American Mineralogist, Volume 106, pages 1488–1502, 2021

Two-stage magmatism and tungsten mineralization in the Nanling Range, South China:
Evidence from the Jurassic Helukou deposit

Jingya Cao1, Huan Li2,*, Thomas J. Algeo3, 4, 5, Lizhi Yang2, and Landry Soh Tamehe2

Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), Guangzhou 511458, China
1

2
Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitoring, Ministry of Education,
Central South University, Changsha 410083, China
3
Faculty of Earth Resources, State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences,
Wuhan 430074, China
4
State Key Laboratory of Biogeology and Environment Geology, School of Earth Sciences, China University of Geosciences, Wuhan 430074, China
5
Department of Geology, University of Cincinnati, Cincinnati, Ohio 42221-0013, U.S.A.

Abstract
The Helukou deposit, with proven reserves of 33 752 t WO3, is one of the newly exploited medium-
scale tungsten (W) deposits in the Guposhan ore field, Nanling Range of South China. Skarn-type
and less abundant altered granite-type tungsten orebodies were identified in this deposit. The ore
mineralization in this district was a product of two-stage magmatism, as shown by LA-ICP-MS U-Pb
dating of zircons and Re-Os dating of molybdenite. The former yielded U-Pb ages of 184.0 ± 3.6 Ma
(MSWD = 0.15) and 163.8 ± 1.5 Ma (MSWD = 0.41) for fine-grained biotite granite and muscovite
granite, respectively, as well as a U-Pb age of 181.5 ± 2.1 Ma (MSWD = 0.75) for zircon grains from
altered granite-type tungsten ore. The latter yielded molybdenite Re-Os ages of 183.5 ± 2.8 Ma (with-
out MSWD owing to a limited number of samples) and 163.4 ± 2.8 Ma (MSWD = 0.71) for altered
granite-type and skarn-type tungsten deposits, respectively. Thus, two separate tungsten mineralization
events occurred during the Early Jurassic and Middle Jurassic. Trace-element compositions suggest
that scheelite I was controlled by the coupled substitution reactions of 2Ca2+ = Na+ + REE3+ and Ca2+
+ W6+ = Nb5+ + REE3+, whereas scheelite II was controlled by the coupled reactions of 2Ca2+ = Na+ +
REE3+ and 3Ca2+ = Ca + 2REE3+ (where  is a site vacancy). High Mo and low Ce contents suggest
that both scheelite I and scheelite II were precipitated from oxidizing magmatic-hydrothermal fluids.
Based on the mineral assemblage of the altered granite-type ores and geochemical characteristics of
scheelite I [i.e., negative Eu anomalies (0.02–0.05; mean = 0.03 and STD = 0.01), and high 87Sr/86Sr
ratios (0.70939–0.71932; mean = 0.71345 and STD = 0.00245)], we infer that fluid-rock interaction
played an important role in modifying Early Jurassic ore-forming fluids. Scheelite II exhibits a geo-
chemical composition [i.e., 87Sr/86Sr ratios (0.70277–0.71471; mean = 0.70940 and STD = 0.00190),
Eu anomalies (0.14–0.55; mean = 0.26 and STD = 0.09), and Y/Ho ratios (16.1–33.7; mean = 27.9
and STD = 2.91)] similar to that of the Middle Jurassic Guposhan granites, suggesting inheritance of
these features from granite-related magmatic-hydrothermal fluids. These results provide new insights
into the two-stage magmatic and metallogenic history of the Nanling Range during the Jurassic Period.
Keywords: scheelite, Re-Os dating, U-Pb dating, W-Sn mineralization, Guposhan

Introduction al. 2019b; Jiang et al. 2019; Tang et al. 2020). The ages of these
The South China, well-known for its huge resources of ore deposits mostly range from 165 to 150 Ma, e.g., Xihuashan
tungsten-tin (W-Sn) and other rare metals, is one of the most (157.8 ± 0.9; Hu et al. 2012), Piaotang (159.8 ± 0.3; Zhang et al.
significant metallogenic domains in the world (Fig. 1; Mao et 2017), Yaogangxian (154.9 ± 2.6; Peng et al. 2006), Xitian (156.6
al. 2007, 2008, 2013; Chen et al. 2013; Hu et al. 2017; Cao et al. ± 0.7 Ma; Cao et al. 2018a) and Furong (159.9 ± 1.9; Yuan et al.
2018a, 2018b, 2020a; Zhou et al. 2018; Li et al. 2019a; Tang et 2011b), and are similar to the ages of Middle Jurassic felsic granites
al. 2019; Xie et al. 2019a, 2019b). Its estimated tungsten and tin in this region (Mao et al. 2007; Li et al. 2017; Jiang et al. 2018a,
reserves are 8 050 000 tons and 5 956 000 tons, respectively (Fu et 2018b; Cao et al. 2018a, 2018b). Recently, using laser ablation
al. 2017a). Several large to super-large W-Sn polymetallic deposits inductively coupled plasma-mass spectrometer (LA-ICP-MS)
occur in the Nanling Range, with the most representative being zircon U-Pb dating technology, numerous Early Jurassic felsic
the Shizhuyuan, Xihuashan, Piaotang, Yaogangxian, Furong, intrusions were identified in the Nanling Range, which include
Xianghualing, Taoxikeng, Dengfuxian, and Xitian deposits (Fig. 1; the Wengang granite (192 ± 1 Ma; Zhu et al. 2010), the Hanhu
Peng et al. 2006; Yuan et al. 2008, 2011a, 2011b; Guo et al. 2011; granodiorite (193 ± 2 Ma; Yu et al. 2010), the Xialan granite (196
Hu et al. 2012; Zhang et al. 2017; Cao et al. 2018a, 2018b; Li et ± 2 Ma; Yu et al. 2010), the Dabaoshan granodiorite (175.8 ± 1.5
Ma; Wang et al. 2011), and the Tiandong granite (188 ± 1 Ma;
* E-mail: lihuan@csu.edu.cn. Orcid 0000-0001-5211-8324 Zhou et al. 2018). However, none of these intrusions was associ-

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 CAO ET AL.: JURASSIC MAGMATISM AND TUNGSTEN MINERALIZATION IN NANLING 1489

2019). This technique is an ideal tool to study tungsten mineraliza-

tion to constrain the source and physico-chemical conditions of
the ore-forming fluids as well as fluid-rock interaction processes.
The Guposhan district, located in the southwestern Nanling
Range, is famous for its large-scale W-Sn mineralization, with
estimated tungsten and tin reserves of 592 000 and 687 000 tons,
respectively (Fu et al. 2017a). Previous studies reported only
Middle Jurassic ages for the granitic magmatism and related
W-Sn mineralization in the Guposhan ore district. In this study,
we report LA-ICP-MS zircon U-Pb and molybdenite Re-Os ages
for the Helukou W deposit, northern Guposhan district that docu-
ment a two-stage (Early and Middle Jurassic) history of granitic
magmatism and related W-Sn mineralization in the Nanling region.
In addition, the in situ trace-element and Sr isotopic compositions
of scheelite from the skarn-type and altered granite-type ores of
the Helukou W deposit constrain the nature of the ore-forming
fluids in this magmatic-hydrothermal system.

