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Article

Geochronology and Geochemistry of Cretaceous Adakitic Rocks of the Dongguashan Cu Deposit in the Lower Yangtze River Belt: Insights into Petrogenesis and Mineralization

by
Zanzan Zhang
1,2,3,
Xiaoyan Jiang
1,*,
Jia Guo
4 and
Kenan Jiang
1
1
State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, China
2
School of Earth and Space Sciences, University of Science and Technology of China, Hefei 230026, China
3
Geological Survey of Anhui Province (Anhui Institute of Geological Sciences), Hefei 230001, China
4
College of Earth Sciences, Chengdu University of Technology, Chengdu 610059, China
*
Author to whom correspondence should be addressed.
Minerals 2023, 13(7), 953; https://doi.org/10.3390/min13070953
Submission received: 29 June 2023 / Revised: 9 July 2023 / Accepted: 14 July 2023 / Published: 17 July 2023
(This article belongs to the Special Issue Mineralization in Subduction Zone)
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Abstract

:
The Lower Yangtze River Belt (LYRB) is a well-known and important base area with regard to Cu polymetallic resources in China. Large Cu polymetallic deposits in the LYRB are strongly associated with Cretaceous adakitic rocks. However, the petrogenesis of the Early Cretaceous adakites and the temporal–genetic relationship with mineralization are still disputable. The Dongguashan (DGS) Cu polymetallic deposit in the Tongling ore cluster is one of the largest Cu deposits in the LYRB. The DGS intrusion mainly comprises quartz monzodiorite, with SiO2 contents varying from 63.7 to 67.9 wt%. Zircons from the quartz monzonite yield a SIMS U-Pb age of 138.9 ± 1.8 Ma, which indicates that the Cretaceous magmatism is coeval with mineralization. The studied rocks show typical geochemical signatures of adakites, characterized by high Al2O3 (14.9–16.2 wt%) and Sr (800–910 ppm) and low Y (15.2–17.5 ppm) and Yb (1.37–1.52 ppm) contents, with consequently high Sr/Y (46–61) and (La/Yb)N (14.8–18.5) ratios. The zircon δ18O values of the DGS adakites range from 5.7‰ to 7.3‰, indicating a heterogeneous source. Whole-rock Sr-Nd isotopic compositions show an enriched character, with ISr ratios from 0.70783 to 0.70794 and εNd(t) values around −11.0, which fall intermediately in the area of MORB (mid-ocean ridge basalt), marine sediment, and the ancient lower crust. Comprehensively, whole-rock geochemical compositions and isotopic values suggest that the adakites are generated from the partial melting of the subducted oceanic crust and possibly with the involvement of sedimentary materials derived from the slab or continental crust. Moreover, the bulk-rock high-Cu composition, and the physical–chemical conditions (high oxygen fugacity and high volatile contents) revealed by apatites, plays critical roles in the formation of Cu mineralization in the DGS Tongling ore cluster, LYRB.

1. Introduction

The LYRB is one of the most important Late Mesozoic magmatic belts and metallogenic provinces in Eastern China [1,2,3]. Over 200 Mesozoic magmatic polymetallic (Cu, Fe, Au, Mo, Zn, Pb, and Ag) ore deposits have been discovered along the LYRB. From west to east, these polymetallic deposits can be divided into seven ore clusters: Edong, Jiurui, Anqing-Guichi, Luzong, Tongling, Ningwu, and Ningzhen, respectively [2,4,5]. These polymetallic ore deposits are not only temporally associated with but also genetically related to adakitic rocks in this region [1,4,5,6,7,8]. Many studies on preliminary geology and geochemistry have been well-conducted and established the relationships between polymetallic mineralization, magmatism, stratigraphy, and tectonics [2,9,10,11]. Mainly three stages of magmatism and mineralization in the LYMB can be classified based on the field investigation along with collected geochronological data: (1) the first stage (148–135 Ma), intermediate-acid intrusions linked to Cu-Au-Mo polymetallic mineralization; (2) the second stage (133–127 Ma), mafic-intermediate volcanic and subvolcanic rocks associated with magnetite–apatite deposits; and (3) the third stage (129–120 Ma), A-type granites and alkaline rocks with U-Au mineralization [5,7,12,13,14,15,16,17,18]. Previous studies suggest that the first episode of high-K calc-alkaline intermediate-acid intrusions is congruously recognized to have adakitic-like features [7,8,17,19]. However, the origins of the ore-bearing adakites in the ore clusters are still debated and can be summarized as follows: (1) partial melting of the subducted oceanic slab of the Paleo-Pacific plate or metasomatized mantle wedge [6,7,8,17,20,21]; (2) partial melting of the thickened or delaminated lower continental crust [22,23,24,25]; (3) generated from mantle-derived magma following assimilation and fractional crystallization [1,26,27,28,29]; and (4) mixing of the mantle-derived and crust-derived magmas [11,30,31,32,33,34].
Accessory minerals in magmatic rocks provide a window into the petrogenesis and ore-forming mechanism for preserving a wealth of information on source components, magmatic evolution, and related mineralization. Both zircon and apatite are robust, long-lasting, and ubiquitous minerals in magmatic rocks. Zircon can preserve the magmatic O isotopic compositions, which is a useful proxy for the primary oxygen isotopic composition in magmas [35]. The mantle is a remarkably homogeneous oxygen isotope reservoir, and igneous oxygen isotopes of zircons in equilibrium with pristine mantle-derived melts have a well-constrained and narrow range of δ18O values (5.3 ± 0.3‰, 1SD) [36,37]. Moreover, zircon oxygen isotopic values (δ18OZrc) are insusceptible to fractional crystallization due to fractionation Δ18O (WR-Zrc) increasing at nearly the same rate as δ18O (WR) in the more evolved and silicic magmas. Apatite is also an important accessory mineral, which is the main host of the volatiles and has great importance in metallogenic studies, especially with regard to the magmatic processes and physio-chemical conditions [16,38,39,40,41,42,43,44].
The DGS deposit, discovered in 1974, is a representative Cu(-Au) ore deposit (0.94 Mt at 1.01% Cu and 22 t at 0.24 g/t Au) in the Tongling ore cluster [11]. The Mesozoic intermediate-acidic magmatic rocks widely developed in DGS are tightly associated with Cu polymetallic mineralization [11,45,46,47]. Knowledge about the petrology and genesis of the Cretaceous intermediate-acidic intrusions is important for revealing the petrogenesis and metallogenesis of the DGS deposit. Therefore, it is of great significance for understanding the petrological nature of the DGS quartz monzodiorite, which provides better constraints on the deposit genesis. This paper focuses on zircon U-Pb dating, O isotopic composition, and bulk rock elemental and Sr-Nd isotopic data of the DGS adakites, which are employed to provide insights into the petrogenesis and metallogenic mechanisms of the ore-bearing intrusion of the DGS deposit, the Tongling ore cluster, in the LYRB.

