Ore Geology Reviews 58 (2014) 148–162

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Ore Geology Reviews

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Petrogenesis and mineralization of the Fenghuangshan skarn Cu–Au

deposit, Tongling ore cluster field, Lower Yangtze metallogenic belt☆
Shuang Li a,b,c, Xiaoyong Yang a,⁎, Yu Huang d, Weidong Sun b,⁎
a
Key Laboratory of Crust–Mantle Materials and Environments, School of Earth and Space Sciences, University of Science and Technology of China, Hefei 230026, China
b
Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, the Chinese Academy of Sciences, Guangzhou 510640, China
c
Graduate University of the Chinese Academy of Sciences, Beijing 100049, China
d
Department of Geology, University of Maryland, College Park, MD 20742, USA

a r t i c l e i n f o a b s t r a c t

Article history: The Fenghuangshan copper–gold deposit, located in the Tongling ore cluster field along the Lower Yangtze
Received 18 June 2013 metallogenic belt (LYRB) in eastern China, mainly consist of skarn ores hosted in granodiorite. U–Pb dating of mag-
Received in revised form 5 November 2013 matic zircons from Fenghuangshan granodiorite yields a weighted mean 206Pb/238U age of 143.1 ± 1.6 Ma. Five
Accepted 10 November 2013
molybdenite samples collected in the Fenghuangshan deposit yield a Re–Os isochron age of 141.7 ± 0.8 Ma, dem-
Available online 22 November 2013
onstrating that the ore formation event is coeval with the Fenghuangshan granodiorite intrusion. The magmatic
Keywords:
zircon ƐHf(T) values vary from −12.0 to − 28.3, corresponding two-stage Hf model ages between 1.6 Ga to
Zircon U–Pb dating 2.4 Ga. Geochemical and isotopic signatures suggest that the Fenghuangshan granodiorite resembles adakite,
Hf isotopic compositions which was derived from partial melting of the subducted oceanic crust towards LYRB during the early Cretaceous.
Biotite thermobarometry The occurrence of inherited zircons shows the intrusive granodiorite was assimilated by old crustal materials dur-
Re–Os dating ing its emplacement. The biotite thermobarometry, zircon Ce(IV)/Ce(III) ratios and Eu anomalies coincidently
PGE analysis demonstrate that the magma source of granodiorite was under high to moderate oxidized condition, conducive
Tongling ore cluster to Cu–Au mineralization. The sulfide ores in Fenghuangshan deposit are enriched in Pd and Pt, which could also
Fenghuangshan deposit
be a consequence of the high oxidized magma source. The high Re abundance in molybdenite and platinum
group element (PGE) contents of sulfide ores suggest that the ore-forming materials are characterized by mixed
sources from the mantle and crust, and were slightly affected by hydrothermal alteration.
© 2013 The Authors. Published by Elsevier B.V. All rights reserved.

1. Introduction
More than 200 Mesozoic magmatic polymetallic (Cu–Fe–Au, Mo, Zn,
Pb, Ag) deposits are formed within a 10 Ma period around 140 Ma
(Mao et al., 2006; Sun et al., 2003; Xie et al., 2009b) in the Middle–
Lower Yangtze metallogenic belt (MLYMB), one of the most important
ore deposit belts in China (Chang et al., 1991; Deng et al., 2002; Pan
and Dong, 1999; Xu and Lin, 2000; Xu and Zhou, 2001; Zhai et al.,
1996). Seven ore clusters scattered along the MLYRB from west to east
are Edong, Jiurui, Anqing–Guichi, Luzong, Tongling, Ningwu and
Ningzhen, respectively. The mineralization of these ore clusters are
associated with the intermediate to acid intrusions. Lots of geological
and geochemical works have been done in the Tongling region (Chen
et al., 1993; Mao et al., 2004; Qu et al., 2010a,b; Q. Wang et al., 2004b;
Wang et al., 2003, 2008; Y.B. Wang et al., 2004a; Y.L. Wang et al.,
2004; Xiaoyong Yang et al., 2011; G.Q. Xie et al., 2008; J.C. Xie et al.,
☆ This is an open-access article distributed under the terms of the Creative Commons
Attribution–NonCommercial–No Derivative Works License, which permits non-
commercial use, distribution, and reproduction in any medium, provided the original
author and source are credited.
⁎ Corresponding authors.
E-mail addresses: xyyang555@163.com (X. Yang), weidongsun@gig.ac.cn (W. Sun).
2008; Xie et al., 2009a,b; Xing and Xu, 1996; X.N. Yang et al., 2011;
Yang and Lee, 2011; Yang et al., 2008; D. Zhang et al., 2006; Zhou
et al., 2011). Most previous scholars believed that the adakitic rocks in
this region were formed through partial melting of the lower continen-
tal crust through delamination, followed by melt/rock interaction with
the mantle peridotites (Q. Wang et al., 2004a,b; Wang et al., 2003,
2007). Recent studies demonstrated that most of the ore-forming
adakitic rocks have components resembling oceanic slab melts (Ling
et al., 2009; Liu et al., 2010; Wang et al., 2013). However, there is no
consensus on the petrogenesis of ore related rocks. The Fenghuangshan
skarn Cu–Au deposit is located in the Tongling ore cluster field along the
MLYMB. A comprehensive study should be taken to explain the
petrogenic and mineralization mechanism of Fenghuangshan deposit.
The goal of this study is to systematically investigate the age, physical
conditions (temperature, pressure, and oxygen fugacity) for the miner-
alization, and the source region of intrusive rocks in the Fenghuangshan
deposit. The petrogenic conditions of the Fenghuangshan granodiorite
are constrained by chemical compositions of biotite and zircons.
In-situ zircon Hf isotopic composition is helpful to define the source
of Fenghuangshan granodiorite. The PGE contents of sulfide ores and
Re content of molybdenite are sensitive indicators of the source of ore
material. In this study, chemical compositions, zircon U–Pb dating and
Hf isotopic composition, biotite thermobarometry, Re–Os dating and

0169-1368/$ – see front matter © 2013 The Authors. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.oregeorev.2013.11.004
 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162 149

Fig. 1. Geological map of the Tongling ore cluster district, east China. A. Geological sketch map of the Tongling ore cluster district, showing distributions of different intrusions and Cu–Au
deposits (modified after Chang et al., 1991; Xie et al., 2009b). B. Geological map of the Fenghuangshan skarn Cu–Au deposit (modified after Chang et al., 1991).
150 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162

Fig. 2. Microphotographs of granodiorite in Fenghuangshan intrusion. The images were taken by the Leica microscope under plane and crossed polars. The scale bar for each image is
100 μm. Kfs—K-feldspar; Pl—plagioclase; Qtz—quartz; Bt—biotite. A—granodiorite composed of plagioclase, quartz, and biotite. B—plagioclase, belonging to oligoclase and andesine. The
plagioclase has sericite alteration. C—euhedral biotite and granular quartz. The quartz appears as subhedral, anhedral crystals. D—The andesine has clean margin texture, with strong
sericite alteration in the central zones and unaltered in the margin. The biotite has strong chloritized alteration. E—The plagioclase and K—feldspar has strong sericite alteration. The quartz
shows clear wavy extinction phenomenon under the crossed polarized microscope. F—The biotite shows strong chloritized alteration under plane polarized microscope.
 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162 151

PGE analysis of sulfide ores are combined to constrain the petrogenic

and mineralization mechanism of the Fenghuangshan Cu–Au deposit.

