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Re?Os Isotopic Age of the Hongqiling Cu-Ni Sulfide Deposit in Jilin Province, NE China and its Geological Significance

Han Chun-Ming1*, Xiao Wen-Jiao1, Zhao Guo-Chun2, Su Ben-Xun1, Ao Song-Jian1, Zhang Ji-En1, Wan Bo1 and Zhang Zhi-Yong1
1Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
2Department of Earth Sciences, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Corresponding Author : Han Chun-ming
Institute of Geology and Geophysics
Chinese Academy of Sciences, Beijing 100029, China
Tel: 8610 62007917
Fax: 8610 62010846
E-mail: cm-han@mail.iggcas.ac.cn
Received February 23, 2014; Accepted March 06, 2014; Published March 14, 2014
Citation: Han CM, Xiao WJ, Zhao GC, Su BX, Ao SJ, et al. (2014) Re–Os Isotopic Age of the Hongqiling Cu-Ni Sulfide Deposit in Jilin Province, NE China and its Geological Significance. J Geophys Remote Sen 3:118. doi:10.4172/2169-0049.1000118
Copyright: © 2014 Han CM, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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Abstract

The major Hongqiling Cu-Ni sulfide deposit in central Jilin Province is located in the eastern part of the Central Asian Orogenic Belt. Rhenium and osmium isotopes in sulfide minerals from the deposit have been used to determine the timing of mineralization and the source of osmium and, by inference, the ore metals. Sulfide ore samples have osmium and rhenium concentrations of 0.28-1.07ppb and 2.39-13.17ppb, respectively. Ten sulfide analyses yield an isochron age of 223 ± 9 Ma, indicating that the Cu-Ni sulfide mineralization formed in the Early Triassic. The initial 187Os/188Os ratio is 0.295 ± 0.019 (MSWD = 1.14). This data indicates that the mineralization was derived mainly from a mantle source with some quantities of crustal components introduced into the rockforming and ore-forming systems during mineralization and magmatic emplacement. Together with the widespread occurrence of late Carboniferous-Permian mafic–ultramafic complexes and associated Permian Cu-Ni deposits in the western part of the Central Asian Orogenic Belt (Northern Xinjiang), we conclude that mantle-crustal interactions were active during the accretion-collisional processes that led to the Cu-Ni mineralization and considerable continental growth in the late Carboniferous-Permian to mid-Triassic.

Abstract

The major Hongqiling Cu-Ni sulfide deposit in central Jilin Province is located in the eastern part of the Central Asian Orogenic Belt. Rhenium and osmium isotopes in sulfide minerals from the deposit have been used to determine the timing of mineralization and the source of osmium and, by inference, the ore metals. Sulfide ore samples have osmium and rhenium concentrations of 0.28-1.07ppb and 2.39-13.17ppb, respectively. Ten sulfide analyses yield an isochron age of 223 ± 9 Ma, indicating that the Cu-Ni sulfide mineralization formed in the Early Triassic. The initial 187Os/188Os ratio is 0.295 ± 0.019 (MSWD = 1.14). This data indicates that the mineralization was derived mainly from a mantle source with some quantities of crustal components introduced into the rock-forming and ore-forming systems during mineralization and magmatic emplacement.

Together with the widespread occurrence of late Carboniferous-Permian mafic–ultramafic complexes and associated Permian Cu-Ni deposits in the western part of the Central Asian Orogenic Belt (Northern Xinjiang), we conclude that mantle-crustal interactions were active during the accretion-collisional processes that led to the Cu-Ni mineralization and considerable continental growth in the late Carboniferous-Permian to mid-Triassic.
 
Keywords

Re–Os isotopic dating; Cu-Ni deposit; Geodynamic process; Hongqiling; NE China
 
Introduction

The complicated orogenic processes of the Central Asian Orogenic Belt (CAOB), characterized by considerable Phanerozoic continental growth and mantle-crust interaction, generated the Central Asian Metallogenic Domain with world-class ore deposits [1-10]. However, the connections between orogenic processes, continental growth, mantle-crust interaction and ore deposit formation unsolved. The main controversy is with regard to the timing of these geodynamic processes. Different groups of researchers have considered that orogeny ended either in the early Paleozoic [11], the Devonian-Carboniferous [12], or even late Permian to middle Triassic [7-8]. However, it is commonly accepted that the major continental growth and large-scale mineralization were in the late Carboniferous-Permian to early Mesozoic [2,13]. Therefore the relationships between these various geodynamic processes require further study.