2. Geological Background

The LYRB is located along the northern margin of the Yangtze Craton and south of the Qinling–Dabie orogenic belt (Figure 1a). The ‘V-shaped’ metallogenic belt is bounded by the northwestern trending Xiangfan–Guangji and Tan–Lu faults and the southeastern trending Chongyang–Changzhou fault (Figure 1b; [4,48]). Extensive Late Mesozoic magmatism and large-scale mineralization occurred in the belt (Figure 1b,c; [2,4]). The Tongling ore cluster located in the central part of the LYRB, is one of the seven major mining regions in the metallogenic belt (Figure 1b). A total of 45 deposits and 76 plutons have been discovered within the district [2]. It comprises three major tectono-stratigraphic units: (1) an Archean to Late Proterozoic metamorphic basement, consisting of a Late Archean to Early Proterozoic metamorphic core complex and a thick flysch sequence intercalated with submarine volcanic rocks and intruded by Late Proterozoic granitioids; (2) a Paleozoic to Early Mesozoic marine sedimentary layer, including Carboniferous carbonate rocks, Permian black shale and limestone, and Triassic argillaceous rocks and carbonate rocks, except for the Middle–Late Devonian Cambrian to Early Triassic marine sediment coverage, including shale, siltstone, and limestone; and (3) Early Mesozoic to Late Mesozoic (Middle Triassic to Cretaceous) volcanic sequences and thick terrestrial sediments are widely covered above those marine deposits, comprising Jurassic and Cretaceous extensive volcanic and intrusive rocks [1,2]. These widespread plutons are developed along the EW-trending Tongling–Nanling fault and intrude Silurian–Triassic sedimentary host rocks. The shape of the Late Mesozoic magmatic rocks is constrained by a series of NE-trending faults and folds. Numerous polymetallic Cu–Au deposits are products of those intermediate–felsic magmatic and relevant hydrothermal activities (Figure 1b) [49]. Ore-bearing intrusions include the DGS, Tongguanshan, Fenghuangshan, Xinqiao, and Shizishan, which mainly consist of intermediate-felsic magmatic rocks, including pyroxene monzodiorite, quartz monzodiorite, and granodiorite [15,50].
DGS is one of the economically most important polymetallic Cu-Au deposits in the Shizishan ore field, the Tongling ore cluster (Figure 1c) [1], and is located at the intersection of the NE-trending Qingshan anticline and the E-trending Tongling–Shatanjiao fold belt [51]. The sedimentary rocks exposed in the area are recognized to be Middle–Upper Silurian to Lower Triassic, with the exception of Lower to Middle Devonian rocks. Major structures consist of the NE-trending Qingshan anticline and the E-trending Datuanshan–Baoerling fault and control the emplacement of regional plutons and orebodies [51]. Quartz monzodiorite, closely related to Cu-Au mineralization [32], is intruded into Silurian to Triassic sedimentary strata [9]. Twelve fresh samples were collected from the drilling core (Figure S1). The samples were mainly quartz monzodiorite, which was light gray in color and medium- to coarse-grained in texture and had a massive structure. They consisted of plagioclase (45–60 vol%), potassium feldspar (10–20 vol%), quartz (5–15 vol%), and small amounts of biotite (Figure 2). Accessory minerals included zircon, apatite, titanite, and magnetite.

3. Analytical Methods

3.1. In Situ SIMS Zircon U–Pb and Oxygen Isotope Analysis

Zircon grains were separated and mounted in epoxy resin disc with standards Plešovice, Penglai, and Qinghu and then polished to expose the crystals. The U–Pb isotope compositions of zircon grains from sample (DGS46) were determined using a Cameca IMS-1280 HR (high-resolution) at the Guangzhou Institute of Geochemistry, Chinese Academy of Sciences (GIGCAS), Guangzhou, China. The operating conditions include ~8 nA primary O2– beam focused to a beam size of 20 × 30 μm at a mass resolving power of ~5400. U–Pb ratios were calibrated against the Plešovice standard (206Pb/238U = 0.05369; age = 337.1 Ma; [52]), and absolute abundances were determined relative to the M257 standard (U = 840 ppm; Th/U = 0.27; [53]). Zricon standard Qinghu was analyzed together with the zircons in this study. The analytical procedures and data-processing procedures were similar to those described by Li et al. [54]. An average present-day crustal composition [55] was used. The concordia plot was processed using Isoplot/Ex v.3.70 [56]. In situ zircon U–Pb dating results are listed in Supplementary Table S1. The analysis shows that 206Pb/204Pb values are generally high, implying insignificant common Pb contents.
Zircon oxygen isotopes (18O and 16O) were determined using a Cameca IMS-1280 HR ion microprobe at the GIGCAS. The sample mount was reground and polished. A focused beam of Cs+ ions was accelerated at 10 kV potential with an intensity of ~2nA. The applied beam diameter was ~20 μm. The oxygen isotopes were measured in multi-collection mode using two off-axis Faraday cups, and nuclear magnetic resonance (NMR) was used to stabilize the magnetic field. Detailed analytical procedures were described by Tang et al. [57]. Each analysis comprised 20 cycles, with an internal precision of better than 0.2‰ (1σ). Measured 18O and 16O were normalized to the Vienna Standard Mean Ocean Water composition (VSMOW; 18O/16O = 0.0020052) and reported in standard per mil notation. The instrumental mass fraction factor (IMF) was corrected using the zircon standard Penglai with δ18OVSMOW = 5.3‰ [58]. In situ oxygen isotopic results are presented in Supplementary Table S2.