2. Geological setting

The Yangtze block is separated from the North China Craton by the
Triassic Dabie orogenic belt to the north, and from the Cathaysian
block by the Neoproterozoic suture to the south. The MLYMB, located
in the Yangtze block, central eastern China, is famous for its abundant
polymetallic deposits. Tongling ore cluster field is located in the central
region of the MLYMB. Dozens of Cu–Au–polymetallic deposits
have been found in this area, such as the Tongguanshan (Cu–Au),
Fenghuangshan (Cu–Au), Baocun (Au), Chaoshan (Au), Jiguanshan
(Au N Ag), East Shizishan (Cu), West Shizishan (Cu N Au), Hucun (Cu),
Datuanshan (Cu N Au), Laoyaling (Cu N Mo), Huashupo (Cu N Au),
Dongguashan (Cu N Au). The igneous rocks in Tongling region consist
mainly of gabbro, pyroxene diorite, diorite, quartz diorite and granodio-
rite, composing a suit of sequential igneous rock combination (Fig. 1A).
The Fenghuangshan Cu–Au deposit is a typical skarn Cu–Au (Mo)
deposit in the Tongling ore cluster field (Chang et al., 1991; Mao et al.,
2006; Wang et al., 2011). It is located in the intersection of Tongling–
Daijiahui EW-trending tectonic–magmatic belt and the Qingshan sec-
ondary anticline of Zhucun NE-trending synclinorium. Surficial exposed
strata are composed of the Middle–Lower Triassic argillaceous
limestone and argillite (Fig. 1B). The Cu–Au related diorite stock is locat-
ed in the core of the Fenghuangshan syncline with outcrops of Silurian
to Middle Triassic strata. The skarn and Cu–Au ores were formed at
the contact of diorite and Middle Triassic limestone (Shao et al., 2003).
Strata of this deposit in some drill holes include the Upper Devonian,
Upper Carboniferous and Permian units, composed of sandstone, con-
glomerate, shale and limestone. Intermediate to acid intrusions were
developed extensively in Fenghuangshan ore field. The intrusive rocks
are mainly quartz monzodiorite, pyroxene monzodiorite, granodiorite,
quartz diorite porphyry and adamellite porphyry, and quartz diorite.
Fenghuangshan deposit is an excellent location to study Cu–Au deposit
due to its large mining scale and easily accessible fresh samples in the
exploration pit.

3. Petrography

The granodiorite and sulfide ore samples were collected from
Fenghuangshan skarn Cu–Au deposit. The granodiorite mainly consists
of plagioclase (~45%), K-feldspar (20%), quartz (~20%), and abundant
biotite (~ 10%), with minor accessory phases, e.g., pyroxene, zircon,
apatite(b5%) (Fig. 2). The plagioclase belongs to oligoclase and
andesine. The oligoclase has tight polysynthetic twins, with strong
sericite alteration. The andesine has zonal structure, with strong sericite
alteration in the central zones and unaltered in the margin, which is
called clean margin texture (Fig. 2A, B, D, E). Quartzs appear as
subhedral, anhedral crystals (Fig. 2A, C, E), with clear wavy extinction
phenomenon under the crossed polarized microscope (Fig. 2A, E). The
biotite shows strong chloritized alteration under the plane polarized
microscope (Fig. 2D, F).
4. Analytical methods
4.1. Major and trace elements of whole rocks
Major elements and trace elements (including rare earth elements)
were analyzed in ALS Laboratory Group — an Australian ICP-MS analyt-
ical lab in Guangzhou. Detailed analytical methods were described by
Liu et al. (1996).
For major element analysis, a calcined or ignited sample (~ 0.9 g)
was added with lithium borate flux (~ 9.0 g, 50% Li2B4O7–LiBO2),
mixed well and fused in an auto fluxer at a temperature between
1050–1100 °C and then cooled to form a flat molten glass disc, which
Fig. 3. Major chemical results of the Fenghuangshan granodiorite. A. The chemical classi-
fication of the TAS diagram of Fenghuangshan granodiorite (after Wilson, 1989). Ir—Irvine
dividing line, above is alkaline, below the sub-alkaline. 1—olive gabbro; 2a—syenogabbro;
2b—gabbro; 3—gabbro–diorite; 4—diorite; 5—granodiorite; 6—granite; 8—alkali–gabbro;
9—alkali–gabbroicdiorite; 10—syenodiorite; 11—quartz monzonite; 12—syenite; 13—
feldspathoid gabbro; 14—feldspathoid monzonite diorite; 15—feldspathoid monzonitic
syenite; 16—feldspathoid syenite; 17—foidite pluton; 18—leucite rock. B. SiO2 vs. K2O
diagram of Fenghuangshan granodiorite (after Peccerillo and Taylor, 1976).
was then analyzed by ME-XRF-06, with analytical precisions as: SiO2:
0.8%; Al2O3: 0.5%; Fe2O3: 0.4%; MgO: 0.4%; CaO: 0.6%; Na2O: 0.3%; K2O:
0.4%; MnO: 0.7%; TiO2: 0.9%; P2O5: 0.8%. Analytical uncertainties were
better than 1%.
Trace elements were analyzed by inducively coupled plasma-mass
spectrometry (ICP-MS) of ME-MS81. We used HNO3 + HF seal dissolu-
tion method for trace elements and REE determination by adding Rh
internal standard and converting the sample solutions into 1% HNO3
medium. The analytical precisions of trace elements were as follow:
Ba: 2.7%; Ta: 2.1%; Nb: 1.6%; Zr: 2.2%; Hf: 2.1%; Th: 2.1%; U: 3.4%; Pb:
3.2%; Ga: 1.9%; Cr: 5.3%; Co: 0.8%; Ni: 11%; Cu: 3.5%; Rb: 2.1%; Sr: 1.7%;
Sc: 4.2%; V: 3.2%; Zn: 3.0%.
Rare earth elements were analyzed by cation exchange separation-
inductively coupled plasma atomic emission spectrometry (ICP-AES)
with analytical precision as: La: 4.7%; Ce: 5.2%; Pr: 1.8%; Sm: 4.7%; Eu:
1.2%; Gd: 1.4%; Tb: 3.2%; Dy: 4.3%; Ho: 2.4%; Er: 3.9%; Tm: 4.8%; Yb:
4.3%; Lu: 3.9%; Y: 1.8%.
152 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162

Table 1
Major element (wt%) and trace element (ppm) data of Fenghuangshan granodiorite in the Tongling region.

Sample no. Rocks SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O Cr2O3 TiO2 MnO P2O5 SrO BaO LOI Total

FHS-6 Granodiorite 64.27 16.08 4.03 4.68 0.89 3.66 3.25 b0.01 0.55 0.08 0.21 0.08 0.08 1.83 99.68
FHS-7 Granodiorite 63.65 16.15 3.84 4.80 1.42 3.80 2.93 b0.01 0.59 0.08 0.22 0.10 0.10 0.96 98.64
FHS-8 Granodiorite 63.93 15.90 3.55 4.81 1.10 3.54 3.37 b0.01 0.55 0.08 0.21 0.11 0.11 1.56 98.82
07FHS-01 Granodiorite 61.75 15.83 4.75 4.87 1.64 3.82 2.86 0.01 0.64 0.10 0.26 0.14 0.18 1.95 98.79
07FHS-02 Granodiorite 60.82 15.85 4.69 5.16 1.04 3.71 2.91 0.01 0.67 0.09 0.26 0.10 0.09 3.32 98.71
07FHS-03 Granodiorite 61.59 16.02 4.52 5.11 0.95 3.72 2.87 0.01 0.67 0.08 0.27 0.13 0.12 3.31 99.37
12FHS-11 Granodiorite 62.39 16.12 3.81 4.75 0.50 3.48 3.25 b0.01 0.58 0.07 0.22 0.08 0.08 4.14 99.44
12FHS-12 Granodiorite 62.34 16.11 3.82 4.63 0.52 3.47 3.15 b0.01 0.58 0.06 0.22 0.08 0.08 4.06 99.10
12FHS-13 Granodiorite 62.25 16.28 3.44 4.30 0.57 3.10 3.25 b0.01 0.58 0.07 0.23 0.08 0.07 4.95 99.14
12FHS-14 Granodiorite 63.11 16.19 3.74 4.67 0.49 3.51 3.27 b0.01 0.58 0.06 0.22 0.08 0.08 3.97 99.96
12FHS-15 Granodiorite 62.70 16.12 3.41 4.03 0.55 2.94 3.42 b0.01 0.58 0.07 0.22 0.08 0.07 4.86 99.03
12FHS-16 Granodiorite 62.30 16.17 4.36 4.81 0.53 3.53 3.06 b0.01 0.59 0.07 0.23 0.08 0.08 4.20 99.98
12FHS-17 Granodiorite 62.01 16.02 3.76 4.93 0.47 3.47 3.10 b0.01 0.56 0.07 0.22 0.08 0.08 4.19 98.93
12FHS-18 Granodiorite 62.13 15.80 3.84 4.60 0.51 3.18 3.20 b0.01 0.55 0.08 0.21 0.08 0.08 4.82 99.05
12FHS-19 Granodiorite 62.74 16.08 3.45 4.47 0.54 3.32 3.28 b0.01 0.57 0.07 0.22 0.08 0.08 4.39 99.26
12FHS-20 Granodiorite 61.54 16.06 4.13 4.99 0.53 3.52 3.03 b0.01 0.57 0.07 0.22 0.08 0.08 4.33 99.13

