparable with previous studies on the Wuduoshan biotite granites [13], and they are younger than the Paleoproterozoic to Mesoproterozoic basement material in NQ as well as the Mesoproterozoic to Neoproterozoic supracrustal units of the Qinling Group [60]. On the other hand, the monzonitic granites have older TMD2 varying between 1.84Ga and 1.96 Ga, which are comparable with those of gneissic rocks from the NQ unit (TMD2 = 1.90 to 2.07 Ga [61]). These Sr–Nd isotopic compositions of the biotite granites and monzonitic granites plot around or along the extension of the mantle array. The ranges of different rocks from the NQ are shown for comparation [60].

5. Discussion

5.1. Age of the Intrusion

Previous studies have reported the intrusion ages of different positions of the Wuduoshan pluton (Figure 1B). The older group of ages are quartz diorite (468.5 ± 4.1 Ma) from the southern part of Wuduoshan and porphyritoid biotite granite (464.1 ± 4.6) from Sikeshu [31] in the northeast, represent the early stage intrusion age of the pluton. The middle group of ages are widespread in the pluton and concentrate mainly from 452 Ma to 428.3 ± 2.1 Ma [13,28,31,32,34]; biotite granite and biotite monzonitic granites are the major rock types [28,32]. The younger group of ages are 414.5 ± 2.3 Ma [33], and they are biotite monzonitic granite from the south part of the pluton [33]. This is consistent with the viewpoint that has been pointed out by Wang [23] about the division of emplacement stages of Paleozoic granites in the NQ: 507–470 Ma, 460–422 Ma and ~415–400 Ma.
The age of granites in Xingshuping deposit has not been studied before. The zircon grains extracted from the biotite granite samples show morphological and geochemical features of a magmatic origin [62]. LA-ICP-MS U–Pb zircon ages suggest the 206Pb/238U age of 445.46 ± 0.96 Ma represent the emplacement timing of biotite granites.

5.2. Petrological Classification and Magmatic Evolution

The biotite granite samples from the Xingshuping deposit have high SiO2 = 70.65–80.72 wt% and are typical of high-K calc-alkaline to shoshonitic series on the basis of its slightly peraluminous nature, which is similar but not identical to available granite data from other part of the Wuduoshan pluton. Abundant K-feldspar, plagioclase, quartz and biotite occur in biotite granite rocks, in conjunction with decreasing Al2O3, MgO, TFe2O3, CaO, TiO2 and P2O5 with increasing SiO2 contents (Figure 8) and depletion in HFSE (Nb, Ta, Zr, Hf, P and Ti), with obviously negative Eu anomalies. They have lower MgO content, which means mafic minerals have been separated during magmatic fractionation. Previous studies show that most granites of the Wuduoshan pluton have I-type to S-type characteristics with few of A-type (Figure 7G), which were considered to be derived from the lower crust with involvement of mantle-derived magma in a collisional setting [23]. Whereas the biotite granites from Xingshuping have relatively high Ce + Nb + Zr + Y (>300 ppm) and low (K2O + Na2O)/CaO values, most are plotted in the typical A-type granites field (Figure 7G) [57], different from the I-type to S-type granites proposed by predecessors. The high Zr + Ce + Y values and Rb/Ba ratios are also plotted in the A-type granites field in Figure 7H. In addition, in the Sr/Y vs. Y (Figure 7E) [63] discrimination diagram, the biotite granites have high Y but lower Sr/Y ratios than the typical adakite rocks, but most of the previous data display strong similarities with adakite rocks for their low Y and high Sr/Y ratios, and few of them are plotted in the normal arc vocanic rocks. In the (La/Yb)N vs. (Yb)N (Figure 7F) [56] diagram, the biotite granites and most of the previous data display strong similarities with typical adakite rocks for their low YbN and high (La/Yb)N ratios. Thus, biotite granites from Xingshuping have characteristics of adakite rocks but are mixed with other materials.
Extensive fractionation of plagioclase and/or K-feldspar would result in significant Eu negative anomalies. The negative Sr–Eu anomalies suggest fractionation of plagioclase, and Eu–Ba anomalies require fractionation of K-feldspar; thus, both plagioclase and K-feldspar were the fractionating phases (Figure 9). Ti depletion is thought to be associated with fractionation of a Ti-bearing phase such as ilmenite and titanite. The P depletion likely resulted from apatite fractionation. Trends on the Rb vs. Sr plot (Figure 10A) suggest garnet/amphibole, plagioclase and K-feldspar fractionation, without muscovite and biotite fractionation, whereas the predecessors mainly show plagioclase, K-feldspar, muscovite and biotite fractionation, and no garnet or amphibole fractionation occurred. As shown on the Ba vs. Sr diagram (Figure 10B), garnet/amphibole, plagioclase and K-feldspar are the main fractionation phases, with few muscovite and biotite fractionation. Trends on the Dy/Yb vs. SiO2 diagram (Figure 10C) suggest garnet and amphibole fractionation.
These geochemical characteristics suggest that biotite granites from Xingshuping are A-type granites [64,65], have some adakite rocks characteristics, and plagioclase, K-feldspar, garnet, amphibole and biotite, apatite and Fe–Ti oxides were the major fractionating phases.
Compared to the biotite granites, the monzonitic granites show lower SiO2, Na2O and MgO but higher K2O, TiO2, CaO, TFe2O3 and P2O5 contents and mainly consist of K-feldspar, plagioclase and quartz with a minor amount of biotite. The variable A/CNK values result in different falling plots of metaluminous and strong peraluminous granites (Figure 7C). The low MgO content also suggests separation of mafic minerals. Al2O3, MgO, TFe2O3, CaO, TiO2 and P2O5 decrease with increasing SiO2 contents (Figure 8), and they also deplete in Ba, Nb, Ta, Zr, Hf, P and Ti, with obviously “V” type negative Eu anomalies, suggesting partial melting and/or fractional crystallization. Different from the A-type biotite granites, the monzonitic granites are plotted in fractionated granites to unfractionated I-type or S-type granite field in Figure 7G,H, based on their lower Ce + Nb + Zr + Y and Zr + Ce + Y value, corresponding with previous studies. Moreover, in the Sr/Y vs. Y [51] diagram (Figure 7E), the monzonitic granites have higher Y (>50 ppm) value that out of the frame, and in the (La/Yb)N vs. (Yb)N [52] diagram (Figure 7F), have low (La/Yb)N and higher YbN and present similarities with normal arc volcanic rocks.
The significant “V” type negative anomalies in the REE diagram require extensive fractionation of plagioclase and K-feldspar (Figure 9). The Ti and P depletions are likely the result of ilmenite, titanite and apatite fractionation, respectively. Trends on the Rb vs. Sr plot (Figure 10A) and Ba vs. Sr diagram (Figure 10B) suggest plagioclase and K-feldspar fractionation and minor muscovite and biotite fractionation but no garnet/amphibole fractionation. As shown on the Dy/Yb vs. SiO2 diagram (Figure 10C), further proof of no garnet or amphibole fractionation is displayed.
In conjunction with previous studies on the Wuduoshan pluton, both the biotite granites and monzonitic granites exhibit a positive correlation between La and La/Sm (Figure 11A), suggesting that partial melting or source characteristics were major controlling factors. A positive relationship between Tb/Yb versus Yb (Figure 11B) and La/Yb versus Yb (Figure 11C), both suggesting partial melting, was a major controlling factor for the biotite granites. On the other hand, the relationships between Tb/Yb versus Yb (Figure 11B) and La/Yb versus Yb (Figure 11C) suggest that fractional crystallization was the controlling factor for the monzonitic granites with minor or no partial melting. In summary, the geochemical and isotopic variations of the intrusions at Xingshuping were controlled by partial melting for the biotite granites and fractional crystallization for the monzonitic granites, respectively.

