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Article

The Age of Hubi Copper (Cobalt) Ore Mineralization in the Zhongtiao Mountain Area, Southern Margin of the Trans-North China Orogen: New Constraints from U-Pb Dating of Rutile and Monazite

by
Mengqi Wang
*,
Jingwen Mao
*,
Huishou Ye
and
Hongying Li
Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral and Resources, Chinese Academy of Geological Sciences, Beijing 100037, China
*
Authors to whom correspondence should be addressed.
Minerals 2022, 12(3), 288; https://doi.org/10.3390/min12030288
Submission received: 20 January 2022 / Revised: 22 February 2022 / Accepted: 23 February 2022 / Published: 25 February 2022
(This article belongs to the Special Issue Rare Metal Ore Formations and Rare Metal Metallogeny)
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Abstract

:
The Hubi copper (cobalt) ore district, one of the largest typical examples of the sediment-hosted stratiform type in the Zhongtiao Mountain area, is located on the southern margin of the Trans-North China Orogen within the North China Craton (NCC) and has a copper reserve of 0.79 Mt. Mineralization is mainly hosted by the Zhongtiao Group, a sequence of metasedimentary rocks deposited from ~2168 Ma to ~2059 Ma. Subsequently, a collisional orogeny (Trans-North China Orogen) occurred at ~1.85 Ga. The absolute age of mineralization has not been well constrained due to the lack of suitable minerals for dating. Rutile and monazite are common accessory minerals and are intergrown with Cu mineralization in Cu-bearing veins in the Hubi-type copper (cobalt) deposits. This study presents the first new LA-ICP-MS U-Pb ages of hydrothermal rutile and monazite for the Tongmugou and Laobaotan copper (cobalt) deposits in the ore district, which yield lower intercept rutile U-Pb ages of 1815 ± 30 Ma (Mean Squared Weighted Deviation, MSWD = 5.0) and 1858 ± 27 Ma (MSWD = 5.2) for Tongmugou and 1876 ± 30 Ma (MSWD = 5.9) for Laobaotan. Monazite crystals separated from Cu-bearing carbonate veins within the orebody of Tongmugou yield a weighted mean 207Pb/206Pb age of 1856 ± 14 Ma (MSWD = 1.9), which is close to that of rutile within error. Mineralogical observations and geochemical characteristics suggest that both monazite and rutile crystallized in the hydrothermal fluid system and are closely related to Cu sulfide mineralization. Therefore, their nearly identical U-Pb isotope age of ca. 1850 Ma directly reflects the timing of metamorphic hydrothermal Cu mineralization. This age is indistinguishable from that of metamorphism during the collisional orogeny (Trans-North China Orogen) that led to the final amalgamation of the Eastern and Western Blocks. According to previous studies, the primary sedimentary mineralization of the Hubi-type copper (cobalt) deposits was synchronous with the deposition of the Zhongtiao Group. From the perspective of mineralization age, both the Congolese–Zambian Copperbelt and the Hubi copper (cobalt) ore district experienced early preorogenic sedimentary diagenetic mineralization and late metamorphic hydrothermal mineralization related to orogenesis, and the Hubi-type copper (cobalt) deposits may also be some of the oldest sediment-hosted stratiform-type deposits in the world. Moreover, this metamorphic hydrothermal Cu mineralization spread throughout the Zhongtiao Mountain area.

1. Introduction

The Zhongtiao Mountain area is located in the southern part of the North China Craton (NCC) and has undergone a long period of geological evolution (Figure 1b). In this process, different types of deposits have developed, with proven copper reserves of more than 3.9 million tons, accompanied by ore-forming elements such as cobalt, gold, molybdenum and silver [1,2]. Therefore, the Zhongtiao Mountain area is also one of the most important copper concentration areas in China.
Within this area, the largest and most attractive deposits are the Tongkuangyu porphyry copper deposit and the Hubi copper (cobalt) ore district, which contains several medium- to large-sized copper (cobalt) deposits in metasedimentary rocks, such as the Tongmugou, Laobaotan, Bizigou and Nanhegou copper (cobalt) deposits (Figure 1a) usually defined as Hubi-type copper (cobalt) deposits in China. According to previous studies and compared with typical strata-controlled deposits that have Cu-Co as the main ore type, the Hubi-type copper (cobalt) deposits reflect a mineralization process that is similar to that of the sediment-hosted stratiform copper-cobalt deposits (SSCs) in the Central African Copperbelt [2].
Sediment-hosted stratiform copper or sedimentary copper deposits are important sources of copper, cobalt and silver [3,4], contributing ~15% of the world’s copper resources [5]. Representative superlarge SSC deposits include the Siberian Paleoproterozoic Udokan copper deposit [6,7], the Central African Neoproterozoic Copperbelt [4] and the European Permian Kupferschiefer copper deposit [8]. The low–medium-temperature, oxidizing Cu-rich brine in the basin migrates to the redox interface in the sedimentary layer to cause metal sulfide precipitation, which is a widely accepted genetic model of sediment-hosted stratiform Cu deposits [9,10,11]. Reliable ages of mineralization for sediment-hosted stratiform Cu deposits are essential for a better understanding of copper deposition and their relationship with regional geological processes such as metamorphism and deformation. However, the age of mineralization is also the most controversial issue and has directly generated academic debates about syndiagenetic [4,10,12,13] or synorogenic timing [14,15,16,17,18], as well as evolution into multistage mineralization [10,11,19,20,21,22,23,24,25].
The age of the Hubi copper (cobalt) district in the Zhongtiao Mountain mining district has not been well constrained. On the one hand, some of the research results are from the older literature, when the test methods were not accurate enough; on the other hand, the age is debatable partly because of the lack of suitable dating minerals. It was suggested that the Hubi-type copper (cobalt) deposits formed at 1830 ± 34 Ma based on U-Pb dating of uraninite and brannerite in disseminated and vein ores of the Hubi-type copper (cobalt) deposits [26]. Moreover, uranium mineralization and copper mineralization have an obvious spatial relationship [26]. The authors of [27] reported the Re-Os age of molybdenite associated with a small amount of Cu-bearing sulfide within molybdenite veins along the fault from the Hubi-type copper (cobalt) deposits and obtained the model age of 1901 ± 24 Ma, which was close to the timing of copper mineralization. Recently, chalcopyrite in Cu-bearing quartz veins of the Hubi-type copper (cobalt) deposits yielded a mean model Re-Os age of 1952 ± 39 Ma [28].
Rutile and monazite are common accessory minerals in a wide range of sedimentary, magmatic and metamorphic rocks, and they are considered reliable dating minerals in some hydrothermal ore deposits due to the trace amounts of U in their structure and have a high closure temperature (usually >500 °C) for U-Pb diffusion [29,30,31,32,33]. As a result, these minerals have great potential as U-Pb geochronometers to solve geological issues; U–Pb analysis has been successfully applied in the dating of mineral deposits where rutile and monazite are associated with ore minerals [34,35,36,37,38,39].
In this study, we carried out laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb analysis for dating rutile and monazite to determine the mineralization age of the Hubi-type copper (cobalt) deposits. This is the first time that the method has been employed for dating the Hubi-type copper (cobalt) deposits. These new age data also provide constraints on the regional metallogeny and tectonic background.