Regional and ore deposit geology

Regional geology
The South China Craton is composed of the Yangtze Block
Figure 1. Geological sketch map of the South China Craton in the northwest and Cathaysia Block in the southeast (Fig. 1).
(modified from Zhou et al. 2006), showing the distribution of Mesozoic The Nanling Range, located in the central part of the Cathaysia
granitic-volcanic rocks and the Sn-W deposits in the Nanling Range. Block, is one of the largest metallogenic belts in China and is
NLR = Nanling Range. (Color online.) characterized by giant W-Sn, and other rare metal deposits (Hua
et al. 2005, 2007; Mao et al. 2007; Hu et al. 2012, 2017; Chen
ated with W-Sn mineralization. Recently, the ore-forming age of et al. 2013; Chen et al. 2016; Cao et al. 2018b; Wu et al. 2018;
the Dading Fe-Sn deposit in the southeastern Nanling Range was Li et al. 2018a, 2018b, 2018c). In this region, the stratigraphic
reported at 185.9 ± 1.2 Ma, using Ar-Ar isotopic dating technol- succession consists of metamorphosed Proterozoic-Lower
ogy on phlogopite from stratiform skarn-type ore bodies (Cheng Paleozoic siliciclastic and volcanic rocks, overlain by Upper
et al. 2016; Fig. 1). This was the first Early Jurassic mineralization Paleozoic-Mesozoic carbonate and siliciclastic rocks (Cao et al.
event reported from the Nanling Range, and it was corroborated 2018b). These units were deformed tectonically, which produced
by a molybdenite Re-Os age of 185.9 ± 4.9 Ma for the skarn-type folds and faults widely across the Nanling Range (Wang et al.
ore bodies in this deposit (Zhao et al. 2019). These ages are also 2003, 2013; Mao et al. 2007, 2008, 2013). In addition, Mesozoic
consistent with a U-Pb zircon age of 187.5 ± 1.8 Ma (Cheng et al. tectonic events exerted great influence on this region, leading
2016) and a zircon U-Pb of 189.0 ± 1.5 Ma for the related Shibei to the development of E-W-trending faults and folds before the
granitic pluton (Zhao et al. 2019). Hence, the Early Jurassic gran- Middle Jurassic (i.e., during the Indosinian Orogeny) and NE-
itoids of the Nanling Range provide insight into not only the Early trending faults after the Middle Jurassic (i.e., during subduction
Jurassic magmatism of this region but also its contemporaneous of Paleo-Pacific Plate) (Shu et al. 2004; Mao et al. 2007). Jurassic
metallogenic evolution. intrusives (165–150 Ma), which are widespread in the Nanling
As one of the major W-bearing minerals, scheelite (CaWO4) Range, are composed of granitic and minor mafic rocks (Mao
occurs not only in quartz vein-, skarn-, greisen-, and altered et al. 2008, 2011). These intrusives are highly fractionated and
granite-type W deposits but also in hydrothermal Au, Sn, and originated from partial melting of Proterozoic basement rocks
Mo deposits (Ghaderi et al. 1999; Brugger et al. 2002; Guo et of the South China Craton (Chen et al. 2013; Li et al. 2014a,
al. 2016; Hazarika et al. 2016; Raju et al. 2016; Fu et al. 2017b; 2014b; Cao et al. 2018b).
Mackenzie et al. 2017; Orhan 2017; Liu et al. 2019; Sciuba et al. The Guposhan ore district, located in the southwestern Nan-
2019). Scheelite commonly accommodates significant amounts of ling Range, hosts a series of W-Sn deposits such as the Helukou,
rare earth elements (REEs), Mo, Nb, Na, and Sr via substitution Shuiyuanba, and Xinlu deposits (Fig. 2; Li et al. 2015). The ore
for Ca or W in the crystal structure, and these components provide mineralization ages of these deposits are 160–165 Ma, consistent
clues to the source, physicochemical conditions, and evolutionary with the age of the Guposhan granitic pluton (Gu et al. 2007;
history of the ore-forming fluids (Raimbault et al. 1993; Ghaderi et Li et al. 2015; Cao et al. 2020b). Gu et al. (2007) proposed the
al. 1999; Brugger et al. 2000, 2002, 2008; Song et al. 2014; Kozlik division of the Guposhan pluton into three units, namely the East
et al. 2016). Recently, laser ablation multiple collector inductively unit (160.8 ± 1.6 Ma), the West unit (165.0 ± 1.9 Ma), and the
coupled plasma mass spectrometry (LA-MC ICP-MS) has been Lisong unit (163.0 ± 1.3 Ma). The outcropping granites in the
widely used to measure the trace-element and Sr-Nd isotopic northern part of the Guposhan ore field belong to the West unit
compositions of scheelite (e.g., Fu et al. 2017b; Sun and Chen (Fig. 2) and consist mainly of fine-grained and medium–fine-
2017; Peng et al. 2018; Zhao et al. 2018; Liu et al. 2019; Sun et al. grained biotite granites.

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Ore deposit geology The dominant skarn-type ore bodies, which comprise more than
The Helukou W deposit, with total estimated tungsten reserves 75% of the total tungsten reserves, are found mainly within the
of >33 752 tons, is located in southwestern Hunan Province endo- and exo-contact zones between Devonian Huanggongtang
(northeastern Guposhan district; Fig. 2). The outcropping strata Formation carbonates and Middle Jurassic Guposhan granites
in the mining district mainly consist of Devonian shallow-marine (Fig. 4c). These stratiform and/or lenticular ore bodies are mostly
siliciclastic and carbonate rocks (Fig. 3a) belonging to the NE-trending, with a length of 50–750 m, a thickness of 1–107 m,
Tiaomajian, Huanggongtang, and Qiziqiao formations (Zeng et and a WO3 grade of 0.06–0.70%. The scheelite- and molybdenite-
al. 2008). The Huanggongtang Formation comprises dolomite and bearing skarns with a massive structure are composed mainly of
impure limestones, and hosts the main ore-bearing strata for the garnet, epidote, and vesuvianite (Figs. 4d–4i). Ore minerals of
skarn-type W ore bodies (Fig. 3b; Zeng et al. 2008). Faults in the the skarn-type deposits consist mainly of scheelite, molybdenite,
mining district can be classified into two groups: NW-SE-trending pyrite, chalcopyrite, galena, ilmenite, and xenotime (Figs. 5e–5i),
and quasi-N-S-trending faults, with the latter being the main ore- and gangue minerals include hessonite, andradite, almandine, K-
controlling structures (Fig. 3a; Zeng et al. 2008). Hydrothermal feldspar, apatite, quartz, fluorite, and zircon (Figs. 5e–5i). Scheelite
alteration processes affecting these deposits include skarnization, in the skarn-type ores (scheelite II) is xenomorphic-subhedral, has
greisenization, sericitization, silicification, and albitization, al- grain sizes of 0.08–3.0 mm, and displays intergrown textures with
though skarnization and albitization are primarily associated with garnet, epidote, and vesuvianite (Figs. 5e–5i).
the skarn-type and altered granite-type W deposits, respectively.
Magmatic rocks mainly consist of medium to fine-grained biotite Sampling and analytical techniques
granites with ages of 165.0 ± 1.9 Ma (Gu et al. 2007). Sample collection and description
A total of 33 tungsten ore veins, mainly skarn-type and altered Granites and skarn-type ore samples were collected from mining tunnels of the
granite-type, were identified in this deposit. The non-exposed Helukou W deposit, whereas samples of the altered granite-type ores were collected
altered granite-type ore bodies, which consist of scheelite-bearing from drill cores (Fig. 3a). Prior to mineral chemical analyses, thin sections of rock
and ore samples were prepared and photographed using optical and backscattered
disseminated ore, are hosted by the upper domain of the Early Ju-
electron (BSE) microscopy. For LA-ICP-MS U-Pb dating, zircon grains were taken
rassic granites (Figs. 4a–4b). The main ore minerals are scheelite, from three samples including a fine-grained muscovite granite (Sample No. HLK-
molybdenite, pyrite, ilmenite, magnetite, and galena (Figs. 5a–5d), 1-1), a fine-grained biotite granite (Sample No. HLK-6), and an altered granite-type
and gangue minerals include K-feldspar, quartz, fluorite and cal- ore (Sample No. HLK-3). For Re-Os dating, molybdenite grains were separated
cite (Figs. 5a–5d). Scheelite in the altered granite-type ore bodies from six skarn-type and two altered granite-type ore samples. Additionally, schee-
lites from altered granite type- (scheelite I) and skarn type-ores (scheelite II) were
(scheelite I) occurs as xenomorphic and/or subhedral crystals, has chosen for in situ LA-ICP-MS trace-element analyses and in situ LA-MC-ICP-MS
grain sizes of 0.01–0.91 mm, and exhibits intergrown textures with Sr isotopic analyses.
plagioclase, fluorite, and quartz (Figs. 5a–5d). The fine-grained muscovite granites are light gray in color, have a massive