In this study, we present new Re-Os isotopic data on Cu-Ni-bearing sulfide ores from the Hongqiling intrusion in the eastern part of the Central Asian Orogenic Belt to constrain the timing of mineralization, and to further discuss the issues raised above. The new data provide important insights into understanding of the mineralization processes and geodynamic setting of the Hongqiling Cu–Ni ore deposit in NE China.
 
Geological Background

The study area is situated in central Jilin Province, NE China, representing the eastern extension of the Central Asian Orogenic Belt (CAOB), developed between the North Craton to the south and the Siberia Craton to the north (Figure 1). This pair of NE China is divided into three blocks [3,5,14-16]; the Xing'an Block in the northwest, Songliao Block in the middle, and Jiamusi Block in the southeast, which are separated by the Mudanjiang and Nenjiang Faults, respectively (Figure 1).

The Songliao Block consists of Paleozoic to Mesozoic accreted arc complexes, the Mesozoic to Cenozoic Songliao Basin and Mesozoic granites that make up the Zhangguangcai Range (Figure 1) [7]. Local amphibolite facies metamorphic rocks have been identified, including the Dongfengshan Group in the north and the Hulan Group in the south [7,17,18]. However, Phanerozoic granites occupy the majority of the block. The Songliao Basin formed in the late Mesozoic over a basement of Phanerozoic granites and Palaeozoic strata [7]. The Hulan Group mainly crops out in the Hongqiling–Piaohechun area, and is composed predominantly of mica schist, gneiss, amphibolite and marble which were interpreted as the final products related to the closure of the Paleo-Asian Ocean [7,19,20].

The late Paleozoic strata are distributed mainly in the Panshi area and consist of sandstone, siltstone, shale, mudstone and carbonate, indicating a shallow marine sedimentary environment. However, it should be pointed out that the environment changed from an oceanic to an arc setting in the Late Permian with the development of intermediate-acid volcanic rocks, including andesite and rhyolite [7].

In NE China, more than 1000 mafic–ultramafic complexes have been identified [3], some of which are characterized by Cu and Ni mineralization, especially in the Hongqiling and Piaohechuan complexes (Figures 1 and 2a). Most of the important magmatic Cu–Ni sulfide deposits are developed in the Songliao Block, including those at the Hongqiling, Piaohechuan, Changren, Zhangxiang, Chajianling, Erdaogou, Sandaogang and Sanmen deposits (Figure1; Table.1), only the Wuxing Cu-Ni deposit is located in the Jiamusi Block, of which the most representative and largest is the Hongqiling Cu-Ni deposit.
 
Geology of the Hongqiling Area

Located 38 km east-southeast of Panshi city, central Jilin Province, the Hongqiling copper-nickel deposit is the largest and economically most important deposit in the eastern CAOB, with explored reserves of 271,720 tons of Ni and 6,9940 tons of Cu [21]. The ore deposit was discovered in 1958 and exploited during the period of 1959-1961, with the construction of the present-operating mine commencing in 1964. Since the discovery of the deposit, numerous studies have been carried out on its mineralization and the host mafic-ultramafic rocks [4,22-24].

The host rocks of the Hongqiling Cu-Ni deposit are hosted by metamorphic rocks of the Lower Paleozoic Hulan Group (Figure 2a), which consists predominantly of garnet mica gneiss, biotite gneiss, amphibolite, muscovite schist, all of which show strong ductile deformation. Five mafic-ultramafic intrusions distributed in the Hongqiling deposit mining district, of which two intrusions (Nos. 1 and 7) in the southern part of the deposit area (Figure 2b) are well differentiated and zoned, and have Cu-Ni mineralization [21].

The No. 1 intrusion is 980 m long and up to 270 m wide. It extends as much as 576 m down-dip and, on the surface outcrop occupies an area of ~0.20 km2 (Figure 3a). In plan view, the intrusion is an irregular lens in shape, but in vertical cross-section, the intrusion is a funnel-shaped body and become vein-like at depth (Figure 3a). The No. 1 intrusion intrudes the Hulan Group and contains four intrusive units with the following rock types from the base upwards [4,23]: olivine websterite (4%) and lherzolite (89%) in the lower part, pyroxenite (6%) and gabbro (1%) in the upper part. The nature of the contacts between the different units is unclear in the field [4].

The No. 7 intrusion is located 10km southeast of Hongqiling town (Figure 2b). Its long axis strikes 300° and dips at 75-80° to NE (Figure 3b). It is 700m in length, and has an average width of 35m, a maximum extension of about 600 m, and a surface outcrop of ~0.013 km2 [4,23].The intrusive units include orthopyroxenite (96%), and minor norite and peridotite [4,23].
 
