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Geology Reviews 53 (2013) 422–433

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Ore Geology Reviews

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Geology and Re–Os age of the Dahutang -related veinlets-disseminated ore field in the Jiangxin Province, China

Zhihao Mao a,⁎, Yanbo Cheng a,⁎, Jiajun Liu a, Shunda Yuan b, Shenghua Wu b, Xinkui Xiang c, Xiaohong Luo d a Faculty of Earth Science and Resources, China University of Geosciences, Beijing 100083, China b MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China c No. 916 Geological Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration and Development, Jiujiang 332000, China d Northwestern Geological Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration and Development, Shahe 332100, China article info abstract

Article history: This is a brief research report about the recently-discovered and currently being explored Dahutang tungsten de- Received 15 October 2012 posit (or ore field) in northwestern Jiangxi, south-central China. The deposit is located south of the Middle–Lower Received in revised form 12 February 2013 Yangtze River valley Cu–Au–Mo–Fe porphyry– belt (YRB). The mineralization is genetically associated with Accepted 13 February 2013 Cretaceous porphyritic biotite granite and fine-grained biotite granite and is mainly hosted within a Available online 19 February 2013 Neoproterozoic biotite granodiorite batholith. The Dahutang ore field comprises veinlets-disseminated (~95% of the total reserve), (~4%) and – (~1%) ore styles. The mineralization and Keywords: Veinlets-disseminated tungsten deposit alteration are close to the shell between the Cretaceous porphyritic biotite granite and Neoproterozoic World-class deposit biotite granodiorite and the three styles of ore bodies mentioned above are related to zoned hydrothermal Molybdenite Re–Os age dating alteration that includes greisenization, K-feldspar alteration, silicification, carbonatization, chloritization and Middle–Lower Yangtze River Valley fluoritization arranged in time (early to late) and space (bottom to top). New tungsten belt Five samples of molybdenite from the three types of have been collected for Re/Os dating. The results show Re/Os model ages ranging from 138.4 Ma to 143.8 Ma, with an isochron age of 139.18±0.97 Ma (MSWD=2.9). The quite low Re content in molybdenite falls between 0.5 ppm and 7.8 ppm that is indicative of the upper crustal source. This is quite different from molybdenites in the YRB Cu–Au–Mo–Fe porphyry–skarn deposits that contain between 53 ppm and 1169 ppm Re, indicating a mantle source. The Dahutang tungsten system is sub-parallel with the YRB porphyry–skarn Cu–Au–Mo–Fe system. Both are situated in the north margin of the Yangtze Craton and have a close spatial–temporal relationship. This pos- sibly indicates a comparable tectonic setting but different sources. Both systems are related to subduc- tion of the Paleo-Pacific plate beneath the Eurasian continent in Early Cretaceous. The Cu–Au–Mo–Fe porphyry–skarn ores are believed genetically related to granitoids derived from the subducting slab, whereas the porphyry W deposits are associated with S-type granitoids produced by remelting of the upper crust by heat from upwelling asthenoshere. © 2013 Elsevier B.V. All rights reserved.

1. Introduction 2011). A substantial progress in understanding both types of ore de- posits, their relation to granitic magmatism, and their setting has been The Middle–Lower Yangtze (or Chang Jiang) River Basin (hereinafter achieved in the past decades (Chang et al., 1991; Ling et al., 2009; Mao referred to as YRB) is a host to a major metallogenic province in et al., 2006, 2011; Pan and Dong, 1999; Zhai et al., 1992; Zhou et al., East-Central China that has a great economic value. The massive reserves 2008). of high grade Cu and Fe ores and locally supportive mining conditions ac- Recently a number of granite-related W and W–Mo deposits have count for a long mining history that can be traced back to the Bronze Age been discovered and explored to the south of the YRB, along the (~3800 years before present). Even after several millennia of metal min- Yangxing–Changzhou Fault (Fig. 1) and this includes the Dahutang ing, the YRB still shows a strong vitality and active exploration and min- (DHT) ore field. Dahutang was initially discovered by the Jiangxi ing continue to this day. YRB is characterized by both porphyry–skarn Bureau of Geology in 1957, by heavy mineral prospecting. Subsequent Cu–Au–Mo–Fe deposits, and – deposits (Mao et al., exploration in 1958, 1966, 1979 and 1984 proved the existence of a small tungsten deposit there. Detailed exploration (including drilling programs, underground working and trenches at surface), restarted in 2010, has so far established a tungsten resource that exceeds 1.1 ⁎ Corresponding authors. Tel.: +86 13810919614. E-mail addresses: [email protected] (Z. Mao), [email protected] Mt tons of WO3 (~880 Kt W) at an average grade of 0.152% W. (Y. Cheng). There is also 500 Kt Cu @ 0.12% and 80.2 Kt Mo @ 0.098% Mo. Further

0169-1368/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.oregeorev.2013.02.005 Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433 423