2. Geological Background

2.1. Regional Geology

The North China Craton is composed of several microcontinents, but its tectonic evolution is controversial [40,41,42,43,44,45]. In recent years, an increasing number of scholars believe that the North China Craton was formed by the collision of the Eastern and Western Blocks along the Trans-North China Orogen [40,41,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61]. The Zhongtiao Mountain region is located on the southern margin of the Trans-North China Orogen [40,41], and it is one of the hot areas in research on the Precambrian geology of the North China Craton. According to much research on metamorphic petrology, geochronology, geochemistry and tectonic geology in the Trans-North China Orogen, more geological evidence indicates that the collisional orogeny occurred at approximately 1.85 Ga [40,46,53,57,58,59,62,63,64,65].
The relatively complete Precambrian rock tectonic units exposed in the Zhongtiao Mountain region, from bottom to top, can be divided into the Neoarchean Sushui Complex, Palaeoproterozoic Jiangxian Group, Zhongtiao Group, Danshanshi Group and Mesoproterozoic Xiyanghe Group (Figure 1a) [66,67,68,69]. These rock units generally experienced various degrees of metamorphism except for the Xiyanghe Group.
The Sushui Complex is the oldest rock unit and mainly consists of a series of tonalite-trondhjemite-granodiorite (TTG) gneisses (2.70~2.55 Ga) and metamorphic supercrustal rocks [70,71]. It shows unconformity contacts between the Jiangxian Group and Zhongtiao Group.
The Jiangxian Group contains important ore-bearing strata of the Tongkuangyu porphyry deposit, mainly distributed north of Zhongtiao Mountain. This group can be divided into the Henglingguan Subgroup and Tongkuangyu Subgroup. The Henglingguan Subgroup is a set of metamorphic clastic sedimentary rocks and schists (killas) formed by metamorphism from carbonaceous argillaceous to semi-argillaceous rocks. The Tongkuangyu Subgroup is composed of a set of shallow marine facies clastic rocks and mudstone sedimentary formations in the lower part and a set of marine facies volcanic sedimentary rocks in the upper part. According to previous studies, the formation age of the Jiangxian Group is ca. 2.2 to ~2.1 Ga [2,66,67,72,73,74,75,76].
The Zhongtiao Group crops out widely on the eastern flank of the Shangyupo anticline, which also contains significant ore-bearing strata of the Hubi-type copper (cobalt) deposits. The Zhongtiao Group unconformably covers the Sushui Complex and the Jiangxian Group and comprises a sequence of low-grade metamorphic rock series of sandy-argillaceous and carbonate rocks affected by regional metamorphism, such as quartzite, schist, slate and marble. The total thickness is approximately 6000 m. There have been several studies on the deposition time of the Zhongtiao Group. The result of single-grain zircon U-Pb dating of the metatuff is 2059 ± 5 Ma [68]. The authors of [77] determined that the three youngest detrital zircons defined a weighted mean age of 2168 ± 5 Ma through LA-ICP-MS dating from the quartz schist of the Zhongtiao Group, limiting the maximum sedimentary age. The authors of [76] reported a secondary ionization mass spectrometry (SIMS) zircon U-Pb age of ca. 2168 Ma for the plagioclase amphibolite interlayer of the Zhongtiao Group. In summary, the Zhongtiao Group was deposited from ca. 2168 Ma to 2059 Ma.
The Danshanshi Group is unconformably in contact with the Lower Zhongtiao Group and consists of metaconglomerate and quartzite, which are considered to be molasse formations. The maximum depositional age is ca. 1848 Ma based on detrital zircon U-Pb dating [75].
The Xiyanghe Group, also named the Xiong’er Group in western Henan Province south of the study region, is mainly distributed in the north and south of Zhongtiao Mountain and comprises thick unmetamorphosed andesites that unconformably cover Paleoproterozoic strata. The authors of [78] considered that the formation age of the Xiyanghe Group was approximately 1800~1750 Ma through sensitive high-resolution ion microprobe (SHRIMP) zircon U-Pb dating of volcanic rocks.
The Zhongtiao Mountain region can be divided into three important tectonic movements which affect the deformation and metamorphism: Jiangxian movement (D1), Zhongtiao movement I (D2), Zhongtiao movement II (D3) [67]. D1 led to the unconformity contact between the Jiangxian Group and Zhongtiao Group, mainly in the form of tensile structures. The unconformity contact between the Zhongtiao Group and Danshanshi Group was caused by D2. It is characterized by isoclinal fold and stretching lineation, and the deformation of the Bizigou Formation in the Zhongtiao Group is characterized by strong foliation. D3 resulted in the formation of a broad fold in this region, such as the Shangyupo-Hujiayu anticline [67]. The metamorphism age of D1 is considered to be ca. 2100 Ma, while D2 occurred at ca. 1900 Ma and D3 occurred at ca. 1850 Ma, representing the peak metamorphism age [52,67]. The Zhongtiao Mountain area was generally affected by regional metamorphism of the greenschist facies to amphibolite facies, and the metamorphic temperature spans approximately 350–600 °C [67,68,69].

2.2. Deposit Geology

The Hubi copper (cobalt) ore district is located on the southeast wing of the Shangyupo-Hujiayu anticline and consists of a series of adjacent copper deposits with similar geological characteristics, including the Tongmugou, Laobaotan, Bizigou and Nanhegou copper deposits (Figure 1a). The copper reserve of the Hubi copper (cobalt) ore district is 0.79 Mt, with an average grade of 1.21%. The Tongmugou and Laobaotan copper deposits are controlled by the Shangyupo anticline structure, so they are distributed in the southeastern part of the anticline in the NNE direction (Figure 1a) and are representative of the Hubi-type copper (cobalt) deposits. The main economic metal in the two deposits is copper (average grade of 1.08% in Tongmugou and 1.13% in Laobaotan), with by-products of cobalt, molybdenum, gold and silver. The main orebodies are all hosted in the Bizigou Formation but have been affected by post-multiple periods and various structural overprints, and the combinations of surrounding rocks are slightly different.
Regionally, the exposed stratigraphic sequence includes the Jiepailiang, Longyu, Yuyuanxia, Bizigou and Yujiashan Formations (Figure 1a). The Jiepailiang Formation is a set of quartzites, while the lithology of the Longyu Formation is mainly calcareous mica schist. The Bizigou Formation hosts the main ore-bearing strata, which are carbonaceous slate and schist. The upper and lower parts of the strata conformably contact with the marble of the Yujiashan and Yuyuanxia Formations, respectively.

2.3. Tongmugou Copper Deposit

In the Tongmugou copper deposit, the quartzite of the Jiepailiang Formation is regarded as the core of the Tongmugou anticline. In the east limb, the Longyu, Yuyuanxia, Bizigou and Yujiashan Formations appear successively, among which the Longyu and Yuyuanxia Formations are very thin and even partially unexposed (Figure 2a). The lithological composition of the Bizigou Formation in the mining area can be divided into three types: silicic albitite, carbonaceous schist and dolomitic marble (Figure 2a). The orebodies are hosted in the Bizigou Formation on the west limb (Figure 2a). The Tongmugou deposit is composed of many lenticular orebodies of different sizes arranged in parallel, among which the No. 3 orebody is the main one. The reserves of the No. 3 orebody account for more than 70% of the total reserve of the ore district. The No. 3 orebody is approximately 1000 m long, and its thickness varies to a certain extent. It gradually thickens from south to north approximately tens of meters, and the local orebody is lenticular and stratiform with a maximum grade of 13.6% and an average grade of 1.17% and partly controlled by three NNE-trending reverse faults (Figure 2b). Its dip is NW–SE with a dip angle of approximately 40°.
The orebodies are mainly hosted in silicic albitite and dolomitic marble (Figure 2b), and carbonaceous schist is often mineralized by sulfide parallel to foliation, but this mineralization is obviously weaker than the other two. Two different mineralization stages have been recognized: (1) The early mineralization stage (stage I) is characterized by veinlet and disseminated sulfides. The main host rocks of stage I are carbonaceous schist and silicic albitite, and mineralized veins (usually <0.5 cm) are parallel to the foliation (Figure 3a,b,e). The ore minerals are mainly pyrite and pyrrhotite with small amounts of chalcopyrite and cobaltite. Gangue minerals are mostly quartz, dolomite, biotite, graphite and sericite (Figure 4). These minerals can be seen in hand specimens with certain deformation and stretching and exhibit quartz nodules associated with sulfides (Figure 3a). In addition, disseminated sulfides intergrown with quartz grains are observed under the microscope to be directional, elongated and deformed, suggesting that they were probably emplaced during diagenesis. This stage does not constitute the main mineralization stage but may be a source bed that provided a material basis for later mineralization [79]. (2) The late mineralization stage (stage II) is dominated by thick (usually several centimeters to tens of centimeters) sulfide-bearing veins. The ore veins hosted in silicic albitite and dolomitic marble often cross-cut the stratigraphy of the host rock, and the early-stage sulfide-bearing disseminated and ore veins are controlled by extensional tectonic fractures (Figure 3c,d). In this stage, the sulfide content and grade increased, and the grain size of ore and gangue minerals became coarser than that in stage I. The boundaries between the veins and host rock in this stage are continuous and straight, and stage II can be divided into two substages according to the mineral assemblage (Figure 3d,f). Stage II-a is marked by sulfide-quartz (dolomite) veins, and the vein minerals consist of chalcopyrite, pyrite, pyrrhotite and quartz with minor sphalerite, clausthalite, cubanite, siegenite, dolomite and rutile (Figure 3c and Figure 4). The coarser sulfides are disseminated and veined along the fissures of quartz (dolomite) veins, which cut through veins from stage I and foliation of the host rock (Figure 3c,d). Stage II-b features sulfide-carbonate veins (usually the thickest veins), and its main mineral assemblage is calcite, ferrodolomite, chalcopyrite, pyrite, pyrrhotite and bornite with minor rutile, apatite and monazite (Figure 3d,h,i and Figure 4). In this substage, vein-like mineralization is significant, in which subhedral to anhedral sulfides are massive and disseminated, filling the carbonate veins (Figure 3i).
Previous study shows that the ore-forming fluids of stage I are characterized by high salinity (22–40 wt.% NaCl equiv.) and a moderate temperature (120–280 °C). Meanwhile, stage II is characterized by CO2 enrichment, high salinity and a high temperature and underwent significant unmixing at a temperature interval of 240–480 °C, and compositions of the ore-forming fluids in stage II are interpreted to be metamorphic hydrothermal solutions [80].