3.2. Whole-Rock Major and Trace Elements and Sr–Nd Isotopes

Rock samples were crushed to smaller than 200 mesh (<0.75 μm in diameter). The powder samples were dried at 105 °C for 4 h and treated to produce fused glass discs that were analyzed using an X-ray fluorescence spectrometer at ALS Laboratory Group, Analytical Chemistry and Testing Services, Guangzhou, China. The analytical uncertainties for major element concentrations were less than 5%. Whole-rock trace element analyses were conducted using an Agilent 7700e inductively coupled plasma–mass spectrometer (ICP–MS) at Wuhan SampleSolution Analytical Technology, Wuhan, China. The sample digestion procedure and the analytical precision and accuracy during ICP–MS analyses were identical to those of Liu et al. [59]. The instrumental signal drift was monitored using an internal standard Rh solution. The AGV-2, BHVO-2, BCR-2, and RGM-2 standards were used for instrument calibration and quality control. For most trace and rare earth elements, the precision was estimated to be better than 2%–5% RSD (relative standard deviation). The data are given in Supplementary Table S3.
Strontium and Nd isotopic compositions of the powdered samples were determined using a Micromass Isoprobe multi-collector ICP–MS instrument (MC–ICP–MS) at the State Key Laboratory of Isotope Geochemistry, GIGCAS. The powder samples were dissolved in HF + HNO3 acid in Teflon containers. Strontium and rare earth elements (REE) were separated in cation columns, Nd fractions were further separated using HDEHP-coated Kef columns. Analytical procedures were similar to those described by Li et al. [60]. The MC–ICP–MS was operated in static mode. The measured 87Sr/86Sr of the NBS SRM 987 standard and the measured 143Nd/144Nd of the Shin Etsu JNdi-1 standard yielded the values of 0.710242 ± 10 (2σ, n = 9) and 0.512115 ± 10 (2σ, n = 8), respectively, which were identical within the error of the recommended values of 87Sr/86Sr = 0.71025 and 143Nd/144Nd = 0.512115 [61]. To correct for mass fractionation during analysis, measured Sr and Nd isotope ratios were normalized to a composition of 86Sr/88Sr = 0.1194 and 146Nd/144Nd = 0.7219. Isotopic compositions and calculated initial 87Sr/86Sr (ISr) and εNd (t) values are shown in Supplementary Table S3.

3.3. Apatite Major Elements Analysis

Apatite grains from the sample (DGS46) were separated and selectively mounted in epoxy resin and then polished to expose crystal mid-sections for observation and analysis. Photomicrographs and cathodoluminescence (CL) images were obtained to characterize the internal structures of apatite grains. Major element analyses were conducted using wavelength-dispersive spectrometers on a JEOL JXA-8230 electron microprobe at the Testing Center of the Shandong office of the China Metallurgical Geology Bureau, Jinan, China. The operating conditions include an accelerating voltage of 15 kV, a beam current of 10 nA, and a defocused beam 10 μm in diameter. Norbergite standard was used for F, Ba5(PO4)3Cl for Cl, and apatite for Ca and P contents. In order to avoid volatile loss, count times analyzed for F and Cl were 10 s and was 20 s for other elements. Fluorine and Cl were analyzed using the Kα line on an LDE1 and PET crystal, respectively. The analytical precision was estimated to be better than 1% for most of the major elements and was ~5% for F and Cl contents. The major element contents of apatite are listed in Supplementary Table S4.

4. Results

4.1. Zircon U-Pb Age and O Isotopic Compositions

Zircon grains from quartz monzodiorite (DGS46) are transparent and colorless. Most crystals are euhedral to subhedral in morphology. The selected grains have lengths up to 100–300 μm, with length-to-width ratios between 2:1 and 3:1. They are all characterized by euhedral concentric zoning in CL images, indicating their magmatic origin. A total of 16 U-Th-Pb measurements on 16 zircons yielded moderate concentrations of Th (70–536 ppm) and U (98–695 ppm), with variable Th/U ratios ranging from 0.34 to 1.02. Only one inherited zircon crystal showed an age of 829 Ma. The other 15 points define a concordia age of 138.9 ± 1.8 Ma (n = 15, MSWD = 0.77) (Figure 3), which is considered to be the best estimate of the crystallization age of the DGS intrusion.
Oxygen isotope analyses on the dated zircon grains from sample DGS46 yielded a relatively wide range of δ18O values (5.7‰ to 7.3‰), with one xenocrystic zircon crystal showing a δ18O value of 5.6‰. Taking into account the SiO2 contents of the host rock and using the equation δ18OWR ≈ δ18OZir + 0.0612 (wt% SiO2) −2.5 [35], the corresponding δ18O values for the quartz monzodiorite were calculated at 7.3‰–8.8‰.