Fig. 1. Map showing the distribution of the mineral deposits along the Middle–Lower Yangtze River belt (YRB) and the porphyry–skarn W and W–Mo deposits south of it. YCF Yangxing–Changzhou Fault, TLF Tancheng–Lujiang Fault, XGF Xiangfan–Guangji Fault. investigation is underway and the local geological survey department outcrops in the south of the YCF zone include the Neoproterozoic speculates that the WO3 resource could reach up to 2,000,000 t. Shuangqiaoshan Group phyllite and Banxi Group of metamorphosed There are two distinct metallogenic provinces in South-Central slate locally intercalated with basalt–rhyolite volcanics in the Jiangnan China: 1) the Cu–Au–Mo–Fe porphyry–skarn YRB province, and 2) the massif (or shield). SHRIMP zircon U–Pb determination performed by broadly contemporaneous W–Sn province in the Nanling area, in the Gao et al. (2011) on volcanic rocks from both Groups indicated their for- central part of the Cathaysia Block (Fig. 1)(Chang et al., 1991; Chen et mation ages as 822 Ma±10 Ma and 803 Ma±7.6 Ma, respectively. A al., 1989; Mao et al., 2004, 2012; Zhai et al., 1992). The newly explored Phanerozoic cover is generally developed outside the Jiangnan massif Dahutang ore field and the other previously known veinlets and skarn and it includes clastic and rocks. There, as in the YRB, the WandW–Mo deposits in the same belt (Fig. 1) are situated along the Silurian to Early Triassic strata are marine clastic and carbonate rocks, northern margin of the Yangtze Craton, close to the YRB, but their char- Middle Triassic to Early Jurassic are paralic clastic rocks, whereas Middle acteristics have more similarities with the granite-related W and W–Sn to Late Jurassic–Cretaceous are sedimentary and volcanic rocks occur deposits in the Nanling area (see the inset of Fig. 1). This makes under- within a series of NE-trending continental basins. standing of their geology, formation age and tectonic environment of Neoproterozoic and Yanshanian granitic rocks are present in the great scientific and practical importance. This paper is a contribution area. The Jiuling Neoproterozoic granitic intrusion, the largest composite to understanding the geological characteristics of the Dahutang tung- granitoid complex in south-eastern China with an outcrop area greater sten ore field, integrated with new molybdenite Re/Os age determina- than 2500 km2 (Zhong et al., 2005). Mesozoic (Yanshanian) granitic tions, leading to a discussion about the metallogeny and geodynamics. rocks (more details below) in the study area occur as many small stocks, intruding in both Neoproterozoic granodiorite batholith and Precambri- an strata. 2. Regional geological background Mao et al. (2011) distinguished two ore types in the YRB: the Cu– Au–Mo–Fe porphyry–skarn type dated at 143–137 Ma, and the The YRB is located at the northern margin of the Yangtze Craton, “porphyrite ore” of magnetite–apatite (close to the Kiruna south of the North China Craton and Qinling–Dabie orogenic belt, type) dated at 135–123 Ma. The tungsten veinlet-disseminated and characterized by several large strike-slip fault systems, i.e. the skarn belt located south of the YRB includes the Xianglushan, Xiangfan–Guangji Fault in the northwest, the Tancheng–Lujiang Dahutang, Yangchuling, Qimei, Matou, Jitoushan and other deposits, Fault in the northeast and the Yangxing–Changzhou Fault (YCF) in shown in Fig. 1. the south (Fig. 1). Five successions of exposed rocks are generally found in YRB, from base to top: 1) Mesoproterozoic low-grade metamorphic basement; 2) Neoproterozoic to Silurian clastic rocks; 3. Geology of the Dahutang tungsten ore field 3) Middle Devonian to Early Triassic ; 4) Middle Triassic to Early Jurassic marine and terrigenous sedimentary rocks; and 5) Early The Dahutang tungsten ore field is located in the western segment Cretaceous units which comprise four cycles of andesitic volcanic rocks of the Jiuling-Zhanggong uplift within the Yangtze Craton; all tung- controlled by several parallel NE-trending extensional basins. Rocky sten mineralizations are found within the Neoproterozoic Jiuling 424 Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433 granodiorite batholith (Fig. 2). The relatively monotonous strata in between 100 m and 500 m, can be observed within the mining area, the mine area include the gray–green to dark gray phyllite and slate where they contain wolframite–scheelite quartz veins. As another im- of the Neoproterozoic Shuangqiaoshan Group, intercalated with portant ore-controlling structure, the stockwork fractures are densely meta-sandstone characterized by rhythmic turbiditic (flysch) banding. developed at the contact of the Cretaceous porphyritic biotite granite These rocks are discontinuously distributed as roof pendants in the and the surrounding country rocks of the Neoproterozoic biotite grano- Jiuling biotite granodiorite and they include a relatively large outcrop batholith, and are interpreted as the result of post-emplacement area in the southern part of the mine area, south of the Shiweidong dilation due to volume reduction of the solidifying Cretaceous granite ore deposit (Fig. 2). Products of thermal in the rock stock. units at contact with the Neoproterozoic biotite granodiorite are The exposed intrusive rocks within the mining area are part of the hornfelsed and characterized by andalusite and cordierite spots in Neoproterozoic Jiuling composite intrusion of predominantly gray, slate and greywacke, or silicification. medium to coarse crystalline quartz-phyric granodiorite composed Deformation structures are extensively distributed in the area and of 25–30% quartz, 20–40% plagioclase, 5–10% K-feldspar, 6–13% include faults and joints. An EW-striking ductile shear zone formed in biotite, 1–5% cordierite, and 2–5% . Zircon, apatite, garnet, the Neoproterozoic biotite granodiorite batholith within the Shimensi magnetite and are the most common accessory . deposit area, with outcrop width of approximately 100 m. The shear The Cretaceous biotite granite emplaced into the Jiuling granodiorite zone crosses the Xin'anli W property (Fig. 2) in the east and extends batholith (Fig. 2) consists of porphyritic biotite granite, fine-grained outside Fig. 2 at both sides. This shear zone displays a significant biotite granite, and granite porphyry dykes. The porphyritic biotite zoning of the fault rock, from the periphery to the center: mylonitic granite is gray to white with ~60 vol.% of plagioclase and ~40 vol.% of biotite granodiorite→mylonite→phyllonite→mylonitic schist. In the quartz phenocrysts in fine-grained matrix. The common length of pla- mine area the shear zone is highly silicified and mainly acted as an gioclase phenocrysts is 0.5–1 cm, with the largest reaching up ore-controlling structure. North of the Shimensi deposit this shear zone to 2 cm. The matrix is composed of 30 vol.% quartz, 40–50 vol.% plagio- is intersected by the NNE-trending Xianguoshan–Dahutang-Shiweidong clase, and 5–10% biotite. The gray fine-grained granite has 20–21% of basement fault with total length of up to 25 km. These two sets of faults plagioclase, 33–34% of K-feldspar, 39–40% of quartz and ~7% of biotite. are considered to have been the channels of the ore fluids, and they not The tabular plagioclase crystals that measure between 0.6×0.8 and only controlled the distribution of the deposits, but also determined the 1.4×2.4 mm are subhedral and commonly exhibit polysynthetic emplacement of Cretaceous granite. In addition to this, several NNE–NE twins, less often as compound carlsbad–albite twins. Biotite flakes are and NNW–NW trending, NW and NE dipping faults of variable length mainly euhedral. Post-mineralization medium to fine-grained, light

