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Minerals 2019, 9(9), 534; https://doi.org/10.3390/min9090534

Article
Re-Os Geochronology and Sulfur Isotopes of the Lyangar W-Mo Deposit: Implications for Permian Tectonic Setting in South Tianshan Orogen, Uzbekistan
1
Laboratory of Dynamic Diagenesis and Metallogenesis, Institute of Geomechanics, Chinese Academy of Geological Sciences, Beijing 100081, China
2
Key Laboratory of Paleomagnetism and Tectonic Reconstruct, Ministry of Natural Resources, Beijing 100081, China
3
State Key Laboratory of Nuclear Resources and Environment, East China University of Technology, Nanchang 330013, China
4
Institute of Geology and Geophysics, Tashkent 100041, Uzbekistan
5
School of the Earth Sciences and Resources, China University of Geosciences (Beijing), Beijing 100029, China
*
Author to whom correspondence should be addressed.
Received: 19 July 2019 / Accepted: 30 August 2019 / Published: 1 September 2019

Abstract

:
The Lyangar W-Mo skarn deposit is located in the Nuratau area (western Uzbekistan), South Tianshan Orogen. The skarn system is distributed along the contact zone between the Aktau granitoid and the upper Paleozoic sedimentary rocks. Six molybdenite samples from the Lyangar deposit yielded a Middle Permian Re-Os isochron age of 268.0 ± 12.0 Ma (MSWD = 0.43) and a weighted mean age of 263.8 ± 1.5 Ma (MSWD = 0.22). Molybdenites have low Re contents (12.49 to 16.65 ppm), indicative of a continental crust-dominated source. The molybdenite δ34S values fall inside a narrow range (1.0 to 3.8‰; average 2.3‰), implying that the ore metals were likely derived from the granite intrusion. We concluded that the Lyangar W-Mo deposit was formed in a post-collisional setting caused by continental collision between the Tarim and Kazakhstan cratons.
Keywords:
Lyangar W-Mo deposit; molybdenite Re-Os ages; sulfur isotopes; skarn; south Tianshan orogen

1. Introduction

Tungsten (W) skarn deposits host the world’s principal W resource, many with high grades and large tonnages [1]. The largest W mineral provinces in the world include South China, Central Europe, Southeast Asia, Western Canada, and East Australia [2,3]. Located in the southern part of the Central Asia Orogenic Belt (CAOB; [4]), the South Tianshan Orogen experienced a long-lived arc-basin evolution, and finally took shape through late Paleozoic collision between the Tarim and Kazakhstan-Yili blocks [5]. The region is favorable for hydrothermal mineralization of various types, according to the petrogenic and metallogenic models of oceanic plate subduction [6,7,8,9,10] and continental collision [7,8,11,12,13,14,15,16,17]. Many mineral occurrences were discovered in the South Tianshan Orogen (e.g., Au, W, Hg, Sb, Pb, and Zn), including some world-class orogenic-type gold deposits (e.g., Muruntau, Amantaitau, Daugyztau, and Zarmitan; [18,19,20,21]), large Al deposits (Boruhskoe and Hodgaachkan), together with large W-Sn (Trudovoe) and W (Meliksu and Kumysh-Tash) deposits [22,23]. In the Uzbekistan South Tianshan Orogen, four W-(Mo) deposits have been discovered, i.e., Ingichko, Lyangar, Yahton, and Sautbay, but their ages and tectono-metallogenic setting are still unclear [24].
Molybdenite Re-Os geochronology can be used to as a powerful tool to determine the age of mineralization [25,26]. Isotopic compositions of the ore sulfides provide insights into the nature and source of the ore-forming fluids [7,27,28,29,30,31,32]. The Lyangar W-Mo deposit is representative in the Nuratau area (western Uzbekistan) of the South Tianshan Orogen. Previous studies reveal that the skarn orebody presents along the contact zone between the Aktau intrusion and the lower Paleozoic sedimentary rocks [24]. However, no reliable age data have been reported for the deposit. This paper reports new molybdenite Re-Os and S isotopic data of the Lyangar W-Mo deposit, and thereby discusses the source of ore-forming fluids, and constrains the age of mineralization and tectonic setting of the deposit.

