Geochronology and Geochemistry of The Shilu Cu-Mo Deposit in The

Ore Geology Reviews 67 (2015) 382–398
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Ore Geology Reviews

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Geochronology and geochemistry of the Shilu Cu–Mo deposit in the

Yunkai area, Guangdong Province, South China and its implication
Wei Zheng a,⁎, Jing-wen Mao b, Franco Pirajno c, Hai-jie Zhao b, Cai-sheng Zhao d,
Zhi-hao Mao a, Yong-jian Wang e
a
School of the Earth Science and Mineral Resources, China University of Geosciences, Beijing 100083, China
b
MLR Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China
c
Centre for Exploration Targeting, University of Western Australia, 35 Stirling Highway, Crawley, WA 6008, Australia
d
Technology and International Cooperation Department, Ministry of Land and Resources, Beijing 100812, China
e
CNNC Beijing Research Institute of Uranium Geology, Beijing 100029, China
a r t i c l e i n f o a b s t r a c t
Article history: Shilu is a large porphyry–skarn deposit in the Yunkai district in Guangdong Province, South China. The Shilu
Received 4 December 2014 granitic intrusion in the mine area is a granodiorite which is genetically related to Cu mineralization. Plagioclase
Accepted 11 December 2014 in the granodiorite has a zoned texture and is mainly andesine with minor amounts of labradorite, whereas
Available online 24 December 2014
the K-feldspars exhibit Carlsbad twins and some are also characterized by a zonal texture. K-feldspars from the
granodiorite show high contents of Or (87–92 wt.%) with minor Ab (8–13 wt.%) and negligible An value of 0–
Keywords:
Shilu Cu–Mo deposit
0.3 wt.%. Biotite can be classified as magnesio-biotite, and is characterized by Mg-rich [Mg/(Mg + Fe) = 0.54–
Mineral chemistry 0.60] and AlVI-low (average values = 0.11). Hornblende is chiefly magnesiohornblende and tschermakite. LA-
LA-ICP-MS zircon U–Pb dating ICP-MS zircon U–Pb age of the Shilu granodiorite is 107 ± 0.7 Ma, which is consistent with molybdenites Re–Os
Yunkai area age of 104.1 ± 1.3 Ma. Geochemical data indicate that the Shilu granodiorite is silica-rich (SiO2 = 63.43–
South China 65.03 wt.%) and alkali-rich (K2O + Na2O = 5.45–6.05 wt.%), as well as calcium-rich (CaO = 4.76–5.1 wt.%).
Trace element geochemistry results show enrichments in large ion lithophile elements (e.g., Rb, K, and Ba) and de-
pletions in some high field strength elements (e.g., Nb, P, Ta, and Ti). The total rare earth element (REE) content of
the granodioritic rocks is low (∑REE b 200 ppm), and is characterized by light REE enrichment [(La/Yb)N N 9] and
moderately negative Eu anomalies (Eu/Eu* = 0.83–0.90). These mineralogical, geochronological, and geochemical
results suggest that the Shilu granodiorite has a mixed crust–mantle source with a geochemical affinity to I-type
granitoids. Hornblende thermobarometry yielded magmatic crystallization temperatures of 686–785 °C and crys-
tallization pressures between 1.0 and 2.34 kbar, which is converted to depths in a range of 3.31 to 7.71 km. Biotite
thermobarometry yielded similar temperatures and lower pressures of 680–780 °C and 0.8–2 kbar (depth 2.64–
6.6 km), respectively. The parent magma had a high oxygen fugacity. The Shilu granodiorite has a relatively low
εNd/t–t value and high (87Sr/86Sr)i value, and Nd isotopes yield two-stage depleted mantle Nd model ages of
969–1590 Ma. Our new data, combined with previous studies, imply that the granodiorite and the associated
Shilu Cu–Mo deposit was formed in an extensional environment, closely related to remelting of
residual subducted slab fragments in the Jurassic.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction two periods: 180–135 Ma and 125–90 Ma (Mao et al., 2011a,b, 2013,
2014) (Fig. 1a). The Shilu copper deposit is a typical porphyry–skarn