2.4. Laobaotan Copper Deposit

In the Laobaotan copper deposit, the outcropping strata are mainly the Zhongtiao Group, which can be divided into quartzite of the Jiepailiang Formation, calcareous mica schist of the Longyu Formation, dolomite marble of the Yuyuanxia Formation, carbonaceous schist and silicic marble of the Bizigou Formation and gray marble of the Yujiashan Formation from bottom to top. The structure of the mining area is the Laobaotan anticline, which is a secondary structure in the southeastern Shangyupo-Hujiayu anticline. The core of the Laobaotan anticline is the Jiepailiang and Longyu Formations, but some areas are barely exposed and even disappear. The flanks of the anticline are mainly composed of different lithologic sections of the Bizigou Formation. The bedded orebodies mainly occur in the Bizigou Formation, and the local mineralization is at the contact between the Bizigou Formation and the lower part of the Yujiashan Formation (Figure 5a). The No. 7 orebody is the main industrial mining orebody. It is approximately 400 m long and can extend to 500 m. The thickness varies greatly (0.7–18.6 m) with an average value of 1.9 m. The orebody formed in layers, lenses and “crescent shapes” on the plane (Figure 5b). Due to the influence of tectonic activity, the occurrence of the orebody is unstable; it trends SE–NW, and the dip angle is approximately 30°. The copper grade changes obviously, with the highest grade of 21.4% and an average grade of 0.9%, and gradually becomes poor along the trend from NE to SW. Carbonaceous schist and silicic marble are considered the host rocks of the copper ore. According to the field work and previous study, the mineralization type is similar to that of Tongmugou, which can be divided into an early mineralization stage (stage I, diagenetic mineralization) and a late mineralization stage (stage II, metamorphic hydrothermal mineralization). The early diagenetic mineralization is characterized by disseminated veins on a small scale, and the main mineral assemblage is quartz + calcite + dolomite + chalcopyrite + pyrite ± pyrrhotite ± albite ± biotite ± sericite. The fine sulfide-bearing quartz veins are intermittent and nodular along the rock foliation, which may be caused by differential compaction in the diagenetic stage (Figure 6a,d). In the late metamorphic hydrothermal stage mineralization, ore-bearing veins are thick and usually 2–20 cm wide with mineral paragenesis, including quartz+ calcite + dolomite ± ankerite + chalcopyrite + pyrite ± biotite (Figure 7). Quartz and calcite often occur as coarse euhedral–subhedral crystals, and chalcopyrite and pyrite are distributed in the cleavage of calcite and quartz intersections as blocky masses (Figure 6e,f). The veins of this stage are obviously controlled by tectonic fractures, cutting through early stage I veins and carbonaceous schist foliation (Figure 6b,c). In general, stage II hydrothermal vein mineralization is also evidently stratabound and limited to the whole stratified orebody, reflecting the affinity and inheritance relationship between the late mineralization and early mineralization and indicating that the migration distance for reactivation of ore-forming elements is not long.

3. Sampling and Analytical Methods

The rutile and monazite samples were taken from the underground tunnel of the Tongmugou and Laobaotan copper deposits. All the samples analyzed in this study are sulfide-bearing albite quartz veins (stage II-a) and sulfide-bearing carbonate quartz veins (stage II-b), which consist of subhedral to anhedral rutile and monazite grains associated with sulfides from Tongmugou and Laobaotan. First, the samples were made into polished thin sections for microscopic observation to recognize the morphology, textures and paragenesis of ore-related minerals. Then, the grains of rutile and monazite were identified and located by optical microscopy and scanning electron microscopy equipped with energy-dispersive spectrometry (SEM-EDS) to obtain back-scattered electron (BSE) images. The polymorphs of target minerals were analyzed through laser micro-Raman spectroscopy using a Renishaw System-2000 equipped with a 514.50 nm Ar+ laser (20 mW incident power) and a full-area charge-coupled device detector. The chemical compositions of the selected minerals were determined by electron microprobe analysis (EPMA) using a JXA-8230. All of the above experiments were conducted at the Institute of Mineral Resources, Chinese Academy of Geological Sciences (CAGS), in Beijing.
The rutile and monazite grains were separated from the veins using heavy liquids and magnetic separation and hand-picked under a microscope. The grains were then prepared as grain mounts (separated grains embedded in epoxy) for isotopic measurements. Photomicrographs and BSE images were used to find crack-free and rutile and monazite grains without inclusions.
The U-Pb geochronology analyses of rutile were conducted by LA-ICP-MS with a Photon Machines Analyte G2 excimer laser ablation system (λ = 193 nm) and a Thermo Neptune Plus MC-ICP-MS with Jet Interface at the Mineral Exploration Research Centre Isotope Geochemistry Lab, Laurentian University, in Canada. The detailed instrument parameters used for the analyses are summarized in Table 1. Using R10 (1090 Ma) as the primary standard, R19 (489.5 Ma) and Sugluk (1719 ± 14 Ma) were interspersed as unknown samples in order to monitor the external uncertainties. During the dating, the results were 480 ± 45 Ma and 1782 ± 55 Ma for R19 and Sugluk, respectively, which are consistent with the standard reference within error, indicating the results are reliable. Analytical techniques were employed according to [31,81,82]. The U-Pb geochronology analyses of monazite were carried out by LA-ICP-MS with a RESOlution LR laser ablation system and Agilent Technologies 7700× quadrupole ICP-MS at Nanjing FocuMS Technology Co., Ltd. The 193 nm ArF excimer laser was homogenized by a beam delivery system and focused on the surface of the target minerals with an energy density of 8.0 J/cm2. Each acquisition of monazite consisted of a background of 20 s (gas blank) followed by a spot diameter of 33 μm at a repetition rate of 6 Hz for 40 s. Helium (370 mL/min) was used as a carrier gas to transport the aerosol out of the ablation cell and was mixed with argon (~1.15 L/min) through a T-connector before entering the ICP torch. During the test process, monazite standard 44069 (424.9 Ma) and glass NIST610 were used as external standards for U-Pb dating and trace element calibration, respectively. Raw data reduction was performed offline by ICPMSDataCal software [83,84]. A concordia diagram was created using Isoplot/Exsoftware [85].

4. Results

4.1. Rutile Mineralogy and Texture and Composition

Samples T343-8 (sulfide-bearing albite quartz vein, stage II-a), T25-19 (sulfide-bearing carbonate quartz vein, stage II-b) and PD776 (sulfide-bearing quartz vein, stage II) contain a certain amount of rutile intergrown with pyrite and chalcopyrite in the veins from the Tongmugou and Laobaotan deposits. Rutile usually appears as subhedral to anhedral crystals with sizes of 10–200 μm under optical microscopy and scanning electron microscopy, and some rutile crystals show distinct light and dark patchy or oscillatory zoning in BSE images (Figure 8f–h). Partial rutile crystals display relatively homogeneous characteristics; nevertheless, some inclusions are developed on the edges and inside some rutile crystals (Figure 8g).
Laser micro-Raman spectroscopy is a technique that can effectively identify mineral polymorphs of TiO2 minerals such as brookite, anatase and rutile [29]. A compilation of Raman spectra for the three texture TiO2 polymorphs is shown in Figure 9. Rutile is characterized by four peaks at wavenumbers 143, 247, 447 and 612 cm−1, which can be clearly distinguished from brookite and anatase. The peaks of brookite are mainly 153, 247, 322 and 636 cm−1, while those of anatase are mainly 144, 197, 400, 516 and 640 cm−1 [29,86,87]. Laser micro-Raman analysis was performed on the bright and dark zoning of the TiO2 mineral grains (sample PD776) from sulfide-bearing quartz-carbonate veins (stage II) in this study, and the spectrum shows that the peaks at wavenumbers of 142, 244, 447 and 612 cm−1 and 140, 236, 430 and 605 cm−1 are most similar to rutile (Figure 9).
Through EPMA, the chemical compositions of the selected rutile crystals from the sulfide-bearing quartz veins are shown in Table 2. Clearly, there are certain differences in the composition of the rutile crystals, which cause the irregular dark and light zoning of the rutile grains. The dark zones of the rutile crystals contain 96.92 to 98.84 wt% TiO2, with a mean value of 97.98 wt%, and trace elements including Nb2O5, Cr2O3, FeO, WO3 and V2O3. The content of Nb2O5 is 0.17–0.74 wt%, with a mean value of 0.32 wt%. The abundance of Cr2O3 is 0.03–0.36 wt%, with a mean value of 0.19 wt%. The abundance of FeO ranges from 0.07 to 0.52 wt%, with a mean value of 0.33 wt%. The content of WO3 varies from 0.01 to 0.20 wt%, with a mean value of 0.14 wt%. The content of V2O3 ranges from 0.42 to 1.12 wt%, with a mean value of 0.57 wt%. However, the light zoning of the rutile crystals has distinctly lower concentrations of TiO2 (91.74–96.90 wt%, an average of 93.87 wt%) and evidently higher WO3 contents (1.24–5.20 wt%, an average of 2.32 wt%). Then, the abundances of FeO (0.63–1.65 wt%, an average of 1.08 wt%) and Nb2O5 (0.15–2.66 wt%, an average of 1.25 wt%) are slightly higher than those in the dark zoning. There is little difference in the contents of Cr2O3 (0.04–0.65 wt%, an average of 0.33 wt%) and V2O3 (0.46–1.21 wt%, an average of 0.74 wt%) between the light and dark zoning of rutile. The concentrations of SiO2, Ta2O5 and ZrO2 show no significant differences, and a few of the data are below the detection limit. The authors of [88] compiled electron microprobe (EMP) compositional data of rutile from various Au deposits, and a ternary diagram was developed whereby Ti, 100* (Fe + Cr + V) and 1000* W abundances (Figure 10) were plotted to highlight rutile with anomalous W contents. Above the data plotted on the ternary diagram, it is shown that a majority of the rutile grains plot within ore or sub-ore alteration zones, indicating rutile from ore zones and sub-ore zones had elevated W contents.