Geology of the Ore Deposit

As stated above, the Hongqiling Cu-Ni deposit consists of the No.1 and No.7 orebodies. Cu–Ni sulfide ores are hosted in the olivine websterite unit and the No. 1 orebody contains 15,200 t of Cu and 71,600 t of Ni, based upon average ore grades of 0.54% Ni and 0.11% Cu [21]. The No.7 orebody is hosted in the orthopyroxenite, norite and peridotite units and contains 204,000 t of Ni and 39,000 t of Cu, based upon the average ore grades of 2.30% Ni and 0.63% Cu [21]. In addition, 3,100 t of Co may be recovered as by-products [21].

Mineralogically, the ore minerals of the Hongqiling Cu-Ni deposit are dominantly pyrrhotite, pentlandite, chalcopyrite, violarite, pyrite, valleriite, millerite, nickeline, ilmenite, galena and magnetite, and the gangue minerals are olivine, pyroxene, plagioclase, hornblende, biotite, chlorite and serpentine.

The textures of the ore minerals include euhedral, subhedral, anhedral, subhedral-anhedral, gabbroic, poikilitic, reaction rim, sideronitic, interstitial and corrosion textures, and the ore structures are mainly massive, disseminated, sparsely disseminated, spotted and banded.

Based on cross-cutting relationships between minerals and mineral assemblages, mineralization in the Hongqiling orebody can be subdivided into the following three stages (Figure 4). The first is the magmatic crystallization stage, characterized by disseminated and massive ores with pentlandite+violarite+millerite+magnetite. The second is the auto-metamorphic stage that is characterized by the formation of massive and vein-like high grade Cu and Ni ores, and forming Cu- and Ni-bearing minerals, represented by chalcopyrite and pyrrhotite. The third is the magmatic–hydrothermal stage that is characterized mainly by chlorite and carbonate alteration, forming the carbonate+pyrite+chalcopyrite assemblage that occurs as veins.

Wall–rock alteration related to mineralization in the Hongqiling Cu–Ni ore deposit includes chloritization, carbonatization, serpentinization, talcization, uralitization, sericitization, tremolitization [23]. Characteristic minerals in the alteration zones are talc, chlorite, serpentine, sericite and carbonate.
 
Analytical Techniques

We collected ten samples from the Hongqiling deposit for Re-Os dating, all from fresh open-pit mining faces. To make the samples more representative, we chose samples from different ore types, including disseminated (samples HQL-1,4,5,7,9) and massive Cu-Ni ores (samples HQL-2,3,6,8,10). Variable chalcopyrite-pyrrhotite-pentlandite percentages in the samples provide a range of Re/Os ratios, since chalcopyrite-rich assemblages tend to have higher Re/Os ratios than those of the pyrrhotite-rich assemblages [25,26]. The relatively large range of Re/Os ratio is an important factor for obtaining precise Re-Os isochron ages [26].

Re-Os isotopic analyses were performed at the National Research Center of Geoanalysis. The details of the chemical procedure are described by [27-29], and are briefly summarized as follows.

The carius tube (a thick-walled borosilicate glass ampoule) digestion technique was used. The weighed sample was loaded in a carius tube through a long thin-neck funnel. The mixed 190Os and 185Re spike solution and 2 ml of 10 N HCl and 6 ml of 16 N HNO3 were added while the bottom part of the tube was frozen at -80 to - in an ethanol-liquid nitrogen slush; the top was sealed using an oxygen-propane torch. The tube was then placed in a stainless-steel jacket and heated for 10 h at 230°C. Upon cooling, the bottom part of the tube was kept frozen, the neck of the tube was broken, and the contents of the tube were poured into a distillation flask and the residue was washed out with 40 ml of water.

Separation of osmium by distillation and separation of rhenium by extraction was performed based on the analytical method from [30]. A TJA PQ-EXCELL ICP-MS was used for the determination of the Re and Os isotope ratio.

Average blanks for the total carius tube procedure were ca. 10 pg Re and ca. 1 pg Os. The analytical reliability was tested by repeated analyses of molybdenite standard HLP-5 from a carbonate vein-type molybdenum-lead deposit in the Jinduicheng-Huanglongpu area of Shaanxi Province, China. Fifteen samples were analyzed over a period of 5 months. The uncertainty in each individual age determination was about 0.35% including the uncertainty of the decay constant of 187 Re, uncertainty in isotope ratio measurement, and spike calibrations. The average Re-Os age for HLP-5 is 221.3 ± 0.3 Ma (95% confidence limit) [31]. Median age and mean absolute deviation were 221.34 ± 0.12 Ma. The average Re concentration was 283.71 ± 1.54 µg/g. The average Os concentration was 657.95 ± 4.74 ng/g.
 