5.3. Source Nature

The geochemical characteristics of the rocks from both of the biotite granites and monzonitic granites are characterized by low MgO; depleted Ti and Sr; low Mg# ratios (13.6–29.6 and 27.8–28.4); low Cr (9–18 ppm and 5–19 ppm) and Ni (0.4–2.8 ppm and 0.2–0.7 ppm) values; and high LREE and LILE with negative whole-rock εNd (t), suggesting a source enriched in LREE and LILE much closer to a lower continental crust (Mg# ratios 10–40, Cr 5–33 ppm and Ni 3–39 ppm).
The Nd and Hf isotope data are thought to be robust tracers of parental reservoirs of granites [66]. The Xingshuping biotite granite and monzonitic granite rocks have narrow ranges of initial 87Sr/86Sr ratios (0.701201–0.709437 and 0.707542–0.708316) and εNd (t) values (−7.12 to −4.31 and −11.17 to −12.92), with different old TMD2 age of 1.37–1.56 Ga and 1.84–1.96 Ga, which were plotted around or along the extension of the mantle array in (87Sr/86Sr)i vs. εNd (t) diagram (Figure 12). Biotite granite zircon Hf isotopic compositions also have a narrow range of εHf (t) values (−5.2 to −0.7). Moyen [67] has documented that rocks generated from melting of the lower continental crust with garnet residue may have signatures similar to adakitic trace elements. However, their Sr–Nd isotopic compositions are significantly different from those of lower continental crust (LCC) and upper continental crust (UCC) [64] and Neoproterozoic gneisses and amphibolites of the Qinling Group, even though the biotite granites have some adakitic trace element characteristics and older TMD2 ages than their crystallization ages. Thus, the granites from Xingshuping do not simply form by an exclusive lower-crustal source; mantle-derived melts played an important role in the formation. The lower εNd (t) values and older TMD2 age of monzonitic granites suggest more continental crust and less mantle-derived materials in the formation.
The εHf(t) and 176Hf/177Hf values all fall around the line of the lower crust [69] (Figure 13A,B), indicating that the magma of the biotite granites was derived from either the partial melting of the ancient enrichment lithospheric mantle materials or depleted mantle-derived melts that mixed significantly with mature continental crustal materials [70]. However, the Hf isotope crustal model ages of TDM2 (1.34–1.59 Ga) agree with the εNd (t) TMD2 of 1.37–1.56 Ga and indicate further that the granite may have resulted from the partial melting of Late Paleoproterozoic to Early Mesoproterozoic crustal materials, with contributions from mantle-derived magmas [71].
Partial melting of different source rocks such as amphibolite, metagreywacke and metapelite will produce various magma compositions under variable melting conditions [73,74]. The biotite granites and monzonitic granites from Xingshuping exhibit relatively high Rb/Ba (0.46–10.5) and Rb/Sr (1.83–7.18) and are dominantly plotted in the clay-rich sources field, which are different from previous studies that show they are mainly from a clay-poor source Figure 14A. Combined with their relatively high CaO/Na2O (generally >0.3) (Figure 14B), we can conclude their derivation from clay-rich and plagioclase-rich psammitic sources.
In summary, the granites from Xingshuping may have resulted from partial melting (minor fractional crystallization) of a clay-rich and plagioclase-rich psammitic lower continental crust source, with contributions from mantle-derived magmas at a relatively low temperature (~714.2 °C).