Sample no. Na2O + K2O Na2O/K2O Ba Ce Co Cr Cs Cu Dy Er Eu Ga Gd Hf Ho La

FHS-6 6.91 0.89 647.00 71.10 6.90 10.00 2.84 53.00 3.19 1.92 1.21 19.00 4.29 4.70 0.64 39.80
FHS-7 6.73 0.77 987.00 74.10 7.60 10.00 1.92 10.00 3.63 2.11 1.32 20.70 4.90 5.10 0.71 38.50
FHS-8 6.91 0.95 932.00 63.40 6.20 10.00 2.31 21.00 3.05 1.82 1.21 19.10 4.24 4.60 0.61 34.00
07FHS-01 6.68 0.75 1590.00 76.90 11.20 10.00 2.36 17.00 3.33 1.83 1.37 20.40 4.76 5.10 0.62 39.90
07FHS-02 6.62 0.78 815.00 82.10 12.10 20.00 2.78 26.00 3.33 1.89 1.44 20.90 5.01 5.10 0.64 43.30
07FHS-03 6.59 0.77 1090.00 74.40 10.50 10.00 3.02 19.00 2.94 1.66 1.31 20.20 4.56 5.00 0.56 39.50
12FHS-11 6.73 0.93 720.00 40.70 4.30 14.00 2.66 17.60 2.64 1.51 0.90 21.00 2.77 6.00 0.50 18.70
12FHS-12 6.62 0.91 720.00 52.50 5.10 12.00 2.76 353.00 3.08 1.75 1.11 20.60 3.41 5.50 0.57 24.70
12FHS-13 6.35 1.05 650.00 39.90 4.70 10.00 3.30 106.50 2.17 1.30 0.84 19.45 2.65 6.00 0.44 18.20
12FHS-14 6.78 0.93 720.00 39.90 4.30 13.00 2.82 54.60 2.20 1.34 0.85 20.10 2.71 6.00 0.46 17.80
12FHS-15 6.36 1.16 660.00 45.80 5.80 11.00 3.25 730.00 2.20 1.22 0.87 20.70 2.79 6.00 0.44 20.80
12FHS-16 6.59 0.87 690.00 47.30 4.50 13.00 2.75 27.10 2.35 1.39 0.94 21.10 3.09 6.00 0.48 21.50
12FHS-17 6.57 0.89 700.00 35.40 4.40 12.00 2.81 197.50 2.17 1.35 0.75 19.95 2.50 6.00 0.45 15.80
12FHS-18 6.38 1.01 660.00 35.20 4.50 12.00 2.99 36.60 2.20 1.35 0.75 19.00 2.50 5.50 0.47 16.00
12FHS-19 6.60 0.99 700.00 45.80 4.90 10.00 3.27 252.00 2.36 1.43 0.93 19.80 2.93 6.00 0.49 21.10
12FHS-20 6.55 0.86 700.00 43.80 4.70 11.00 3.04 12.50 2.31 1.38 0.87 20.70 2.80 6.00 0.48 20.00

Sample no. Lu Mo Nb Nd Ni Pb Pr Rb Sm Sn Sr Ta Tb Th Tl Tm

FHS-6 0.28 13.20 26.40 14.00 7.42 140.50 4.60 2.00 606.00 1.00 0.59 14.25 0.26
FHS-7 0.30 13.60 28.90 13.00 7.99 112.00 5.15 2.00 910.00 1.10 0.68 11.00 0.27
FHS-8 0.27 11.80 24.20 12.00 6.70 130.00 4.26 2.00 967.00 0.80 0.58 10.00 0.24
07FHS-01 0.26 12.10 30.50 12.00 8.39 102.50 5.13 2.00 1220.00 0.80 0.64 10.15 0.25
07FHS-02 0.26 12.30 32.50 14.00 8.87 108.00 5.47 2.00 869.00 0.80 0.67 10.35 0.24
07FHS-03 0.25 12.30 29.10 12.00 8.06 105.50 4.96 2.00 1170.00 0.80 0.59 9.69 0.21
12FHS-11 0.23 2.31 13.30 17.70 2.70 18.20 4.48 90.40 3.35 1.80 773.00 1.09 0.41 8.40 0.70 0.22
12FHS-12 0.25 2.69 13.60 22.90 2.40 18.90 5.73 97.10 4.18 1.80 767.00 1.07 0.49 10.40 0.67 0.25
12FHS-13 0.23 2.63 13.90 15.20 1.20 18.00 4.13 90.10 2.82 2.00 705.00 1.24 0.37 7.60 0.69 0.20
12FHS-14 0.24 2.27 13.20 15.50 1.10 20.40 4.13 87.70 2.90 1.90 761.00 1.22 0.39 7.40 0.70 0.21
12FHS-15 0.22 35.60 14.00 17.50 1.40 19.70 4.76 98.60 3.17 2.40 725.00 1.20 0.39 8.20 0.77 0.19
12FHS-16 0.24 2.30 14.20 18.20 1.30 18.80 4.96 89.30 3.39 1.90 768.00 1.23 0.43 8.50 0.67 0.22
12FHS-17 0.24 2.26 13.20 13.50 1.40 19.60 3.64 80.90 2.57 1.80 741.00 1.16 0.36 6.50 0.67 0.22
12FHS-18 0.24 2.39 12.80 13.30 1.50 17.80 3.61 86.70 2.55 1.70 705.00 1.11 0.37 6.70 0.66 0.22
12FHS-19 0.25 16.00 13.30 17.20 1.10 20.20 4.69 94.90 3.15 1.90 752.00 1.17 0.42 8.80 0.71 0.22
12FHS-20 0.24 2.29 14.10 16.70 1.40 18.30 4.53 86.50 3.06 1.90 761.00 1.19 0.40 7.90 0.63 0.22

Sample no. U V W Y Yb Zn Zr ΣREE δEu Sr/Y LaN/YbN

FHS-6 4.11 62.00 4.00 17.20 1.84 59.00 161.00 163.54 0.83 35.23 15.52
FHS-7 2.91 81.00 2.00 18.40 1.92 51.00 177.00 170.48 0.80 49.46 14.38
FHS-8 2.39 79.00 8.00 16.20 1.76 46.00 158.00 146.34 0.87 59.69 13.86
07FHS-01 2.96 91.00 2.00 16.70 1.70 63.00 179.00 175.58 0.85 73.05 16.84
07FHS-02 2.47 92.00 2.00 17.40 1.75 69.00 180.00 187.47 0.84 49.94 17.75
07FHS-03 2.72 91.00 3.00 15.20 1.58 65.00 178.00 169.68 0.84 76.97 17.93
12FHS-11 1.70 70.00 1.40 11.50 1.50 37.00 249.00 95.61 0.90 67.22 8.94
12FHS-12 1.90 71.00 1.40 14.00 1.68 35.00 247.00 122.60 0.90 54.79 10.55
12FHS-13 1.20 68.00 1.60 11.50 1.41 37.00 252.00 89.86 0.94 61.30 9.26
12FHS-14 1.40 67.00 1.50 11.40 1.46 37.00 243.00 90.09 0.93 66.75 8.75
12FHS-15 1.30 67.00 1.50 12.40 1.29 37.00 262.00 101.64 0.89 58.47 11.57
12FHS-16 1.70 68.00 1.50 13.30 1.42 37.00 267.00 105.91 0.89 57.74 10.86
12FHS-17 1.30 68.00 1.50 11.20 1.44 38.00 256.00 80.39 0.90 66.16 7.87
12FHS-18 1.20 65.00 1.40 12.10 1.48 41.00 244.00 80.24 0.91 58.26 7.75
12FHS-19 1.40 66.00 1.50 12.90 1.49 35.00 244.00 102.46 0.94 58.29 10.16
12FHS-20 1.30 68.00 1.40 13.00 1.45 41.00 265.00 98.24 0.91 58.54 9.89
 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162 153

4.2. Biotite major elements
Major elements of biotite were determined by using a wavelength-
dispersive JEPL JXA-8800R electron microprobe (EMP) at the Instru-
mental Analysis and Research Center, Sun Yat-sen University. The
analysis was taken with an accelerating voltage of 15 kV, a low beam
current (10 nA), and a defocused beam (1 μm). The calibration was
based on a suite of mineral standards and oxide standards from the
American standard committee.
temperature was 1150 °C. Then the crushed NiS button was dissolved
in 6 mol/L HCl, and the PGEs were collected by Tellurium co-
precipitation. Solutions were analyzed for PGEs by ICP-MS (TJA Pro
Excel series) and gold using IRIS. The Os, Ir, Ru, Rh, Pt, Pd were
determined by isotope dilution method, and the analytical precision is
better than 10%.