4.2. Whole-Rock Major and Trace Elements and Sr-Nd Isotope

The quartz monzodiorites contain 63.2–67.9 wt% SiO2, 14.9–16.2 wt% Al2O3, and 5.86–8.02 wt% total alkalies contents, with Na2O/K2O ratios from 1.48 to 1.71 (Figure 4). These samples fall into the metaluminous field in the A/CNK-A/NK diagram (Figure 4). In the K2O vs. SiO2 diagram, the samples are mainly plotted in the high-K calc-alkaline series and exhibit a strong positive correlation between K2O and SiO2 (Figure 5e). Significantly negative correlations exist between the SiO2 content and TiO2, MgO, CaO, and P2O5 content.
The chondrite-normalized REE patterns of the quartz monzodiorite (Figure 6a) are characterized by moderate to high LREE enrichment relative to HREE [(La/Yb)N ratios > 14.6] and pronounced negative Eu anomalies (Eu/Eu* = 0.30−0.34). The primitive mantle-normalized trace element patterns are shown in Figure 6b. The quartz monzodiorites are characterized by high Ba (588–1040 ppm), Sr (800–991 ppm), and LREE contents, as well as low Rb (44.3–111 ppm) and HREE contents. The quartz monzodiorite shows enrichment in LILE (Rb and Pb) and depletion in HFSE. The concentrations of HFSE are relatively low, with Zr ranging from 146 to 173 ppm, Nb from 12.3 to 14.3 ppm, Ta from 0.79 to 0.96 ppm, and Y from 15.2 to 17.5 ppm. These geochemical characterizations imply that the formation of the DGS quartz monzodiorite is related to the subduction scenario [64,65].
Two DGS samples (DGS46 and DGS53) were measured for Sr–Nd isotopic compositions. Both Sr and Nd isotopic compositions vary narrowly within a small range (Figure 7). The measured 87Sr/86Sr ratios vary between 0.70855 and 0.70856, corresponding to the initial 87Sr/86Sr ratio (ISr) between 0.70783 and 0.70794. 147Sm/144Nd vary in a small range (0.0864–0.0995), with 143Nd/144Nd ratios and εNd(t) values of 0.51198–0.51199 and −11.0 to −11.1, respectively.

4.3. Apatite Geochemistry

Most apatite grains from DGS46 quartz monzodiorite are subhedral and euhedral, ~100–300 μm in length with length, with width ratios of 1:1 to 3:1. They are characterized as clean, homogeneous, and transparent under plane-polarized light. The CL images exhibit concentric and oscillatory zoning. All those features are interpreted to be due to the magmatic origin [72]. Euhedral–subhedral apatite grains with no inclusions were selected for analysis. The analyzed apatite grains have CaO content from 54.0 to 55.1 wt% and P2O5 in a range of 41.6 to 43.1 wt%. Apatite grains have Na2O content below 0.06 wt% and SO3 content ranging from 0.08 to 0.28 wt%. The relatively positive correlation between Na2O and SO3 (Figure 8a) reveals that they were incorporated in apatite at the same time via a coupled substitution mechanism (e.g., SO42− + Na+ = PO43− + Ca2+; [73]). They yielded higher F (1.88–3.16 wt%) compared to Cl (0.06–0.16 wt%) contents (Figure 8b). Assuming that the halogen site is fully occupied by XF-ap + XCl-ap + XOH-ap = 1 (X = mole fractions modal of F, Cl, and OH), the OH content in apatite is calculated via stoichiometry based on eight anions [74]. The calculated OH contents range from 0.09 to 0.45 apfu (Figure 8c).
Using the method of Piccoli and Candela [74], the estimated apatite saturation temperature (956 °C; Supplementary Table S4) was attained based on the whole-rock data. Such a high temperature suggests that apatite in the DGS quartz monzodiorite is an early crystallized mineral phase [75]. Moreover, the analyzed apatites are generally ~100–300 μm in length, much larger than the euhedral and fine-grained ones (25 μm) crystallizing from the intercumulus melt but cannot record bulk magma information [76,77]. Considering the apatite morphology and contact relationship, we concluded that apatite grains in the quartz monzodiorite are in the early crystallizing phase and can be used to evaluate the physicochemical conditions of the parental magma.