5.4. Tectonic Setting and Geodynamic Mechanisms

The granites at Xingshuping and most previous granite data from the Wuduoshan pluton are mainly plotted in the common area between the compression and extension field (Figure 15A), but the trends suggest that, with the evolution of magma, the crust gradually transited from compression to extension. In the R1 versus R2 tectonic discrimination diagram (Figure 15B), the samples mainly fall within the fields of syn-collision, minor samples plot in anorogenic to post orogenic domains. The biotite granites and most literature data are mainly plotted in the syn-collision granites (Syn-COLG) and volcanic arc granite (VAG) domains and minorly plotted in the within plate granite (WPG) domain, whereas the monzonitic granites mainly fall in the WPG domain on tectonic discrimination diagrams (Figure 15C–E). This is consistent with magma that originated from partial melting of continental crust in an extensional setting [76]. Moreover, the trends exhibited from VAG to Syn-COLG and then to WPG domains are consistent with the trend of increasing extension. In the Nb-Y-Ce diagram [77] (Figure 15F), all the samples have a trend plot from the post-orogenic A-type granite (A2) domain to the anorogenic A-type granite (A1) domain. To summarize, the biotite granites from Xingshuping were mainly formed in a Syn-COLG extension setting, whereas the monzonitic granites mainly formed in an intraplate transformed from compression to extension setting. The geochemical and isotopic differences between the two kind granites at Xingshuping were likely caused not only by the variable composition of the mixed source and evolution processes but also by the transformation tectonic environment.
The ongoing subduction of the Prototethyan Shangdan oceanic crust resulted in the formation of arc magmatism events in Late Ordovician to Early Silurian at ca. 450–420 [82,83,84]. As the oceanic slab continuously subducted, slab steepening and rollback occurred in response to progressive eclogitization at the tip of the slab, subsequently giving rise to corner flow within the asthenosphere, upper-plate transited from compression to extension and incipient back-arc rifting [85,86]. The slab rollback of the Prototethyan oceanic crust would result in asthenosphere mantle upwelling accompanied by partial melting of the mantle wedge in an extension setting and production of adakite magmas with high LILEs, LREE and mantle-like isotope signatures [82,83,84].

6. Conclusions

Geochronological, geochemical and isotopic investigations from the Xingshuping deposit in the Erlangping unit result in the following conclusions:
  • LA-ICP-MS zircon U–Pb dating indicates that the biotite granite was formed at ca. 445.46 ± 0.96 Ma.
  • The petrographic and geochemical data indicate that biotite granites from Xingshuping are A-type granites and exhibit adakite rock affinities; the monzonitic granites are fractioned arc volcanic rocks.
  • The biotite granites are formed by partial melting of a clay-rich and plagioclase-rich psammitic lower continental crust source, with contributions of mantle-derived magmas, whereas the monzonitic granites share the same source with the biotite granites but are mainly formed by fractional crystallization.
  • The biotite granites were mainly formed in a Syn-COLG extension setting, whereas the monzonitic granites mainly formed in an intraplate transformed from compression to extension setting.

Author Contributions

Conceptualization, P.Z. and S.C.; investigation, P.Z., S.C., J.C. and S.L.; data curation, P.Z.; formal analysis, P.Z.; funding acquisition, S.C.; project administration, S.C.; writing—original draft preparation, P.Z.; writing—review and editing, P.Z. and S.C. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Geological Exploration foundation of Henan province (China) (Grant No. 2015-258).

Data Availability Statement

Not applicable.

Acknowledgments

We thank the first geological exploration institute of geology and mineral exploration and development bureau of Henan province (China) in helping us to perform sampling work and providing us with support. We want to thank Xin Chen for improving the presentation of the early version of the manuscript. We are also grateful for the reviewer’s constructive comments and suggestions.