Analytical Result

The abundance of Re and Os and the osmium isotopic compositions of the Cu-Ni sulfide ores from the Hongqiling mine are shown in Table 2. Due to different ore types, the Re and Os contents demonstrate relatively large variations. For massive Cu-Ni ores (samples HQL-2, 3, 6, 8, 10), the total Re and Os contents range from 83.78 ± 0.66 to 236.60 ± 2.10 ppb and 0.2899 ± 0.0030 to 1.067 ± 0.014 ppb, respectively, whereas for the disseminated ores (samples HQL-1, 4, 5, 7, 9), the Re and Os contents vary from 93.17 ± 0.7 to 134.7 ± 1.2 ppb and 0.318 ± 0.006 to 0.5200 ± 0.0187 ppb, respectively. A regression analysis was applied to the ten analytical data and yielded an isochron age of 222.9 ± 9.1Ma, with initial 187Re/188Os ratio of 0.295 ± 0.019 and a mean square of weighted deviation (MSWD) of 1.141 (Figure 5). The isochron age was calculated by means of the 187Re decay constant of 1.666×10–11/year [32] using the ISOPLOT software (Model 3) [33]. This isochron age can reflect the ore-forming age of the Hongqiling Cu-Ni deposit.
 
Discussion

 
Initial 187Os/188Os and source of ore-forming metals

The Re–Os isotope system has been recognized as a geochemical tool not only for directly dating mineralization but also for defining the ore forming process of Cu-Ni sulfide deposits, and thus is a powerful tracer of sulfide ore formation and can be a highly sensitive monitor of the extent of crustal involvement during ore genesis [25]. Since the initial 187Os/188Os ratios of the crust (0.2–10) are higher than those of the mantle (0.11–0.15) [34], 187Os/188Os ratios can be used to readily discern different sources [35].

The Hongqiling Cu-Ni sulfides ores possess an initial 187Os/188Os ratio of 0.295 ± 0.019 (Figure 5), which is considerably greater than chondritic value as well as those of the mantle at 222.9 Ma, indicating that crustal components were involved in the Os source of the Hongqiling ores.

In order to describe the Os isotopic composition at a given time, a parameter of γOs was introduced by Walker et al. [36,37].

γOs (T) = 100 [187Os/186Os] sample (T)/ 187Os/186Os] chondrite (T)-1].

Owing to high Re/Os ratios in the crust, γOs will have a large positive value with increasing crustal material entering the magmatic or ore-forming systems, and, by contrast, Re-loss in the systems can cause negative γOs [38]. According to the formula of [36], and with a decay constant of 1.666×10–11/year [32], the γOs values for the Hongqiling Cu-Ni sulfide ores were calculated based on the isochron age of 222.9 ± 9.1Ma and their corresponding initial 187Os/188Os ratios. Table 3 shows that the γOs values for the Hongqiling Cu-Ni sulfide ores range from 119.32 to 142.35. The initial 187Os/188Os ratio of 0.295 ± 0.019 for the Hongqiling sulfides is higher than that of 0.1089 ± 0.00035 reported for the uncontaminated Archean komatite-related Cu-Ni sulfide ores [39]. These data reflect that mafic-ultramafic magmas were mixed with crustal components during the uprise of the magma or within magma chambers in the crust. This process is analogous to the crustal contamination of the Voisey's Bay magma by the Tasiuyak paragneiss where siderophile and chalcophile elements were selectively incorporated [40] and the case of the Jinbulake intrusion in Xinjiang where crustal sulfides were selectively incorporated to magmas [41]. Such features can also be seen in the common Os vs. Re/Os diagram (Figure 6).
 
Age of mineralization and its geodynamic significance

Ten sulfide samples yielded a Re-Os isochron age of 222.9 ± 9.1 Ma (2σ), as shown on the 187Os/188Os versus 187Re/188Os plot (Figure 5). Six pyrrhotite samples separated from massive Ni-Cu sulfide ores of the Fujia (No. 7) deposit yielded a Re-Os isotopic isochron age of 208 ± 21 Ma [42]. SHRIMP U–Pb zircon analyses on a leucogabbro and plagioclase-bearing pyroxenite of the Hongqiling and Piaohechuan complexes yielded weighted mean 206Pb–238U ages of 216 ± 5 Ma and 217 ± 3 Ma, respectively [43]. Taken together, these data suggest that the mafic–ultramafic intrusions were emplaced at 216-217 Ma, the main Cu-Ni mineralization occurred at 208-222 Ma [4].