4.3. Zircon U–Pb isotope

Zircons were separated from the granodiorite sample FHS-9 using

magnetic and heavy liquid separation methods, and purified by
handpicking under binocular microscope. Approximately 100 zircon
grains were mounted on an adhesive tape, enclosed in epoxy resin,
polished, and then photographed under both transmitted- and
reflected-light. The internal structures of zircons were examined using
the cathodoluminescence (CL) image technique in the Analytical Center
of University of Science and Technology of China. The U–Pb isotopic
composition of zircons was analyzed by an Agilent 7500a ICP-MS
coupled with a Resonetic Resolution 50-M ArF-Excimer laser source
(λ = 193 nm) at Guangzhou Institute of Geochemistry, Chinese
Academy of Science, following the procedures outlined by Tu et al.
(2011). The spot size of the ion beam was set at ~31 μm. U–Pb ages of
zircons were calculated by using the ISOPLOT program (Ludwig, 2003).

4.4. In-situ zircon Hf isotope

In-situ zircon Hf isotopic analysis was conducted on the U–Pb dated

spots using an ArF excimer laser ablation system (GeoLas 2005)
attached to a Nu Plasma HR MC-ICP-MS at the State Key Laboratory of
Continental Dynamics, Northwest University, China. The laser-ablated
spot size was 32 μm. The detailed instrumental parameters are the
same as those reported by Yuan et al. (2008). The mass fractionations
of Hf and Yb were calculated with reported 0.7325 for 179Hf/177Hf and
1.1248 for 173Yb/171Yb (Blichert-Toft et al., 1997). The recommended
176
Hf/177Hf ratio of standard zircon 91500 is 0.282289 ± 0.000011
(2σ) (Blichert-Toft, 2008). The obtained Hf isotopic compositions are
0.282036 ± 0.000009 (2σ, n = 4) for GJ-1, 0.282787 ± 0.000007
(2σ, n = 4) for Monastery, respectively.

4.5. Molybdenite Re–Os isotope

The five fine-grain molybdenite samples collected from

Fenghuangshan deposit were formed during the same mineralization
event. These samples were ground down to 100 mesh and washed,
then the molybdenites were handpicked under a binocular microscope
to get purified to more than 99%. The Re–Os isotope compositions of
molybdenites were analyzed using TJA X-series ICP-MS in Beijing
Geological Analysis Center, Chinese Geological Science. Detailed analyt-
ical method has been described by Du et al. (1994). The uncertainty of
determined Re–Os isochron ages is 0.5%, which includes the uncertainty
of the decay constant of 187Re, isotope ratio measurement, and
spike calibrations (Du et al., 1994). The decay constant is λ
(187Re) = 1.666 × 10−11/year (Smoliar et al., 1996).

4.6. Platinum-group elements and gold of ore

The ore samples collected from Fenghuangshan deposit mainly

contain pyrite, chalcopyrite, and sphalerite. The PGEs (Os, Ir, Ru, Rh,
Pt, Pd) and gold (Au) were determined by fire-assay preconcentration
and ICP-MS measurement at the National Research Center for
Geoanalysis. The powdered ore samples were mixed with sodium
carbonate, sodium borate, borax, nickel, sulfur, flour and appropriate
amount of osmium thinner to produce NiS button. The fusion
Fig. 4. Distributions of REE and trace elements of the Fenghuangshan granodiorite
(Primitive mantle, N-MORB and OIB are summarized from Sun and McDonough, 1989;
bulk continent is after Rudnick and Gao, 2003; Chondrite is after Langmuir et al., 1977;
Sun, 1982; Sun and McDonough, 1989). A. Spider diagram of trace elements. B. Chondrite-
normalized REE distribution patterns. C. Spider diagram of transitional elements.
154 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162

Table 2
Representative compositions and structural formula of biotite from the Fenghuangshan granodiorite.

Sample no. 08FHS-016-1 08FHS-016-2 08FHS-016-3 08FHS-016-4 08FHS-016-5 08FHS-016-6 08FHS-016-7 08FHS-016-8

Component oxides (wt%)

SiO2 38.22 38.37 38.98 38.91 39.21 39.73 38.78 38.63
TiO2 4.74 4.61 4.69 4.07 4.26 3.93 4.47 4.45
Al2O3 13.22 13.30 13.18 13.48 13.20 12.88 13.02 12.87
FeO 18.29 18.63 17.87 17.89 18.16 17.81 17.81 17.74
MnO 0.37 0.27 0.25 0.35 0.29 0.37 0.43 0.40
MgO 12.85 13.12 13.21 13.64 13.41 13.79 13.93 13.78
CaO 0.00 0.00 0.03 0.00 0.03 0.02 0.03 0.05
Na2O 0.12 0.09 0.21 0.20 0.13 0.13 0.12 0.16
K2O 9.90 9.74 9.72 9.95 10.01 10.01 10.40 10.22
F 0.58 0.61 0.48 0.65 0.52 0.81 0.58 0.58
Cl 0.18 0.17 0.18 0.17 0.23 0.18 0.16 0.15
Total 98.18 98.66 98.56 99.01 99.19 99.29 99.46 98.78

Mineral formulae based on O = 22

Si 5.64 5.63 5.70 5.67 5.71 5.76 5.64 5.66
AlIV 2.30 2.30 2.27 2.31 2.26 2.20 2.23 2.22
AlVI 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ti 0.53 0.51 0.52 0.45 0.47 0.43 0.49 0.49
Fe3+ 0.52 0.53 0.54 0.49 0.50 0.55 0.42 0.43
Fe2+ 1.74 1.76 1.64 1.69 1.71 1.61 1.75 1.74
Mn 0.05 0.03 0.03 0.04 0.04 0.05 0.05 0.05
Mg 2.82 2.87 2.88 2.96 2.91 2.98 3.02 3.01
Ca 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01
Na 0.03 0.03 0.06 0.06 0.04 0.04 0.03 0.05
K 1.86 1.82 1.81 1.85 1.86 1.85 1.93 1.91
Total 15.48 15.47 15.46 15.51 15.50 15.45 15.58 15.57
Mg/(Mg + Fe) 0.56 0.56 0.57 0.58 0.57 0.58 0.58 0.58
T/°C 751.54 747.75 751.83 734.85 738.92 730.52 748.32 748.09
P/MPa 76.01 76.59 68.03 81.00 66.26 46.25 56.61 53.07
H/km 2.51 2.53 2.25 2.67 2.19 1.53 1.87 1.75

5. Results

5.1. Major and trace elements of whole rocks

The collected samples of Fenghuangshan granodiorite are with SiO2

ranging from 60.82 to 64.27% (Fig. 3A), and total alkali contents ranging
from 6.35 to 6.91% (Table 1). Such granodiorite belongs to high-K calc-
alkaline series (Fig. 3B), and presents strong positive correlation be-
tween SiO2 and K2O (Fig. 3B). These samples have high Al2O3 contents
of 15.8–16.28% and Na2O/K2O ranging from 0.77 to 1.16.
From the perspective of trace elements (including REEs), the
Fenghuangshan granodiorite is characterized by high Ba, Sr and LREEs
contents, and low Ti, P, and HREEs contents. Ba and Sr concentrations
in these samples range from 647 to 1590 ppm, and 606 to 1220 ppm,

Fig. 6. CL images and zircon LA–ICP-MS U–Pb dating. A. CL images of zircons for LA-ICP-MS
Fig. 5. Diagram for biotite classification (after Foster, 1960). U–Pb dating. B. U–Pb concordia diagram for zircons from the Fenghuangshan granodiorite.
 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162 155

Table 3
LA–ICP-MS zircon analytical data of Fenghuangshan granodiorite.