Fig. 2. Geological map of the Dahutang tungsten ore field that includes the Shimensi, Yikuangdai and Shiweidong deposits. The tungsten mineralization developed within the Neoproterozoic Jiuling granodiorite intrusion and is genetically related to Cretaceous (Yanshanian) granitic intrusions. (Modified from No. 916 Geological Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration and Development, 2012). Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433 425

flesh-colored granite porphyry dykes intersect the above-mentioned phyllite and slate (Fig. 4). The ore body has usually a layered to lenticular granitoids and the ore veins. They have 10–15% plagioclase, 20% quartz form with a maximum thickness of ~390 m. Subeconomic tungsten and 5% biotite phenocrysts in matrix of K-feldspar, quartz and mineralization is more widespread, especially between the delineated sericite. The Dahutang tungsten ore field consists of three ore de- higher grade zones. posits (or sections): the Shimensi deposit in the north, Dalingshang (or Yihaomai) deposit in the center and the Shiweidong deposit in 4. Alteration and mineralization the south (Fig. 2). Shimensi was explored by the No. 916 Geological Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration 4.1. Mineralization styles and Development proving a reserve of 758,500 t @ 0.19% WO3. Shiweidong was explored by the Northwestern Geological Team, Three mineralization styles are represented in the Dahutang ore Jiangxi Bureau of Geology, Mineral Resources, Exploration and De- field: 1) Veinlet-disseminated (Fig. 5a, b); 2) quartz vein (Fig. 5c); velopment who calculated a reserve of up to 299,000 t @ 0.17% and 3) hydrothermal breccia (Fig. 5d). Style 1 accounts for more

WO3. At present, more drilling is in progress around the Dalingshang de- than 90% of total tungsten reserve. These three styles frequently posit. There, the mineralization is predominantly in the Neoproterozoic co-exist in space and overlap each other (Fig. 6). biotite granodiorite close to contact with the Cretaceous biotite granite Style 1 mineralization is most common in granitoids of both age stock, although some ore bodies are in Cretaceous biotite granite groups. The Neoproterozoic biotite granodiorite hosts more than endocontact (Fig. 3a,b)andafewextendintotheNeoproterozoic 57.3% of the total tungsten reserves of the veinlet-disseminated

Fig. 3. Geological map at elevation 1055 m (a), and A–B–C longitudinal section (b), showing the major ore bodies in the Shimensi deposit of the Dahutang tungsten ore field, hosted mainly by the Neoproterozoic biotite granodiorite. The ore bodies extend towards the east, west and south outside the scope of Fig. 3a. (After No. 916 Geological Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration and Development, 2012). 426 Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433

Fig. 4. The Shiweidong cross section of the Dahutang ore field showing most ore bodies hosted by the Neoproterozoic phyllite and slate and less in the Cretaceous granite (Modified from Northwestern Geological Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration and Development, 2012).