Conflicts of Interest

The authors declare no conflict of interest. No potential conflicts of interest are reported by the authors.

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Figure 1. (A) Geological sketch map of the North Qinling unit and its adjacent area, modified following [12]. (B) Simplified geological map of the Wuduoshan pluton and distribution of the Au deposit, modified following [13].
Figure 1. (A) Geological sketch map of the North Qinling unit and its adjacent area, modified following [12]. (B) Simplified geological map of the Wuduoshan pluton and distribution of the Au deposit, modified following [13].
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Figure 2. Geological map of the Xingshuping Au deposit (the dashed lines represent the two parts of the deposit).
Figure 2. Geological map of the Xingshuping Au deposit (the dashed lines represent the two parts of the deposit).
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Minerals 11 01032 g003 550
Figure 3. Photographs of samples and photomicrographs of minerals from the Xingshuping Au deposit and surrounding area. (A) Biotite granite (XSP18-6); (B) plagioclase, K-feldspar and quartz in biotite granite; (C) monzonitic granite; (D) plagioclase, K-feldspar and quartz in monzonitic granite. Mineral abbreviations: Pl—plagioclase; Kfs—K-feldspar; Q—quartz; Bt—biotite.
Figure 3. Photographs of samples and photomicrographs of minerals from the Xingshuping Au deposit and surrounding area. (A) Biotite granite (XSP18-6); (B) plagioclase, K-feldspar and quartz in biotite granite; (C) monzonitic granite; (D) plagioclase, K-feldspar and quartz in monzonitic granite. Mineral abbreviations: Pl—plagioclase; Kfs—K-feldspar; Q—quartz; Bt—biotite.
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Figure 4. Selected zircon CL images with εHf(t) values and 206Pb/238U ages for the studied granite XSP17-12.
Figure 4. Selected zircon CL images with εHf(t) values and 206Pb/238U ages for the studied granite XSP17-12.
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Figure 5. (A) LA-ICP-MS zircon U–Pb concordant curves for the studied granite XSP17-12; (B) chondrite-normalized rare-earth element patterns for the studied granites. Normalized values for chondrite are from [49].
Figure 5. (A) LA-ICP-MS zircon U–Pb concordant curves for the studied granite XSP17-12; (B) chondrite-normalized rare-earth element patterns for the studied granites. Normalized values for chondrite are from [49].
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Figure 6. Histograms of zircon εHf (t) values (A) and two stage Hf model ages (TDM2) (B) for the studied granite.
Figure 6. Histograms of zircon εHf (t) values (A) and two stage Hf model ages (TDM2) (B) for the studied granite.
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Figure 7. Geochemical classifications of the rocks: (A) total alkalis–silica (TAS) diagram (after [53]), (B) SiO2 vs. K2O (after [54]), (C) ANK vs. A/CNK, diagrams for the studied granites (after [55]), (D) Mg# vs. SiO2 (wt%) diagram, (E) Plots of Sr/Y vs. Y and (F)(La/Yb)N vs. YbN (after [56]). (G) (K2O + Na2O)/CaO vs. (Ce + Nb + Zr + Y) and (H) Rb/Ba vs. (Zr + Ce + Y) discrimination diagram (after [57]). Literature data are from [13,29,30,32,33]).
Figure 7. Geochemical classifications of the rocks: (A) total alkalis–silica (TAS) diagram (after [53]), (B) SiO2 vs. K2O (after [54]), (C) ANK vs. A/CNK, diagrams for the studied granites (after [55]), (D) Mg# vs. SiO2 (wt%) diagram, (E) Plots of Sr/Y vs. Y and (F)(La/Yb)N vs. YbN (after [56]). (G) (K2O + Na2O)/CaO vs. (Ce + Nb + Zr + Y) and (H) Rb/Ba vs. (Zr + Ce + Y) discrimination diagram (after [57]). Literature data are from [13,29,30,32,33]).
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Figure 8. Plots of SiO2 versus major elements (Al2O3, MgO, TFe2O3, CaO, K2O, Na2O, TiO2 and P2O5) of granites from Xingshuping (a–h). Literature data are from [13,29,30,32,33].