Spot Element (ppm) Isotopic ratios Ages (Ma)

232 238 207
Th U Th/U Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ 207
Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ

Weighted mean age = 143.1 ± 1.6 Ma (MSWD = 0.4)

FHS-9-01 482.7 311.5 1.55 0.04247 0.00236 0.13048 0.00735 0.02227 0.00038 0 0 124.5 6.6 142.0 2.4
FHS-9-02 610.3 1250.6 0.49 0.07234 0.00457 0.23076 0.01625 0.02251 0.00043 995.4 129.6 210.8 13.4 143.5 2.7
FHS-9-03 222.8 245.1 0.91 0.06279 0.00367 0.18616 0.01113 0.02164 0.00053 701.9 124.1 173.3 9.5 138.0 3.3
FHS-9-04 107.5 181.7 0.59 0.05559 0.00344 0.16848 0.01025 0.02265 0.00049 435.2 134.2 158.1 8.9 144.4 3.1
FHS-9-05 168.0 215.8 0.78 0.04827 0.00280 0.15369 0.00937 0.02279 0.00038 122.3 120.4 145.2 8.2 145.3 2.4
FHS-9-06 253.6 332.4 0.76 0.04516 0.00257 0.14162 0.00821 0.02265 0.00041 0 0 134.5 7.3 144.4 2.6
FHS-9-07 142.5 149.3 0.95 0.05483 0.00386 0.16784 0.01126 0.02246 0.00047 405.6 163.9 157.5 9.8 143.2 2.9
FHS-9-08 154.9 160.7 0.96 0.05583 0.00393 0.17545 0.01256 0.02236 0.00046 455.6 157.4 164.1 10.8 142.5 2.9
FHS-9-09 209.6 302.0 0.69 0.05133 0.00311 0.15865 0.00957 0.02246 0.00037 257.5 140.7 149.5 8.4 143.2 2.3
FHS-9-10 113.1 175.2 0.65 0.05027 0.00352 0.15071 0.00963 0.02244 0.00044 209.3 162.9 142.5 8.5 143.1 2.7
FHS-9-11 97.2 124.7 0.78 0.06533 0.00589 0.19672 0.01744 0.02226 0.00045 784.9 190.7 182.3 14.8 141.9 2.9
FHS-9-12 132.6 120.8 1.10 0.06254 0.00282 1.12575 0.04874 0.12905 0.00175 694.5 96.3 765.7 23.3 782.5 10.0
FHS-9-13 97.7 94.5 1.03 0.06023 0.00275 1.12097 0.04926 0.13489 0.00189 613.0 100.0 763.4 23.6 815.7 10.8
FHS-9-14 95.4 298.7 0.32 0.13373 0.00451 6.93905 0.23647 0.36829 0.00504 2147.8 58.9 2103.7 30.3 2021.3 23.7

REE concentration (ppm) in the zircons

Spot La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu EuN/EuN* Ce(IV)/Ce(III)

FHS-9-01 0.12 20.40 0.07 1.14 1.78 0.69 11.11 4.43 58.57 24.37 122.18 31.20 336.15 69.22 0.48 398.23
FHS-9-02 0.80 28.57 0.13 1.17 1.80 0.79 11.63 4.29 56.23 23.05 113.67 28.23 301.18 62.72 0.53 492.27
FHS-9-03 0.03 17.09 0.05 0.66 1.71 0.69 8.60 3.39 44.39 18.94 97.03 24.88 279.47 58.85 0.55 316.15
FHS-9-04 2.50 40.10 0.71 5.08 4.95 2.06 21.53 7.80 94.61 38.65 182.98 44.59 473.92 94.65 0.61 142.65
FHS-9-05 0.04 21.50 0.07 1.29 2.39 0.68 10.93 4.22 53.34 21.13 103.68 25.77 279.27 52.45 0.41 179.72
FHS-9-06 0.18 32.51 0.10 1.72 3.59 1.52 19.33 5.94 72.93 27.77 129.95 30.74 314.84 60.95 0.56 139.18
FHS-9-07 0.53 27.44 0.11 1.11 2.69 1.24 13.12 5.03 60.18 22.73 107.74 26.23 274.41 54.11 0.64 184.92
FHS-9-08 0.06 29.25 0.12 1.74 3.59 1.29 19.43 6.54 82.35 34.13 164.49 41.76 452.79 101.80 0.47 212.8
FHS-9-09 0.31 20.35 0.12 0.89 1.40 0.64 9.72 3.59 45.13 18.11 86.85 21.42 215.88 43.53 0.53 400.13
FHS-9-10 1.17 16.82 0.22 1.60 2.45 1.00 11.53 4.39 56.11 22.26 112.29 29.52 321.93 63.59 0.57 162.79
FHS-9-11 0.21 32.59 0.15 2.13 3.84 1.39 20.34 7.56 89.66 36.84 184.36 43.36 473.35 104.79 0.48 211.92

respectively. The low Rb contents, ranging from 80.9 to 140.5 ppm, lead
to high K/Rb ratios. The contents of high field-strength elements (HFSEs)
are relatively low, with Zr ranging from 158.00 to 267.00 ppm, Nb rang-
ing from 11.80 to 14.20 ppm, Ta ranging from 0.80 to 1.24 ppm, Y rang-
ing from 11.20 to 18.40 ppm, and Th ranging from 6.50 to 14.25 ppm.
Spider diagram normalized to primitive mantle (Sun and
McDonough, 1989) is shown in Fig. 4A. The Fenghuangshan granodi-
orite and other intrusive samples from Tongling region show similar
features, exhibiting a relatively sharp left–right slope, enrichment of
large ion lithophile elements (Rb, Ba, K, Sr), depletion of high field
strength elements (Nb, Ta, Ti), which are all consistent with the sce-
nario of a subduction-related magmatism for their formation (Pearce
et al., 1984; Sajona et al., 1993). And the large Pb positive anomalies
also indicate the magma was metasomatized by subduction-related
fluid (Fitton et al., 1991). The chondrite-normalized REE patterns of
the Fenghuangshan granodiorite (Fig. 4B) exhibit high degree of
fractionation between LREEs and HREEs, and slightly negative Eu
anomalies. The enrichment of LREEs and depletion of HREEs lead to
high La N/Yb N ratios (N7.75). The spider diagram of transitional
elements (Fig. 4C) in Fenghuangshan granodiorite show strong
fractionation compared to the continental crust (Rudnick and Gao,
2003), with obvious Cu positive anomalies and strong depletion of
mantle compatible elements (Sc, Cr, Co, Ni). The relative enrichment
of Cu in the granodiorite is likely to be a result of Cu mineralization in
Fenghuangshan deposit.
5.2. Biotite composition
The biotite grains in Fenghuangshan granodiorites have high MgO
contents of 12.85–13.94%, and low Al2O3, FeO contents of 12.87–13.48%,
17.74–18.63%, respectively (Table 2). The XMg values (Mg/(Mg + Fe))
for the biotite grains are from 0.56 to 0.58, and such small variations sug-
gest that these biotite grains are primary and have not been altered.
When projecting the biotites in the Mg–(Fe2++Mn)–(Fe3++AlVI + Ti)
diagram (Fig. 5), it is shown that they are magnesian biotites (Foster,
1960).

Table 4
LA–MC-ICP-MS zircon Hf isotopic compositions of Fenghuangshan granodiorite in the Tongling region.
176
–Spot Age (Ma) Yb/177Hf 176
Lu/177Hf 176
Hf/177Hf 2σ εHf(0) εHf(t) tDM1 tDM2 fLu/Hf

FHS-9-01 142 0.027626 0.000988 0.282110 0.000014 −24.40 −21.38 1677 2115 −0.97
FHS-9-02 144 0.019234 0.000692 0.282374 0.000012 –15.06 –11.98 1299 1641 –0.98
FHS-9-03 138 0.017498 0.000642 0.282239 0.000012 −19.84 −16.87 1484 1885 −0.98
FHS-9-04 144 0.032192 0.001179 0.282260 0.000014 −19.10 −16.06 1476 1848 −0.96
FHS-9-05 145 0.022956 0.000873 0.282012 0.000070 −27.85 −24.75 1807 2288 −0.97
FHS-9-06 144 0.028761 0.001146 0.282119 0.000010 −24.07 −21.02 1671 2099 −0.97
FHS-9-07 143 0.019595 0.000715 0.282248 0.000009 −19.52 −16.45 1475 1868 −0.98
FHS-9-08 143 0.044339 0.001633 0.282192 0.000011 −21.49 −18.52 1590 1971 −0.95
FHS-9-09 143 0.020942 0.000821 0.282097 0.000080 −24.84 −21.79 1687 2137 −0.98
FHS-9-10 143 0.029190 0.001091 0.282150 0.000011 −22.97 −19.94 1626 2044 −0.97
FHS-9-11 142 0.023166 0.000850 0.281915 0.000010 −31.28 −28.25 1939 2461 −0.97
FHS-9-12 782 0.019994 0.000779 0.282221 0.000014 −20.47 −3.61 1514 1729 −0.98
FHS-9-13 815 0.056943 0.001848 0.282222 0.000010 −20.43 −3.44 1556 1746 −0.94
FHS-9-14 2147 0.070129 0.002311 0.281611 0.000087 −42.05 2.63 2450 2523 −0.93
156 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162

Table 5
Re− Os isotopic data of molybdenite from the Fenghuangshan Cu− Au deposit in the Tongling region.
187 187
Sample no. Weight(g) Re(ng/g) 2σ Common Os(ng/g) 2σ Re ng/g 2σ Os ng/g 2σ model age 2σ
measured measured measured measured measured

FHS-1 0.00604 1314 22 0.0401 0.1349 825.735 14.017 1.967 0.024 142.8 3.2
FHS-2 0.00509 66421 560 0.0473 0.1060 41746.749 351.946 98.393 0.819 141.3 2.0
FHS-3 0.00550 127021 969 0.0932 0.0985 79835.454 609.113 187.905 1.506 141.1 1.9
FHS-4 0.00560 381991 3372 0.0915 0.2417 240088.784 2119.361 569.624 5.006 142.2 2.1
FHS-5 0.00662 44519 351 0.0363 0.0814 27981.280 220.771 66.440 0.536 142.4 2.0
187 −11
Note: Decay constant: λ( Re) = 1.666 × 10 /year (Smoliar et al., 1996).