style and the ore has a relatively high grade (0.18–0.40% WO3). 4.2. Mineralization and alteration events Wolframite is slightly more common than scheelite among the ore minerals. The corresponding ore style in the Cretaceous biotite In the light of mineral paragenesis, cross-cut relationships, tex- granite accounts for up to 32.7% of the total resource but the grade tures/structures and related wall rock alteration, the ore forming of 0.16–0.30% WO3 is slightly lower. The ore consists of fine-grained events at Dahutang can be divided into three stages: 1) Cretaceous anhedral scheelite, wolframite, and other metallic biotite granite emplacement accompanied by thermal metamorphism minerals in a gangue of quartz, biotite and muscovite. The distribu- and pegmatite formation; 2) magmatic-hydrothermal alteration tion of veinlet-disseminations ranges from sparse to dense (Fig. 5a). and mineralization that can be further subdivided into a pre-ore Breccia-hosted mineralization is developed in central parts of the K-feldspathization, ore-related silicification and greisenization, and Shimensi and Shiweidong deposits, in apical part of the Cretaceous post-ore carbonatization; and 3) post-Cretaceous supergene modifica- biotite granite stock (Fig. 6). The breccia fragments have been derived tion. This paragenetic sequence is illustrated in Fig. 7. more from the Neoproterozoic granodiorite than from the Cretaceous Thermal metamorphism resulted from the intrusion of granitic porphyritic biotite granite. Most of the exhibit internal magma into roof rocks. The degree of resulting changes is controlled jigsaw texture (hydraulic fracturing) filled by quartz-dominated ore by the heat regime and the nature of the rocks undergoing thermal component (Fig. 5d). The interfragmental hydrothermal fill has, in metamorphism, especially their composition. Therefore, changes pro- addition to quartz, subordinate muscovite, biotite, K-feldspar, fluorite, duced by the emplacement of the Cretaceous granite into Proterozoic and other gangue minerals. Wolframite, scheelite, chalco- granodiorite in the Dahutang area are slight to barely discernible. On and molybdenite have the form of scattered lumps, dissemina- the other hand, wall rocks other than this granodiorite were tions and diffuse admixtures in the gangue and rarely in the breccia subjected to substantial thermal modifications, such as hornfelsing fragments. It is interesting to see the presence of dendritic biotite, and porphyroblastic growth of minerals. The Shuangqiaoshan Group within the breccia ore, growing inward towards the cementing mate- schist in Cretaceous granite exocontact is spotted with and andalusite rial. This ore style contributes some 5% of the total WO3 reserve in the and cordierite porphyroblasts and is locally silicified. ore field. Generally Sn–W orthomagmatic pegmatite shells or Quartz, wolframite, and scheelite veins cut through the entire lenses overlap with hydrothermally altered rocks, dominated by area. They follow the NE-, NW- and NS-striking faults, are most wide- K-feldspar and/or albite (Pirajno, 2012). The pegmatoidal shells in spread in the western and central areas, and account for about 1% of the classical localities such as those of the central European Erzgebirge the total ore reserve. In these veins, wolframite usually occurs in (Altenberg) (Rösler et al., 1968), seem to combine both volatile magma thick tabular crystals, rooted in both vein walls, forming a symmetri- emplacement and hydrothermal alteration, and are often transitional cal comb-like structure (Fig. 5c). This ore variety has a higher tung- into (quartz, muscovite) and quartz, , , cassiter- sten grade (average of 0.282% WO3) compared with the remaining ite, and wolframite ore veins that fill concentric dilations in granite ore types in the deposits, and wolframite is more common than parallel with cupola surfaces as in Cínovec, (Štemprok scheelite. It also can be seen that scheelite aggregations replace the et al., 1995). In the Dahutang ore field such pegmatoidal shells are devel- wolframite crystals. The ore are vertically zoned, from the oped along contacts of Cretaceous granite cupolas against the Proterozoic top downwards: W→W+Cu→Cu+Mo. granitoid exocontact. They consist of K-feldspar, quartz, and small Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433 427

Fig. 5. Veinlet scheelite ore exhibited in drill cores (a), and in the underground mine (b), a thick quartz–wolframite (scheelite) vein ore showing large crystals of wolframite that grew inward from the wall towards the vein center, with interstitial scheelite, molybdenite and chalcopyrite assemblages (c); scheelite-mineralized ore in jigsaw-style hydrothermal breccias (d). amounts of biotite and muscovite perpendicular to the contact zone proportional to the vein thickness, ranging from several centimeters to (Fig. 8a, b). True magmatic pegmatite veins, however, also exist in the cu- tens of centimeters. In the breccia ore greisenization also occurs in the polas. They have cross-cutting relationships, sharp contacts, and are country rocks along the quartz–wolframite–scheelite cements. Carbon- composed of K-feldspar megacrysts, albite, and quartz with interstitial ate veinlets and short discontinuous veins of purple fluorite infill dila- muscovite. Metallic mineralization, however, is absent here. tions in the closing, post-ore stage of the hydrothermal event and they In the initial magmatic-hydrothermal stage potassic alteration are superimposed on all ore style varieties as well as on unmineralized converted albite in the Neoproterozoic granodiorite to K-feldspar. granitoids. This was followed by the introduction of ore metals producing the Retrograde supergene modification of the hypogene ores, as well three ore styles described above (veinlets-disseminations, hydrother- as their host rocks, took place after erosion that removed several mal breccias, wolframite–scheelite quartz veins) with the following thousand meters of the roof and exhumed the primary mineraliza- mineral associations: tion. Oxidation and hydration at the higher supergene levels were responsible for conversion of sulfides into goethite, , covel- quartz–K-feldspar–wolframite– lite and , whereas wolframite and scheelite were oxidized quartz–muscovite–wolframite–scheelite–cassiterite into . In the deeper secondary sulfides zone chalcocite and quartz–wolframite–scheelite covellite replaced chalcopyrite and , whereas wolframite and quartz–wolframite–scheelite–chalcopyrite scheelite remained as relics. Silicate minerals weathered into hydromica and kaolinite locally pigmented by , and carbonate and fluo- quartz–scheelite–chalcopyrite–(bornite) rite were leached out. quartz–molybdenite–chalcopyrite. Among them the quartz–wolframite–scheelite veins, veinlet and 5. Sampling, analytical methods and results breccias are dominant. Greisen and silica alterations are closely associat- ed with the mineralization. Pervasive quartz–muscovite greisenization Re/Os isotope analysis of molybdenite is a powerful method to de- is the standard feature of the veinlet-disseminated ore style, whereas termine the ore-forming ages. It has been extensively applied to date the quartz–wolframite–scheelite veins have greisen selvages that are ores in past fifteen years (e. g. Mao et al., 1999; Stein et al., 1997). In 428 Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433