Porphyry–skarn copper deposits are an economically important copper deposit located in the Yangchun basin of western Guangdong
copper resource supplying about 75% of the world's copper (Sillitoe, Province, China. Previous studies mainly focused on the geological
2010). Such deposits form above subduction zones and are preferential- characteristics of the Shilu Cu–Mo deposit (Sun et al., 2008; Yu et al.,
ly associated with calc-alkaline magmas (Cooke et al., 2005; Sillitoe, 1988; Zhang, 2008; Zhao et al., 2012), but little research has been
2010). Numerous porphyry–skarn copper deposits occur in eastern conducted on geochemical characteristics of the Shilu intrusion (Li
China along a NE–SW trending belt. Previous studies indicate that et al., 2000; Ma et al., 1985). In addition, there is controversy over the
China's Mesozoic porphyry–skarn copper deposits formed mainly in timing of the granodioritic intrusion in this deposit. Three ages,
122 Ma (Rb–Sr), 126 Ma (U–Pb), and 99–101 Ma (40Ar–39Ar), have
⁎ Corresponding author. Tel.: +86 188 10553516. been reported for the granodiorite (Yu et al., 1988). Moreover, the
E-mail address: [email protected] (W. Zheng). mineralogical characteristics, physical and chemical conditions,
http://dx.doi.org/10.1016/j.oregeorev.2014.12.009
0169-1368/© 2014 Elsevier B.V. All rights reserved.
W. Zheng et al. / Ore Geology Reviews 67 (2015) 382–398 383
384 W. Zheng et al. / Ore Geology Reviews 67 (2015) 382–398
Fig. 2. Hand specimens and photomicrographs of granodiorite from the Shilu deposit. (a) Hand specimens of granodiorite with little alteration; (b) endoskarn; (c) exoskarn;
(d) granodiorite showing quartz and plagioclase with a zoned texture (crossed polarized light); (e) euhedral hornblende (crossed polarized light); (f) biotite and the K-feldspar in the
granodiorite (crossed polarized light). Abbreviations: Qz = Quartz, Bt = Biotite, Kf = K-feldspar, Pl = Plagioclase, and Hb = Hornblende.
source, tectonic environment and evolution of the Shilu granodiorite 2002). Recent exploration work indicates that Mesozoic rift basins
rocks are still not very clear. controlled the distribution of mineralization, and that the majority of
Herein, we present a systematic mineralogical, precise LA-ICP-MS the ore deposits are located in and around Cretaceous or Cretaceous–
zircon U–Pb geochronological, and geochemical study of the Shilu intru- Tertiary basins, including the Luoding, Huaiji, and Yangchun basins
sion. We use these data to constrain the timing, petrogenesis, and tec- (Mao et al., 2011a,b).
tonic setting of magmatism of the Shilu Cu–Mo deposit, which in turn Yangchun is a NE–SW-trending fault-bounded basin with a sequence
enhances our understanding of the dynamics of Mesozoic magmatism of Triassic rocks forming a synclinorium (Li et al., 2000). The Yangchun
in the Yangchun basin of western Guangdong province. basin is located in the southwest of South China fold belt (Ren et al.,
1990), at the junction of Yunkai block and central Guangdong block
2. Regional geology (Fig. 1b). Bounded by Wuchuan–Sihui fault, the northwest of Yangchun
basin is the Yunkai ancient uplift zone in which thick flysch and flyschoid
The Yunkai (Fig. 1b) is an important tungsten–tin–copper and sediments accumulated from Sinian to Cambrian, forming the basement
polymetallic metallogenic area of South China. Several intense magmatic of the region. The Caledonian orogenic movement and associated region-
events and related mineralization have been recognized (Cai et al., al metamorphism gave rise to the formation of greenschist facies–am-
Fig. 1. (a) Simplified geological map showing the spatial and temporal distribution of Mesozoic porphyry–skarn copper deposits in eastern China, (b) sketch geological map of the Yunkai
area, (c) geological map and cross section of the Shilu Cu–Mo deposit.