Figure 2. Geological sketch map of Guposhan ore field, showing the location and ages of the Sn-W deposits (modified from Li et al. 2015).
(Color online.)

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structure and porphyritic texture, and contain K-feldspar (~38%), plagioclase (~25%), injection into the ICP. A “wire” signal smoothing device was included in this laser
quartz (~30%), muscovite (~5%), and hornblende (~2%), with zircon, apatite, titanite, ablation system (Hu et al. 2015). The spot size and frequency of the laser were set
sphene, magnetite, and ilmenite as accessory minerals (Figs. 6a–6c). The medium- to 32 μm and 5 Hz, respectively. Trace-element compositions of minerals were
fine-grained biotite granites have a massive structure and porphyritic texture, and calibrated against various reference materials (BHVO-2G, BCR-2G, and BIR-1G)
contain K-feldspar (~30%), plagioclase (~15%), quartz (~45%), biotite (~8%), and without using an internal standard (Liu et al. 2008). Each analysis incorporated
hornblende (~2%), with zircon, apatite, titanite, sphene, magnetite, and ilmenite as a background acquisition of ~20–30 s followed by 50 s period of sample data
accessory minerals (Figs. 6d–6f). acquisition. The measurement accuracy was better than 97% (1σ). An Excel-based
software ICPMSDataCal was used to perform off-line selection and integration of
background and analyzed signals, time-drift correction, and quantitative calibra-
Cathodoluminescence (CL) imaging
tions (Liu et al. 2008).
Zircon and scheelite grains were separated by conventional magnetic and heavy
liquid techniques and hand-picked using a binocular microscope at the Wuhan Sample In situ LA-MC-ICP-MS strontium isotopic analysis of
Solution Analytical Technology Co., Ltd. (Wuhan, China). They were then mounted
in epoxy resin blocks and polished to obtain flat surfaces. CL imaging permitted
scheelite
observation of the internal structures of individual zircon and scheelite grains, using a Sr isotopic measurements of scheelite were performed using a Neptune Plus
scanning electron microscope (SEM) housed at the Key Laboratory of Crust-Mantle MC-ICP-MS (Thermo-Fisher Scientific, Bremen, Germany) in combination with
Materials and Environments, Chinese Academy of Sciences, University of Science a Geolas HD excimer ArF laser ablation system (Coherent, Göttingen, Germany)
and Technology of China (Hefei, China). The imaging condition was 10.0–13.0 kV at the Wuhan Sample Solution Analytical Technology Co., Ltd. (Wuhan, China).
voltage, 80–85 μA current, and two minutes for imaging. The Neptune Plus was equipped with nine Faraday cups fitted with 1011 Ω resis-
tors. The Faraday collector configuration of the mass system was composed of
Zircon U-Pb dating an array from L4 to H3 to monitor Kr, Rb, Er, Yb, and Sr. A combination of a
high-sensitivity X-skimmer cone and a Jet-sample cone was employed. In the
U-Pb age determinations were performed using a LA-ICP-MS system at the laser ablation system, helium was used as the carrier gas for the ablation cell. For
Mineral Geochemistry Lab, Ore Deposit and Exploration Centre (ODEC), Hefei
University of Technology (Hefei, China). An Agilent 7900 Quadrupole ICP-MS
coupled to a Photon Machines Analyte HE 193 nm ArF Excimer laser ablation
system was used for the analyses. Zircon 91500 and synthetic silicate glass NIST
SRM610 were applied as external standards for U-Pb dating and trace-element
analyses, respectively. Helium was used as a carrier gas to enhance the transport
efficiency of the ablated material, and argon was used as the make-up gas and
mixed with helium in the ablation cell before injection into the ICP to maintain
stable and optimum excitation conditions. The flow rate of helium was set at 0.6 L/
min and a laser beam of 32 μm in diameter with an ablation depth of about 20 μm
was adopted. U-Pb ages of zircon were calculated based on U decay constants of
238
U = 1.55125 × 10–10 year–1 and 235U = 9.8454 × 10–10 year–1 (Jaffey et al. 1971).
The 91500 standard was dated at 1062 ± 6.6 Ma in this experiment, which is con-
sistent with a previously reported age of 1062 ± 4 Ma for 91500 (Wiedenbeck et
al. 1995). Analytical errors for individual samples are presented as 1σ in Table 1,
whereas uncertainties in weighted mean ages are quoted at 2σ (95% confidence)
in concordia diagrams. The measurement accuracy was better than 96% (2σ).
Quantitative calibrations for zircon U-Pb dating and trace-elements were performed
by ICPMSDataCal 10.7 (Liu et al. 2010). Common Pb was corrected based on the
model of Andersen (2002). Weighted mean age calculations and concordia diagrams
were generated using Isoplot 3.0 (Ludwig 2003).

Molybdenite Re-Os dating

Molybdenite grains were first separated with a knife and then hand-picked
under a binocular microscope. The procedures of powdered sample digestion, Os
distillation, and Re extraction were conducted following the methods described
by Stein et al. (2001) and Du et al. (2004). The Re and Os isotope ratios were
determined using an inductively coupled plasma mass spectrometer (TJA X-series
ICP-MS) at the National Research Center of Geoanalysis, Chinese Academy of
Geological Sciences (Beijing, China). The molybdenite standard GBW04435
(HLP) was used to test analytical reproducibility. The uncertainty for individual
age determinations, representing the sum of uncertainties associated with the decay
constant of 187Re, isotope ratio measurements, and spike calibrations, was about
0.02%. Average blanks for the total Carius tube procedure were ca. 10 pg Re and
ca. 1 pg Os. The Re-Os isochron age was calculated using Isoplot 3.0 (Ludwig
2003). The decay constant used in the age calculation was λ187Re = 1.666 × 10–11
year–1 (Smoliar et al. 1996).

In situ LA-ICP-MS trace-element analysis of scheelite

Trace-element analysis of scheelite was conducted by LA-ICP-MS at the
Wuhan Sample Solution Analytical Technology Co., Ltd. (Wuhan, China). Detailed
operating conditions for the laser ablation system and the ICP-MS instrument and
data reduction are the same as given in Zong et al. (2017). Laser sampling was
performed using a GeolasPro laser ablation system consisting of a COMPexPro
102 ArF excimer laser (wavelength of 193 nm and maximum energy of 200 mJ)
and a MicroLas optical system. An Agilent 7700e ICP-MS instrument was used to Figure 3. (a) Geological sketch map of northern Guposhan ore
acquire ion-signal intensities. Helium was used as the carrier gas, and argon was field, showing the sampling location; (b) No. 30 line geological section
used as the make-up gas and mixed with the carrier gas via a T-connector before of the Helukou deposit (modified from Zou et al. 2005). (Color online.)