In the Middle Triassic, large scale magmatism and Cu-Ni mineralization in NE China may have been triggered by the re-melting of Paleozoic accretion-collision complexes and older continental margins [44], possibly resulted from the delamination of the subcontinental lithospheric mantle, which caused the upwelling of asthenospheric mantle and partial melting of the overlying lithospheric mantle [42,45]. It is suggested that a significant amount of crustal contamination during magmatic crystallization is not a necessary condition for the formation of the Cu–Ni sulfide deposits, although the presence of marble xenoliths decarbonatized to diopside-rich skarns and of high CaO/SiO2 in the Jinchuan intrusion does indicate appreciable carbonate contamination, and the assimilation of the carbonate-rich fluids increased the oxygen fugacity of the magma, which led to the segregation of the Cu-Ni sulfides [46]. Since the Cu–Ni sulfides occur exclusively at the base of the associated igneous bodies in the studied complexes, we suggest dense sulfide and olivine were carried along in rapidly flowing magma in the narrow parts of conduits feeding the intrusion, and where these conduits widened out on entering the main body [42]. Similar processes have been proposed elsewhere, such as in the Jinchuan and Kalatongke Cu-Ni deposits [47].

Therefore we conclude that crust contamination was active during the accretion-collision processes that led to the Cu-Ni mineralization and considerable continental growth in the late Carboniferous-Permian to mid-Triassic. U-Pb isotopic analysis of detrital zircons from a kyanite-garnet schist of the Hulan Group indicate a maximum deposition age of 287 ± 6 Ma, and Rb-Sr mineral isochron ages indicate that metamorphism occurred at ~250 Ma for the Hulan Group [5] (Table 3). The field geological, petrological and geochemical signatures of these rocks of the Fulan Group show they are related to the final closure of the Paleo-Asian Ocean [7]. Thus the final closure time has been put as late as Triassic. This is in good agreement with the regional tectonic analysis which also suggests that the termination time of the Central Asian Orogenic Belt was in the end-Permian to mid-Traissic [8] (Figure 7). This is consistent with the fact that new SHRIMP and LA-ICP-MS U-Pb zircon data from para- and ortho-gneisses and granitoids confirm the latest Triassic-Early Jurassic termination of the eastern Central Asian Orogenic Belt, the development of which was transferred to the Pacific tectonic domain [48,49].
 
Conclusions

The Hongqiling magmatic Cu–Ni sulfide ore deposit in the eastern part of the Central Asian Orogenic Belt Orogenic Belt has a Re–Os isochron age of 223 ± 9 Ma. The sulfide ores possess an initial187Os/188Os ratio of 0.295 ± 0.019, and γOs values of 119.32-142.35, reflecting a result of significant crustal contamination to the metal-rich magmatic system.

The major Cu–Ni orebodies of the Hongqiling deposit were hosted in mafic–ultramafic intrusions which are considered to have formed by the accretional-collisional processes of the Central Asian Orogenic Belt (CAOB), possibly resulting from the delamination of the subcontinental lithospheric mantle, causing the upwelling of asthenospheric mantle and partial melting of overlying lithospheric mantle in the Middle Triassic.

(1) Os in Re/Os is common Os. Common Os and common 187Os are calculated according to the Nier value. (2) The calculation formula

isγOs=100[(187Os/188Os)sample(T)/(187Os/188Os)chondrite(T)-1], where(187Os/188Os)chondrite=0.09531+0.40186(eλRe*4.558E9-eλRe*t)=0.125519 at222.9Ma, using the 187Re decay constant λ=1.666×10-11/year; aRe and Os uncertainty<1% at 2 standard errors of the mean, including error samples and spike weighting, spike calibration, mass spectrometric analysis, fractionation correction and measured isotope ratios in the samples. b187 Os /188 Os uncertainty <1% at 2 standard errors of the mean, including error in mass spectrographic analysis, fractionation correction and measured isotope ratios in the samples.
 
Acknowledgements

We are indebted to Bin Cui, Kezhang Qin, Lianchang Zhang, Tianlin Ma, Zhiliang Wang, and Jianming Yang for thoughtful discussions. Many of the ideas in this paper were initiated and rectified during these discussions. We are grateful to S.A. Wilde and B.F. Windley for their constructive discussions and comments on an early version of the manuscript, which led to substantial improvements to the paper. The authors wish to thank Holly Stein and a anonymous reviewers for their useful comments on the manuscript and Andy Whitham for his editorial assistance. This study was financially supported by funds from the NSFC Projects (41272107 and 40973036), and the State 305 project (2011BAB06B04-01). This paper is a contribution to the ILP (ERAS) and IGCP 480.
 
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