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Decoupling of Sr-Nd Isotopic Composition Induced by Potassic Alteration in the Shapinggou Porphyry Mo Deposit of the Qinling–Dabie Orogenic Belt, China

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Decoupling of Sr-Nd Isotopic Composition Induced by Potassic Alteration in the Shapinggou Porphyry Mo Deposit of the Qinling–Dabie Orogenic Belt, China minerals Article Decoupling of Sr-Nd Isotopic Composition Induced by Potassic Alteration in the Shapinggou Porphyry Mo Deposit of the Qinling–Dabie Orogenic Belt, China Jun He 1,2 , Xiaochun Xu 2,*, Zhongyang Fu 2, Yuhua An 2, Tianhu Chen 2,3, Qiaoqin Xie 2,3 and Fukun Chen 1 1 School of Earth and Space Sciences, University of Science and Technology of China, Hefei 230026, China; [email protected] (J.H.); [email protected] (F.C.) 2 School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009, China; [email protected] (Z.F.); [email protected] (Y.A.); [email protected] (T.C.); [email protected] (Q.X.) 3 Laboratory for Nanomineralogy & Environmental Material, School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009, China * Correspondence: [email protected] Abstract: In our previous study on petrogenesis of quartz syenite and granite porphyry, the host rocks of the Late Mesozoic Shapinggou Mo deposit in the Qinling–Dabie orogenic belt, we found that the initial Sr isotopic composition of the host rocks is strongly affected by the degree of K-alteration. Here, we provide further isotopic evidence of the host rocks and their minerals to investigate the geochemical behaviour of trace elements and isotopes during the alteration and to explain the phenomenon of decoupling of Sr–Nd isotopic composition. The quartz syenite and granite porphyry Citation: He, J.; Xu, X.; Fu, Z.; An, Y.; are altered by K-alteration in varying degrees and have high K2O and Rb contents and low Na2O, CaO, Chen, T.; Xie, Q.; Chen, F. Decoupling Sr, and Ba contents. Rock samples of both quartz syenite and granite porphyry have variable Rb/Sr of Sr-Nd Isotopic Composition ratios and initial 87Sr/86Sr values (even < 0.70) but contain quite homogeneous " (t) values (−12.8 Induced by Potassic Alteration in the Nd − 87 86 Shapinggou Porphyry Mo Deposit of to 14.8). Minerals from the rocks of moderate to intense K-alteration have very low initial Sr/ Sr 87 86 the Qinling–Dabie Orogenic Belt, values (even < −17), while those from the weakly altered rocks have Sr/ Sr(t) values of 0.7044 to China. Minerals 2021, 11, 910. 0.7084. The same phenomenon of the decoupling in Sr–Nd isotopic composition can be observed https://doi.org/10.3390/ from several Mo deposits within the eastern Qinling–Dabie orogenic belt. This fact suggests similar min11080910 hydrothermal features and a comparable origin for both the magmatic rocks and hydrothermal fluids in this belt. A comparison between porphyry Mo and porphyry Cu deposits shows that elements Academic Editor: and the Rb–Sr isotope system have different behaviours during the K-alteration, implying distinct Panagiotis Voudouris material sources and igneous rocks for porphyry Mo and porphyry Cu deposits, respectively. Received: 8 July 2021 Keywords: Qinling–Dabie belt; porphyry Mo deposit; K-alteration; thermal fluid; isotopic decoupling Accepted: 19 August 2021 Published: 23 August 2021 Publisher’s Note: MDPI stays neutral 1. Introduction with regard to jurisdictional claims in published maps and institutional affil- Radiogenic isotopic inhomogeneity of granitoid rocks derived by crustal anatexis is iations. commonly attributed to inhomogeneity in the source, incomplete magma mixing, assim- ilation and contamination, and incongruent melting [1,2]. However, in the last decade, Sr isotopic inhomogeneity of the ore-bearing granite porphyries, previously reported in several studies [3–7] on molybdenum (Mo) deposits within the eastern Qinling–Dabie orogenic belt, is hard to explain through the abovementioned causes, as many of them Copyright: © 2021 by the authors. 87 86 Licensee MDPI, Basel, Switzerland. have very low initial Sr/ Sr values, even lower than the recommended value for Basaltic This article is an open access article Achondrite Best Initial (0.69899) [8,9]. Yet, they have a consistent Nd isotopic composition. distributed under the terms and In contrast to the Sm–Nd isotope system hosted mainly by accessory phases (such as apatite, conditions of the Creative Commons monazite, rutile, and titanite), the Rb–Sr isotope system is controlled dominantly by major Attribution (CC BY) license (https:// rock-forming minerals (such as K-feldspar, plagioclase, biotite, and muscovite) [1,2]. This creativecommons.org/licenses/by/ may cause the Sr isotopic inhomogeneity and decoupling of Sr–Nd isotopic compositions of 4.0/). the host rocks triggered by the exogenesis (such as hydrothermal alteration or weathering). Minerals 2021, 11, 910. https://doi.org/10.3390/min11080910 https://www.mdpi.com/journal/minerals Minerals 2021, 11, 910 2 of 16 Potassic (K-) alteration, as a dominant alteration in porphyry Mo–, Cu–, and Cu– Mo deposits, has been widely recognised by previous studies [3,7,10–14]. Research on K-alteration has focused on its geologic nature, fluid source, and mineralisation [15–22]. K-alteration, mainly