5. Discussion

5.1. Petrogenesis of the DGS Quartz Monzodiorite

Adakitic rocks have attracted extensive attention worldwide, as they are not only record magmatic processes and mantle–crustal interaction but are also associated with major Cu deposits. The term ‘adakite’ was initially considered to be partial-melting products of subducted hot, young oceanic crust metamorphosed in the garnet amphibolite or eclogite facies [78]. Adakites are intermediate to felsic igneous rocks characterized by SiO2 contents (≥56 wt%), high Al2O3 contents (≥15 wt%), Sr concentrations (mostly ≥ 400 ppm), and Sr/Y (≥20) ratios but low Y and Yb concentrations (generally ≤18 ppm and ≤1.9 ppm, respectively) and a lack of Eu anomalies [78,79]. The DGS quartz monzodiorites have high SiO2 and Al2O3 contents varying from 63.2 to 67.9 wt% and 14.9 to 16.2 wt%, respectively. They have high Sr (800–991 ppm), low Y (15.2–17.5 ppm) and Yb (1.37–1.52 ppm) concentrations, and resultant high Sr/Y (46–61) and (La/Yb)N (14.8–18.5) ratios, which are all typical geochemical features of adakites [78]. In the discrimination diagrams (Figure 9), most of the samples fall in or on the boundary of the adakite field.
Due to the importance of understanding the genesis of adakitic rocks, their origin is still hotly debated. In addition to slab melting, an increasing number of studies have proposed alternative processes that could form adakitic magmas in different tectonic backgrounds, not only island arc settings but also intraplate environments [78,79,80,81,82,83,84]. The mechanisms that generate adakitic rocks could be summarized as partial melting of thickened or delaminated mafic rocks in the lower continental crust [85,86,87,88], garnet or amphibole fractionation under different pressures [89,90,91], and partial melting of the upper mantle metasomatized by slab-derived melt [92,93]. The sources and genesis of the ore-bearing adakitic rocks in the Tongling ore cluster are still controversial. Previous studies proposed several processes that could generate these adakites, such as partial melting of the subducted Paleo-Pacific oceanic crust or mantle wedge metasomatized by the Paleo-Pacific plate [6,7,8,13,17,20,21], partial melting of delaminated or thickened lower continental crust [22,23,24,25], or mixing of mantle-derived and evolved felsic crust-derived magmas [11,30,31,32,33,34].
Minerals 13 00953 g009 550
Figure 9. Discrimination diagrams for DGS adakitic rocks. Sr/Y versus Y (a) and (La/Yb)N versus YbN (b) after Drummond and Defant [78]. A two-stage modeled Rayleigh fractionation from a calc-alkaline andesite melt modeled after Li et al. [94]. Dark-blue line represents the first-stage magmatic fractionation (from andesite to dacite); dark-green line indicates the second-stage magmatic fractionation (from dacite to rhyolite). FC = fractional crystallization, AFC = assimilation and fractional crystallization. Literature data are from Wang et al. [11] and Wang et al. [63].
Figure 9. Discrimination diagrams for DGS adakitic rocks. Sr/Y versus Y (a) and (La/Yb)N versus YbN (b) after Drummond and Defant [78]. A two-stage modeled Rayleigh fractionation from a calc-alkaline andesite melt modeled after Li et al. [94]. Dark-blue line represents the first-stage magmatic fractionation (from andesite to dacite); dark-green line indicates the second-stage magmatic fractionation (from dacite to rhyolite). FC = fractional crystallization, AFC = assimilation and fractional crystallization. Literature data are from Wang et al. [11] and Wang et al. [63].
Minerals 13 00953 g009
Adakitic rocks generated from partial melting of the continental or oceanic crust may be distinguished by some geochemical features. Based on these features, the DGS adakitic rocks could not be products of continental crust melting. First, the melts with garnet as the residual mineral in the source area will have high ratios of Yb/Lu (8–10) and a steep HREE distribution pattern [95]. The DGS adakitic rocks have relatively low Yb/Lu ratios (6.0–7.2) and flat HREE distribution patterns, which do not agree with this model. Second, experimental petrology studies suggest that the magma originated from partial melting of the basaltic lower crust and is usually enriched in Na2O (>4.3 wt%) [85,96]. However, the Na2O content of DGS adakitic rocks (3.6 to 4.2 wt%) is lower and inconsistent with the model of delaminated or thickened lower continental crust. Moreover, the diagram of Sr/Y versus (La/Yb)N can also provide information for distinguishing between partial melting from the subducted oceanic slab and lower continental crust [13,20,87]. Under such conditions, in the amphibole- or garnet-bearing and plagioclase-free residues, both Y and Yb are compatible, whereas Sr and La are incompatible. A positive correlation exists between the (La/Yb)N and Sr/Y ratios in the adakites, which are products of the partial melting of thickened lower continental crust with an eclogite or garnet amphibolite residue. In modern subduction zones, adakites produced by the melting of oceanic crust might have variably high Sr/Y but considerably lower (La/Yb)N ratios compared to those of the lower continental crust [13,97,98,99]. The DGS adakitic rocks have high and variable Sr/Y ratios but considerably lower (La/Yb)N ratios than those derived from the lower continental crust, and all plot in the field of partial melting of subducting oceanic crust (Figure 9). Therefore, the mechanism of partial melting of the lower continental crust could not explain the genesis of DGS adakitic rocks.
Moreover, fractional crystallization plays an important role in the varied geochemical compositions of the DGS adakitic rocks. The negative correlations observed between P2O5, TiO2, Y, and SiO2 (Figure 5) imply that the separation of accessory minerals buffering P and Ti leads to decreased REE and Y contents during magmatic evolution. Considering the strong depletion of Nb (Figure 6) and the varied and overall subchondritic Nb/Ta ratios (13.5–16.2), Nb-Ta fractionation might have happened under the geothermal gradient in the incipient stage of subduction [100,101,102,103].
Only a few studies have reported the zircon δ18O values of adakitic rocks in the LYRB. Most zircon δ18O values vary between 6.5‰ and 8.0‰, corresponding to 8.0‰–9.5‰ for δ18O values of the ore-bearing magmas (Figure 10). In this study, the zircon δ18O values of the DGS adakitic rocks were first analyzed and reported as 5.7‰ to 7.3‰, corresponding to 7.3‰ to 8.8‰ for the magma. Considering that only one xenocrystic zircon is found among the dated zircons, contamination of the crustal materials during ascent might be very limited. Therefore, the oxygen isotope is a good indicator of the primitive nature of magmatic sources. The calculated magmatic δ18O values (7.3‰–8.8‰) are higher than melts from hydrothermally altered gabbros from the oceanic crust interior (δ18O = ca. 2‰–5‰) but lower than those from partial melting of sediments and/or basaltic rocks in the upper part of the oceanic crust (δ18O = 9‰–20‰) [104]. In addition to the high and variable oxygen isotopic compositions, the DGS adakitic rocks display rather high initial ISr (0.70783 to 0.70794) and enriched εNd(t) (−11) values. The Sr-Nd isotopic data for the adakitic rocks in DGS lie in the area among MORB, marine sediment, and the ancient lower crust (Figure 7). All these isotopic features indicate the progressive addition of ancient crustal materials in the magma source. These materials could be the subducted sediments involved in the magma source during slab melting or continental crust materials incorporated through magma mixing or crustal contamination. Therefore, the integrated higher δ18O and ISr values and lower εNd (t) values of the DGS adakitic rocks can be attributed to the mantle source involved in a fraction of sedimentary melts, whereas the crustal contamination had little role, if any, in their genesis.

5.2. Temporal Relationship between the Adakitic Rocks and Cu polymetallic Mineralization in the DGS Deposit

Given the Late Mesozoic magmatic activities in the LYRB, adakitic rocks developed at ca. 150–130 Ma have been tightly associated with intense Cu-Au-Mo-Fe mineralization [7,13,15,17]. Previous geochronological studies on the DGS deposit mainly focused on the mineralization ages, including the mineralized quartz veins Rb-Sr age (~136 Ma; [105]), molybdenite Re-Os age (~139 Ma; [106]), garnet U-Pb ages (from ~135 to 136 Ma; [107]), and titanite U-Pb ages (from ~139 to 137 Ma; [108]). There are also some crystallization ages of the ore-related pluton, with zircon U-Pb dating results varying between ~135 Ma and ~140 Ma [11,29,45,108,109].
In this study, our new zircon U-Pb dating result is 138.8 ± 1.8 Ma for magmatic zircons from the DGS quartz monzodiorite, which directly constrained the timing of ore-related adakitic rocks and agreed well with previously published ages for the DGS deposit. Therefore, DGS Cu mineralization is temporally related to the adakitic rocks at ~140 Ma –135 Ma from the period of intense Cu-Au-Mo-Fe mineralization in the LYRB.