Figure 8. Plots of SiO2 versus major elements (Al2O3, MgO, TFe2O3, CaO, K2O, Na2O, TiO2 and P2O5) of granites from Xingshuping (a–h). Literature data are from [13,29,30,32,33].
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Figure 9. Primitive mantle-normalized multi-element spider (A) and chondrite-normalized rare-earth element (B) diagrams for the studied granites. The values of chondrite and primitive mantle are from [57,58], respectively. The data of metasedimentary rocks in the North Qinling unit are from [59].
Figure 9. Primitive mantle-normalized multi-element spider (A) and chondrite-normalized rare-earth element (B) diagrams for the studied granites. The values of chondrite and primitive mantle are from [57,58], respectively. The data of metasedimentary rocks in the North Qinling unit are from [59].
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Figure 10. Plots of (A) Sr vs. Rb, (B) Sr vs. Ba and (C) SiO2 vs. Dy/Yb for the samples from Xingshuping. Pl: plagioclase; Kf: K-feldspar; Bt: biotite; Ms: muscovite; Grt: garnet; Amp: amphibole. Literature data are from [13,29,30,32,33].
Figure 10. Plots of (A) Sr vs. Rb, (B) Sr vs. Ba and (C) SiO2 vs. Dy/Yb for the samples from Xingshuping. Pl: plagioclase; Kf: K-feldspar; Bt: biotite; Ms: muscovite; Grt: garnet; Amp: amphibole. Literature data are from [13,29,30,32,33].
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Figure 11. (A) La vs. La/Sm, (B) Yb vs. Tb/Yb and (C) Yb vs. La/Yb diagrams of the samples from Xingshuping. Literature data are from [13,29,30,32,33].
Figure 11. (A) La vs. La/Sm, (B) Yb vs. Tb/Yb and (C) Yb vs. La/Yb diagrams of the samples from Xingshuping. Literature data are from [13,29,30,32,33].
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Figure 12. (87Sr/86Sr)i vs. εNd(t) plot for granites from the Xingshuping. Whole-rock Sr–Nd isotopic of Wuduoshan biotite granite and monzomitic granite from [13]. Fields for the upper continental crust (UCC) and lower continental crust (LCC) are from Jahn et al. [64], and the mantle array is from Depaolo and Wasserburg [68]. Whole-rock Sr–Nd isotopic compositions of the Neoproterozoic Qinling Group and Fushui mafic complex are from Liu et al. [65] and references therein and Wang et al. [12], respectively. (87Sr/86Sr)i and εNd(t) values are based on t = 446.2 Ma.
Figure 12. (87Sr/86Sr)i vs. εNd(t) plot for granites from the Xingshuping. Whole-rock Sr–Nd isotopic of Wuduoshan biotite granite and monzomitic granite from [13]. Fields for the upper continental crust (UCC) and lower continental crust (LCC) are from Jahn et al. [64], and the mantle array is from Depaolo and Wasserburg [68]. Whole-rock Sr–Nd isotopic compositions of the Neoproterozoic Qinling Group and Fushui mafic complex are from Liu et al. [65] and references therein and Wang et al. [12], respectively. (87Sr/86Sr)i and εNd(t) values are based on t = 446.2 Ma.
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Figure 13. (A) Zircon εHf (t) vs. U–Pb age and (B) 176Hf/177Hf vs. U–Pb age diagram for the studied granites. The Hf isotope ratios of the ancient crust basement are delimited by 1.5 Ga, and juvenile crust evolution trends are calculated by assuming the 176Lu/177Hf of average continental crust (0.015) [72].
Figure 13. (A) Zircon εHf (t) vs. U–Pb age and (B) 176Hf/177Hf vs. U–Pb age diagram for the studied granites. The Hf isotope ratios of the ancient crust basement are delimited by 1.5 Ga, and juvenile crust evolution trends are calculated by assuming the 176Lu/177Hf of average continental crust (0.015) [72].
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Figure 14. (A) Rb/Ba vs. Rb/Sr and (B) CaO/Na2O vs. Rb/Sr (after [75]) from Xingshuping. Literature data are from [13,29,30,32,33].
Figure 14. (A) Rb/Ba vs. Rb/Sr and (B) CaO/Na2O vs. Rb/Sr (after [75]) from Xingshuping. Literature data are from [13,29,30,32,33].