4.2. Monazite Mineralogy and Composition

T29-10 is the sample of Cu-bearing carbonate veins (stages II-b), where monazite grains are found within the orebody of the Tongmugou deposit. The mineral assemblage of the mineralization vein is mainly composed of pyrite, chalcopyrite, calcite and quartz (Figure 4). Translucent, colorless monazite crystals are generally associated with stage II-b chalcopyrite in the hydrothermal veins. In the BSE images, monazite crystals are generally homogeneous with sizes of 10–50 μm, and the surfaces are smooth without inclusions, occurring as an accessory mineral associated with chalcopyrite (Figure 8i).
The chemical compositions of the selected monazite grains from the Cu-bearing carbonate veins are shown in Table 3. These partial trace element data were obtained during the LA-ICP-MS U-Pb dating process. Some indicative elements, such as Sc with contents of 0.07–0.30 ppm, Y (3675–11358 ppm), Sm (16563–27464 ppm), Eu (1257–3080 ppm), Gd (8035–13459 ppm), Th (2–378 ppm) and U (209–912 ppm), have Th/U ratios of 0–1.35. Enrichment or depletion of these elements may indicate the origin of monazite.

4.3. Age of Rutile U-Pb Dating

T343-8 and T25-9 represent typical samples of metamorphic hydrothermal mineralization (stage II) in the Tongmugou deposit, while PD776 represents a sample of the Laobaotan deposit in the same mineralization stage. The U-Pb data are listed in Table 4 and presented on Tera–Wasserburg diagrams (Figure 11). Sample T343-8 contains a population of rutile intergrown with chalcopyrite and pyrite in sulfide-bearing albite quartz veins from the Tongmugou deposit, and 36 analyses of 33 rutile grains yielded a lower intercept age of 1815 ± 30 Ma (MSWD = 5.0, N = 36) (Figure 11a). Sample T25-9 includes a number of rutile crystals intergrown with chalcopyrite, while pyrite occurs in sulfide-bearing carbonate quartz veins from the Tongmugou deposit, and 36 analyses of 32 rutile grains yielded a lower intercept age of 1858 ± 27 Ma (MSWD = 5.2, N = 36) (Figure 11b). Forty-one analyses of thirty-seven rutile grains yielded a similar lower intercept age of 1876 ± 30 Ma (MSWD = 5.9, N = 41) (Figure 11c) in sample PD776, which are intergrown with chalcopyrite and pyrite in sulfide-bearing quartz veins from the Laobaotan deposit.
Taken together, all the rutile age data indicate crystallization as a hydrothermal alteration mineral during the metamorphic hydrothermal mineralization event at ca. 1.85 Ga.

4.4. Age of Monazite U-Pb Dating

The U-Pb isotope analyses of monazite from sample T29-10 are summarized in Table 5. The monazite grains have a U content of 209–912 ppm and a Th concentration of 2–378 ppm, giving Th/U ratios of 0–1.35. Monazite grains occur as euhedral to subhedral grains, with a size of 40–120 μm. The surface of the grains is smooth and does not show light–dark patchy or oscillatory zoning in the BSE images. Ten analyses of ten monazite grains yielded a concordia age of 1846 ± 3 Ma (MSWD = 5.5, N = 10) (Figure 12a), a lower intercept age of 1841 ± 3 Ma (MSWD = 0.62, N = 10) (Figure 12b) and a weighted mean 207Pb/206Pb age of 1856 ± 14 Ma (MSWD = 1.9, N = 9) (Figure 12c), which is close to that of rutile mentioned above. The monazite age data suggest that the metamorphic hydrothermal mineralization event probably occurred at approximately 1.85 Ga.

5. Discussion

5.1. Origin of Monazite and Rutile

U-bearing accessory minerals such as zircon, monazite and rutile are widely distributed in various types of rocks and ore deposits, and their U-Pb ages can be used to constrain the ages of geological events [89]. Regardless of magmatic, hydrothermal or sedimentary origin, the identification of monazite genetic types restricts the reasonable interpretation of geological age [90,91,92]. Hydrothermal monazite can be identified from the mineral morphology, mineral paragenetic association and geochemical characteristics: e.g., the grain size is smaller than that of magmatic origin, and crystals often cluster in the form of granular geometry, are associated with sulfides and oxides and have lower contents of trace elements Th (<1%), Y, U, Sc, Sm and Gd and Th/U ratios but are enriched in light rare-earth elements such as La, Ce, Eu and Tb [93,94,95]. Monazite crystals from sample T29-10 of Cu-bearing carbonate veins are typically intergrown with hydrothermal mineral assemblages, including chalcopyrite, pyrite, carbonate, quartz and sericite with sizes of 10–50 μm (Figure 8i), indicating that the crystallization of monazite was coeval with copper deposition from the ore-forming fluid. Furthermore, partial trace element data in Table 3 display low Th (2–378 ppm), U (209–912 ppm) and Th/U (0–1.35) ratios, which also supports a typical hydrothermal origin.
Rutile is the common titanium dioxide polymorph as an accessory mineral, is widely distributed in metamorphic, igneous and sedimentary rocks and occurs in almost all deposits [29,88]. Rutile is also an “indicator” form and is preserved in many hydrothermal and metamorphic environments [88]. Although the main formula of rutile is TiO2, there are several possible element substitutions for titanium, including Al, V, Cr, Fe, Nb, Ta, Zr, Hf, Sn, Sb, W and U [96,97,98,99]. The change in the geochemical composition of the TiO2 is dependent on the polymorph, the host rock and the hydrothermal fluids, which can trace the source of rutile and characterize the chemical and physical properties of rutile during its formation [29,88,97,100,101,102,103,104,105,106,107]: e.g., rutile from metallic hydrothermal deposits is usually characterized by high abundances of W, V, Sr, Cu, Sn and Sb, which can be used to distinguish hydrothermal rutile crystals from those in igneous and metamorphic rocks [88,103,104]. In the BSE images, rutile grains in the sulfide-bearing quartz veins from the Tongmugou and Laobaotan deposits display bright–dark patchy zoning (Figure 6f–h), which may be mainly caused by high W anomalies or perhaps related to variations in Fe and Nb, based on the fact that the extremely small inclusions in the bright zones are CaWO4. The data in Table 2 show that the bright zones are more enriched in WO3 (1.24–5.20 wt%), FeO (0.63–1.65 wt%), Nb2O5 (0.15–2.66 wt%) and V2O3 (0.46–1.21) than the dark zones. The high W abundance in rutile crystals may suggest the participation of hydrothermal fluids in the process of precipitation [88]. The high concentration of V in rutile grains is a favorable indicator of a hydrothermal origin [103]. More importantly, depending on the mineral assemblage, the rutile grains in the veins occur in association with sulfides such as chalcopyrite and pyrite, indicating that rutile precipitated simultaneously with copper mineralization in the hydrothermal veins. In summary, according to mineralogical and geochemical characteristics, both monazite and rutile are believed to have crystallized in a hydrothermal fluid system and to be closely related to copper mineralization. Therefore, monazite and rutile are of hydrothermal origin, and their nearly identical U-Pb isotope age of ca. 1850 Ma directly reflects the timing of stage II metamorphic hydrothermal copper mineralization.