5.3. Metallogenic Implications for the Cretaceous Adakites in the LYRB

The adakites produced via partial melting of the subducted oceanic slab have a genetic association with Cu mineralization worldwide. The high initial Cu contents of the magmas generated from the oceanic crust are an important parameter that makes the slab melt the best candidate for Cu mineralization [13,21,82,83,98]. The Cu concentration of MORB is ~100 ppm, which is much higher than that of the primitive mantle and the continental crust [99]. The spider diagram of bulk continental crust-normalized transitional elements (Figure 11) shows strong fractionation of DGS adakitic rocks compared to the continental crust, with pronounced positive Cu anomalies and strong depletion of mantle compatible elements (Sc, Cr, and Ni). Moreover, the contents of ore-forming element Cu in the DGS samples reach up to 227 ppm, with an average of 166 ppm, significantly higher than Cu in the bulk continental crust (27 ppm; [99]). The relative enrichment in Cu in the quartz monzodiorite indicates the potential to provide ore-forming materials and the genetic relationship of Cu mineralization with adakites in the DGS deposit.
The association between Cu deposits and adakitic intrusions in subduction zones suggests that magma oxygen fugacity controls the partitioning and transport of Cu in magmas before mineralization [81,110,111,112,113]. Copper is a highly chalcophile element and is enriched in sulfides. The oxygen fugacity controls the sulfur species, and the stability of sulfides controls the Cu partitioning in magmas. During partial melting, high oxygen fugacity is favorable for the liberation of Cu when sulfur is extracted as sulfate and during the enrichment in Cu in the melt during differentiation before partitioning into an exsolved fluids phase [110,114,115,116].
As apatite is an early-stage crystallization product, it can provide records of the oxidation states of the host magma [75,76,77,117]. The Mn concentration of apatite is used to determine the redox conditions of granitic magmas due to the increasing concentration with decreasing magma oxygen fugacity (fO2) (e.g., [73,118,119,120]). Accordingly, Miles et al. [119] proposed that the Mn concentration can be used to calculate oxygen fugacity and is shown to vary linearly and negatively with logfO2, which can be illustrated by the equation logfO2 = –0.0022 (± 0.0003) Mn (ppm) − 9.75 (± 0.46). Apatite grains in this study have MnO contents of 0.03–0.12 wt.%, which yield logfO2 values from −9.8 to −11.8. Besides, the valence state of sulfur in apatite is controlled by oxygen fugacity [121,122]. Based on the equilibration experiment, a recent study proposed the following equation to estimate oxygen fugacity: ΔFMQ = 0.423 (±0.034) − 0.2 (±0.026) × ln[(0.964 (± 0.001) − 0.086 (±0.033))/(S6+/ΣSmeasured − 0.086 (±0.033)) − 1] [121]. Sulfur in apatite is assumed to exist only as S2+ and S6+, and the S6+/ΣS ratio was estimated according to Wang et al. [75] (S6+ content in apatite was obtained by EPMA apatite S content with the subtraction of 36.88 ppm). According to the equation [121], the regional magmatic oxygen fugacities are calculated to be ΔFMQ + 0.89 to ΔFMQ + 1.28 (Supplementary Table S4), representing the lower bound. The oxygen fugacities estimated by Mn (log fO2 from −9.8 to −11.8) and S (ΔFMQ + 0.89 to ΔFMQ + 1.28) contents of the apatites indicate that the DGS Cu ore-bearing adakitic magmas are generated in an oxidized environment.
Volatiles play an important role in magmatic evolution and metal enrichment and mineralization [123,124]. Apatite is the main accessory mineral for buffering volatiles (F, Cl, and OH) in magmatic rocks [125,126]. Boyce and Hervig [127] found that variations in F and OH contents in apatite are in line with F and H2O change in the coexisting melt inclusion. The OH concentration of apatite can reflect the abundance of H2O in the melt where the apatite crystallized [128,129,130]. The relatively high OH content contained by apatite grains from the DGS quartz monzodiorite (Figure 8) might indicate high water content of the parental magma. Fluorine and Cl are important for mineralization due to their great significance in depolymerizing the melt structure and facilitating hydrothermal metal transport and enrichment during degassing and exsolution of the fluid phase [38,131,132]. As Cu is more sensitive to Cl than F and the increase in Cl content will markedly increase the solubility of Cu, Cl-rich fluids are essential for the transportation and deposition of Cu [133,134,135]. The studied apatite grains have high F (1.88–3.35 wt%) and low Cl (0.06–0.16 wt%) contents (Figure 8), with lower Cl/F ratios (0.01 to 0.06). The mantle usually has low Cl contents (<0.1 wt%) and is not significantly influenced by Cl recycling [136]. Magmas are derived from anatexis of the continental crust, which have low Cl/F ratio [124]. Apatite crystallized from the supracrustal material also has low Cl content [137]. The Cl content and Cl/F ratio of apatite grains preclude the generation from mantle-derived magma or supracrustal components. However, Cl is highly incompatible and preferentially enters the liquid phase in the stage of slab dehydration [138]. Comparing our results with apatite from Late Mesozoic granodiorite and polymetallic mineralization in southern Anhui Province, which are identified as fluorapatite with high F (2.69–4.13 wt%) and low Cl contents (mainly < 0.2 wt%) [17,124], slab-derived components with high Cl/F ratios might be incorporated into the formation of adakitic rocks in the DGS deposit.
To summarize, the high Cu content, high oxygen fugacity and volatile-rich adakitic magmas benefit the extraction and transportation of Cu, which finally formed the DGS Cu polymetallic deposits [13,17,81,111,112]. Based on the analysis of previous studies, we suggest that the diagenesis of Cretaceous adakitic rocks and mineralization of the DGS deposit are the same as other large-scale Cu polymetallic deposits in the LYRB. The hydrous and oxidized subducted altered oceanic crust is potentially favorable for Cu–Au mineralization [17].