Panel a is after Mao et al. (2014), panel b is after Peng et al., 2006 and panel c is after Zhao et al. (2012).
Table 1
Electron microprobe analyses of selected plagioclases (wt.%) for the Shilu granodiorite.
Sample SL-1 SL-2 SL-3 SL-4 SL-5 SL-6 SL-7 SL-8 SL-9 SL-10 SL-11 SL-12
SiO2 57.53 56.04 54.97 56.26 55.03 56.33 56.01 54.89 56.03 55.48 56.05 55.86
Al2O3 27.03 27.50 27.55 27.43 27.81 26.97 27.51 28.12 27.30 27.43 27.08 26.55
MgO 0.02 0.00 0.02 0.01 0.00 0.01 0.02 0.01 0.04 0.01 0.02 0.03
MnO 0.02 0.00 0.01 0.00 0.00 0.00 0.02 0.00 0.00 0.02 0.01 0.00
FeO 0.10 0.15 0.10 0.13 0.17 0.18 0.10 0.05 0.10 0.13 0.10 0.02
TiO2 0.02 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.01 0.02 0.03
CaO 9.06 9.90 10.47 9.93 10.26 9.29 9.79 11.03 9.32 10.23 9.66 9.67
Na2O 6.17 5.47 5.21 5.66 5.41 6.00 5.56 5.10 5.69 5.56 5.79 5.63
K2O 0.23 0.14 0.17 0.13 0.19 0.16 0.20 0.17 0.27 0.20 0.16 0.45
Total 100.26 99.35 98.52 99.61 98.98 99.08 99.32 99.47 98.91 99.27 98.92 98.59
Si 2.576 2.537 2.513 2.540 2.507 2.557 2.536 2.490 2.547 2.523 2.547 2.557
Al 1.426 1.467 1.484 1.459 1.493 1.443 1.468 1.504 1.462 1.470 1.450 1.433
Ca 0.435 0.480 0.513 0.480 0.501 0.452 0.475 0.536 0.454 0.499 0.470 0.474
Na 0.535 0.480 0.461 0.495 0.477 0.528 0.488 0.448 0.501 0.490 0.510 0.499
K 0.013 0.008 0.010 0.007 0.011 0.009 0.011 0.010 0.015 0.011 0.009 0.026
An 44.2 49.6 52.1 48.9 50.6 45.7 48.8 53.9 46.8 49.8 47.5 47.4
Ab 54.5 49.6 46.9 50.4 48.3 53.4 50.1 45.1 51.7 49.0 51.5 49.9
Or 1.3 0.8 1.0 0.7 1.1 0.9 1.2 1.0 1.6 1.1 0.9 2.6
phibolite facies metamorphic rocks, and the formation of migmatites in 4. Samples and analytical techniques
some localities of the area (Zhang et al., 1993). Since the Caledonian,
the Yangchun basin experienced several tectonic movements, related Eight representative samples of the Shilu granodiorite were collect-
to Indo-China, Yanshan, Himalayan tectonics with dominant NE–NNE ed for geochemical analyses, and four samples for Sr–Nd isotopic analy-
trending structures. Cai et al. (2001, 2002) believed that the Mesozoic ses. LA-ICP-MS zircon U–Pb dating was carried out on a fresh
lithosphere in western Guangdong experienced three stages of tectonic granodiorite sample (SLH). The sampling location is shown in Fig. 1c.
evolution, namely, collision and compression (224–265 Ma), transition In some samples, rock-forming minerals show with various degrees of
from compression to extension (154–163 Ma) and finally extension alteration, including chloritization of hornblende and biotite, and
(80–120 Ma). The complex structural features in the area, provide sericitization of plagioclase.
suitable channel ways for the emplacement of endogenic polymetallic The preparation of samples for zircon dating and whole-rock geo-
deposits. So far, more than 50 deposits have been found in the basin chemistry was conducted in the Laboratory of the Institute of Geology
and surrounding areas, including the Shilu Cu–Mo deposit, the and Mineral Resources, Langfang, Hebei Province, China. An ultraclean
Mange'ling Cu–Fe deposit, the Yingwuling W–Sn polymetallic deposit, ball mill was used to grind whole-rock samples to 200 mesh.