5.2. Geochronology of Mineralization and Comment

Geochronological studies in the Hubi copper (cobalt) ore district from the Zhongtiao Mountain area have involved a variety of methods over recent decades (Table 6), including uraninite U-Pb, whole-rock Rb-Sr, molybdenite Re-Os and chalcopyrite Re-Os (Figure 13), which offer controversial interpretations and make it difficult to understand the SSC deposit model.
The author of [26] was the first to obtain an age of 1830 ± 34 Ma by U-Pb dating of uraninite and brannerite from Zhongtiao Group strata in the Bizigou copper deposit and inferred that these U-bearing minerals are associated with mineralization, suggesting that the age represents the timing of copper mineralization. The age is consistent within error with the results from rutile and monazite in this study. On the one hand, the excessive U content may cause the U-Pb age to be lower than the actual mineralization age; on the other hand, the occurrence of the measured object is sparse, which may create confusion. Therefore, such ages may be difficult to interpret [28,105].
Subsequently, [66] conducted whole-rock Rb-Sr isochron dating for the host rocks of the Nanhegou, Laobaotan and Tongmugou copper deposits and obtained an isochron age of 1832 ± 26 Ma, which is considered the metallogenic age and close to the results in this study.
Molybdenite Re-Os dating is one of the few reliable methods to directly determine the timing of mineralization. Three previously published molybdenite Re-Os ages of 1919–1980 Ma, 1901 ± 24 Ma and 1577 ± 31 Ma represent different viewpoints and explanations [27,108]. However, the following problems have emerged: 1. Unavailable descriptions of the samples and occurrences lead to meaningless ages [108]. 2. A potential cogenetic association between molybdenum and copper within the ore-forming fluids is still ambiguous in the Hubi copper (cobalt) deposits: e.g., molybdenite occurred along faults and interlayer fracture zones [27], which makes the interpretation of molybdenite Re-Os ages uncertain; thus, they may not represent the timing of copper mineralization. 3. The gap in age results is too large, i.e., 1577 ± 31 Ma [109] to ca. 1900 Ma, and indicates a long age span (~330 myr), implying additional mineralization events. In summary, molybdenite Re-Os ages remain controversial and difficult to determine.
Recently, [28] performed Re-Os dating of chalcopyrite in Cu-bearing quartz veins (stage II) from the Nanhegou deposit in the Hubi ore district and reported an isochron age of 1932 ± 140 Ma and a mean model age of 1952 ± 39 Ma, representing the age of vein-like copper mineralization in the Nanhegou copper deposit and considered to be contemporaneous with regional metamorphism. However, the effectiveness of the chalcopyrite Re-Os system, especially closure, needs to be considered. At present, there are relatively few theoretical studies on the closure temperature of the sulfide Re-Os isotope system [110]. Due to the lack of support from experimental thermodynamic data, the closure temperature of the chalcopyrite Re-Os isotope system is still unclear, and the sealing temperature of chalcopyrite and bornite is estimated to be greater than approximately 300 °C [111,112,113]. Note that the Zhongtiao Mountain area was generally affected by regional metamorphism of the greenschist facies to amphibolite facies, and the metamorphic temperature spans approximately 350–600 °C [36,68,69,114]. In addition, the fluid inclusion data also indicate that the temperature of the ore-forming fluid (stage II) was approximately 240–480 °C [80]. Moreover, if chalcopyrite and molybdenite coexist, the 187Os in the molybdenite will enter the chalcopyrite by surface adsorption or diffusion, which also causes the chalcopyrite Re-Os isotope system to reset [115]. However, through the results of the age, old Re-Os ages of >ca. 1.9 Ga do not seem to have been reset.
The U-Pb dating of monazite and rutile can strongly resist resetting due to their high closure temperatures exceeding 700 °C and 500 °C [29,31,33,35,95,116], respectively, which are generally higher than most metamorphic and hydrothermal events; thus, this system has become a stable and reliable dating method for ore deposits. As mentioned above, it is convincingly proven that monazite and rutile are hydrothermal products from the aspects of mineral structure, paragenetic association of minerals and geochemical characteristics. Meanwhile, the LA-ICP-MS U-Pb isotope ages of hydrothermal monazite (1856 ± 14 Ma) and rutile (1858 ± 27 Ma) are consistent within error, also confirming the accuracy of the test results in this paper. Therefore, the new geochronological data directly represent the timing of the metamorphic hydrothermal copper mineralization event at ca. 1.85 Ga in the Hubi copper (cobalt) deposits.

5.3. Implication for Genesis and Metallogeny in Zhongtiao Mountain

The absolute ages of various ore deposits provide important constraints on the feasibility of genetic models and the coupling of geological events. However, in the case of sediment-hosted stratiform copper deposits, there is a general lack of ore-related minerals that are suitable for reliable isotope dating systems currently in use [17]. Among the global sediment-hosted stratiform copper deposits, the method of dating U-bearing accessory minerals has become widely accepted. A rutile U-Pb concordia age of 514 ± 2 Ma for ore-bearing veins supports post-peak metamorphic (during the Lufilian orogeny) mineralization in the Musoshi deposit, Zambian Copperbelt [34], which is also supported by monazite U-Th-Pb ages of 537.1 ± 6.6 Ma to 502.8 ± 6.3 Ma [117]. The dating of xenotime and monazite in Spar Lake red bed-associated Cu-Ag deposits indicates that mineralization occurred during late diagenesis [32]. The U-Pb ages of titanite-associated Cu from the large Udokan sediment-hosted stratiform Cu-Ag deposit in Russia imply that mineralization coincided with orogeny and metamorphism [7].
There is a broad consensus that the Trans-North China Orogen represents a collisional belt forming a suture between the Eastern and Western Blocks [40,41,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61]. Regarding the evolution of the Neoarchean to Paleoproterozoic tectonic setting of the Trans-North China Orogen, [40,46,77,118] proposed the following points. (1) At ca. 2.56 Ga, the Wutai and Lüliang Complexes, including the Zhongtiao Complex, were part of an active continental margin arc developed on the western margin of the Eastern Block, which was separated from the Western Block by an old ocean. Subsequently, the oceanic lithosphere continuously subducted under the Eastern Block at a high angle to form a series of TTG rocks. (2) At ca. 2.1 Ga, due to the continuous subduction of the Western Block beneath the Eastern Block, a back-arc basin system developed by extension behind the active continental margin magmatic arc. The Jiangxian Group and Zhongtiao Group (and other shallow metamorphosed supercrustal rocks in the Trans-North China Orogen) were formed here [41,63,77,119,120,121,122,123,124], and greenschist facies metamorphism occurred during the subsequent collisional orogeny. (3) At ca. 1.85 Ga, the continental collision of the Eastern and Western Blocks began, which resulted in significant crustal thickening, the formation of a foreland basin and the deposition of siliceous clastic rocks mainly composed of molasse formations, namely, the Danshanshi Group. Meanwhile, the ages of tectonic thermal events in the Trans-North China Orogen indicate that deformation related to crustal thickening occurred from 1843 to 1817 Ma [125], the peak and retrograde metamorphism ages were limited from 1849 to 1814 Ma [42,52,57,58,65,126] and the emplacement time of syncollisional granites was ca. 1832 Ma [118]. Therefore, the new data presented in this paper are consistent with the age of peak and retrograde metamorphism caused by the collisional orogeny at ca. 1.85 Ga.
Traditionally, two stages of mineralization are considered to have occurred in the Hubi copper (cobalt) ore district: the early sedimentary diagenetic stage and the late hydrothermal stage. Although the Hubi copper (cobalt) ore district was transformed by metamorphism and has characteristics of a metamorphic origin, the sedimentary conditions were the dominant controlling factors of mineralization in previous detailed studies [2,80,127]. Similar to the situation in the Zambian Copperbelt, an earlier pre-Lufilian mineralization event cannot be ignored based on evidence from decades of careful geological work [22,25]. Consequently, the primary sedimentary mineralization of the Hubi copper (cobalt) ore district was synchronous with the deposition of the Zhongtiao Group at ca. 2168 Ma to ca. 2059 Ma, as mentioned above, despite the absence of direct dating data. The subsequent synorogenic metamorphic hydrothermal mineralization age can be confirmed as 1850 Ma. From the perspective of mineralization age, the typical SSC-type deposits in both the Zambian Copperbelt and the Hubi copper (cobalt) ore district experienced early preorogenic sedimentary diagenetic mineralization and late metamorphic hydrothermal mineralization related to orogenesis, i.e., the Trans-North China Orogen and the Lufilian Orogen, respectively [10,17,21,22,25]. Moreover, the Hubi copper (cobalt) deposits are the oldest SSC-type deposits in China and even in the world and are equivalent to the Udokan deposit in Russia [18].
In our research, we also found an interesting metallogenic regularity; that is, all the different types of copper deposits in the Zhongtiao Mountain ore area developed during almost the same stage of metamorphic hydrothermal mineralization. A recent study by [38] confirmed that the Tongkuangyu porphyry deposit experienced the original porphyry copper mineralization at ca. 2.1 Ga, followed by metamorphic hydrothermal remobilization of copper during the orogeny at ca. 1.8 Ga through U-Pb dating of hydrothermal monazite (1832 ± 16 Ma, 1810 ± 14 Ma and 1809 ± 12 Ma) and Re-Os dating of pyrite (1807 ± 4 Ma). The authors of [36] dated the monazite of mineralization veins in the Henglingguan deposit and obtained a U-Pb age of 1863 ± 17 Ma, indicating that Cu mineralization formed during the retrograde cooling stage related to the postorogenic stage. Moreover, within the widely exposed mafic dikes that intruded into the Zhongtiao Group, abundant Cu-bearing quartz dolomite veins developed. Ar-Ar dating of muscovite associated with chalcopyrite in the veins shows a plateau age of 1857.9 ± 14.2 Ma and an isochron age of 1859.7 ± 14.5 Ma (unpublished), representing the timing of thermal events and copper mineralization. The above data indicate that the influence of metamorphic hydrothermal events is extremely large, not only transforming the original mineralization of various types of deposits in the ore area but also causing remobilization of mafic dikes with a certain concentration of copper, leading to copper precipitation in hydrothermal veins. In summary, mineralization ages of ~1.80 Ga to ~1.85 Ga are of great significance to interpret the genesis and prospecting of the deposits.