2. Regional Geology

The Tianshan Orogen, which extends for over 2000 km from the Aral Sea to Xinjiang in NW China, constitutes an important component of the Central Asian Orogenic Belt (CAOB; Figure 1A; [3,4,33]). The Tianshan Orogen comprises three tectonic units, i.e., (from north to south) Northern Tianshan, Central Tianshan, and Southern Tianshan. These units are bounded by the North Tianshan, Nikolave Line-North Nalati, Atbashi-Inlychek-South Nalati, and the North Tarim faults, respectively (Figure 1B; [34,35,36]). The South Tianshan Orogen took shape through continental collision between the Tarim and Kazakhstan-Yili blocks [5].
The Nuratau area is located in the western part of the South Tianshan Orogen (Figure 1B), and geologically comprises mainly Meso-Neoproterozoic and Paleozoic successions [18]. Meso-Neoproterozoic rocks consist of schists, quartzite, amphibolite, sandstone, and chert. The Cambrian sequences mainly include greenschist- to amphibolite-facies metamorphosed siltstone, carbonaceous shale, chert, and minor dolomite. The unconformably-overlying Ordovician-Lower Silurian flysch sequences comprise of shale, siltstone, and sandstone interbeds. These sequences are unconformably overlain by thick Devonian-Carboniferous carbonate rocks [18], which are in turn overlain by Carboniferous molassic sequences.
These aforementioned lithostratigraphic units are intruded by late Paleozoic granitoids, such as the Aktau and Koshrabad complexes [18,37]. These granitoids occur as northwest-elongated plutons, parallel to the major regional structures (Figure 1C; [18]), suggesting a structural control on the granitoid emplacement. The available zircon U-Pb ages show that the granitoids are predominantly early Permian (ca. 287–276 Ma; [37]), coeval and possibly associated with the late Paleozoic collision between the Tarim and Kazakhstan-Yili blocks in the South Tianshan Orogen [4,18,37,38].

3. Deposit Geology

The Lyangar deposit is located in the southern Nuratau area (Figure 1). The ore hosts include mainly the Lower Devonian and Carboniferous sedimentary rocks [24] (Figure 2). The Lower Devonian Bahiltau Formation consists mainly of limestone and marble. These rocks are highly fractured and are interpreted to be favorable for the ore-fluid migration. The Carboniferous Darasay Formation comprises mainly shale and sandstone. Orebodies at Lyangar are hosted in the garnet skarn zone between Aktau intrusion and these upper Paleozoic sedimentary rocks (Figure 2).
Magmatic rocks at Lyangar include the south-western parts of the Aktau pluton, which comprises mainly biotite granite, granodiorite, and adamellite, among which the former is closely W mineralization related. The intrusive contact is commonly gentle (10–35°) and discordant (Figure 2). Alteration styles include albite, silicic, and muscovite alterations. Seltmann et al. [37] reported a SHRIMP zircon U-Pb of 276 ± 9 Ma for the Aktau granite.
Skarn alteration minerals include mainly garnet, diopside, scapolite, epidote, and wollastonite (Figure 3A). The intrusive contact zone varies from a few hundred meters to 1–1.5 km wide.
The medium-sized Lyangar skarn W-Mo deposit includes seven W-Mo prospects being discovered so far (Figure 2). Among these seven prospects, the “Main Orefield” hosts the majority of the ore reserves. Individual orebodies are 5 to 40 m thick and up to 500 m long, with depths continue to at least 400 m. The ore grades vary from 0.1% to 2% WO3 [24]. The orebodies occur as nest-like and tabular bodies (Figure 2). Ore minerals include mainly scheelite and molybdenite, and minor pyrite, pyrrhotite, chalcopyrite, arsenopyrite, sphalerite, bismuthinite, and gold. Non-metallic minerals include mainly skarn minerals (e.g., garnet and diopside), epidote, quartz, and calcite (Figure 3). Garnet from Lyangar is dominated by euhedral to subhedral and coarse-grained (generally up to 1 cm), which have oscillatory zoned form (Figure 3B,C). Diopside is subhedral to anhedral, up to 5 cm long and 0.05–2 cm wide (Figure 3C). The epidote is euhedral to subhedral with varying sizes (0.05–6 mm) (Figure 3C). Calcite is commonly coarse-grained (0.05–5 cm) (Figure 3B). Molybdenite appears as disseminated flakes or aggregates (Figure 3C) or films (Figure 3D).

4. Analytical Methods

4.1. Molybdenite Re-Os Isotope Analysis

Molybdenite were separated from the ore samples using pincers and then crushed into 40–60 mesh. After panning and filtering, inclusion-free molybdenite grains were picked under a binocular microscope. The molybdenite separates were digested using HCl and concentrated HNO3 in a sealed Carius tube and equilibrated with 185Re and 190Os spikes [39]. Osmium was distilled as OsO4 from the matrix, and rhenium was separated from the remaining solution by solvent extraction and cation exchange resin chromatography. The Re and Os contents in the samples were determined by the isotopic dilution assay method. The Re-Os isotope ratios were performed on a TJA X-series ICP-MS manufactured by the Thermo Electron Corporation, Waltham, MA, USA, at the Re-Os Laboratory of the National Research Center of Geoanalysis in Beijing, using the methods outlined by Du et al. [40]. The analytical reliability was tested using reference material GBW04435 (JDC). Re-Os isochron and weighted mean calculations were made using Isoplot [41], with a 187Re decay constant of 1.666 × 10−11/year.