and the Chadi Pb–Zn deposit. Cathodoluminescence (CL) images were taken for the zircons prior
to LA-ICP-MS analysis and CL images were acquired with a JEOL JXA-
8900RL electron microprobe at the Institute of Mineral Resources
3. Ore deposit geology of the Chinese Academy of Geological Sciences, CAGS, Beijing. Zircon
U–Pb dating was performed using a Finnigan Neptune multi-collector
Shilu (111°38′37″E, 22°10′22″N) is a porphyry–skarn Cu–Mo depos- ICP-MS with a Newwave UP213 laser-ablation system at Institute of
it with average grades of 0.91% Cu, 0.21% Mo, 12.52 g/t Ag, 11.20% TFe,
and 2.33% S (tonnage information not available at the time of writing).
The stratigraphic sequence in the Shilu mine area comprises Carbonifer-
ous rocks and Quaternary sediments (Fig. 1c). The Carboniferous rocks
are widespread in the south, east, and southwest of the Shilu basin
and mainly comprise limestone and arenaceous shale. The principal
structures in the mine area consist of NE- to NNE-trending compres-
sional faults and inferred NW- to NNW-trending transtensional faults
(Sun et al., 2008). The Shilu granodiorite is closely related to the miner-
alization and distributed in the north and center of the mine area. The
NE- and SE-trending granodioritic intrusion has an irregular ellipsoidal
shape with an outcrop area of 4.7 km2, and intrudes middle–upper
Carboniferous dolomite and dolomitic limestone (Fig. 1c). In cross
section the intrusion is a nearly vertical cylinder with a high angle
contact with the country rocks, but locally the granodiorite contacts
with the country rocks exhibit irregular shapes (Fig. 1c). Cu–Mo
orebodies are hosted in skarn and adjacent marble, distributed dis-
continuously around the Shilu granodiorite intrusion in the shape
of an irregular band. Dioritic enclaves are commonly found in the
Shilu granodiorite intrusion. They are mainly composed of plagio-
clase, K-feldspar, quartz, biotite, and hornblende, with much higher
proportion of plagioclase than K-feldspar (Ma et al., 1985). The
Shilu granodiorite (Fig. 2) is composed of plagioclase (45–55%), K-
feldspar (~ 20%), quartz (~ 20%), biotite (5–8%) and hornblende
(~ 5%) and accessory minerals (~ 1%) of magnetite, titanite, apatite, Fig. 3. Classification diagram of feldspars.
zircon, and allanite. After Pan et al. (1994).
Table 2
Electron microprobe analyses of selected K-feldspars (wt.%) for the Shilu intrusion.
Sample SL-1 SL-2 SL-3 SL-4 SL-5 SL-6 SL-7 SL-8 SL-9 SL-10 SL-11 SL-12 SL-13
SiO2 64.28 64.77 65.05 62.77 64.75 63.74 64.33 64.18 64.44 64.20 64.48 63.60 64.14
Al2O3 18.18 18.39 18.55 18.47 18.26 18.23 18.29 18.36 18.12 18.29 18.13 18.26 18.03
MgO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MnO 0.00 0.02 0.01 0.01 0.03 0.03 0.00 0.01 0.00 0.00 0.01 0.06 0.04
FeO 0.01 0.14 0.07 0.07 0.07 0.05 0.04 0.09 0.01 0.04 0.01 0.07 0.01
CaO 0.01 0.00 0.00 0.07 0.00 0.01 0.01 0.05 0.01 0.02 0.00 0.01 0.01
Na2O 0.95 0.98 1.10 1.10 1.05 1.07 0.96 1.57 1.01 1.12 1.30 1.13 1.13
K2O 16.37 16.47 16.39 15.46 16.19 16.46 16.28 16.56 16.40 16.25 16.23 15.80 15.99
Total 99.91 100.78 101.21 97.99 100.54 99.63 99.93 101.06 100.13 100.04 100.37 99.02 99.36