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Figure 15. (A) Lg[CaO/(Na2O + K2O)] vs. SiO2 (%) (after [78]); (B) R1 vs. R2 (after [79]); (C) Nb vs. Y (after [80]) and (D) Ta vs. Yb (after [80]). (E) Rb vs. (Y + Nb) (after [81]) and (F) Nb-Y-Ce (after [77]) diagram of the granite rocks from Xingshuping. 1: Mantle fractionates; 2: pre-plate collision; 3: post-collision up lift; 4: late orogenic; 5: anorogenic; 6: syn-collision; 7: post-orogenic; WPG: within plate granites; VAG: volcanic arc granites; ORG: ocean ridge granites; Syn-COLG: syn-collision; A1: anorogenic A-type granite; A2: post-orogenic A-type granite. Literature data are from [13,28,29,32,33].
Figure 15. (A) Lg[CaO/(Na2O + K2O)] vs. SiO2 (%) (after [78]); (B) R1 vs. R2 (after [79]); (C) Nb vs. Y (after [80]) and (D) Ta vs. Yb (after [80]). (E) Rb vs. (Y + Nb) (after [81]) and (F) Nb-Y-Ce (after [77]) diagram of the granite rocks from Xingshuping. 1: Mantle fractionates; 2: pre-plate collision; 3: post-collision up lift; 4: late orogenic; 5: anorogenic; 6: syn-collision; 7: post-orogenic; WPG: within plate granites; VAG: volcanic arc granites; ORG: ocean ridge granites; Syn-COLG: syn-collision; A1: anorogenic A-type granite; A2: post-orogenic A-type granite. Literature data are from [13,28,29,32,33].
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Table
Table 1. Major, minor and rare earth element data of granites in this study area (wt% for major elements and ppm for minor and trace elements).
Table 1. Major, minor and rare earth element data of granites in this study area (wt% for major elements and ppm for minor and trace elements).
SampleXSP18-7XSP18-6ZK702-5ZK702-23ZK702-19XSP17-12ZK702-24ZK702-20
granitebiotite granitemonzogranite
SiO280.7274.3772.4671.2770.8070.6565.2160.22
TiO20.040.020.310.320.070.410.321.37
Al2O310.1714.5814.1613.2915.3614.1713.4416.33
Fe2O3T1.580.882.121.961.302.334.908.20
MnO0.010.060.030.040.040.030.070.11
MgO0.160.070.450.340.190.490.981.59
CaO0.310.631.321.801.501.513.200.36
Na2O1.804.863.292.604.732.722.481.20
K2O3.224.075.015.524.435.774.829.44
P2O50.010.010.060.090.020.110.080.08
LOI1.650.470.902.161.701.643.611.12
Total99.67100.02100.1199.39100.1499.8399.11100.02
A/NK1.581.171.311.291.221.321.441.34
A/CNK1.451.081.070.981.001.050.891.27
Mg#16.7113.6129.6025.5722.4529.4128.3827.75
K106.92135.15166.36183.29147.10191.59160.05313.46
Ti0.180.091.431.480.321.891.486.32
P0.460.462.764.130.925.053.683.68
Rb266.00419.00365.00312.00869.00358.00189.50283.00
Sr145.50148.10123.50154.50121.00145.0073.40108.50
Ba577.0039.90369.00649.00725.00610.00239.00187.00
U5.381.2712.756.5821.75.398.2316.15
Th69.86.6781.941.8181.571.92435.4
Pb34.533.742.599756.045.951240.0
Sc4.17.33.53.016.83.52.26.2
Ga19.5034.6022.5019.0536.0022.0015.4525.60
Nb17.6074.2023.9020.4088.7020.8038.5089.80
Ta0.910.11.21.15.51.33.76.8
Zr233.0012.00224.00245.00990.00337.0032.00124.00
Hf0.50.81.90.74.31.00.92.4
V1451316672044
Cr18101091515195
Ni1.92.80.60.41.01.00.70.2
Cu63.27.93.731.31.02.017.55.9
Zn641473669284634810104
La79.608.1097.4079.70222.0092.4023.6025.20
Ce158.0015.90201.00162.50457.00185.5045.9053.30
Pr16.951.9922.5017.2050.3019.455.126.44
Nd58.907.9076.1056.60169.0068.4018.0024.20
Sm9.702.5114.758.7730.9010.204.977.99
Eu0.940.130.600.770.750.900.540.64
Gd5.972.4810.555.5120.206.116.609.81
Tb0.650.401.380.662.470.701.321.99
Dy3.041.976.552.9411.253.239.3312.70
Ho0.530.371.080.511.850.522.272.66
Er1.280.962.431.184.331.166.678.18
Tm0.170.150.270.150.530.140.941.31
Yb0.971.011.310.953.030.825.588.66
Lu0.140.150.170.160.460.140.781.30
Y14.2015.2030.5014.1050.5014.0056.4077.40
∑REE336.8444.02436.09337.6974.07389.67131.62164.38
LREE324.0936.53412.35325.54929.95376.8598.13117.77
HREE12.757.4923.7412.0644.1212.8233.4946.61
LREE/HREE25.424.8817.3726.9921.0829.402.932.53
La/Sm8.213.236.609.097.189.064.753.15
La/YbN58.865.7553.3360.1852.5580.833.032.09
δEu0.380.160.150.340.090.350.290.22
δCe1.050.971.051.081.061.071.021.03