4.2. Sulfur Isotopes

Molybdenite grains were extracted from the samples through conventional techniques including crushing, oscillation, heavy liquid, and magnetic separation, and were selected by handpicking under a binocular microscope (purity > 99%). Sulfur isotopes analyses were conducted on a MAT253 continuous flow isotope ratio mass spectrometer (Thermo Electron Corporation, Waltham, MA, USA) coupled to an elemental analyzer (EA-IRMS, Thermo Electron Corporation, Waltham, MA, USA) at the State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences. The powders of molybdenite were packed in tinfoil, and converted into purified SO2 for sulfur isotopic analysis under a vacuum and high temperature (~1000 °C) conditions. Sulfur isotope compositions are expressed using δ34S value in per mil (‰) relative to the Vienna Canyon Diablo Troilite standard (V-CDT), with an analytical precision of ±0.2‰. Sulfur isotopic data are calibrated by international standard samples GBW-4414 (Ag2S, δ34S = −0.07‰) and GBW-4415 (δ34S = 22.15‰).

5. Results

5.1. Molybdenite Re-Os Isotopes

The analytical data on Re-Os isotope of six molybdenite samples from Lyangar are presented in Table 1 and illustrated in Figure 4. The molybdenite 187Re and 187Os contents are 12.49–16.65 ppm and 34.36–46.11 ppb, respectively. These samples yielded individual Re-Os isotope model ages from 262.2 ± 3.8 Ma to 264.8 ± 3.6 Ma (2σ). This gave an isochron age of 268.0 ± 12.0 Ma (MSWD = 0.43) and an initial 187Os/188Os of −0.5 ± 1.8 (Figure 4A). The extremely low initial 187Os/188Os ratios (near zero), indicate that the Re-Os ages are reliable and can represent the crystallization age of molybdenite. The weighted mean age for all the molybdenite samples is 263.8 ± 1.5 Ma (MSWD = 0.22; Figure 4B)

5.2. Sulfur Isotopic Compositions

Sulfur isotope compositions of molybdenite for the Lyangar ores are presented in Table 2. The molybdenite δ34S values fall into a narrow range (1.0–3.8‰, average 2.3‰). This isotopic homogeneity of the Lyangar molybdenite suggests a single reservoir or common source for the ore-forming fluids.

6. Discussion

6.1. Timing of Mineralization

The Aktau granite, main W ore-related intrusive rocks at Lyangar, was SHRIMP zircon U-Pb dated to be 276 ± 9 Ma [37]. This age is largely coeval (within error) with the molybdenite Re-Os isochron age (268.0 ± 12.0 Ma). Thus, the Aktau granite and the W mineralization have a close temporal and probably genetic link.

6.2. Source of Ore-Forming Components

Contents of Re in molybdenite from various hydrothermal deposits show a large variation from ppm to percent, and can be used to determine the ore-forming material source and tectonic setting [25,42,43]. In general, the molybdenites from the mantle and/or subducted oceanic crust generally contain higher Re contents (n × 102 ppm) than those from the continental crustal rocks (nn × 10 ppm; [25,42,44,45,46]). The Re contents in molybdenite from Lyangar vary from 12.49 to 16.65 ppm (average 14.31 ppm; Table 1), which are comparable to those of many W-Mo skarn deposits in NW China, such as Xiaoliugou (6.23–14.87 ppm; [47]) and Xiaobaishitou (40.33−64.67 ppm; [3]) in which the ore-forming materials were inferred to be derived mainly from the continental crust.
The molybdenite δ34S values of the Lyangar ores range from 1.0‰ to 3.8‰, similar to those of the average granitic rocks (ca. −2‰ to 8‰; [48]), indicating a magmatic sulfur source. Considering the close relationships between the granitic rocks and the Lyangar W-Mo deposit (Figure 2 and Figure 3), the Aktau granitic rocks were likely a significant source of ore metals in the development of the Lyangar orebodies.