Si 2.989 2.986 2.984 2.968 2.992 2.978 2.987 2.969 2.991 2.983 2.988 2.982 2.993
Al 0.996 0.999 1.003 1.029 0.994 1.004 1.001 1.001 0.991 1.001 0.990 1.009 0.991
Ca 0.000 0.000 0.000 0.003 0.000 0.001 0.000 0.002 0.000 0.001 0.000 0.000 0.000
Na 0.085 0.087 0.098 0.101 0.094 0.097 0.087 0.141 0.091 0.101 0.117 0.102 0.103
K 0.971 0.969 0.959 0.933 0.955 0.981 0.964 0.977 0.971 0.963 0.959 0.945 0.952
An 0.0 0.0 0.0 0.3 0.0 0.1 0.0 0.2 0.0 0.1 0.0 0.0 0.0
Ab 8.1 8.3 9.3 9.7 9.0 9.0 8.3 12.6 8.6 9.4 10.9 9.8 9.7
Or 91.9 91.8 90.7 90.0 91.0 91.0 91.7 87.2 91.4 90.5 89.1 90.2 90.3
Mineral Resources, CAGS, Beijing. Helium was used as the carrier gas to 2 × 10−8 A, and beam diameter of 5 μm, with the analytical error of
enhance the transport efficiency of the ablated material. The analyses lower than 0.01% (Xu et al., 2010).
were conducted with a beam diameter of 25 lm with a 10 Hz repetition Major and trace elements, and Sr–Nd isotopes were analyzed at the
rate and a laser power of 2.5 J/cm2 (Hou et al., 2007). The masses 206Pb, CNNC Beijing Research Institute of Uranium Geology. Major elements
207
Pb, 204(Pb + Hg) and 202Hg were measured by multi-ion-counters, were measured using X-ray fluorescence spectrometry (XRF) on fused
while the masses 208Pb, 232Th, 235U and 238U were collected by Faraday glass beads, with a precision better than 1%. Trace elements were
cup. Zircon GJ1 was used as the standard and zircon Plesovice was used analyzed with inductively coupled plasma-mass spectrometry (ICP-
to optimize the machine. U, Th and Pb concentrations were calibrated MS), and the precision for minor element content is better than 5%,
using 29Si as the internal standard and zircon M127 (U: 923 ppm; which is extremely low (b 10− 8). Sr–Nd isotopic tests used the
Th: 439 ppm; Th/U: 0.475, Nasdala et al., 2008) as the external standard. ISOPROB-T thermalionization mass spectrometer, according to GB/
207
Pb/206Pb and 206Pb/238U ratios were calculated using the ICPMS T17672-1999 “Determinations for isotopes of lead, strontium and neo-
DataCal 4.3 program. The common-Pb was not corrected because of dymium in rock samples”. The ICP-MS method measured Rb, Sr, Sm,
the high 206Pb/204Pb ratios (N1000). Data with abnormally high 204Pb Nd contents in order to calculate 143Sm/144Nd (Zhao et al., 2010). Test
counts were deleted. The zircon Plesovice is dated as unknown samples precision of 87Rb/86Sr and 143Nd/144Nd is better than 2% and 0.5%,
and yielded weighted mean 206Pb/238U age of 337 ± 2 Ma (2SD, n = respectively.
12), which is in good agreement with the recommended 206Pb/238U
age of 337.13 ± 0.37 Ma (2SD) (Sláma et al., 2008). The age calculation
and plotting of concordia diagrams was performed using Isoplot/Ex 3.0 5. Results
(Ludwig, 2003).
Mineral chemistry was carried out at the Electron Microprobe Labora- 5.1. Mineralogy and mineral chemistry
tory of the Chinese Academy of Geological Sciences (CAGS) in Beijing,
China. A JXA-8800 electron microprobe was used for these measure- We focused on the characteristics and mineral chemistry of the pla-
ments and was operated at a voltage of 20 kV, beam current of gioclase, K-feldspar, hornblende, and biotite of the Shilu granodiorite.