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Figure 4. Photographs of ore bodies and tungsten ores from the Helukou deposit. (a) Hand specimen of altered granite-type ore. (b) Hand
specimen of altered granite-type ore showing location of scheelite (under a tungsten lamp). (c) Field photograph showing the contact zone between
the Middle Jurassic granites and the skarn-type W ore body. (d) Field photograph of garnet-epidote skarn. (e) Field photograph of garnet-vesuvianite
skarn. (f) Field photograph of garnet skarn crossed by quartz vein. (g) Hand specimen of garnet skarn-type ore. (h) Hand specimen of garnet
skarn-type ore showing the location of scheelite (under a tungsten lamp). (i) Hand specimen of molybdenite-bearing skarn-type ore. (Color online.)

single-spot laser ablation, the spot diameter ranged from 60 to 160 μm depending Results
on Sr signal intensity. The pulse frequency was from 8 to 15 Hz, and the laser
fluence was held constant at ~10 J/cm2. The data reduction for LA-MC-ICP-MS Zircon U-Pb ages
analysis was conducted using ICPMSDataCal (Liu et al. 2010). The interference
correction strategy was the same as that reported by Tong et al. (2016). The regions LA-ICP-MS zircon U-Pb age data for two granites and one
of integration for both gas background and sample were initially selected, and no altered granite type ore sample from the Helukou W deposit are
additional Kr peak stripping was applied following the background correction, reported in Table 1. Most zircon grains from the fine-grained
which removed the background Kr+ signals. Then, interferences were corrected muscovite granite (HLK-1-1) are euhedral, have lengths of 100–
in the following sequence: (1) interferences of 168Er++ on 84Sr, 170Er++ and 170Yb++
on 85Rb, 172Yb++ on 86Sr, and 174Yb++ on 87Sr were corrected based on the measured
200 μm and aspect ratios of 1:1 to 3:1, and show internal oscillatory
signal intensities of 167Er++, 173Yb++, and the natural isotope ratios of Er and Yb zoning, suggesting a magmatic origin (Hoskin and Schaltegger
(Berglund and Wieser 2011); and (2) the isobaric interference of 87Rb on 87Sr was 2003; Fig. 7). The Th and U contents of these zircon grains are
corrected by monitoring the 85Rb signal intensity and a user-specified 87Rb/85Rb 147–458 ppm and 252–1340 ppm, respectively, with Th/U ratios
ratio using an exponential law for mass bias. The user-specified 87Rb/85Rb ratio
of 0.25–0.79 (mean = 0.48 and STD = 0.09). Sixteen analyses of
was calculated by measuring some reference materials with a known 87Sr/86Sr
ratio. Following the interference corrections, mass fractionation of Sr isotopes magmatic domains are plotted on the concordia diagrams. The
was corrected by assuming 88Sr/86Sr = 8.375209 (Tong et al. 2016) and applying grains yield 206Pb/238U ages ranging from 162 to 169 Ma (Table
the exponential law. Two natural apatite crystals (Durango and MAD) were used 1), with a weighted average of 163.8 ± 1.5 Ma (MSWD = 0.41;
as unknown samples for in situ Sr isotopic analyses of apatite. The uncertainty of Figs. 8a–8b). This age can be interpreted as the crystallization age
the 88Sr/86Sr ratio (2σ) for single measurements was 0.0003–0.0004. The analyzed
88
Sr/86Sr ratios of Durango and MAD crystals in this study are 0.706346 ± 0.000516
of the fine-grained muscovite granite.
and 0.711879 ± 0.000157, respectively, which are within error of the reported ratios Zircon grains from the altered granite-type ore (HLK-3) are
of 0.71180 and 0.70632, respectively (Yang et al. 2014). mostly euhedral or subhedral and have lengths of 150–200 μm and

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Figure 5. BSE images of skarn-type (a–e) and altered granite-type (f–i) W ores from the Helukou deposit showing the main mineral assemblages.
(a) Scheelite coexisting with fluorite and apatite. (b) Xenomorphic scheelite surrounded by fluorite. (c) Fluorite surrounded by euhedral scheelite.
(d) Xenomorphic scheelite coexisting with galena and magnetite. (e) Sharp contact between garnet and scheelite. (f) Irregular molybdenite
surrounded by andradite. (g) Ilmenite surrounded by xenomorphic scheelite. (h) Scheelite coexisting with pyrite. (i) Chalcopyrite and galena
surrounded by K-feldspar. Alm = almandine; Ap = apatite; Ard = andradite; Cal = calcite; Ccp = chalcopyrite; Fi = fluorite; Gn = galena; Grs =
grossular; Ilm = ilmenite; Kfs = K-feldspar; Mag = magnetite; Mo = molybdenite; Py = pyrite; Qtz = quartz; Sch = scheelite; Xtm = xenotime; Zr
= zircon. (Color online.)

aspect ratios of 1:1–3:1. CL imaging revealed that the cores of these Pb/235U ratios and plot on or close to the concordia curve (Fig.
207

zircons show internal oscillatory zoning but the grain margins did 8c). The 206Pb/238U ages of these zircon grains range from 177 to
not, with clear boundaries between the edges and cores (Fig. 7). 185 Ma (Table 1), yielding a weighted average age of 181.5 ± 2.1
This pattern suggests that these zircons experienced metamictiza- Ma (MSWD = 0.75; Fig. 8d).
tion, i.e., in which fluids altered the structure of grain margins to Zircon grains from the fine-grained biotite granite (HLK-6) are
varying degrees (Rizvanova et al. 2000; Liati et al. 2002). These mostly euhedral, have lengths of 50–200 μm and aspect ratios of
zircon grains have variable Th (152–2500 ppm) and U contents 1:1–4:1, and display internal oscillatory zoning, indicating a mag-
(397–9018 ppm), yielding Th/U ratios of 0.25–0.64 (mean = 0.38 matic origin (Hoskin and Schaltegger 2003; Fig. 7). These grains
and STD = 0.10). Based on their petrographic and Th/U character- have variable Th (79.2–1206 ppm) and U contents (181–7488
istics, these zircons are inferred to have a magmatic origin, and the ppm), with Th/U ratios of 0.16–0.49 (mean = 0.36 and STD =
U-Pb dates represent their crystallization age, although they have 0.06). Eleven of the magmatic zircons have concordant 206Pb/238U
experienced various degrees of hydrothermal alteration. Twelve and 207Pb/235U ratios when plotted on concordia diagrams (Fig. 8e).
analyses of magmatic domains yield concordant 206Pb/238U and The 206Pb/238U ages of these zircons range from 180 to 189 Ma