6.3. Mineralization and Tectonic Setting

In the late Paleozoic, many types of metallic deposits were formed in the South Tianshan Orogen and were associated with intensive granitic magmatism [49,50,51]. In Uzbekistan, Mörelli et al. [52] obtained arsenopyrite Re-Os isochron age of 287.5 ± 1.7 Ma for the Muruntan orogenic gold deposit, and Goldfarb et al. [21] reported pyrite Re-Os age of 286 Ma for the Zarmitan orogenic gold deposit. In NW China, Zhang et al. [35] reported pyrite Re-Os isochron ages of 323.9 ± 4.8 Ma and 282 ± 12 Ma for the Sawayaerdun orogenic gold deposit, Zhao et al. [53] obtained quartz Rb-Sr isochron age of 258 ± 15 Ma for the Bulong Ba-Au deposit, and Li and Chen [54] reported quartz Rb-Sr isochron age of 265 ± 12 Ma for the Huoshibulake Mississippi Valley Type (MVT) Pb-Zn deposit. The molybdenite Re-Os isochron age (268 ± 12 Ma) from Lyangar is similar to these Au-Pb-Zn mineralization ages, and suggests that late Paleozoic time was a significant metallogenic period in South Tianshan Orogen.
Tectonic setting of the Early to Middle Permian South Tianshan Orogen is still debated to be syn-/post-collisional [5,37,55,56,57,58]) or continental arc setting before the final South Tianshan Ocean closure [59,60,61]. The 298–260 Ma post-collisional granitoids have been found in the South Tianshan Orogen, which are mainly characterized by A-type, calc-alkaline I-type, and minor S-type rocks [5,37], as exemplified by the granitoids at North Tamdinsky (287.5–293.3 Ma; [62]), Aktau (276 ± 9 Ma; [37]), Altyntau (281 ± 2 Ma; [37]), Dzhizlan-Chatti (293 ± 5 Ma; [37]), Temirkobuk (287 ± 2 Ma; [37]), Gatcha (281 ± 1 Ma; [37]), and Koshrabad (286 ± 2 Ma; [37]) in Uzbekistan, Karavshuy (259–267 Ma; [63]), Inylchek (268 ± 8 Ma; [64]), Uchkoshkon (273–279 Ma; [57,64]), Djangart (296 Ma; [58,65]), Mudrym (281 ± 2 Ma; [57]), and Kok-Kiya (281 ± 3 Ma; [57]) in Kyrgyzstan, and Heiyingshan (285 ± 4 Ma; [66]) and Baleigong (273–291 Ma; [67,68,69]) in China. Gao et al. [5] reported a zircon U-Pb age of 285 ± 2 Ma for an undeformed granite dyke crosscutting high-pressure (HP) metamorphic units in the Chinese South Tianshan Orogen, which constrains the upper time limit for the HP metamorphism. It is interpreted that these late Paleozoic (298–260 Ma) deposits and coeval magmatic rocks (Figure 1), were both formed in the post-collisional extension and thinning caused by the Tarim-Kazakhstan continent-continent collision (Figure 5).
The Lyangar W-Mo deposit is temporally and genetically related to the Aktau intrusive rocks. Geochemical characteristics of the Aktau granite at Lyangar suggest that it belongs to high-K calc-alkaline I-type rocks occurred in a post-collisional environment [70]. H-O-C isotopic data indicate that the ore-forming fluids mainly drive from magmatic-hydrothermal fluids, and the limestone is at least a source of ore metals [70]. Furthermore, our Re-Os and S isotope data also support the interpretation that the Lyangar deposit is magmatic hydrothermal associated with the emplacement of the Aktau granite.
The Molybdenite from the Lyangar W-Mo shows mineralization ages of 268.0 ± 12.0 Ma. Similar mineralization events have been reported in South Tianshan Orogen, including orogenic gold deposit, MVT deposit (Figure 1B) [21,35,52,53,54], related to post-collisional tectonism. Integrating ore geology, geochronology and S isotope data, we conclude that the Lyangar W-Mo deposit was a skarn-type system formed in the Tarim-Kazakhstan collision setting as illustrated in Figure 5. During the post-collision between the Tarim and Kazakhstan cratons in Permian, lithospheric extension and thinning resulted in the partial melting of the continental curst, and generated widespread development of granitic magmatism [56,71,72]. These magmatic fluids migrated upward and provided numerous ore-forming metals such as W, Mo. Hydrothermal fluids could fill and replace the metals from the upper Paleozoic sedimentary rocks (e.g., limestone), and then formed Lyangar W-Mo orebodies.