including K-feldspathisation and biotitisation, is strongly linked to Mo deposits [15,23]. The eastern Qinling–Dabie orogenic belt contains the largest Mo metallogenic belt (also termed as the eastern Qinling–Dabie Mo metallogenic belt) in the world and contains >8 Mt of Mo metal [7,24,25]. There are several world-class porphyry Mo deposits in this belt, in- cluding, from west to east, the Jinduicheng, Luanchuan, Yuchiling, Donggou, Qian’echong, Tangjiaping, and Shapinggou deposits [13,14,26–32]. Previous studies have shown com- mon geologic and geochemical characteristics of ore-bearing granite porphyries, such as extensive K-alteration, Sr isotopic inhomogeneity, and Nd isotopic homogeneity, in, for example, the Yuchiling, Shangfanggou, Tianmugou, Tangjiaping, and Shapinggou deposits [3,12–14,33,34]. The Shapinggou deposit is the largest in this Mo metallogenic belt and has been studied for its geology [35], geochronology and related magmatism [7,36–42], rock-forming scenarios and genesis [43], fluid inclusions [25], and potassic alteration [3,43]. Ore forma- tion occurred between 114 Ma and 111 Ma, based on ages obtained from molybdenite Re–Os dating [25,36,37,40]. It is thought that the ore formation is temporally concurrent with and spatially related to granite porphyry of ~114 Ma to ~112 Ma and quartz syenite of ~117 Ma to ~112 Ma [7,38,40], which formed in a regime of repetitive and rapid de- compression [43]. The K-alteration has been widely observed within quartz syenite and granite porphyry, especially in the granite porphyry. They exhibit distinct inhomogeneity in the initial Sr isotopic composition with anomalously low initial 87Sr/86Sr ratios [3,7]. A reasonable explanation and detailed process for this phenomenon are needed, and its relationship with the Mo mineralisation remains to be clarified. In this study, we focused on the major Mo ore-bearing intrusions, including quartz syenite, and granite porphyry, and their minerals, especially those Sr-hosting minerals, e.g., plagioclase, K-feldspar, quartz, apatite, and biotite, in the Shapinggou porphyry Mo deposit. In order to systematically characterise the nature and extent of hydrothermal alteration and evaluate the cause of anomalously low initial 87Sr/86Sr values and the nature and origin of Mo ore-forming hydrothermal fluids, geochemical and Sr–Nd isotopic data of whole rocks and minerals with various degrees of alteration are reported herein. 2. Geological Setting and the Shapinggou Porphyry Mo Deposit The Qinling–Dabie orogenic belt (Figure1) was formed by multiple collisions of the North China and South China blocks and later by continental subduction during the early Silurian and the late Triassic. Tectonically, this orogenic belt can be divided into the Qinling orogenic belt in the west and the Dabie orogenic belt in the east, adjacent to the Nanyang basin [27,29]. The Qinling orogenic belt is subdivided into four tectonic units, from north to south, and includes the southern margin of the North China Block, North Qinling (NQ), South Qinling (SQ), and the northern margin of the South China (or Yangtze) Block [27,29], which are divided by faults and sutures (the Luanchuan fault, the Shangdan suture, and the Mianlue suture). The Dabie orogenic belt is a fault-bound, wedge-shaped terrane between the North and South China blocks [44] and is subdivided into five tectonic units from north to south based on petrology; these units are the Beihuaiyang low-grade metamorphic zone, North Dabie UHP (ultrahigh pressure) zone, Central Dabie UHP zone, South Dabie UHP zone, and Susong high-pressure zone [25,45]. Minerals 2021, 11, 910 3 of 16 Minerals 2021, 11, x 3 of 16 FigureFigure 1. Sketch 1. mapSketch of the map eastern of Qinling–Dabie the eastern orogenic Qinling–Dabie belt and distribution orogenic of Mo belt deposits and [27,29]. distribution Mo deposit: of (1) Mo Xigou, (2) Huanglongpu, (3) Shijiawan, (4) Jinduicheng, (5) Balipo, (6) Dahu, (7) Mulonggou, (8) Nantai, (9) Yinjiagou, (10)deposits Yechangping,[27,29 (11)]. Zhaiwa, Mo deposit:(12) Shapoling, (1) (13) Xigou, Longme (2)ndian, Huanglongpu, (14) Leimengou, (3)(15) Shijiawan,Huangshui’an, (4) (16) Jinduicheng,Shiyaogou, (17)(5) Majuan, Balipo, (18) (6) Nannihu-Sandaozhuang, Dahu, (7) Mulonggou, (19) Shangfanggou, (8) Nantai, (20) (9) Zhuyuangou, Yinjiagou, (10)(21) Dawanggou, Yechangping, (22) Luocun, (11) Zhaiwa, (23) Saozhoupo, (24) Donggoukou, (25) Laojieling, (26) Nangou, (27) Yuchiling, (28) Banchang, (29) Zhuyuangou, (30) Donggou,(12) Shapoling, (31) Qiushuwan, (13) Longmendian, (32) Tianmushan, (14) (33) Leimengou,Xiaofan, (34) Mushan, (15) Huangshui’an, (35) Doupo, (36) (16) Qian’echong, Shiyaogou, (37) Bao’anzhai, (17) Majuan, (38)(18) Dayinjian, Nannihu-Sandaozhuang, (39) Yaochong, (40) Tangjiaping, (19) Shangfanggou, and (41) Shapinggou. (20) Zhuyuangou, (21) Dawanggou, (22) Luo- cun, (23) Saozhoupo, (24) Donggoukou, (25) Laojieling, (26) Nangou, (27) Yuchiling, (28) Banchang, Within the eastern Qinling–Dabie orogenic belt, most of the Mo ores deposited in (29) Zhuyuangou, (30)three Donggou, pulses occurring (31) Qiushuwan, at ~220 Ma, (32) ~150 Tianmushan,–140 Ma, and (33)~130–110 Xiaofan, Ma [27,29,46].
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