6. Conclusions

Rutile and monazite crystals are common accessory minerals that have a paragenetic association with copper mineralization in Cu-bearing quartz veins of the Tongmugou and Laobaotan deposits from the Zhongtiao Mountain area. Mineralogical and geochemical characteristics suggest that both rutile and monazite are hydrothermal in origin. LA-ICP-MS dating of the rutile grains yielded U-Pb ages of 1815 ± 30 Ma and 1858 ± 27 Ma for Tongmugou and 1876 ± 30 Ma for Laobaotan. Meanwhile, monazite from Tongmugou shows a weighted mean 207Pb/206Pb age of 1856 ± 14 Ma, which is close to that of rutile within error. The new age data directly represent the timing of metamorphic hydrothermal copper mineralization at ca. 1.85 Ga in Tongmugou and Laobaotan, also known as the Hubi copper (cobalt) ore district. These data confirm that this precise age is consistent with that of peak and retrograde metamorphism caused by a collision of the Trans-North China Orogen at ca. 1.85 Ga, and the Hubi copper (cobalt) ore district could be the oldest SSC-type deposit in China and even in the world. Moreover, this mineralization event affected a wide range in the Zhongtiao Mountain region and has great significance.

Author Contributions

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

Funding

This research was funded by the Geological Survey Project of China (DD20160124).