Note: Fe2O3T denotes totally Fe2O3; A/NK = Al2O3/(Na2O + K2O); A/CNK = Al2O3/(CaO + Na2O + K2O); Mg#: [Mg2+/(Mg2+ + Fe2+)] × 100; LREE denotes light rare earth elements; HREE denotes heavy rare earth elements; δEu = (Eu/Eu*)N = EuN/ √ SmN × GdN ; δCe = (Ce/Ce*)N = CeN/ √ LaN × PrN ; where subscript N denotes chondrite normalization.
Table
Table 2. The Sr–Nd isotope ratios of whole rocks from the studied area.
Table 2. The Sr–Nd isotope ratios of whole rocks from the studied area.
SampleAge (Ma)Rb (ppm)Sr (ppm)87Rb/86Sr87Sr/86Sr2SEISrSm
(ppm)		Nd
(ppm)		147Sm/144Nd143Nd/144Nd2SETDM2 (Ma)εNd(t)
XSP18-7446266145.55.3035580.73512160.7014269.758.90.0995490.51207661447.6−5.4
XSP18-6446419148.18.2242570.75612450.7038732.517.90.1920650.51226671555.698−7.0
ZK702-5446365123.58.5911080.75578380.70120114.7576.10.1171660.512185101370.041−4.31
ZK702-23446312154.55.8642050.745378100.7081218.7756.60.0936630.51211321374.553−4.4
XSP17-124463581457.1763980.75503160.70943710.268.40.0901390.51196261564.135−7.1
ZK702-24446189.573.47.504910.75599780.7083164.97180.16690.51197931842.913−11.2
ZK702-20446283108.57.5818810.75571270.7075427.9924.20.1995740.51198551963.085−12.9
Note: SE denotes sigma error range; ISr denotes initial Sr isotopic ratios; TDM2 denotes two-stage Nd model ages; εNd(t) denots deviation value between (143Nd/144Nd)sample(t) and (143Nd/144Nd)CHUR(t) at the appointed age (time).
Table
Table 3. LA-ICP-MS zircon U–Pb ages of the granites in this study.
Table 3. LA-ICP-MS zircon U–Pb ages of the granites in this study.
SamplePbThUTh/U207Pb/206Pb207Pb/235U206Pb/238U207Pb/235U206Pb/238U
ppmppmppmRatio1σRatio1σRatio1σAge (Ma)1σAge (Ma)1σ
XSP17-12-263.98187.56961.790.200.056240.0016470.5518440.0137920.0714670.00053446.29.03445.03.212
XSP17-12-324.00132.63176.410.750.0553990.0031170.5410510.0286580.0721170.00139439.118.9448.98.353
XSP17-12-576.52214.361382.030.160.0561660.0011030.5553550.0107280.0718550.00059448.57.01447.33.539
XSP17-12-6103.46554.26958.520.580.0558650.001170.5517460.0116640.0717130.00061446.17.64446.53.671
XSP17-12-858.24322.52428.540.750.0584180.0016970.5709910.0166290.0709780.00066458.710.8442.03.995
XSP17-12-976.14455.78500.160.910.0588340.0013030.5859420.0132480.0722910.00075468.38.49449.94.513
XSP17-12-1072.93255.251105.580.230.0556960.0013680.544360.0133360.0708420.00059441.38.77441.23.579
XSP17-12-1188.30474.40857.330.550.05550.0017280.5550770.0173180.0720460.00091448.311.3448.55.473
XSP17-12-1290.79459.71996.400.460.056380.0012520.5580780.013330.0716110.00078450.38.69445.94.709
XSP17-12-1357.03178.74905.120.200.0575210.00140.5731630.0142480.0720880.00071460.19.2448.74.248
XSP17-12-1494.47316.141483.650.210.0544840.0013390.5421030.0133680.0722050.00101439.88.81449.46.072
XSP17-12-15113.93372.931883.630.200.0561820.0010970.5604440.0147340.0716390.00096451.89.59446.05.797
XSP17-12-1650.29283.73453.100.630.0530350.0019010.5388760.0198270.0720550.00117437.713.1448.57.014
XSP17-12-1767.76205.481090.950.190.0537480.0011290.5355230.0117970.0719740.00068435.57.81448.04.096
XSP17-12-1971.79235.311132.840.210.0537320.001190.5344960.0105330.0717630.00062434.86.98446.83.743
XSP17-12-2164.36302.26725.450.420.0522340.0017750.5326550.01440.0719540.00148433.69.54447.98.888
XSP17-12-22140.07803.381270.640.630.0548180.001910.549170.020480.0720840.00124444.513.4448.77.454
XSP17-12-23208.981384.471319.151.050.0542530.0013760.5360250.0132620.0713550.00089435.88.77444.35.374
XSP17-12-2473.59128.661495.590.090.05260.0012380.5175370.0116180.0712390.00102423.57.78443.66.153
Table
Table 4. Trace element concentrations (ppm) of zircons from the study area.
Table 4. Trace element concentrations (ppm) of zircons from the study area.
SpotNo.LaCePrNdSmEuGdTbDyHoErTmYbLuEu/Eu*Ce/Ce*Nb/PbTZr
(°C)		ΣREELREE/
HREE
XSP17-12-20.078.460.203.665.650.3217.875.3863.0321.7397.1324.20239.9842.120.0373.660.07676.3529.790.04
XSP17-12-30.1510.980.243.906.120.9625.127.4287.2030.11124.8328.30259.7545.040.0858.620.11756.1630.140.04