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(Table 1), yielding a weighted average 206Pb/238U age of 184.0 ± ppm (mean 5245 ppm, STD = 622 ppm), respectively. Relative
3.6 Ma (MSWD = 0.15; Fig. 8f). This age can be considered as to it, scheelite II (skarn-type ore) has higher and more variable
the crystallization age of the fine-grained biotite granite. Na contents (8.6–184 ppm, mean = 87.6 ppm, STD = 39.4 ppm)
and lower Sr, Nb, and Mo contents (32.8–128 ppm, mean 55.6
Molybdenite Re-Os ages ppm, STD = 12.7 ppm; 22.7–447 ppm, mean 124 ppm, STD =
The Re-Os isotopic compositions of molybdenite samples 59.8 ppm; and 646–3496 ppm, mean 2280 ppm, STD = 497 ppm,
from the Helukou tungsten deposit are given in Table 2. The total respectively). Both scheelite I and scheelite II have relatively low-
Re, 187Re, and 187Os contents of six molybdenite samples from the Rb concentrations (mostly <0.1 ppm).
skarn-type ores vary from 10238 to 48518 ppb, 6436 to 30494 ppb, In terms of rare earth element (REE) compositions, scheelite II
and 18.5 to 85.2 ppb, respectively, yielding a 187Re-187Os isochron has higher and more variable ΣREE (267–2272 ppm; mean 1059
age of 163.4 ± 2.8 Ma (MSWD = 0.71; Fig. 9a). These samples ppm and STD = 594 ppm) than scheelite I (347–724 ppm; mean
have invariant Re-Os model ages ranging from 162.9 to 171.9 467 ppm and STD = 80.1 ppm). Both scheelite I and scheelite II
Ma, yielding a weighted average age of 168.9 ± 2.8 Ma (MSWD have negative Eu anomalies (Eu/Eu* = 0.02–0.05 and 0.14–0.55,
= 3.5; Fig. 9b). These ages indicate that the skarn-type tungsten respectively) and slight positive Ce anomalies (Ce/Ce* = 1.08–
mineralization was related to Middle Jurassic granitic magmatism. 1.20 and 1.20–1.45, respectively; Fig. 10).
Two molybdenite samples from the altered granite-type ore
have total Re, 187Re, and 187Os contents of 9914–30434 ppb, Strontium isotopic compositions of scheelite
6231–19129 ppb, and 18.4–57.9 ppb, respectively, yielding an The strontium isotopic compositions of scheelite from the
isochron age of 183.5 ± 2.8 Ma (Fig. 9c). In addition, the model Helukou tungsten deposit are given in Table 4. The 87Sr/86Sr ratios
ages of these samples are 176.9 and 181.4 Ma, respectively, yield- of scheelite I and scheelite II vary from 0.70939 to 0.71932 and
ing a weighted mean age of 179.3 ± 6.7 Ma (MSWD = 8.1; Fig. 0.70277 to 0.71471, respectively (Fig. 11). In addition, both schee-
9d). This age is consistent with the zircon age of the fine-grained lite I and scheelite II have relatively low 87Rb/86Sr ratios, ranging
biotite granite, indicating that the altered granite-type tungsten from 0.00149 to 0.02030 and from 0.00351 to 0.07324, respectively.
deposit was related to Early Jurassic granitic magmatism.
Discussion
Trace-element compositions of scheelite Timing of W-Sn mineralization in the Nanling Range
The trace-element compositions of scheelite from the Helukou Previous studies reported that the Guposhan pluton is Middle
tungsten deposit are given in Table 3. Scheelite I has Na, Sr, Nb, Jurassic in age with an early stage granite at 165.0 ± 1.9 Ma and
and Mo contents of 18.7–96.3 ppm (mean 38.7 ppm, STD = a late-stage granite at 154.2 ± 3.1 Ma (Gu et al. 2007; Wang et
18.3 ppm), 98.9–128 ppm (mean 113 ppm, STD = 6.46 ppm), al. 2014). In the present study of the Helukou deposit (NE Gu-
124–480 ppm (mean 188 ppm, STD = 61.6 ppm), and 4419–6973 poshan district; Fig. 2), a zircon U-Pb age of 163.8 ± 1.5 Ma for

Figure 6. Hand specimens and photomicrographs of granites from the Helukou deposit. (a) Hand specimen of fine-grained muscovite granite.
(b–c) Photomicrographs of major mineral assemblages of fine-grained muscovite granite. (d) Hand specimen of fine-grained biotite granite.
(e–f) Photomicrographs of major mineral assemblages of fine-grained biotite granite. Bt = biotite; Hbl = hornblende; Kfs = K-feldspar; Pl =
plagioclase; Ms = muscovite; Qtz = quartz. (Color online.)