Data Availability Statement

The data used to support the findings of this study are available from the corresponding author upon request.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Geological map (a) of the Zhongtiao Mountain area (modified from internal material of the project “Investigation of Key Issues and Mineral Geology Mapping in Zhongtiao Mountain, Shanxi Province”, and [38]), with a simplified map (b) of the North China Craton showing the tectonic location of the study area (modified from [40]).
Figure 1. Geological map (a) of the Zhongtiao Mountain area (modified from internal material of the project “Investigation of Key Issues and Mineral Geology Mapping in Zhongtiao Mountain, Shanxi Province”, and [38]), with a simplified map (b) of the North China Craton showing the tectonic location of the study area (modified from [40]).
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Figure 2. Geological map (a) of the Tongmugou copper deposit, with a geological profile (b) of the No.16 exploration line (modified from internal material of the deposit).
Figure 2. Geological map (a) of the Tongmugou copper deposit, with a geological profile (b) of the No.16 exploration line (modified from internal material of the deposit).
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Figure 3. Occurrence of the different stages of mineralization and host rock samples in the Tongmugou deposit. (a,b) Early mineralization stage characterized by veinlet and disseminated sulfides in silicic albitite and carbonaceous schist. (c,d) Late mineralization stage metal sulfide veins cross-cut the stratigraphy of the host rock and early mineralization stage veins. (e,f) Ore samples of stages I and II. (g–i) Selected experimental samples of rutile and monazite. Abbreviations: Py = pyrite; Cpy = chalcopyrite; Q = quartz; Dol = dolomite; Cal = calcite.
Figure 3. Occurrence of the different stages of mineralization and host rock samples in the Tongmugou deposit. (a,b) Early mineralization stage characterized by veinlet and disseminated sulfides in silicic albitite and carbonaceous schist. (c,d) Late mineralization stage metal sulfide veins cross-cut the stratigraphy of the host rock and early mineralization stage veins. (e,f) Ore samples of stages I and II. (g–i) Selected experimental samples of rutile and monazite. Abbreviations: Py = pyrite; Cpy = chalcopyrite; Q = quartz; Dol = dolomite; Cal = calcite.
Minerals 12 00288 g003
Minerals 12 00288 g004 550
Figure 4. Paragenetic sequence of the Tongmugou deposit.
Figure 4. Paragenetic sequence of the Tongmugou deposit.
Minerals 12 00288 g004
Minerals 12 00288 g005 550
Figure 5. Geological map (a) of the Laobaotan copper deposit, with a geological profile (b) of the No. 10 exploration line (modified from internal material of the deposit).
Figure 5. Geological map (a) of the Laobaotan copper deposit, with a geological profile (b) of the No. 10 exploration line (modified from internal material of the deposit).
Minerals 12 00288 g005
Minerals 12 00288 g006 550
Figure 6. Occurrence of the different stages of mineralization and host rock samples in the Laobaotan deposit. (a) Early diagenetic mineralization characterized by disseminated veins. (b,c) Late metamorphic hydrothermal mineralization characterized by thick ore-bearing veins that cross-cut the early mineralization stage veins. (d–f) Hand specimen ore samples of the different stages of mineralization.
Figure 6. Occurrence of the different stages of mineralization and host rock samples in the Laobaotan deposit. (a) Early diagenetic mineralization characterized by disseminated veins. (b,c) Late metamorphic hydrothermal mineralization characterized by thick ore-bearing veins that cross-cut the early mineralization stage veins. (d–f) Hand specimen ore samples of the different stages of mineralization.
Minerals 12 00288 g006
Minerals 12 00288 g007 550
Figure 7. Paragenetic sequence of the Laobaotan deposit.
Figure 7. Paragenetic sequence of the Laobaotan deposit.
Minerals 12 00288 g007
Minerals 12 00288 g008 550
Figure 8. Microphotographs and BSE images of the selected ore samples from the Tongmugou and Laobaotan deposits. (a) Disseminated sulfide veins are directional, elongated and deformed under reflected light. (b–d) Rutile crystals intergrown with sulfides such as chalcopyrite and pyrite in the ore-bearing veins under reflected light. (e) BSE image of the rutile intergrown with sulfides. (f–h) Bright–dark patchy zoning of the rutile crystals and some inclusions are developed inside under BSE. (i) Monazite crystals intergrown with hydrothermal mineral assemblages.
Figure 8. Microphotographs and BSE images of the selected ore samples from the Tongmugou and Laobaotan deposits. (a) Disseminated sulfide veins are directional, elongated and deformed under reflected light. (b–d) Rutile crystals intergrown with sulfides such as chalcopyrite and pyrite in the ore-bearing veins under reflected light. (e) BSE image of the rutile intergrown with sulfides. (f–h) Bright–dark patchy zoning of the rutile crystals and some inclusions are developed inside under BSE. (i) Monazite crystals intergrown with hydrothermal mineral assemblages.
Minerals 12 00288 g008
Minerals 12 00288 g009 550
Figure 9. Raman spectra of the TiO2 polymorphs brookite, anatase, rutile and PD776 from the selected sample.
Figure 9. Raman spectra of the TiO2 polymorphs brookite, anatase, rutile and PD776 from the selected sample.
Minerals 12 00288 g009
Minerals 12 00288 g010 550
Figure 10. Ternary diagram of W contents in rutile, modified from [88]. The circles and squares are dark zones and bright zones of rutile, respectively.
Figure 10. Ternary diagram of W contents in rutile, modified from [88]. The circles and squares are dark zones and bright zones of rutile, respectively.
Minerals 12 00288 g010
Minerals 12 00288 g011 550
Figure 11. Tera–Wasserburg diagrams of rutile. (a) Sample T343-8 in sulfide-bearing albite quartz veins from the Tongmugou deposit. (b) Sample T25-9 in sulfide-bearing carbonate quartz veins from the Tongmugou deposit. (c) Sample PD776 in sulfide-bearing quartz veins from the Laobaotan deposit.
Figure 11. Tera–Wasserburg diagrams of rutile. (a) Sample T343-8 in sulfide-bearing albite quartz veins from the Tongmugou deposit. (b) Sample T25-9 in sulfide-bearing carbonate quartz veins from the Tongmugou deposit. (c) Sample PD776 in sulfide-bearing quartz veins from the Laobaotan deposit.
Minerals 12 00288 g011
Minerals 12 00288 g012 550
Figure 12. Concordia diagram (a), Tera–Wasserburg plot (b) and weighted mean 207Pb/206Pb age (c) of monazite from sample T29-10 in Cu-bearing carbonate veins from the Tongmugou deposit.
Figure 12. Concordia diagram (a), Tera–Wasserburg plot (b) and weighted mean 207Pb/206Pb age (c) of monazite from sample T29-10 in Cu-bearing carbonate veins from the Tongmugou deposit.
Minerals 12 00288 g012
Minerals 12 00288 g013 550
Figure 13. Compilation of geochronological data for the Hubi copper (cobalt) ore district. The data of the age are from [26,27,28,66,108,109].
Figure 13. Compilation of geochronological data for the Hubi copper (cobalt) ore district. The data of the age are from [26,27,28,66,108,109].
Minerals 12 00288 g013
Table
Table 1. LA-ICP-MS parameters for rutile U-Pb isotope analyses.
Table 1. LA-ICP-MS parameters for rutile U-Pb isotope analyses.
Laser Ablation System
Make, model and typePhoton Machines, Analyte G2
Ablation cell and volumeHelex II, large format, two volume
Laser wavelength (nm)193
Pulse width (ns)<4
Fluence (J.cm-2)3
Repetition rate (Hz)7
Ablation duration (secs)30
Ablation pit depth/ablation rate~15 µm/~0.5 µm/s
Spot size (um)35
Sampling mode/patternspot
Carrier gasHe and Ar (after cell) and N2 (after cell)
Cell carrier gas flow (L/min)He1 (cell) = 0.7, He2 (cup) = 0.2, Ar = 0.75, N2 = 0.01
ICP-MS Instrument
Make, model and typeThermo Neptune Plus with Jet Interface
RF power (W)1200
Make-up gas flow (L/min)0.05
Detection system9 Faraday Cups
Masses measured204Pb, 206Pb, 207Pb, 208Pb, 232Th, 238U
Integration time per peak/dwell times (ms)NA
Total integration time per output datapoint (secs)0.25
Table
Table 2. EPMA data of selected rutile crystals from the Tongmugou and Laobaotan copper deposits (wt%).
Table 2. EPMA data of selected rutile crystals from the Tongmugou and Laobaotan copper deposits (wt%).
No.CommentSiO2Ta2O5Nb2O5TiO2Cr2O3FeOZrO2WO3V2O3Total
1Dark zoning-10.0580.0010.1998.720.1430.3430.020.0150.547100.037
2Dark zoning-20.1110.0020.28498.4510.1630.3180.0130.0690.55699.967
3Dark zoning-30.0570.0020.36797.2340.2610.4520.0110.1950.55899.137
4Dark zoning-40.0560.0070.29697.8550.2470.3180.0020.0120.47799.27
5Dark zoning-50.0540.0030.73797.5350.2890.370.0130.020.52799.548
6Dark zoning-60.03800.29998.310.1160.4170.0060.0770.47699.739
7Dark zoning-70.0550.0030.25897.9860.1450.2890.0180.0480.48599.287
8Dark zoning-80.06900.29298.0590.1030.4440.0020.0160.42299.407
9Dark zoning-90.02100.17598.1090.3580.3110.0140.0670.50799.562
10Dark zoning-100.020.0010.20298.3120.3550.4890.0180.0550.553100.005
11Dark zoning-110.00400.28598.8430.2850.0690.0010.050.622100.159
12Dark zoning-120.00600.3497.3820.0320.3450.0060.8741.122100.107
13Dark zoning-1300.0010.22398.2930.0490.2350.0010.0120.63899.452
14Dark zoning-140.00400.28897.8640.0570.170.0020.0980.74699.229
15Dark zoning-15000.50897.7370.2690.2680.0150.1530.42699.376
16Dark zoning-160.0020.0350.39896.9230.1520.5210.0280.5570.48299.098
17Light zoing-10.06201.26792.8110.4051.1320.0423.6230.60199.943
18Light zoing-20.05601.37392.8340.4291.3170.0492.6410.6599.349
19Light zoing-30.04901.31992.4620.4551.4720.0623.2110.66699.696
20Light zoing-40.07100.9295.7530.3110.7410.021.4950.59899.909
21Light zoing-50.050.0292.60192.4970.5331.3020.031.8460.60299.49
22Light zoing-60.0470.0272.59392.5080.5871.4470.0421.7610.62499.636
23Light zoing-70.060.1121.80693.9880.3221.1690.0251.2370.57699.295
24Light zoing-80.06800.14596.8990.160.7760.0231.4430.494100.008
25Light zoing-90.01300.64995.5940.0350.8170.0131.7541.11399.988
26Light zoing-100.00300.39595.1630.1360.7860.0142.2461.03499.777
27Light zoing-110.00100.38794.7210.1270.6910.0192.2231.20899.377
28Light zoing-12000.36995.1140.1110.6290.0161.9371.10199.277
29Light zoing-13000.95891.7410.6451.2480.0525.2020.456100.302
30Light zoing-140.0080.0672.65992.1450.3241.6530.0341.8770.59399.36
Table
Table 3. LA-ICP-MS trace element data of selected monazite crystals from the Tongmugou copper deposit (ppm).