XSP17-12-51.209.740.936.446.930.4426.088.1483.9423.2283.2817.33149.3623.520.039.220.18704.7440.560.06
XSP17-12-60.1010.610.609.1915.640.7652.6914.14146.2044.79173.8237.69335.4055.400.0343.930.03736.3897.020.04
XSP17-12-81.2913.180.777.3010.740.4335.6910.12109.8635.15140.6730.41270.8444.830.0213.250.69711.8711.280.05
XSP17-12-923.1380.6110.3955.9029.350.8366.4616.97169.9851.67199.2542.27370.3159.800.025.200.05757.21176.910.20
XSP17-12-100.034.960.315.2013.460.3554.8215.14136.5033.69111.4521.27171.4626.250.0152.760.03712.6594.880.04
XSP17-12-111.6516.791.0210.5613.980.5747.7913.17135.9141.76161.4133.88294.6047.200.0212.970.04720.0820.290.06
XSP17-12-120.0711.660.375.9711.020.6038.0611.06120.4537.62151.9333.41299.5448.480.0370.320.05710.0770.270.04
XSP17-12-130.106.390.091.494.170.1717.985.9071.7824.59106.6324.65232.5338.520.0267.480.08662.3534.990.02
XSP17-12-140.015.520.132.939.640.2847.3015.40178.7358.81235.5751.58457.4074.520.01160.030.09725.71137.800.02
XSP17-12-150.198.980.445.419.330.2734.3410.16119.7540.43176.4443.38421.5871.040.0231.410.04686.9941.740.03
XSP17-12-161.2114.080.797.3410.130.8132.419.28105.2033.66136.8430.51271.8345.270.0414.380.06745.9699.350.05
XSP17-12-170.014.270.163.008.950.3944.1513.75142.7440.86148.7831.00264.6441.090.0291.250.06707.8743.800.02
XSP17-12-190.344.700.141.785.690.1227.568.9198.6730.87123.6627.74251.8641.810.0121.640.05688.0623.850.02
XSP17-12-210.8212.210.504.757.640.3329.798.96101.6733.67136.4131.12287.3547.780.0219.110.08739.0703.010.04
XSP17-12-2211.3551.525.7937.0029.131.2377.7919.89201.0859.78224.6647.78415.7067.180.036.360.13684.81249.900.12
XSP17-12-230.1721.581.3018.8631.221.66106.8328.07285.0083.96313.1965.11564.2489.980.0345.610.03747.11611.170.05
XSP17-12-240.012.100.060.964.670.1025.738.5396.4029.03114.0825.42229.0537.430.01123.780.05677.5573.550.01
Note: TZr (°C) calculated by using Ti-in-zircon thermometer of Ferry and Watson [44]. Eu/Eu* = EuN/ √ SmN × GdN ; Ce/Ce* = CeN/ √ LaN × PrN ; where subscript N denotes chondrite normalization.
Table
Table 5. Zircon Lu–Hf isotopes for the studied granites.
Table 5. Zircon Lu–Hf isotopes for the studied granites.
Spots176Yb/177Hf176Lu/177Hf176Hf/177Hf±1σt(Ma)εHf(0)εHf(t)±1σTDM1TDM2fLu/Hf
xsp17-12-20.0171980.0006640.2823620.000012445.0−14.5−4.90.6920601245.891572.19−0.98
xsp17-12-30.0191350.0007140.2824180.000010448.9−12.5−2.80.6569351169.301461.46−0.98
xsp17-12-50.0083690.0002710.2824080.000010447.3−12.9−3.10.6443581169.821474.73−0.99
xsp17-12-60.0233930.0009350.2823560.000021446.5−14.7−5.20.9196451263.481588.09−0.97
xsp17-12-90.0249110.0009630.2823960.000016449.9−13.3−3.70.7923041208.001508.42−0.97
xsp17-12-100.0142000.0005270.2823910.000011441.2−13.5−3.90.6706641201.931515.73−0.98
xsp17-12-110.0178790.0006620.2823760.000013448.5−14.0−4.30.7104361226.161543.05−0.98
xsp17-12-120.0230000.0008470.2823930.000024445.9−13.4−3.81.0216611208.801514.44−0.97
xsp17-12-140.0286300.0010460.2824810.000071449.4−10.3−0.72.5584871092.151344.88−0.97
xsp17-12-200.0173660.0005680.2823610.000010448.8−14.5−4.80.6518461243.671570.36−0.98
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Zan, P.; Chen, S.; Chen, J.; Li, S. Early Paleozoic Adakitic Granitoids from the Xingshuping Gold Deposit of East Qinling, China: Petrogenesis and Tectonic Significance. Minerals 2021, 11, 1032. https://doi.org/10.3390/min11101032

AMA Style

Zan P, Chen S, Chen J, Li S. Early Paleozoic Adakitic Granitoids from the Xingshuping Gold Deposit of East Qinling, China: Petrogenesis and Tectonic Significance. Minerals. 2021; 11(10):1032. https://doi.org/10.3390/min11101032

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Zan, Pei, Shouyu Chen, Jinduo Chen, and Shengli Li. 2021. "Early Paleozoic Adakitic Granitoids from the Xingshuping Gold Deposit of East Qinling, China: Petrogenesis and Tectonic Significance" Minerals 11, no. 10: 1032. https://doi.org/10.3390/min11101032

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