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Table 1. LA-ICP-MS zircon U-Pb dating data for the granites and altered-granite type ore from the Helukou deposit
Spot Th(ppm) U(ppm) Th/U 207
Pb/206Pb 207
Pb/235U 206
Pb/238U 208
Pb/232Th 207
Pb/206Pb 207
Pb/235U 206
Pb/238U
Ratio ±1σ Ratio ±1σ Ratio ±1σ Ratio ±1σ Age (Ma) ±1σ Age (Ma) ±1σ Age (Ma) ±1σ
Fine-grained muscovite granite (HLK-1-1)
1 147 597 0.25 0.0494 0.0023 0.1734 0.0080 0.0254 0.0004 0.0084 0.0005 165 139.8 162 7.0 162 2.3
2 312 719 0.43 0.0498 0.0022 0.1752 0.0070 0.0255 0.0004 0.0091 0.0003 187 103.7 164 6.0 163 2.4
3 444 560 0.79 0.0492 0.0019 0.1738 0.0067 0.0255 0.0004 0.0077 0.0003 167 88.9 163 5.8 162 2.7
4 458 1340 0.34 0.0497 0.0021 0.1817 0.0062 0.0265 0.0005 0.0090 0.0004 183 96.3 170 5.4 169 3.1
5 336 883 0.38 0.0492 0.0039 0.1765 0.0166 0.0257 0.0009 0.0090 0.0004 154 190.7 165 14.4 164 5.5
6 213 541 0.39 0.0498 0.0040 0.1772 0.0116 0.0259 0.0008 0.0092 0.0004 187 174.0 166 10.0 165 5.2
7 162 275 0.59 0.0500 0.0042 0.1783 0.0124 0.0261 0.0010 0.0092 0.0006 195 194.4 167 10.7 166 6.0
8 193 417 0.46 0.0502 0.0030 0.1745 0.0088 0.0256 0.0008 0.0091 0.0004 211 143.5 163 7.6 163 4.8
9 198 425 0.47 0.0500 0.0024 0.1785 0.0082 0.0260 0.0004 0.0084 0.0003 195 112.9 167 7.1 165 2.5
10 313 601 0.52 0.0486 0.0016 0.1719 0.0056 0.0255 0.0004 0.0076 0.0002 128 77.8 161 4.9 162 2.5
11 152 252 0.60 0.0493 0.0023 0.1745 0.0082 0.0254 0.0004 0.0076 0.0003 161 138.9 163 7.1 162 2.7
12 176 337 0.52 0.0492 0.0033 0.1745 0.0116 0.0255 0.0007 0.0086 0.0005 167 138.9 163 10.1 162 4.2
13 173 334 0.52 0.0495 0.0023 0.1773 0.0085 0.0259 0.0005 0.0082 0.0004 172 109 166 7.3 165 3.0
14 165 311 0.53 0.0498 0.0023 0.1776 0.0083 0.0260 0.0005 0.0085 0.0003 183 114 166 7.1 165 3.1
15 423 902 0.47 0.0496 0.0016 0.1772 0.0059 0.0258 0.0004 0.0075 0.0003 176 78.7 166 5.1 164 2.7
16 208 548 0.38 0.0484 0.0016 0.1747 0.0061 0.0260 0.0004 0.0075 0.0003 120 77.8 163 5.3 166 2.6
Altered granite-type tungsten ore (HLK-3)
1 566 1363 0.42 0.0500 0.0013 0.2009 0.0061 0.0290 0.0005 0.0078 0.0002 195 63.0 186 5.2 184 3.0
2 813 1484 0.55 0.0516 0.0022 0.2049 0.0078 0.0289 0.0008 0.0085 0.0003 333 98.1 189 6.6 184 4.9
3 767 1452 0.53 0.0512 0.0019 0.2005 0.0068 0.0284 0.0005 0.0076 0.0002 250 89.8 186 5.8 180 3.1
4 407 1600 0.25 0.0504 0.0013 0.1976 0.0052 0.0283 0.0004 0.0087 0.0003 213 59.2 183 4.4 180 2.6
5 412 1131 0.36 0.0505 0.0014 0.2053 0.0066 0.0293 0.0006 0.0090 0.0003 220 64.8 190 5.6 186 3.7
6 409 1193 0.34 0.0497 0.0029 0.1969 0.0111 0.0287 0.0007 0.0096 0.0005 189 135 182 9.4 182 4.4
7 151 574 0.26 0.0518 0.0031 0.1985 0.0113 0.0278 0.0007 0.0093 0.0007 276 139 184 9.6 177 4.3
8 1032 3481 0.30 0.0513 0.0015 0.2065 0.0084 0.0289 0.0009 0.0093 0.0004 257 66.7 191 7.0 184 5.5
9 126 199 0.64 0.0511 0.0051 0.1998 0.0218 0.0285 0.0008 0.0093 0.0008 256 209 185 18.5 181 5.2
10 282 806 0.35 0.0513 0.0025 0.1957 0.0088 0.0278 0.0007 0.0095 0.0003 254 80.5 181 7.5 177 4.2
11 2500 9018 0.28 0.0516 0.0010 0.2089 0.0052 0.0292 0.0005 0.0089 0.0003 333 38.0 193 4.4 185 3.4
12 129 397 0.32 0.0513 0.0040 0.1991 0.0169 0.0279 0.0007 0.0114 0.0007 254 184.2 184 14.4 177 4.6
Fine-grained biotite granite (HLK-6)
1 1206 7488 0.16 0.0501 0.0039 0.1958 0.0136 0.0283 0.0011 0.0139 0.0007 211 181 182 11.5 180 6.7
2 497 1525 0.33 0.0546 0.0022 0.2127 0.0114 0.0290 0.0016 0.0108 0.0004 398 90.7 196 9.6 185 10.3
3 712 2411 0.30 0.0496 0.0022 0.2039 0.0130 0.0297 0.0016 0.0108 0.0007 176 99.1 188 11.0 189 10.2
4 576 1527 0.38 0.0498 0.0060 0.2015 0.0244 0.0293 0.0012 0.0136 0.0006 187 268.5 186 20.6 186 7.3
5 79.2 181 0.44 0.0485 0.0052 0.2017 0.0237 0.0296 0.0012 0.0087 0.0014 120 246 187 20.0 188 7.6
6 174 446 0.39 0.0497 0.0071 0.1979 0.0283 0.0291 0.0015 0.0139 0.0012 183 303.7 183 24.0 185 9.4
7 449 1316 0.34 0.0498 0.0022 0.2019 0.0115 0.0290 0.0009 0.0120 0.0006 187 102 187 9.8 185 5.6
8 178 405 0.44 0.0492 0.0048 0.1974 0.0210 0.0290 0.0013 0.0087 0.0008 167 206 183 17.8 184 7.8
9 268 905 0.30 0.0502 0.0038 0.1984 0.0157 0.0286 0.0009 0.0108 0.0006 206 175.9 184 13.3 182 5.8
10 269 702 0.38 0.0501 0.0027 0.1991 0.0117 0.0286 0.0007 0.0112 0.0005 211 124.1 184 9.9 182 4.5
11 85.5 175 0.49 0.0504 0.0047 0.2010 0.0177 0.0291 0.0008 0.0085 0.0009 213 204 186 14.9 185 5.0
12 483 1219 0.40 0.0509 0.0021 0.2051 0.0089 0.0291 0.0008 0.0091 0.0004 235 92.6 189 7.5 185 4.7

Figure 7. Cathodoluminescence (CL) images of representative zircon grains of samples from the Helukou deposit. White circles represent
LA-ICP-MS dating spots; yellow lines are boundaries between protogenetic and recrystallized areas of zircon grains. (Color online.)

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 1496 CAO ET AL.: JURASSIC MAGMATISM AND TUNGSTEN MINERALIZATION IN NANLING

fine-grained muscovite granite conforms to published ages for et al. 2011; Zhou et al. 2018; Zhao et al. 2019). In the present
the early stage Guposhan granites (Gu et al. 2007). Furthermore, study, a zircon U-Pb age of 184.0 ± 3.6 Ma and a molybdenite
a Re-Os age of 163.4 ± 2.8 Ma for molybdenite from the skarn- Re-Os age of 183.5 ± 2.8 Ma demonstrate coeval magmatism
type tungsten ore is consistent with Ar-Ar ages of ca. 160 Ma for and tungsten mineralization in the Guposhan ore district during
other tungsten deposits in the northern Guposhan ore field (Li et the Early Jurassic. Therefore, our new data, coupled with previ-
al. 2015). ously reported ages, suggest two stages of magmatism (~184 and
The Early Jurassic (205–180 Ma) has long been regarded ~164 Ma) and two stages of W-Sn mineralization (~180 and ~163
as an interval of magmatic and metallogenic quiescence in the Ma) in the Helukou tungsten deposit of the Guposhan ore field.
Nanling Range (Zhou et al. 2006; Jiang et al. 2008). However, These findings provide new evidence for links between Early
recent studies have provided evidence of Early Jurassic mag- Jurassic magmatism and tungsten mineralization in the Nanling
matism, and some have reported related tungsten and/or tin Range, suggesting an extended interval of W mineralization and
mineralization events (Yu et al. 2010; Zhu et al. 2010; Wang a potential metallogenic era in this region.

Figure 8. Zircon U-Pb concordia diagram and weighted-mean ages of zircon grains of samples from the Helukou deposit. (Color online.)

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Figure 9. Molybdenite Re-Os isochron diagram and weighted mean ages of ore samples from the Helukou deposit. (Color online.)

Figure 10. Rare earth element distributions in scheelite from the Helukou deposit. Chondrite normalization based on Taylor and McLennan
(1985). (Color online.)

REE substitution reactions 2Ca2+ = Na+ + REE3+ (1)

The ionic radii of trivalent REEs are similar to that of bivalent Ca2+ + W6+ = Nb5+ + REE3+ (2)
Ca, and, therefore, REE3+ can enter the lattice of scheelite through 3Ca2+ = Ca + 2REE3+, where  is a site vacancy (3)
substitution for Ca2+ (Ghaderi et al. 1999). The most important
coupled substitution reactions between REE3+ and Ca2+ are as In terms of reaction 1, if Na provides the charge balance in
follows (Ghaderi et al. 1999): scheelite, MREEs preferentially enter the lattice by substitu-