Table 3. LA-ICP-MS trace element data of selected monazite crystals from the Tongmugou copper deposit (ppm).
No.ScYZrNbSmEuGdTbDyHoErTmYbLuHfTaPbThUTh/U
T29-10-010.1736751.210.06201751335 85795561762224324205940.290.041223782801.35
T29-10-020.1280501.010.03165631533 9264797321947375052168120.480.091882725140.53
T29-10-030.20113580.890.04251062042 1345911314393639107879263180.690.11139354240.08
T29-10-040.1599431.290.05239153052 12502110042425838935716590.610.10262268150.03
T29-10-050.3053001.420.05167651920 83816482379325470298150.380.06832122091.02
T29-10-060.26104701.030.05203503080 112671039425562199968208130.690.12294129120.01
T29-10-070.1897171.190.06212712959 120381081416057590761182100.590.1125928050.00
T29-10-080.1458211.170.05274641957 131899072819351499308650.440.06143424300.10
T29-10-090.1449061.240.05190261382 87846302188295438288450.280.061632614410.59
T29-10-100.0746091.560.09179221257 80355691987274419278760.320.061573544040.88
Table
Table 4. LA-ICP-MS U-Pb data of rutile from the Tongmugou and Laobaotan copper deposits.
Table 4. LA-ICP-MS U-Pb data of rutile from the Tongmugou and Laobaotan copper deposits.
Sample No.Isotopic RatiosApparent Age (Ma)
207Pb/206Pb2σ207Pb/235U2σ206Pb/238U2σ207Pb/206Pb2σ207Pb/235U2σ206Pb/238U2σ
Rutile T343-8
T343-8-10.35570.009431.51.70.6360.022372039353053316487
T343-8-20.13670.00166.5520.210.34660.0094218118205028191946
T343-8-30.11120.00365.260.240.3480.01182340185938192951
T343-8-40.1130.00165.0760.160.32510.0091184517182827181344
T343-8-50.11320.00295.260.210.3450.012185628185836190955
T343-8-60.11360.00244.990.180.32360.0093185522181230180645
T343-8-70.1190.00335.210.220.31790.0097194135183936177747
T343-8-80.11320.00245.080.180.32520.0089183925182729181443
T343-8-90.20930.007111.550.560.39270.013288643254545213161
T343-8-100.12010.00155.5960.170.33670.0092195616191227187044
T343-8-110.11620.00525.440.310.33180.011187754186943184553
T343-8-120.11430.00524.870.250.31420.01181152176944175850
T343-8-130.14820.00276.850.240.33270.0094231529208231185046
T343-8-140.12230.00235.310.20.31770.01197728186732177549
T343-8-150.14670.00656.690.420.33270.011223363203651185253
T343-8-160.18690.008810.460.880.3840.014265466238659208763
T343-8-170.2680.0119.91.40.510.019325657300665265080
T343-8-180.13850.00286.460.250.3360.0096219831202833186646
T343-8-190.1130.00185.0470.170.32380.0095184018182328180646
T343-8-200.120.00585.520.310.33560.011191061187848186153
T343-8-210.12610.00616.260.370.36050.013198864196254198164
T343-8-220.11390.00175.0350.160.32030.0089186017182127179243
T343-8-230.16880.00278.460.310.36040.011253524227433198250
T343-8-240.14980.00327.110.270.34790.0099233331211534192347
T343-8-250.11360.00234.810.170.30580.0089186021177830172143
T343-8-260.29720.009222.91.60.5430.023342947318363278091
T343-8-270.120840.00125.6010.180.33280.0094196616191327185145
T343-8-280.11420.00375.10.220.32670.0099185339182437182048
T343-8-290.24220.009514.360.90.41590.014308161272457224163
T343-8-300.12530.00275.960.230.34360.0096202330195933190246
T343-8-310.12310.00326.020.280.35080.011198940195838193650
T343-8-320.14890.00387.610.40.36060.012231941216745198256
T343-8-330.12180.0026.20.210.35940.01198519200131197849
T343-8-340.11570.00265.180.180.32640.0093188127184131182045
T343-8-350.11310.00425.280.250.34910.012183943185640192856
T343-8-360.14170.00157.120.250.36260.011224515211931199250
Rutile T25-19
T25-19-10.12180.00185.660.190.33470.0097198519192129185947
T25-19-20.20980.009810.850.80.36550.012284267244960200258
T25-19-30.12110.00385.820.240.35070.011196837193936193452
T25-19-40.1190.00365.410.230.32780.01193534187237182751
T25-19-50.12610.0025.780.190.33530.0095203424193828186345
T25-19-60.1120.001550.160.32520.0091182817181727181444
T25-19-70.12820.00385.880.260.32890.0094205541194135183245
T25-19-80.5830.0166.33.50.8050.0354455254224523780120
T25-19-90.15240.00257.330.250.34690.0094236424214530191945
T25-19-100.5850.02281.97.80.9350.06643826643701104200220
T25-19-110.2920.01219.31.40.4570.016335863297566242470
T25-19-120.12180.00185.640.190.33650.0098198418191730186747
T25-19-130.1130.00124.9750.160.31690.0092184814181428177344
T25-19-140.11740.00255.170.190.31860.0095190729184133178146
T25-19-150.12540.00256.270.220.37070.011202824201132203153
T25-19-160.13030.00436.260.270.3560.011208043200740196354
T25-19-170.13120.00316.230.250.34770.011210331199936191953
T25-19-180.12830.00446.040.340.34410.011208858196644191150
T25-19-190.5110.0124830.6550.034261353905633239120
T25-19-200.11880.00235.270.190.32130.009193426185830179744
T25-19-210.11730.00265.080.180.31780.0094191028182832177746
T25-19-220.11610.00255.560.20.35040.01189028190232193450
T25-19-230.2590.01115.51.10.430.016319265280163229769
T25-19-240.20560.005310.260.430.36390.011286141244539200155
T25-19-250.1210.00365.820.250.35080.011195638193336193553
T25-19-260.25090.009114.340.860.40790.013317255275057220361
T25-19-270.12810.00376.110.260.3580.011206139198837197154
T25-19-280.14940.00417.570.320.36490.011232837217638200353
T25-19-290.12860.00385.990.250.3310.0096207240196737184246
T25-19-300.16290.00447.930.360.35170.01247139220939194149
T25-19-310.450.01235.82.10.5730.023406038362857290489
T25-19-320.3270.01521.91.80.4650.022352573308282244291
T25-19-330.3770.01725.92.20.4840.022377966330579254799
T25-19-340.12930.00245.930.220.34210.011208723196232189553
T25-19-350.15180.00477.470.340.35890.011234746215238197549
T25-19-360.23080.007913.090.740.41060.013301150265651221760
Rutile PD776
PD776-10.11090.0054.810.250.31630.01178356176145176751
PD776-20.11160.00724.830.330.32550.011178171175161181155
PD776-30.11530.00685.120.320.33060.012184082180857183459
PD776-40.12360.00925.490.450.3270.013194986184467181663
PD776-50.11260.00725.020.350.32930.013181568178360182662
PD776-60.11110.00384.810.220.3190.0099179843177039178248
PD776-70.11330.0055.110.270.33350.011182250180545185153
PD776-80.11430.00495.050.250.32460.0099182755180144181249
PD776-90.11150.00485.050.250.33050.011181746180243184052
PD776-100.11430.0075.070.350.33040.011181781181057183554
PD776-110.1210.00555.490.30.33560.011192359186949186251
PD776-120.11510.0065.140.30.33260.012184659180951184457
PD776-130.1290.0115.670.550.3380.019208465191480187792
PD776-140.11230.00785.010.350.33230.013180187176069184360
PD776-150.11140.0055.220.280.34480.011180658184149191752
PD776-160.11480.00675.370.330.35050.012182267184554193059
PD776-170.11330.0065.260.310.34090.012184364184050188556
PD776-180.13660.00596.770.350.37070.013214152205246202660
PD776-190.11710.00655.620.360.35430.012184776186555194957
PD776-200.1130.00355.450.240.35280.011184238188137194451
PD776-210.4670.03764120.860.1363011037101603620290
PD776-220.11440.00575.640.310.36320.013183362187952199160
PD776-230.11790.0075.60.330.35560.013188762189551195861
PD776-240.11210.00595.440.330.35740.013182168186954196861
PD776-250.2190.0510.31.50.4190.033280016023301402180150
PD776-260.11220.00585.280.290.34430.012181464183053190157
PD776-270.1140.00435.640.270.36510.011185543191241200452
PD776-280.11310.00635.530.330.36010.013180669186058197660
PD776-290.12460.00736.320.420.3710.012198081197963202957
PD776-300.10960.00614.850.30.31490.012177374176456176661
PD776-310.11050.00594.680.260.31420.011178160173149175752
PD776-320.11860.00665.220.350.31940.01187166180651178251
PD776-330.10970.00595.270.310.34250.012178466181654189258
PD776-340.1090.0114.870.490.3230.0151830110173485179776
PD776-350.15970.00887.640.530.35190.013234479212965193660
PD776-360.1230.0125.450.540.3370.0172060110187480186281
PD776-370.11630.0065.30.310.33060.012185765182754183557
PD776-380.1690.0177.760.660.3730.022410100214883202792
PD776-390.1160.00565.220.290.32880.012185650182949182657
PD776-400.12590.00915.30.380.3190.013196588180771177867
PD776-410.12010.00595.260.280.32150.01192159182949179351
Table
Table 5. LA-ICP-MS U-Pb data of monazite from the Tongmugou copper deposit.
Table 5. LA-ICP-MS U-Pb data of monazite from the Tongmugou copper deposit.
Sample No.Isotopic RatiosApparent Age (Ma)
207Pb/206Pb1σ207Pb/235U1σ206Pb/238U1σrho207Pb/206Pb1σ207Pb/235U1σ206Pb/238U1σ
T29-10-10.11200.00105.09190.07060.33520.00240.5165183218183512186412
T29-10-20.11200.00075.07850.06070.33410.00210.5179183212183310185810
T29-10-30.11260.00085.07580.06070.33230.00210.5366184312183210184910
T29-10-40.11390.00085.14990.07450.33250.00290.5935186313184412185014
T29-10-50.11320.00135.11260.08630.33250.00300.5318185421183814185014
T29-10-60.11470.00085.18630.06680.33260.00240.5493187611185011185111
T29-10-70.11470.00085.14150.06830.33000.00250.5658187613184311183812
T29-10-80.11280.00095.11950.06510.33450.00210.4945184413183911186010
T29-10-90.11440.00095.14360.07130.33100.00250.5418187013184312184312
T29-10-100.11740.00105.24480.07620.32930.00300.6313191615186012183515
Table
Table 6. Previous studies of age in Hubi copper deposits.
Table 6. Previous studies of age in Hubi copper deposits.
AgeMethodSample and OccurrenceDepositReference
1830 ± 34 MaUraninite and brannerite U-PbDisseminated ore vein/Zhongtiao GroupBizigou[26]
1832 ± 26 MaRb-Sr isochronCarbonaceous schistNanhegou[66]
Quartz albititeNanhegou
Quartz albititeLaobaotan
Quartz marbleTongmugou
1919~1980 MaMolybdenite Re-OsUnknownBizigou[108]
1901 ± 24 MaMolybdenite Re-OsMolybdenite along faults and interlayer fracture zones, the relation with mineralization is unknownTongmugou[27]
1952 ± 39 MaChalcopyrite Re-OsChalcopyrite-bearing thick veins,
stage II		Nanhegou[28]
1577 ± 31 MaMolybdenite Re-OsMolybdenite sulfide-bearing quartz veinsBizigou[109]
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Wang, M.; Mao, J.; Ye, H.; Li, H. The Age of Hubi Copper (Cobalt) Ore Mineralization in the Zhongtiao Mountain Area, Southern Margin of the Trans-North China Orogen: New Constraints from U-Pb Dating of Rutile and Monazite. Minerals 2022, 12, 288. https://doi.org/10.3390/min12030288

AMA Style

Wang M, Mao J, Ye H, Li H. The Age of Hubi Copper (Cobalt) Ore Mineralization in the Zhongtiao Mountain Area, Southern Margin of the Trans-North China Orogen: New Constraints from U-Pb Dating of Rutile and Monazite. Minerals. 2022; 12(3):288. https://doi.org/10.3390/min12030288

Chicago/Turabian Style

Wang, Mengqi, Jingwen Mao, Huishou Ye, and Hongying Li. 2022. "The Age of Hubi Copper (Cobalt) Ore Mineralization in the Zhongtiao Mountain Area, Southern Margin of the Trans-North China Orogen: New Constraints from U-Pb Dating of Rutile and Monazite" Minerals 12, no. 3: 288. https://doi.org/10.3390/min12030288

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