Re contents of molybdenite in some other Cu–Au deposits in the Tongling region

Deposit Sample Age(Ma) Method Re content (ppm) Refs

Datuanshan Molybdenite 139.1 ± 2.7 Re− Os isochron ages 149.8–1000 [1]

Nanyangshan Molybdenite 139.3 ± 1.3 Average of 7 Re− Os model ages 53.02–184.9 [1]
Shatanjiao Molybdenite 140.3 ± 1.8 Average of 6 Re− Os model ages 174.2–1169 [1]
Laoyaling Molybdenite 139 ± 0.3 Re− Os model age 12.68 [2]

[1] Mao, J. W., Stein, H., Du, A.D., Zhou, T. F., Mei, Y. X., Li, Y. F., Zang, W. S., and Li, J. W., 2004; [2] Xie, Z., Sun, W. D., Chai, Z. F., Du, A.D., Li, C. S. and Mao, X. Y., 2002.

5.3. Zircon U–Pb geochronology Table 6. These massive ores have relatively low contents of PGEs. The Pt,
Pd and Ir are ranging from 0.22 to 10.4 ppb, 0.77 to 18.6 ppb, 0.02 to
Zircons from Fenghuangshan deposit are mostly euhedral 0.97 ppb, respectively. The Pd/Pt, Pd/Ir ratios are ranging from 1.04 to
in morphology, transparent, and light brown in color. The 11.04, 19.17 to 121.5, respectively. The gold contents are from 0.22 to
cathodoluminescence (CL) images show concentric oscillatory zoning 12.6 ppm. On the chondrite-normalized PGEs and gold diagram (Fig. 8),
in the zircons with low to variable luminescence (Fig. 6A), indicating
their magmatic origin. The zircon U–Pb data are reported in Table 3. Elev-
en zircons separated from granodiorite (FHS-9) have high contents of Th
(97–610 ppm) and U (124–1250 ppm), with Th/U ratios ranging from
0.48–1.55, providing more evidence for that these zircon crystals
have a typically magmatic genesis (Möller et al., 2003; Rubatto and
gebauer, 2000) (Table 3). These magmatic zircons form a tight
cluster on Concordia and yield a weighted mean 206Pb/238U age
of 143.1 ± 1.6 Ma (n = 11, MSWD = 0.4, 95% confidence level,
(Fig. 6B), which is interpreted as the crystallization time of the
Fenghuangshan intrusion at the early Cretaceous. Two other zircons
yield the concordant ages of 782.5 ± 10.0 Ma and 815.7 ± 10.8 Ma,
respectively. The CL images of these zircons show they are probably
inherited zircons from older material (Fig. 6A). Another inherited zircon
yield a discordant age of 2147.8 ± 59.0 Ma, which can be a consequence
of the assimilation of Paleo-proterozoic crustal material (Fig. 6A).

5.4. Zircon Lu–Hf isotope composition

Thirteen dated zircons from FHS-9 were analyzed for their Hf isotopic
composition, and the results are reported in Table 4. Eleven magmatic
zircons (ca. 140 Ma) exhibit ƐHf(T) values from − 12.0 to–28.3 and
the corresponding two-stage Hf model age is from 1.6 to 2.4 Ga.
The inherited zircons (ca. 782 Ma, 815 Ma and 2147 Ma) have ƐHf(T)
of −3.61, −3.44, and 2.63, respectively. The corresponding two-stage
Hf model age is 1.7 Ga, 1.7 Ga, 2.5 Ga, respectively.

5.5. Ages of mineralization

Five molybdenite samples were dated by Re –Os isochron for

the mineralization age of the Fenghuangshan ore deposit and corre-
sponding analytical results are listed in Table 5. The concentrations of
Re and 187Os range from 1.3 to 381 ppm, and 1.97 to 569.62 ppb, re-
spectively. The five samples give Re –Os model ages ranging from
141.1 to 142.8 Ma and a weighted mean age of 141.83 ± 0.94 Ma,
and yield an isochron age of 141.71 ± 0.82 Ma with initial 187Os of
0.015 ± 0.042 ppb using the ISOPLOT/Ex program (MSWD = 0.60,
Ludwig, 2003) (Fig. 7A, B).

5.6. PGEs and gold

The massive ores mainly consist of pyrite, chalcopyrite, galena and Fig. 7. Re–Os isotopic dating of molybdenite samples from the Fenghuangshan Cu–Au
sphalerite. The PGEs and gold contents of these massive ores are list in deposit. A. Re–Os isotopic isochron age; B. Re–Os isotopic weighted mean age.
 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162 157

Table 6
PGEs and gold contents of massive sulfide ores from the Fenghuangshan deposit.

Sample no. Au(μg/g) Pt(ng/g) Pd(ng/g) Rh(ng/g) Ru(ng/g) Ir(ng/g) Os(ng/g) Pd/Ir Pd/Pt

12FHSa-11 12.60 0.68 2.45 0.15 0.14 0.07 0.33 35.00 3.60
12FHSa-12 0.76 1.35 2.06 0.47 0.51 0.04 0.08 51.50 1.53
12FHSa-13 0.37 10.40 18.60 1.03 0.36 0.97 0.40 19.18 1.79
08FHS-30 1.34 2.22 2.31 0.12 0.07 0.02 0.05 115.50 1.04
08FHS-31 4.95 0.22 2.43 6.82 0.51 0.02 0.02 121.50 11.05
08FHS-35 0.22 0.24 0.77 3.00 0.30 0.04 0.05 19.25 3.21

the massive ores from Fenghuangshan deposit show steep, left-leaning (Di et al., 2005; Du et al., 2007; Lou and Du, 2006; Y.B. Wang et al.,
distribution patterns. 2004b,c,d; Wang et al., 2008; Xu et al., 2004, 2008; Yang et al., 2007).
The Re–Os isochron age of molybdenite samples is 141.71 ± 0.82 Ma,
6. Discussion suggesting the ore formation event is coeval with the Fenghuangshan
granodiorite intrusion.
6.1. Geochronology of Fenghuangshan ore deposit

Zircon U–Pb dating show that Fenghuangshan granodiorite intrusion
was formed at 143.1 ± 1.6 Ma, consistent with the previous studies
Fig. 8. Chondrite-normalized PGEs and gold diagram. Chondrite normalized data is after
Anders and Grevesse (1989).
6.2. Source materials
The Fenghuangshan granodiorite (with SiO2 N 60.82%) shows
distinct geochemical signatures as: enrichment of large ion lithophile
elements (Rb, Ba, K, Sr) and LREE, depletion of high field strength ele-
ments (Nb, Ta, Ti) and HREE, slightly negative Eu anomalies. The strong
Nb–Ta negative anomalies suggest that the formation of granodiorite is
likely to be associated with subduction-related magma (Pearce et al.,
1984; Sajona et al., 1993). The granodiorite has obviously adakitic signa-
tures: such as high Sr (606–1220 ppm), Al2O3 (15.8–16.28%), Na2O/K2O
(0.77–1.16), low Y (11.2–18.4 ppm), Yb (1.29–1.92 ppm). These
adakitic rocks belong to LYRB adakite, and were derived from partial
melting of the subducted oceanic crust towards LYRB during the early
Cretaceous (Ling et al., 2009; Liu et al., 2010; Wang et al., 2013; Xie
et al., 2009b).
We also compile the published Sr–Nd isotope data for
Fenghuangshan granodiorite and other intrusions in Tongling region
(Table 7). The Sr–Nd isotopic signatures of the Fenghuangshan granodi-
orite plot toward the EM-2 end member (Fig. 9A), and are also similar
to those of early Cretaceous mafic igneous rocks in the LYRB formed
by melting of lithospheric mantle, which was metasomatized by
subducted slab-derived melts/fluids. (Li et al., 2009; Ling et al., 2009;