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 1498 CAO ET AL.: JURASSIC MAGMATISM AND TUNGSTEN MINERALIZATION IN NANLING

to 184 ppm, respectively, indicating that reaction 1 is a likely

candidate, an inference supported by enrichment of scheelite I
in MREEs (Fig. 10a). Furthermore, some samples of scheelite
II plot along the 1:1 line between Na (atom) and REE+Y-Eu
(atom), also supporting operation of reaction 1 during formation
of scheelite II (Fig. 12a).
Reaction 2 was not important in the study units, as shown by
the Nb contents of scheelite I and scheelite II (137 to 480 ppm
and 22.7 to 447 ppm, respectively) being lower than their REEs
concentrations. Also significant is that scheelite I plots near the
Figure 11. 87Sr/86Sr ratios of scheelite from the Helukou deposit, 1:1 line of Nb (atom) and REE+Y-Eu (atom), whereas scheelite
compared with Middle Jurassic ore-related granites at Guposhan (Gu et al. II plots away from the 1:1 line (Fig. 12b). The strong positive
2007). (Color online.) correlation between Na+Nb (atom) and REE+Y-Eu (atom) for

tion in the Ca site because of their similar ionic radii, which Table 4. LA–MC–ICP–MS Sr isotopes of the scheelite from the
results in MREE-rich patterns and high-Na concentrations Helukou deposit
(Ghaderi et al. 1999; Brugger et al. 2002). Reaction 2 results Spot Sr/
84
2σ 84
Sr/ 2σ 87
Rb/ 2σ 87
Sr/ 2σ
no. Sr 88Sr 86Sr 86Sr
86
in Nb concentrations that are high and nearly equal to ΣREE
scheelite
content (Dostal et al. 2009). Reaction 3 leads to a relatively flat 1 0.0575 0.0047 0.00687 0.00056 0.00172 0.000184 0.71142 0.00081
chondrite-normalized REE pattern (Ghaderi et al. 1999). In the 2 0.0572 0.0050 0.00682 0.00059 0.00487 0.000133 0.70939 0.00082
present study, both scheelite I and scheelite II have relatively 3 0.0571 0.0044 0.00681 0.00052 0.01530 0.005317 0.71698 0.00268
4 0.0585 0.0042 0.00699 0.00050 0.00167 0.000117 0.71281 0.00061
high-Na contents, ranging from 18.7 to 96.3 ppm and from 39.3 5 0.0499 0.0068 0.00596 0.00081 0.00771 0.000756 0.71507 0.00104
6 0.0578 0.0050 0.00690 0.00059 0.00345 0.000657 0.71271 0.00085
Table 2. Molybdenite Re-Os isotopic data for the skarn-type tungsten 7 0.0595 0.0040 0.00710 0.00048 0.00149 0.000114 0.71210 0.00064
8 0.0557 0.0043 0.00665 0.00052 0.00155 0.000128 0.71125 0.00071
ore from the Helukou deposit 9 0.0551 0.0043 0.00658 0.00051 0.02030 0.000843 0.71932 0.00078
Sample no. Re (ng/g) 2σ 187Re (ng/g) 2σ 187Os ng/g 2σ T (Ma) 2σ scheelite II
Molybdenite from the skarn-type tungsten ore 1 0.0436 0.0023 0.00520 0.00028 0.01688 0.000266 0.70852 0.00042
GPS-1 48518 623 30494 391 85.24 0.586 167.5 2.9 2 0.0549 0.0101 0.00655 0.00120 0.00389 0.000253 0.70970 0.00143
GPS-2 40323 358 25345 225 70.18 0.339 166.0 1.7 3 0.0577 0.0105 0.00689 0.00125 0.00455 0.000295 0.71027 0.00191
GPS-3 41443 609 26048 383 70.80 0.542 162.9 3.1 4 0.0617 0.0104 0.00737 0.00124 0.00382 0.000297 0.71079 0.00167
GPS-4 41778 703 26258 442 72.57 0.451 165.6 3.4 5 0.0535 0.0151 0.00639 0.00180 0.00410 0.000397 0.71040 0.00241
GPS-5 22353 269 14050 169 38.71 0.270 165.1 2.8 6 0.0156 0.0155 0.00186 0.00185 0.07324 0.000467 0.70277 0.00266
GPS-6 10238 45 6436 28 18.46 0.083 171.9 1.08 7 0.0132 0.0161 0.00158 0.00192 0.06863 0.001111 0.71471 0.00279
Molybdenite from the altered granite-type tungsten ore 8 0.0497 0.0089 0.00593 0.00106 0.00351 0.000217 0.71003 0.00129
AG-1 30434 210 19129 132 57.89 0.421 181.4 1.8 9 0.0487 0.0122 0.00582 0.00145 0.00524 0.000342 0.70852 0.00186
AG-2 9914 73 6231 46 18.39 0.140 176.9 2.6 10 0.0438 0.0115 0.00523 0.00137 0.00890 0.000442 0.70824 0.00160

Table 3.LA–ICP–MS trace element compositions of the scheelite from the skarn- and altered granite-type tungsten ore in the Helukou deposit (ppm)
Spot Na Rb Sr Nb Mo La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y ΣREE LREE HREE δEu δCe Y/Ho
no.
Scheelite II
1 90.34 0.07 45.9 122 1866 97.7 452 73.0 448 93.0 7.46 96.3 11.8 80.8 13.0 34.2 2.70 11.2 0.67 402 1422 1171 251 0.24 1.25 30.9
2 101.94 0.02 52.5 114 2346 26.1 170 34.9 257 64.9 4.55 76.0 9.06 59.6 9.37 23.3 1.67 6.12 0.38 250 743 557 185 0.20 1.32 26.7
3 89.06 0.00 48.2 43.7 2415 18.6 138 26.7 177 42.5 6.68 44.1 4.85 33.0 4.57 10.9 0.91 2.89 0.14 123 511 409 101 0.47 1.45 27.0
4 8.64 0.02 49.4 206 3496 16.3 106 24.4 192 45.7 1.95 25.2 1.74 8.41 0.92 1.64 0.12 0.54 0.043 27.6 425 387 39 0.18 1.25 30.1
5 13.39 0.04 52.9 27.0 2355 36.7 182 29.9 184 50.7 6.94 68.3 9.84 75.8 12.6 33.5 2.55 9.44 0.47 413 703 491 213 0.36 1.29 32.7
6 13.61 0.02 38.1 22.7 2816 11.9 65.2 11.3 72.9 20.7 2.86 26.3 3.67 27.8 4.72 13.5 1.07 4.77 0.30 145 267 185 82 0.37 1.32 30.7
7 70.33 0.04 63.9 112 1753 293 1108 152 819 149 7.22 135 15.2 94.9 13.5 31.1 2.16 7.09 0.47 454 2827 2528 299 0.16 1.23 33.7
8 39.23 0.01 41.3 96.5 2409 77.6 401 62.8 367 78.9 6.38 85.0 10.8 77.3 12.5 33.3 2.57 10.7 0.61 389 1226 994 233 0.24 1.35 31.1
9 118.20 0.06 65.9 163 1719 12.8 75.7 17.1 141 52.2 3.01 81.8 11.0 76.0 12.0 30.7 2.31 9.86 0.65 313 526 301 224 0.14 1.20 26.1
10 175.26 0.11 60.3 126 1926 82.4 425 69.3 397 72.5 6.08 59.7 6.53 39.3 5.08 11.6 0.84 2.70 0.15 139 1178 1052 126 0.28 1.32 27.4
11 95.03 0.02 54.7 124 2094 131 636 93.1 509 75.3 3.19 60.4 5.96 35.0 5.05 11.7 0.83 2.99 0.16 139 1569 1447 122 0.14 1.35 27.5
12 105.69 0.00 46.7 30.6 2643 17.5 129 25.5 180 44.8 3.65 51.9 6.64 45.4 7.19 19.1 1.31 5.44 0.39 177 538 400 137 0.23 1.43 24.6
13 123.89 0.04 32.8 447 3492 32.2 208 41.8 300 81.0 5.17 104 13.7 96.7 16.5 42.8 3.24 12.6 0.68 462 959 668 290 0.17 1.33 28.0
14 184.24 0.07 128 125 646 356 1081 122 554 141 22.2 110 15.5 98.6 13.3 36.4 4.24 32.9 4.43 214 2591 2276 315 0.55 1.21 16.1
15 85.04 0.03 53.4 94.7 2228 11.8 71.9 15.2 116 39.0 3.50 50.3 6.97 48.6 7.83 22.3 1.88 9.84 0.87 205 406 257 149 0.24 1.26 26.2
Scheelite I
1 18.73 0.00 118 180 5720 33.1 126 20.7 115 30.7 0.33 29.2 3.64 17.1 2.76 5.88 0.58 2.15 0.28 60.8 387 326 61.5 0.03 1.13 22.0
2 31.52 0.14 109 165 4778 37.2 148 24.6 129 32.3 0.23 29.5 3.63 16.8 2.84 5.98 0.61 2.17 0.24 60.8 433 371 61.8 0.02 1.14 21.4
3 47.14 0.13 108 168 4419 23.6 126 26.5 171 49.5 0.40 53.0 6.63 30.8 5.50 10.9 1.01 3.22 0.36 92.8 509 397 111.4 0.02 1.18 16.9
4 34.05 0.06 114 174 4721 31.7 141 26.3 156 42.7 0.41 38.9 4.61 21.2 3.23 5.81 0.51 2.07 0.22 58.8 475 399 76.6 0.03 1.14 18.2
5 45.18 0.04 109 137 5637 22.7 123 25.5 169 47.3 0.41 49.7 5.59 26.0 4.02 7.41 0.61 2.43 0.34 71.1 484 388 96.0 0.03 1.19 17.7
6 21.24 0.22 128 174 4672 22.3 96.8 18.7 116 32.0 0.43 35.4 4.72 23.2 4.29 8.62 0.87 3.52 0.41 76.1 367 286 81.0 0.04 1.11 17.7
7 48.56 0.16 111 132 5071 29.2 141 27.5 166 44.6 0.41 43.8 5.15 24.4 3.88 7.65 0.66 2.30 0.26 67.5 497 408 88.1 0.03 1.17 17.4
8 25.01 0.08 122 124 6068 17.7 89.0 18.7 121 32.9 0.42 32.6 3.85 19.0 3.11 5.94 0.65 2.53 0.34 58.9 347 279 68.0 0.04 1.15 18.9
9 96.32 1.25 98.9 141 4983 31.5 159 30.5 180 47.1 0.47 48.0 6.11 31.7 5.35 11.4 1.17 3.89 0.39 98.2 556 448 108 0.03 1.20 18.3
10 37.66 0.00 103 480 4649 20.1 110 25.9 193 91.5 1.21 111 15.5 85.0 15.5 36.1 3.95 14.2 1.41 295 724 441 283 0.04 1.13 19.0
11 19.71 0.03 117 192 6973 42.1 133 19.9 95.2 23.1 0.34 22.3 2.64 13.2 2.28 5.18 0.56 2.33 0.29 55.4 362 314 48.7 0.05 1.08 24.3