Fig. 6. NW–SE cross-section of the Shimensi deposit showing three tungsten ore types: veinlets-disseminated breccia and wolframite (scheelite)–quartz vein. (After No. 916 Geo- logical Team, Jiangxi Bureau of Geology, Mineral Resources, Exploration and Development, 2012).

order to establish the precise mineralization age of the Dahutang simultaneous emplacement. Our data, processed using the ISOPLOT/ porphyry tungsten system we collected five molybdenite samples Ex program (Ludwig, 2004), yielded an isochron age of 139.2± numbered DHT-1, DHT-7, DHT-8, DHT-13 and DHT-14 from the 1.0 Ma, with MSWD=1.7 (Fig. 10). The identical model ages and iso- Shimensi deposit for analysis. The sample set comprised two repre- chron ages of the five samples suggest that the analytical results are sentatives of the veinlet-disseminated style, two from the quartz– reliable. wolframite–scheelite veins and one from the breccia style. In the first ore style molybdenites occur as fine-crystals in veinlets- 6. Discussion disseminated ores hosted in porphyritic biotite granite (Fig. 9a). In the vein ore style molybdenite flakes tend to accumulate along the 6.1. Principal characteristics of granite-related tungsten deposits vein-wall rock contact and reach into the altered selvage (Fig. 9b). In the breccia-hosted ore molybdenite is scattered in the internal Both skarn and wolframite–quartz vein types of tungsten deposits fragmental space. are the major source of tungsten metal in China and the world (Černý Molybdenite concentrates for analysis were prepared using the et al., 2005; Laznicka, 2006, 2010; Li, 1993; Mao et al., 2009; Pirajno, conventional method. After crushing the samples were subjected to 2009). Compared to the porphyry Cu–Mo deposits, porphyry tungsten gravity and magnetic separation after which the molybdenite grains deposits are less known. So far, several porphyry W–Mo, W–Mo–Sn de- were handpicked under a binocular microscope to achieve >99% posits are reported in New Brunswick, (Noble et al., 1984; Parrish sample purity. The analyzed molybdenite was fine-grained (b0.1 mm) and Tully, 1978; Sinclair, 2007), the Logtung deposit, south-central to minimize possible decoupling of Re and Os within large molybdenite Yukon Territory (Noble et al., 1984), the Lianhuashan porphyry W de- grains (Selby and Creaser, 2004; Stein et al., 2003). The analyses were posit, the Yangchuling W–Mo deposit and Jitoushan porphyry W–Mo de- performed in the Re–Os Laboratory, National Research Center of Geo posit (Man and Wang, 1988; Song et al., 2012; Tan, 1985), and Weolag analysis, Chinese Academy of Geological Sciences in Beijing using a Ther- and Dae Hwain Korea (Shelton et al., 1987; So et al., 1983a,b). However, mo Electron TJA X-series ICP-MS. The analytical procedures followed these porphyry W deposits are small scale with less economic value those described by Shirey and Walker (1995), Mao et al. (1999) and (Sinclair, 2007). Among them the Lungton is described as a large

Du et al. (2004). The model ages were calculated following the equation: tonnage, low-grade W (scheelite)–Mo porphyry deposit, its WO3 reserve t=[ln (1+187Os/187Re)]/λ,whereλ is the decay constant of 187Re, is 210,600 t (Noble et al., 1984; Sinclair, 2007), much less than 1.666×10−11/year (Smoliar et al., 1996). the Dahutang tungsten deposit. It's worth to point out that porphyry In our samples the concentrations of 187Re and 187Os ranged from Cu–Mo, porphyry Cu–Au and porphyry Mo deposits usually have a typi- 354 to 4952 ppb to 0.82 to 11.60 ppb, respectively. In order to check cal alteration zoning, i.e. potassic alteration, quartz sericite and propylitic the accuracy we have ran a duplicate analysis of sample DHT-7. We alteration from the core outwards. However, the porphyry tungsten de- have obtained a range of Re–Os model ages of 138.4–143.8 Ma, with posits are characterized by strong greisenization, and weak potassic al- a weighted mean age of 140.4±1.9 Ma. All three styles of ore distri- teration and propylitization. In this case, Davis and William-Jones bution returned the same mineralization age, implying an almost (1985) named it as porphyry–greisen tungsten deposit. Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433 429

Fig. 7. Paragenetic sequence of alteration and ore minerals in the Dahutang tungsten deposit.