7. Concluding Remarks

(1) Molybdenite grains from the Lyangar W-Mo deposit are characterized by low Re contents (12.49–16.65 ppm), and the δ34S values cluster between 1.0‰ and 3.8‰. This suggests that the ore-metals dominantly originated from the continental crust, probably from the Aktau granitic magmatism.
(2) Molybdenite from the Lyangar W-Mo deposit yielded a Permian Re-Os isochron age of 268.0 ± 12.0 Ma, which represents the timing of the Lyangar W-Mo mineralization.
(3) The Lyangar W-Mo mineralization likely occurred in a post-collisional setting related to the late Paleozoic Tarim-Kazakhstan collision.

Author Contributions

Field sampling and data analysis, Z.-J.Z., Z.-L.C., B.N., S.S., F.-B.H., Z.-X.W., W.-F.X., X.-Q.Y.; Original draft preparation, Z.-J.Z., Z.-L.C.; Manuscript discussion, Z.-J.Z., Z.-L.C., W.-F.X., B.N.; Manuscript review and editing, Z.-J.Z., Z.-L.C.

Funding

This work was jointly granted by the National Natural Science Foundation of China (Nos. 41772085, U1403292, 41402061), National Key Technology Research and Development Program of the Ministry of Science and Technology of China (2018YFC0604005, 2015BAB05B04), and the China Geological Survey Bureau (1212011120335, 12120114006201).

Acknowledgments

We thank Jing Gu for the sulfur isotope experiment, and Chao Li for his assistance with molybdenite Re-Os dating.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. (A) Schematic tectonic map of Asia, showing the location of South Tianshan Orogen (modified after [4]). (B) Tectonic map of the South Tianshan Orogen and adjacent regions (modified after [35]). (C) Geologic map of the Nuratau area (modified after [18]). Abbreviations: NCC = North China Craton.
Figure 1. (A) Schematic tectonic map of Asia, showing the location of South Tianshan Orogen (modified after [4]). (B) Tectonic map of the South Tianshan Orogen and adjacent regions (modified after [35]). (C) Geologic map of the Nuratau area (modified after [18]). Abbreviations: NCC = North China Craton.
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Figure 2. Simplified geologic map of the Lyangar W-Mo deposit (modified after [24]).
Figure 2. Simplified geologic map of the Lyangar W-Mo deposit (modified after [24]).
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Figure 3. Field and thin section photos of the Lyangar W-Mo deposit. (A) skarn in the contacts to limestone; (B) coarse-grained, euhedral-subhedral garnet; (C) coarse-grained epidote and molybdenite aggregates; and (D) molybdenite displaying flakes or films texture. Abbreviations: Cal = calcite; Mo = molybdenite; Grt = garnet; Di = Diopside; Ep = epidote.
Figure 3. Field and thin section photos of the Lyangar W-Mo deposit. (A) skarn in the contacts to limestone; (B) coarse-grained, euhedral-subhedral garnet; (C) coarse-grained epidote and molybdenite aggregates; and (D) molybdenite displaying flakes or films texture. Abbreviations: Cal = calcite; Mo = molybdenite; Grt = garnet; Di = Diopside; Ep = epidote.
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Figure 4. Isochron (A) and weighted mean ages (B) of molybdenite from the Lyangar W-Mo deposit.
Figure 4. Isochron (A) and weighted mean ages (B) of molybdenite from the Lyangar W-Mo deposit.
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Figure 5. Schematic diagram for the tectono-magmatic-metallogenic setting in Permian South Tianshan Orogen (Base map modified after [3]).
Figure 5. Schematic diagram for the tectono-magmatic-metallogenic setting in Permian South Tianshan Orogen (Base map modified after [3]).
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Table 1. Molybdenite Re-Os isotopic data for the Lyangar W-Mo deposit.
Table 1. Molybdenite Re-Os isotopic data for the Lyangar W-Mo deposit.
SampleWeight
(g)
Re
(ppm)
Common Os
(ppb)
187Re
(ppm)
187Os
(ppb)
Model Age
(Ma)
Measured2σMeasured2σMeasured2σMeasured2σAge2σ
L1-50.02013.960.100.180.028.770.0638.790.24264.83.6
L1-60.01113.300.090.150.068.360.0636.850.25264.13.6
L1-70.01214.960.1200.040.059.400.0841.390.30263.73.8
L1-80.01116.650.130.040.0410.470.0846.110.32263.83.7
L1-90.01112.490.100.060.037.850.0634.360.25262.23.8
L1-120.01514.480.120.150.039.100.0840.160.29264.33.9
Table 2. The δ34S values of molybdenite from the Lyangar ores.
Table 2. The δ34S values of molybdenite from the Lyangar ores.
No.Sample No.δ34SVCDT
1L1-53.8
2L1-61.0
3L1-72.1
4L1-81.6
5L1-91.9
6L1-103.8
7L1-111.2
8L1-122.6
Average2.3 ± 1.1

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