Table 7
Sr–Nd Isotopic data of intermediate-acid intrusive rocks in the Tongling region.
147
Location Sample No. Rock type Sm/144Nd 143
Nd/144Nd t (Ma) εNd (t) 87
Rb/86Sr 87
Sr/86Sr (87Sr/86Sr)i Refs

Jinkouling V-4 Quartz diorite 0.1104 0.511920 137 −12.50 0.0636 0.708115 0.708000 [1]
Tian'ebaodanshan 85-ZI-1 Diorite 0.0983 0.511961 137 −11.49 0.0901 0.708553 0.708378 [1]
Tian'ebaodanshan 85-ZI-2 Diorite 0.0881 0.511914 137 −12.23 0.1399 0.708825 0.708553 [1]
Jinkouling V-41 Quartz diorite 0.1112 0.512017 137 −10.62 0.0657 0.707778 0.707650 [1]
Tongguanshan TGS-2 Quartz diorite 0.1111 0.512010 136 −10.80 0.0326 0.707280 0.707200 [2]
TGS-3 Quartz diorite 0.1108 0.511980 136 −11.30 0.1998 0.707690 0.707340 [2]
TGS-7 Quartz diorite 0.1154 0.511980 136 −11.40 0.2277 0.707690 0.707230 [2]
Dongguashan 98FC019-1 Granodiorite 0.1091 0.511943 137 −12.03 0.2381 0.708586 0.708100 [3]
98FC019 Granodiorite 0.1091 0.512029 137 −10.35 0.2283 0.708705 0.708300 [3]
Shizishan 98FC 030-3 Granodiorite 0.1072 0.511937 137 −12.12 0.3609 0.708697 0.708000 [3]
98FC031 Quartz diorite 0.1058 0.512046 137 −9.96 0.2798 0.707974 0.707400 [3]
Tongguanshan AI-4-2 Quartz diorite 0.1055 0.511949 137 −11.85 0.1729 0.707895 0.707600 [4]
AI-4-10 Quartz diorite 0.1063 0.511946 137 −11.92 0.2265 0.707666 0.707200 [4]
Tongguanshan CJ-6 Quartz diorite 0.1078 0.512000 130 −11.00 0.1640 0.707774 0.707500 [5]
Shizishan CJ-11 Quartz diorite porphyry 0.1074 0.512020 130 −10.50 0.2540 0.708226 0.707800 [5]
Fenghuangshan CJ-13 Quartz diorite porphyry 0.1065 0.512080 130 −9.50 0.3620 0.710008 0.709300 [5]
CJ-14 Granodiorite 0.1068 0.512050 130 −10.00 0.4080 0.709892 0.709100 [5]
CJ-15 Granodiorite 0.1069 0.511970 130 −11.60 0.5440 0.710887 0.709900 [5]
Jiguanshan CJ-23 Granodiorite 0.1072 0.512210 130 −6.90 0.2440 0.707430 0.707000 [5]
Baimangshan 1 Pyroxene monzodiorite 0.1085 0.512225 135 −6.50 0.2633 0.706580 0.706070 [6]
Jiguanshan 2 Pyroxene monzodiorite 0.1072 0.512166 135 −7.70 0.1967 0.707290 0.706880 [6]
Tongguanshan 7 Quartz diorite 0.1014 0.511941 137 −11.90 0.1769 0.707540 0.707200 [6]
Fenghuangshan 8 Granodiorite 0.1056 0.511721 137 −16.30 0.5166 0.711000 0.710100 [6]
Baimangshan 9 Pyroxene monzodiorite 0.1022 0.512056 135 −7.90 0.1879 0.707410 0.707000 [6]
Shizishan 13 Quartz diorite 0.1088 0.511962 137 −11.70 0.2220 0.707840 0.707400 [6]

[1] Chen, J. F., Zhou, T. X. and Li, X. M., 1993; [2] Liu, S.-A., Li, S. G., He, Y.S . and Huang, F., 2010; [3] Wang, Q., Xu, J. F., Zhao, Z. H., Xiong, X. L. and Bao, Z. W., 2003a; [4] Wang, Q., Zhao, Z. H., Xu,
J. F., Li, X. H., Bao, Z. W., Xiong, X. L., and Liu, Y. M., 2003b; [5] Wang, Y. L., Wang, Y., Zhang, Q., Jia, X. Q. and Han, S., 2004 g; [6] Xing, F. M. and Xu, X., 1996.
158 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162
Fig. 9. Results of Sr–Nd–Pb isotopes of Cu–Au bearing intrusions in the Tongling region. A.
Initial Sr–Nd isotopic compositions of Fenghuangshan granodiorite and other intrusion in
Tongling region. Data sources: Cenozoic slab-derived adakites, (Defant and Kepezhinskas,
2001); thickened Yangtze lower crust-derived low-Mg adakitic rocks, e.g., in the Dabie
orogen (He et al., 2010; Wang et al., 2007), in the Sulu belt (Guo et al., 2006) and in the
MLRMB (Q. Wang et al., 2004a), and early Cretaceous mafic igneous rocks in the
MLYMB (Yan et al., 2008); MORB and marine sediments, (Hofmann, 2003); Yangtze
lower crust, (Jahn et al., 1999), collected data of the Fenghuangshan granodiorite and
other intrusions in Tongling region (Table 4). B. ƐHf(t) vs. U–Pb age diagram of zircons
in Fenghuangshan granodiorite.
Liu et al., 2002, 2010; Wang et al., 2001, 2006, 2013; Xie et al., 2006; Yan
et al., 2008). Both the geochemical and compiled Sr–Nd isotope data in-
dicate the Fenghuangshan intrusion was derived from the partial melt-
ing of subducted oceanic slab. In Fig. 9B, the magmatic zircons displace
between the Archean and Paleo-proterozoic crustal evolution line,
while the inherited zircons plot near the chondrite line, at the intercepts
of Archean and Paleo-proterozoic crustal derivatives. Since Hf isotopes
could be greatly enriched during magmatic evolution, Fenghuangshan
granodiorite might have been assimilated by old crustal materials like
old metamorphic rocks. The Archean Kongling group and Paleo-
proterozoic Dongling group basement rocks could be the source for
the inherited zircons (Chen and Jahn, 1998; Chen et al., 1993, 2001;
Wu et al., 2009; Xiaoyong Yang et al., 2011; X.N. Yang et al., 2011; S.B.
Zhang et al., 2006).
6.3. Temperature, oxygen fugacity and petrogenesis
The temperature is the critical control factor for the Ti content in
biotite (Henry et al., 2005; Patiño Dounce, 1993; René et al., 2008),
thus the Ti concentration could be used as a biotite geothermometer.
Using the empirical formula provided by Henry et al. (2005), the
crystallization temperature of Fenghuangshan granodiorite is in the
range of 730~752 °C, suggesting that the intrusive magma has relatively
higher temperature. Our estimated temperature based on biotite
geothermometer is consistent with the result inferred from Ti–Mg/
(Mg + Fe) diagram (Fig. 10A).
The total cations of Al in biotite has a positive correlation with the
consolidation pressure of granite (Etsuo et al., 2007), following the
equation as:
T
Pð
100 MPaÞ ¼ 3:03
Al−6:53ð0:33Þ ð1Þ
The TAl is the total cations of Al in biotite with assumed 22 oxygen
atoms. The crystallization pressure of biotite in Fenghuangshan grano-
diorite intrusion is from 46 MPa to 81 MPa, equivalent to a depth of
1.53 km to 2.67 km.
Chemical composition of biotite can also reflect oxidation condition
during the magma crystallization. The concentrations of Fe3+, Fe2+, and
Mg2+ in biotite, which is paragenetic with K-feldspar and magnetite,
can be used to calculate the magmatic oxygen fugacity (Albuquerque,
1973; Barriére and Cotton, 1979; Noyes et al., 1983; Wones, 1989;
Wones and Eugster, 1965). The Fe3 +–Fe2 +–Mg diagram (Fig. 10B)
shows that the biotite from Fenghuangshan granodiorite was plotted
between Ni-NiO buffer line and Fe2O3–Fe3O4 buffer line, indicating a
high oxygen fugacity associated with the crystallization of biotite
(Wones, 1989). Wones and Eugster (1965) built the Logf (O2)–T dia-
gram to evaluate the magmatic oxygen fugacity balanced with the
biotite + sanidine + magnetite (Hu et al., 2006; Jiang et al., 2006;
Lalonde and Bernard, 1993; Shabani et al., 2003; Zhang et al., 2011;
Zhao et al., 2005). With this approach the oxygen fugacity is estimated
to be 10−11 to 10−13 bars (Fig. 10C), indicating a moderate oxidation
condition during magma crystallization.
The composition of biotite can reflect the magmatic material source
(Abdel-Rahman, 1994; Batchelor, 2003; Shabani et al., 2003; Wones and
Eugster, 1965; Zhang, 1982; Zhou, 1988). The FeO/( FeO + MgO) vs.
MgO diagram (Fig. 10D) shows the Fenghuangshan granodiorite was
derived from crust–mantle mixed source.
The Ce(IV)/Ce(III), EuN/EuN* ratio of zircon are good indicators for the
magmatic oxygen fugacity, while most of the hydrothermal–magmatic
Cu–Au deposits have great relationship with the calc-alkaline intrusions
which have high oxygen fugacity (Ballard et al., 2002; Blevin and
Chappell, 1992; Candela, 1992; Hedenquist and Lowenstern, 1994; Sun
et al., 2007). The intrusions with Ce(IV)/Ce(III) N300,EuN/EuN* N 0.4
are conducive to mineralization (Ballard et al., 2002). The chondrite-
normalized REE patterns show the Fenghuangshan zircons have
strong Ce anomalies (Fig. 11A). The calculated Ce(IV)/Ce(III), EuN/EuN*
ratios of Fenghuangshan zircons range from 116.77–492.27, 0.40–0.64,
respectively. The data show the magma was under moderate oxidation
conditions, which is consistent with the estimate based on biotite
composition. The oxygen fugacity here is similar with the ore-bearing
porphyry in Chile (Fig. 11B), which is conducive to Cu–Au mineraliza-
tion. The relatively high oxygen fugacity can release the Cu–Au sulfides
in mantle, and are conducive to the Cu–Au enrichment in the magmas
(Liu et al., 2010; Sun et al., 2010; Wang et al., 2013).
6.4. Metallogenic significances
The rhenium content in molybdenite could be a sensitive indicator
for the source of ore materials. High Re content in the molybdenite
has been attributed to involvement of mantle materials in an arc
subduction environment (Zimmerman et al., 2003), since it decreases
gradually from hundreds of ppm for a mantle source, to dozens of
ppm for a mantle–crust mixed source, and to several ppm for a crust
source (Mao et al., 1999; Stein, 2006; Stein et al., 1997, 2001).
 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162 159