6. Conclusions

Based on zircon in situ U–Pb geochronology and O isotope, as well as bulk rock major and trace element and Sr–Nd isotopic compositions of the DGS adakitic rocks associated with the Cu polymetallic deposit in the Tongling ore cluster, LYRB, the following conclusions are drawn:
(1)
The DGS intrusion mainly consists of quartz monzodiorite. The whole-rock compositions show geochemical features of adakite, characterized by high Sr and low Y and Yb concentrations and, consequently, high Sr/Y and (La/Yb)N ratios. According to the comprehensive geochemical data, the adakites are most probably produced by the partial melting of a subducted altered oceanic crust and possibly incorporated sediments.
(2)
Highly precise and accurate SIMS in situ zircon U–Pb age suggests that the adakites crystallized at 138.9 ± 1.8 Ma, which is coeval with the Cu mineralization in the DGS deposit, Tongling ore cluster, and implies a close temporal relationship between the adakites and Cu polymetallic mineralization in the LYRB.
(3)
The high Cu content, high oxygen fugacity, and volatile contents of the DGS adakite imply an oxidized and volatile enriched environment, which is conducive to the formation of large-scale Cu polymetallic mineralization.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min13070953/s1, Figure S1: Photographs of DGS adakitic rocks from drill holes in the DGS deposit; Table S1: SIMS U-Pb zircon age data of adakitic rocks in the DGS deposit; Table S2: In situ zircon oxygen isotopic compositions of adakitic rocks in the DGS deposit; Table S3: Whole-rock major and trace element data and Sr-Nd isotopic compositions of adakitic rocks in the DGS deposit; Table S4: Major element compositions of apatite from the adakite in the DGS deposit.

Author Contributions

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

Funding

This research was funded by the Guizhou Provincial Science and Technology Projects, (No. ZK[2021] 207 and No. ZK[2023] 052), the CAS ‘Light of West China’ Program, and the Natural resources Science and Technology Project of Anhui Province (No. 2022-K-9), and a special fund managed by the State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences.

Data Availability Statement

The original contributions presented in the study are included in the Supplementary Materials.