Rundqvist et al. (1971) recognized greisen Sn (W) at the cupolas of muscovite, cassiterite and minor wolframite occurs as massive and dis- granite intrusions in the Erzgebirge area of Germany and Czech, Tasma- seminated ore styles. There are a few typical greisen tungsten deposits nia, and Mongolia. The greisen ore mainly consisting of quartz, in China. Feng et al. (2011a,b) reported a greisen tungsten deposit in

Fig. 8. Pegmatite shell between the Cretaceous porphyritic biotite granite stock and the Neoproterozoic biotite granodiorite batholith in Shimensi (a) and Dalingshang (b), mainly consisting of K-feldspar, quartz and a small amount of biotite and muscovite that are aligned perpendicularly to the contact. 430 Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433

Fig. 9. Sample of veinlets-disseminated W ore from which emolybdenite samples were collected for Re/Os dating, showing disseminated coexisting molybdenite and chalcopyrite in porphyritic biotite granite (a); Molybdenite in the quartz–wolframite (scheelite) vein usually occurs along the vein/wall rock contact and in altered vein selvages (b).

south Jiangxi province, Nanling region, where an elongated greisen ore of biotite. On the whole, the Dahutang ore field shares similarities to body mainly consisting of quartz, muscovite, and wolframite developed both porphyry and greisen ore systems. along a within the Jiulongnao biotite granite batholith. The other example is Shizhuyuan, a world class skarn–greisen W–Sn–Mo– 6.2. Timing of metal introduction and metal sources in the Dahutang ore Bi deposit in southern China, where the large stockwork greisen ores field and comparison with other W deposits in southern China comprising quartz–biotite, quartz–muscovite and quartz–topaz ore veins overprint the skarn ores (Mao and Li, 1996). Unlike the typical grei- We consider the geochronological data obtained by application of sen deposits, the Dahutang contains veinlets-disseminated, wolframite the Re/Os dating technique to Dahutang molybdenite samples (model and scheelite quartz vein and hydrothermal breccia-hosted ore styles. ages ranging from138.4 Ma to143.8 Ma; Table 1,Re–Os isochron age They have limited amounts of muscovite and cassiterite but are of 139.18±0.97 Ma (MSWD=2.9) (Fig. 10)) to closely approximate enriched in wolframite, scheelite, and chalcopyrite within the veinlets the age of molybdenite crystallization and tungsten mineralization. and quartz vein and breccia ores. All three ore types have the same min- These mineralization age data also compare well with the ages eral associations and are characterized by strong greisenization mainly reported from other porphyry W–Mo deposits in the same ore belt comprising quartz and muscovite, and weak potassic and propylitic al- in the Middle–Lower Yangtze River region. Song et al. (2012) teration. Hydrothermal potassic (K-feldspar) alteration at the base of reported the Re/Os molybdenite age of 137 Ma for the W ore, and the exposed mineral system overlaps with pegmatite and is gradational U–Pb zircon age of 138 Ma for the parent granite, in the Jitoushan to greisen in the mid-section (especially in the Shimensi deposit), indic- porphyry W–Mo deposit. Man and Wang (1988) obtained muscovite ative of extensive Ca, Na and Mg removal from the host granites. Silici- K–Ar ages of 137.1±3.4 Ma and 137.8±3.1 Ma for breccia ore, and fication (in the Shiweidong deposit) or dilations-filling by quartz whole rock Rb–Sr isochron ages of 140.5±4.7 Ma for ore-related followed, all spatially associated with mineralization. In the distal envi- granodiorite in the Yangchuling porphyry W deposit. It explains the ronment as in the Neoproterozoic granodiorite, chlorite formed in place Dahutang granite related tungsten ore field shares a nearly contem- poraneous age with the porphyry W–Mo deposits and the porphyry– skarn Cu–Au–Mo–Fe deposits in the mineral province. The trace Re content in molybdenite has been used to trace the source of the Mo in the ores and by implication of the associated metals such as W. Literature data indicate progressive Re decrease from >100 ppm in Mo derived from mantle sources through tens of ppm for mixed mantle/crust source to b10 ppm for crustal sources (Berzina et al., 2005; Mao et al., 1999, 2008). As shown in Table 1, the Re contents in the Dahutang molybdenite are between 0.5 ppm and 7.8 ppm, suggesting an upper crustal Mo source genetically relat- ed to granitic magmas formed by partial melting of the continental lithosphere. The same order of magnitude of trace Re in molybdenite (Re: 0.03–2.6 ppm) was reported by Li and Mao (1996), Peng et al. (2006), Mao et al. (2004, 2007) and Feng et al. (2011a,b) for the granite-related W–Sn deposits in the Nanling region in South China. This, however, contrasts with the Re in molybdenite values in porphyry–skarn type Cu–Au–Mo–Fe in the Middle–Lower Yangtze region, reported as ranging from 53 ppm to 1169 ppm and con- sidered sourced from melts derived from the subducting slab (Mao et al., 2006, 2011)and/oroceanicridge(Ling et al., 2009). The metallogenic contrast between two roughly parallel mineral- ized belts of approximately the same age in the Yangtze ore province Fig. 10. Molybdenite Re/Os age of the Shimensi ore section constructed using ISOPLOT mentioned earlier: the YRB porphyry–skarn Cu–Au–Mo–Fe belt and software of Ludwig (1999). The calculated isochron age using the decay constant: λ(187Re) is 1.666×10-11/year (Smoliar et al., 1996); absolute uncertainty at 2σ has the granite-related W-(Mo, Cu) belt but have different metal sources. error of 1.02%. On the other hand, the latter is comparable with the Nanling W–Sn Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433 431

Table 1 Molybdenite Re/Os values of the Dahutang tungsten deposits, northwestern Jiangxi, China.