Fig. 10. Results of mineral compositions by EPMA. A. diagram of Ti–Mg/(Mg + Fe) for biotites from Fenghuangshan granodiorite (after Henry et al., 2005). B. diagram of Fe3+–Fe2+–Mg
for biotites from Fenghuangshan granodiorite (after Wones and Eugster, 1965). C. diagram of logfO2 –T for biotites from Fenghuangshan granodiorite (after Wones and Eugster, 1965).
D. diagram of FeO/ FeO + MgO vs. MgO for biotites from Fenghuangshan granodiorite (after Zhou, 1986).

Rhenium contents in molybdenites from Fenghuangshan deposit
vary from 1.3 ppm to 382.0 ppm, with an average of 124.2 ppm
(Table 5). The collected Re contents of molybdenites from other de-
posits in the Tongling region are relatively high (Table 5, Fig. 12):
149.8–1000 ppm in the Datuanshan stratabound Cu–Au–Mo deposit
(Mao et al., 2004); 29.41–184.9 ppm in the Nanyangshan skarn Cu–
Mo deposit (Mao et al., 2004); 174.2–1169 ppm in the Shatanjiao
skarn Cu–Mo deposit (Mao et al., 2004); and 12.68 ppm in the
Laoyaling stratiform Mo deposit (Xie et al., 2002). The relatively
high Re contents of molybdenites from deposits in the Tongling re-
gion indicate that the ore materials originated from sources between
crust and mantle.
Some previous reports show the PGE enrichment in porphyry Cu
deposits in China: 3 to 50 ppb in ore samples from Dexing porphyry
Cu deposit; 3.4 t of PGE prospective reserves in Yulong porphyry Cu de-
posit (Wang et al., 2014; Xiang and Ru, 1999). And some porphyry–
skarn deposits in the Middle–Lower Yangtze Metallogenic belt
(MLYMB) also have both Pd and Pt enrichments (Gu and Chen, 1993;
Tan, 2001, 2002). The Pd and Pt contents in Fenghuangshan ore samples
are 0.77 ~ 18.6 ppb, 0.22 ~ 10.4 ppb, respectively. To generate elevated
Pt and Pd contents in porphyry Cu deposits, enriched mantle and
oxidized alkaline magmas are the prerequisites (Wang et al., 2014).
PGE-enriched materials in the mantle can supply PGE to the porphyry
stocks or hydrothermal systems, and the oxidized alkaline arc magmas
allow the noble metals to remain in the magmas (Mclnnes
and Cameron, 1994; Wang et al., 2014). The source magma for
Fenghuanghshan granodiorite is associated with a moderate to high
oxygen fugacity. The biotite from Fenghuangshan granodiorite was
plotted between Ni-NiO buffer line and Fe2O3–Fe3O4 buffer line in the
Fe3 +− Fe2 +–Mg diagram. (Fig. 10B). The high oxidized condition
inhibits the fractionation of sulfides, because the sulfur was present as
sulfates. Then Au, Pt and Pd were retained in the melt, conducive to
the subsequent mineralization.
The source of PGEs should be attributed to the chemical compo-
sition of the upper mantle or the subducted oceanic crust (Tarkian
and Stribrny, 1999). The intrusive rocks, such as geological age,
chemical composition and magma type cannot influence PGE-
contents in sulfide ores (Sillitoe, 1979; Tarkian and Stribrny,
1999). The Pd/Ir ratio is a good indicator of source for sulfide ores.
Iridium has an even higher partition coefficient than Pd (Keays,
1982, 1995). Iridium can rapidly co-precipitate with early crystalliz-
ing phases, and is not easily leached from the source rocks or
transported by fluids. Because of the fractionation between Pd and
Ir during alteration (Barnes et al., 1985), magmatic sulfide ores have
relatively low Pd/Ir ratios, whereas hydrothermal sulfide ores have very
high Pd/Ir ratios, with Ir b 2 ppb, Pd/Ir N 80 (Keays, 1982, 1995; Wang
and Zhou, 2006). The Pd/Ir ratios in Fenghuangshan sulfide ore are
from 19.25 to 121.5, and the Ir contents are from 0.02 to 0.97 ppb, indi-
cating the sulfide ores had magmatic origin and were slightly modified
by hydrothermal alteration.
160 S. Li et al. / Ore Geology Reviews 58 (2014) 148–162
Fig. 11. Results of zircon ICP-MS measurements. A. Chondrite-normalized REE distribution
patterns of zircons from Fenghuangshan granodiorite. Chondrite normalized data is after
Sun and McDonough (1989). B. Zircon Ce(IV)/Ce(III) vs. EuN/EuN*oxygen fugacity dis-
crimination diagram of zircons from Fenghuangshan granodiorite (background data
from (Ballard et al., 2002)Ballard et al., 2002).
7. Conclusion
(1) The zircon U–Pb dating of Fenghuangshan granodiorite yields an
age of 143.1 ± 1.6 Ma, and the Re–Os isochron age of molybde-
nite samples is 141.71 ± 0.82 Ma, suggesting that the ore
Fig. 12. Re contents of molybdenite from Tongling ore cluster.
formation event is coeval with the Fenghuangshan granodiorite
intrusion.
(2) The Fenghuangshan granodiorite resembles adakitic rocks,
which was derived from partial melting of the subducted oceanic
crust towards LYRB during the early Cretaceous, and assimilated
by old crustal materials during its emplacement.
(3) The magma source of granodiorite intrusion is supposed under
highly oxidized conditions, which is quite conducive to Cu–Au
mineralization.
(4) The sulfide ores in Fenghuangshan deposit have Pd and Pt
enrichments, and the high oxidized magma is conducive to the
Au, Pd, and Pt mineralization. The ore-forming materials are
characterized with mixed sources from the mantle and crust,
and were slightly affected by hydrothermal alteration.
Acknowledgements
This study is supported by a CAS Knowledge Innovation Project
(KZCX1-YW-15-3), National Natural Science Foundation of China
(Grant Nos. 41173057, 41090372 and 41372078), and fund for mineral
exploration from Anhui Bureau of Land and Mineral Resources (2011-
K8). We wish to thank Prof. Chang Yinfo for his kind guidance.
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