Acknowledgments

Zhekun Zhang and Saijun Sun are acknowledged for help during the fieldwork. We thank Peijun Lin, Yanqiang Zhang, Boqin Xiong, and Qin Yang for technical assistance with experimental works.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. (a) Sketch map with the location of the LYRB; (b) Simplified geological map of intrusive and volcanic rocks and ore clusters in the LYRB (modified after Zhou et al. [48]; Mao et al. [4]); (c) Geological map of Tongling ore cluster, Anhui province (modified after Chang et al. [1]). TLF: Tancheng–Lujiang fault; XGF: Xiangfan–Guangji fault; HPF: Huanglishu–Poliangting fault; CHF: Chuhe fault; CCF: Chongyang–Changzhou fault; JNF: Jiangnan fault.
Figure 1. (a) Sketch map with the location of the LYRB; (b) Simplified geological map of intrusive and volcanic rocks and ore clusters in the LYRB (modified after Zhou et al. [48]; Mao et al. [4]); (c) Geological map of Tongling ore cluster, Anhui province (modified after Chang et al. [1]). TLF: Tancheng–Lujiang fault; XGF: Xiangfan–Guangji fault; HPF: Huanglishu–Poliangting fault; CHF: Chuhe fault; CCF: Chongyang–Changzhou fault; JNF: Jiangnan fault.
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Figure 2. Microphotographs (cross polarized light) of thin sections of the representative adakitic rocks from the drill holes in the DGS deposit. (a) tabular K-feldspar (b) flaky biotite with polychromatic property (c) and (d) mineral assemblage of quartz + K-feldspar + plagioclase + biotite. Abbreviations in the images: Kf = potassium feldspar; Pl = plagioclase; Qtz = quartz; Bt = biotite.
Figure 2. Microphotographs (cross polarized light) of thin sections of the representative adakitic rocks from the drill holes in the DGS deposit. (a) tabular K-feldspar (b) flaky biotite with polychromatic property (c) and (d) mineral assemblage of quartz + K-feldspar + plagioclase + biotite. Abbreviations in the images: Kf = potassium feldspar; Pl = plagioclase; Qtz = quartz; Bt = biotite.
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Figure 3. SIMS zircon U-Pb Concordia diagram for the DGS quartz monzodiorite. The inset shows representative CL image of the investigated zircon grain, with locations of ion microprobe analysis spots (yellow circle represents the spot of O isotope, and red oval represents U–Pb dating analyses).
Figure 3. SIMS zircon U-Pb Concordia diagram for the DGS quartz monzodiorite. The inset shows representative CL image of the investigated zircon grain, with locations of ion microprobe analysis spots (yellow circle represents the spot of O isotope, and red oval represents U–Pb dating analyses).
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Figure 4. Classification diagrams of DGS quartz monzodiorite. (a) TAS diagram of DGS quartz monzodiorite [62]. (b) A/NK versus A/CNK diagram for DGS quartz monzodiorite. A/NK = Al/(Na + K), A/CNK = Al/(Ca + Na + K) (molar ratios). Literature data of adakitic rocks in the DGS deposit are from the following references: Wang et al. [11] and Wang et al. [63].
Figure 4. Classification diagrams of DGS quartz monzodiorite. (a) TAS diagram of DGS quartz monzodiorite [62]. (b) A/NK versus A/CNK diagram for DGS quartz monzodiorite. A/NK = Al/(Na + K), A/CNK = Al/(Ca + Na + K) (molar ratios). Literature data of adakitic rocks in the DGS deposit are from the following references: Wang et al. [11] and Wang et al. [63].
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Figure 5. Harker diagrams of DGS quartz monzodiorite. (a) Al2O3 vs. SiO2; (b) TiO2 vs. SiO2; (c) MgO vs. SiO2; (d) CaO vs. SiO2; (e) K2O vs. SiO2; (f) Na2O vs. SiO2; (g) P2O5 vs. SiO2; (h) Sr vs. SiO2; (h) Sr vs. SiO2; (i) Y vs. SiO2; (j) Yb vs. SiO2; (k) Mg# vs. SiO2; (l) La/Yb vs. SiO2. Literature data are from Wang et al. [11] and Wang et al. [63].
Figure 5. Harker diagrams of DGS quartz monzodiorite. (a) Al2O3 vs. SiO2; (b) TiO2 vs. SiO2; (c) MgO vs. SiO2; (d) CaO vs. SiO2; (e) K2O vs. SiO2; (f) Na2O vs. SiO2; (g) P2O5 vs. SiO2; (h) Sr vs. SiO2; (h) Sr vs. SiO2; (i) Y vs. SiO2; (j) Yb vs. SiO2; (k) Mg# vs. SiO2; (l) La/Yb vs. SiO2. Literature data are from Wang et al. [11] and Wang et al. [63].
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Figure 6. Chondrite-normalized REE (a) and primitive mantle-normalized trace elements (b) distribution patterns of DGS quartz monzodiorite. Chondrite and primitive mantle-normalized data taken from Sun and McDonough [66].
Figure 6. Chondrite-normalized REE (a) and primitive mantle-normalized trace elements (b) distribution patterns of DGS quartz monzodiorite. Chondrite and primitive mantle-normalized data taken from Sun and McDonough [66].
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Figure 7. Whole-rock Sr-Nd isotopic compositions of DGS intrusive rocks. The fields of PM (primitive mantle) and MORB are according to Hofmann [67]; the field of GLOSS (global subducting sediment) is based on Plank and Langmuir [68]; the fields of Sr-Nd isotopic compositions for the LYRB Cretaceous mafic rocks, NE Yangtze Block and the Archean Kongling Group metamorphic basement and the Dabie Orogen low-Mg adakitic rocks are after compilation of Liu et al. [13], Li et al. [54], Chen et al. [69], Yan et al. [70] and Ames et al. [71]. Literature data are from Li et al. [54]. Abbreviations in the diagram: EM = Enriched Mantle, EMI = Enriched Mantle I, EMII = Enriched Mantle II, STLF = South Tan-Lu fault.
Figure 7. Whole-rock Sr-Nd isotopic compositions of DGS intrusive rocks. The fields of PM (primitive mantle) and MORB are according to Hofmann [67]; the field of GLOSS (global subducting sediment) is based on Plank and Langmuir [68]; the fields of Sr-Nd isotopic compositions for the LYRB Cretaceous mafic rocks, NE Yangtze Block and the Archean Kongling Group metamorphic basement and the Dabie Orogen low-Mg adakitic rocks are after compilation of Liu et al. [13], Li et al. [54], Chen et al. [69], Yan et al. [70] and Ames et al. [71]. Literature data are from Li et al. [54]. Abbreviations in the diagram: EM = Enriched Mantle, EMI = Enriched Mantle I, EMII = Enriched Mantle II, STLF = South Tan-Lu fault.
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Figure 8. Variation diagrams of major element contents for apatite in the DGS quartz monzodiorite. (a) Na2O (wt%) vs. SO3 (wt%); (b) Cl (wt%) vs. F (wt%); (c) F-Cl-OH ternary diagram based on the F-Cl-OH atomic proportions in apatites.
Figure 8. Variation diagrams of major element contents for apatite in the DGS quartz monzodiorite. (a) Na2O (wt%) vs. SO3 (wt%); (b) Cl (wt%) vs. F (wt%); (c) F-Cl-OH ternary diagram based on the F-Cl-OH atomic proportions in apatites.
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Figure 10. Magmatic δ18O values of the DGS adakitic rocks and LYRB adakitic rocks, normal island arc volcanic rocks and other high Sr/Y rocks. The figure is modified after Li et al. [94]. Data sources are after compilation by Li et al. [94] and Bindeman et al. [104].
Figure 10. Magmatic δ18O values of the DGS adakitic rocks and LYRB adakitic rocks, normal island arc volcanic rocks and other high Sr/Y rocks. The figure is modified after Li et al. [94]. Data sources are after compilation by Li et al. [94] and Bindeman et al. [104].
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Figure 11. Transitional elements diagram for the DGS adakites. Bulk continental crust compositions are after Rudnick and Gao [99].
Figure 11. Transitional elements diagram for the DGS adakites. Bulk continental crust compositions are after Rudnick and Gao [99].
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Zhang, Z.; Jiang, X.; Guo, J.; Jiang, K. Geochronology and Geochemistry of Cretaceous Adakitic Rocks of the Dongguashan Cu Deposit in the Lower Yangtze River Belt: Insights into Petrogenesis and Mineralization. Minerals 2023, 13, 953. https://doi.org/10.3390/min13070953

AMA Style

Zhang Z, Jiang X, Guo J, Jiang K. Geochronology and Geochemistry of Cretaceous Adakitic Rocks of the Dongguashan Cu Deposit in the Lower Yangtze River Belt: Insights into Petrogenesis and Mineralization. Minerals. 2023; 13(7):953. https://doi.org/10.3390/min13070953

Chicago/Turabian Style

Zhang, Zanzan, Xiaoyan Jiang, Jia Guo, and Kenan Jiang. 2023. "Geochronology and Geochemistry of Cretaceous Adakitic Rocks of the Dongguashan Cu Deposit in the Lower Yangtze River Belt: Insights into Petrogenesis and Mineralization" Minerals 13, no. 7: 953. https://doi.org/10.3390/min13070953

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