Analyzed no. Sample no. Ore types Weight (g) Re ng/g 187Re ng/g 187Os ng/g Model ages (Ma)

Measured 2σ Measured 2σ Measured 2σ Measured 2σ

120605-17 DHT-1 Type 2 0.10222 4059 36 2551 23 5.994 0.050 140.9 2.1 120605-18 DHT-13 Type 1 0.15423 2417 24 1519 15 3.569 0.033 140.8 2.2 120605-19 DHT-14 Type 1 0.15054 2508 22 1576 14 3.651 0.037 138.9 2.2 120525-18 DHT-7 Type 3 0.10486 7872 67 4948 42 11.42 0.09 138.4 2.0 120516-1 DHT-7 Duplication 0.10100 7879 62 4952 39 11.60 0.14 140.4 2.3 120510-3 DHT-8 Type 3 0.30124 549.5 5.7 345.4 3.6 0.8281 0.0082 143.8 2.4

Note: Type 1: veinlets-disseminated ore, type 2: crypto-explosive brecciated ore, type 3: wolframite–scheelite quartz veins. Decay constant: The ISOPLOT software of Ludwig (1999) was used to calculate the isochron age, decay constant: λ(187Re)=1.666×10–11/year (Smoliar et al., 1996), uncertainties are absolute at 2σ with error on Re and 187Os concentrations and the uncertainty in the 187Re decay constant.

province of crustal derivation (Chang et al., 1991; Chen, 1983; Chen et oblique subduction, underwent reactivation at ca. 160 Ma. High-K al., 1989; Zhai et al., 1992). In the early 1980's, the Yangchuling calc-alkaline granitoid magmas, derived from slab melting with porphyry W–Mo deposit was discovered and explored in the north- inputs from the crust, were intruded at N–EandE–W fault inter- ern margin of the Yangtze Craton, followed by the Xianglushan sections, followed by the YRB Fe–Cu–Au–Mo-deposits between skarn-type tungsten deposit explored in 1990's (Fig. 1). Although 143 and 137 Ma. geographically close to the YRB, the metallogenic type and ore style The peraluminous (S-type, ilmenite-series) granites, generated by are more similar to the Nanling Sn–W system related to crustal gra- partial melting of crustal material, with their genetically-related nitic melts. NYCT tungsten metallogenic belt, developed in the same tectonic Our results integrated with published data, now make it possible setting as the YRB, but from different magma source materials. to define an independent tungsten metallogenic belt that is parallel During the 143–137 Ma period the asthenosphere rising along with the long known Yangtze River Fe–Cu–Au–Mo porphyry–skarn the window in the subducting slab induced melting of the overly- belt (YRB). We propose to name the Dahutang ore field and deposits ing continental crust producing the peraluminous magma (Fig. 11a). in the same area as the North Yangtze Craton tungsten belt (NYCT). In The ascent of the fractionating volatiles-rich buoyant magma into the addition to the near super large Dahutang tungsten ore field it also near-surface region resulted in exsolution of the magmatic contains Jitoushan and other recently discovered porphyry W–Mo de- posits (Fig. 1). Both metallogenic belts originated at approximately the same time with ages between 143 and 137 Ma(Li et al., 2010; Mao et al., 2006, 2011; Xie et al., 2007; Zhao et al., 2006; Zhou et al., 2008).