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Figure 12. (a) Na vs. ΣREE + Y-Eu (as 100 atoms per CaWO4 formula unit); (b) Nb vs. ΣREE + Y-Eu (as 100 atoms per CaWO4 formula unit);
(c) Na + Nb vs. ΣREE + Y-Eu (as 100 atoms per CaWO4 formula unit); (d) Eu/Eu* vs. Mo; (e) Mo vs. Ce; and (f) Y vs. Ho. Note: a, b, and c are
modified from Ghaderi et al. (1999). (Color online.)

scheelite I indicates control of substitutions by coupled reactions positive correlation between Na (atom) and REE+Y-Eu (atom),
1 and 2 (Fig. 12c). On the other hand, the similar correlations REE substitution in scheelite II is unlikely to have been con-
between Na + Nb (atom) and REE+Y-Eu (atom) and between trolled exclusively by reaction 1. Scheelite II is characterized
Na (atom) and REE+Y-Eu (atom) for scheelite II suggest that by relatively flat chondrite-normalized REE patterns inherited
reaction 2 can be ruled out for this mineral phase (Figs. 12a from the source fluids, supporting the operation of reaction 3 in
and 12c). However, because scheelite II does not show a strong this mineral phase.

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Geochemical significance of scheelite and the Middle Jurassic ore-forming granites (0.09–0.57) and their
Ce can enter the scheelite lattice as either Ce or Ce along
3+ 4+ relatively flat chondrite-normalized REE patterns, the Sr isotope
with other REE3+ ions, but Ce3+ enters the scheelite lattice more data indicate that scheelite II inherited the REE signature of the
easily than Ce4+ because of the similar ionic radii of Ce3+ (1.14 Å) fluid from which it formed, and that these signatures represent the
and Ca2+ (1.12 Å) (Shannon 1976; Ghaderi et al. 1999; Sun et al. initial 87Sr/86Sr compositions of Middle Jurassic granites in the
2019). Therefore, scheelite precipitated from oxidizing fluids tends Guposhan region. Thus, scheelite that crystallizes from primary
to contain low Ce concentrations. Mo concentrations in scheelite magmatic-hydrothermal fluids not experiencing intense fluid-rock
can also be a sensitive tracer of the redox conditions of the ore- interactions can retain the Sr isotopic signature of the related
forming fluids (Raimbault et al. 1993; Rempel et al. 2009). Under granites, providing a new tool to constrain genetic relationships
oxidizing conditions, Mo6+ readily enters the scheelite lattice via between scheelite and ore-related granites.
substitution for W6+, leading to Mo enrichment (Raimbault et al.
Implications
1993; Rempel et al. 2009). In contrast, under reducing conditions,
Mo4+ does not substitute easily for W6+ in scheelite, resulting in (1) Our study provides evidence of two-stage magmatism and
low Mo contents. Both scheelite I and scheelite II have high Mo related tungsten mineralization in the Guposhan region, i.e., an
contents, 646–3496 ppm (mean 2280 ppm) and 4419–6973 ppm Early Jurassic (~180 Ma) event and a Middle Jurassic (~163 Ma)
(mean 5245 ppm) (Fig. 12d), respectively, which accords with event, expanding the known temporal range of these processes
the high-Mo concentrations of scheelite in the nearby giant Zhuxi and the ore-prospecting potential in the Nanling Range, since the
tungsten deposit (prograde skarn stage; 1171–3291 ppm; Sun et Early Jurassic tungsten mineralization in Nanling range is poorly
al. 2019). Furthermore, negative covariation of Mo and Ce in both known to date.
scheelite I and scheelite II supports oxidizing conditions in the (2) Trace elements and Sr isotopes of scheelite can be a good
ore-forming fluids (Fig. 12e). tool to reveal the physical-chemical conditions of ore-forming
Due to the similar ionic radii and valences of Y and Ho, Y/Ho fluids and to demonstrate genetic relationships between scheelite
ratios tend to remain fairly stable in a given magmatic-hydrother- and ore-related granites.
mal system, allowing their use as a fluid source indicator (Bau and
Funding
Dulski 1995; Bau 1996; Irber 1999). Relatively invariant Y/Ho
This work was financed by the Open Found of Research Center for Petrogen-
ratios are shown by both scheelite I (16.9–24.3, mean 19.3) and esis and Mineralization of Granitoid Rocks, China Geological Survey (Grant No.
scheelite II (16.1–33.7, mean 27.9). In addition, both scheelite I and PMGR202008), PI Project of Southern Marine Science and Engineering Guang-
dong Laboratory (Guangzhou) (Grant No. GML2020GD0802) and National Key
scheelite II exhibit strong positive correlations between Y and Ho Research and Development Plan (Grant No. 2018YFC0603902).
[R2 = 0.99 and 0.86, respectively (Fig. 12f)], indicating that these
two mineral phases were precipitated from a single source fluid. References cited
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