6.3. Geodynamic interpretation

Both metallogenic belts defined above: YRB and NYCT, are close in space and time, but have a different selection of the ore metals. This suggests different source relationships at the onset of development of the ore-forming system. Chang et al. (1991) and Zhai et al. (1992) proposed a strong inter- action between mantle and crust to explain the origin of the Yanshanian I-type granitoids parental to the YRB metallogenic belt. Zhang et al. (2001a,b) compared the same granitoids with the adakites, produced by partial melting of intermediate-mafic granu- lites in the deep lower crust under high P–T conditions. Mao et al. (2006) placed the origin of the porphyry–skarn Cu–Au–Mo–Fe de- posits into the 160 to 135 Ma time interval during which the principal N–S stress field in eastern China continent changed progressively to an E–W orientation, due to the subduction of the Paleo-Pacific Plate beneath the Eurasian Plate. Ling et al. (2009), by contrast, proposed a Cretaceous oceanic ridge subduction to explain the 140–125 Ma magmatism and associated metallogenesis. Most recently, using geo- logical observations, petrochemistry and Sr/Nd isotopic data, Mao et al. (2011) concluded that the eastern part of the Eurasian continent was an active continental margin at ca. 180 Ma, as the Izanagi Plate subducted orthogonally beneath the continent. At ca. 160 Ma this plate rotated clockwise towards the north with subduction orienta- tion becoming oblique with respect to the continental margin. This triggered emplacement of large amounts of granite magma in the back-arc setting associated with metallic mineralization con- trolled by regional NE–SW strike-slip faults. The geochronological Fig. 11. Proposed model showing the spatial disposition of the W deposits, related to data obtained for the Middle–Lower Yangtze River region consis- crustal melting along NYCT and the porphyry–skarn Cu–Mo–Au–Fe deposits along – tently indicate that the Tan Lu regional strike-slip fault zone was the YRB (a), triggered by slab window, and the three types of tungsten ores: initiated between 233±6 and 225±6 Ma and, due to the Izanagi veinlets-disseminated, quartz–wolframite (scheelite) vein and breccia ores (b). 432 Z. Mao et al. / Ore Geology Reviews 53 (2013) 422–433 hydrothermal fluid resulting in strong alkali , Laznicka, P., 2006. Giant Metallic Deposits, Future Sources of Industrial Metals. Springer, fi Heidelberg (732 pp.). greisenization and silici cation in the roof zones and roof pendants ac- Laznicka, P., 2010. Giant Metallic Deposits, Future Sources of Industrial Metals, 2nd Edition. companied by, or followed by, the W-(Mo, Cu) metallic mineralization Springer, Heidelberg (961 pp.). in three styles (Fig. 11b). Li, Y.D., 1993. Poly-type models for tungsten deposits and vertical structural zoning model for vein-type tungsten deposits in South China. In: Kirkham, R.V., Sinclair, W.D., Duke, J.M. (Eds.), Mineral Deposit Modeling: Geol. Assoc Can. Special paper, 7. Conclusions 40, pp. 555–568. Li, H.Y., Mao, J.W., 1996. Re–Os isotopic chronology of molybdenites in the Shizhuyuan polymetallic tungsten deposit, South China. Geol. Rev. 42, 261–267 (in Chinese The recently discovered and explored Dahutang is the world's with English abstract). largest tungsten ore fields. It is located south of the Middle– Li, J.W., Deng, X.D., Zhou, M.F., Liu, Y.S., Zhao, X.F., Guo, J.L., 2010. Laser ablation ICP-MS – – – – – titanite U–Th–Pb dating of hydrothermal ore deposits: a case study of the Tonglushan Lower Yangtze River Fe Cu Au Mo porphyry skarn belt dated – – – – Cu Fe Au skarn deposite, SE Hubei Province, China. Chem. Geol. 270, 56 67. at 143 137 Ma. In this contribution we discuss the essential char- Ling, M.X., Wang, F.Y., Ding, X., Hu, Y.H., Zartman, R.E., Xiong, X.L., Sun, W.D., 2009. Cre- acteristics of the Dahutang deposit in terms of geology, style of taceous ridge subduction along the Lower Yangtze River belt, Eastern China. Econ. mineralization, hydrothermal alteration and mineralization. We Geol. 104, 303–321. Ludwig, K.R., 1999. Isoplot/Ex, version 2.0: a geochrological toolkit for Microsoft Excel. also provide new Re/Os isotopic data in molybdenite, resulting Special Publication, 1a. Geochronology Center, Berkeley. in a model age of the W mineralization ranging from 138.4 Ma Ludwig, K.R., 2004. Isoplto/Ex, Version 3.0: A Geochronological Toolkit for Microsoft to 143.8 Ma, and an isochron age of 139.18±0.97 Ma (MSWD=2.9). Excel. Berkeley Geochronology Center, Berkeley, California. Man, F.S., Wang, X.S., 1988. Isotopic geochronolgy of the Yangchuling porphyry The very low trace Re content in molybdenite of 0.5 to 7.8 ppm in- tungsten– deposit. Geol. Miner. Resour. (1) (6-1-66 (in Chinese)). dicates the involvement of upper continental crustal as a source for Mao, J.W., Li, H.Y., 1996. Geology and metallogeny of the Shizhuyuan skarn–greisen de- the parental granite magmas. This contrasts with the 53 ppm to posit, Hunan Province, China. Int. Geol. Rev. 38, 1020–1039. – 1169 ppm Re values in molybdenites from the YRB Fe–Cu–Au–Mo Mao, J.W., Zhang, Z.C., Zhang, Z.H., Du, A.D., 1999. Re Os dating of molybdenites in the Xiaoliugou W-(Mo) deposit in the northern Qilian Mountains and its geological metallogeny, indicative of a mantle source for parent magmas significances. Geochim. Cosmochim. Acta 63, 1815–1818. and metals. We have defined a new NYCT tungsten-dominated Mao, J.W., Xie, G.Q., Li, X.F., 2004. Mesozoic large scale mineralization and multiple – metallogenic belt along the northern margin of the Yangtze Craton lithospheric extensions from South China. Earth Sci. Front. 11 (1), 45 56 (in Chinese with English abstract). that, despite the close time–space relationship and comparable set- Mao, J.W., Wang, Y.T., Lehmann, B., Yu, J.J., Du, A.D., Mei, Y.X., Li, Y.F., Zang, W.S., Stein, ting with the YRB belt, had a different source of magmas; this was H.J., Zhou, T.F., 2006. Molybdenite Re–Os and albite 40Ar/39Ar dating of Cu–Au–Mo responsible for the formation of two subparallel mineralized belts and magnetite porphyry systems in the Changjiang valley and metallogenic impli- cations. Ore Geol. Rev. 29, 307–324. with contrasting selection of ore metals. Mao, J.W., Xie, G.Q., Guo, C.L., Chen, Y.C., 2007. 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