Table 3
Electron microprobe analyses of selected biotites (wt.%) for the Shilu granodiorite.
Sample SL-1 SL-2 SL-3 SL-4 SL-5 SL-6 SL-7 SL-8 SL-9 SL-10
SiO2 36.61 36.83 36.82 37.28 36.65 36.46 36.52 36.87 37.63 36.80
TiO2 2.63 3.14 3.36 3.33 3.98 3.41 3.47 3.26 2.08 2.64
Al2O3 14.86 14.41 14.52 14.71 14.38 14.50 14.47 14.61 14.67 14.69
FeO 17.28 18.35 18.07 17.90 17.29 16.40 17.95 18.57 16.99 18.19
MnO 0.29 0.34 0.34 0.22 0.30 0.23 0.36 0.30 0.22 0.28
MgO 12.75 12.59 12.29 12.15 12.83 13.55 12.23 12.28 13.12 12.53
CaO 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.02 0.04 0.06
Na2O 0.29 0.17 0.11 0.13 0.47 0.11 0.19 0.14 0.08 0.17
K2O 10.12 10.00 10.40 10.22 10.07 10.14 10.25 9.98 10.18 10.02
Total 95.13 96.02 96.21 96.26 96.46 95.05 95.79 96.29 95.23 95.67
Si 2.799 2.798 2.797 2.819 2.772 2.778 2.788 2.796 2.857 2.805
AlIV 1.201 1.202 1.203 1.181 1.228 1.222 1.212 1.204 1.143 1.195
AlVI 0.138 0.088 0.096 0.130 0.054 0.080 0.090 0.101 0.169 0.125
Ti 0.151 0.179 0.192 0.189 0.226 0.195 0.199 0.186 0.119 0.152
Fe3+ 0.105 0.125 0.127 0.161 0.119 0.123 0.125 0.141 0.133 0.117
Fe2+ 1.000 1.041 1.021 0.971 0.974 0.922 1.021 1.036 0.945 1.042
Mn 0.019 0.022 0.022 0.014 0.019 0.015 0.023 0.019 0.014 0.018
Mg 1.453 1.426 1.392 1.369 1.446 1.539 1.391 1.388 1.485 1.424
Ca 0.000 0.000 0.000 0.000 0.002 0.000 0.000 0.001 0.003 0.005
Na 0.042 0.024 0.016 0.019 0.069 0.017 0.028 0.021 0.011 0.025
K 0.987 0.969 1.007 0.986 0.971 0.986 0.998 0.966 0.986 0.975
Mg/(Mg + Fe) 0.57 0.55 0.55 0.55 0.57 0.60 0.55 0.54 0.58 0.55
TAl 1.34 1.29 1.30 1.31 1.28 1.30 1.30 1.31 1.31 1.32
Fig. 4. Classification diagrams for (a) biotites and (b) for amphiboles. ANa + AK b 0.5, Ti b 0.5.
Panel a is after Foster (1960) and panel b is after Leake et al. (1997).
5.1.1. Plagioclase tabular) (Fig. 2B, C). Most K-feldspars exhibit Carlsbad twins and some
Plagioclase, one of the main rock-forming minerals in the granodio- are zoned. K-feldspars were analyzed in polished sections using the
rite, occurs as tabular and prismatic shapes, subhedral to euhedral, 0.4– electron microprobe (Table 2). The analytical results show that K-
3 mm in size, and usually exhibiting a well-developed polysynthetic feldspars contain a little CaO (0.00%–0.07%). They have high contents
twinning (Fig. 2B, D, F). Representative plagioclase major element com- of Or (87–92 wt.%), minor Ab (8–13 wt.%), and negligible An component
ponents analyzed by microprobe are given in Table 1. SiO2 contents of of 0–0.3 wt.%.
the plagioclase vary from 54.89 to 57.53 wt.% (average = 55.87 wt.%).
Its composition ranges from An54Ab45Or1 to An44Ab55Or1, indicating 5.1.3. Biotite
that the plagioclase in the Shilu intrusion is mainly andesine with Biotite is a common mineral in the Shilu granodiorite, it occurs as
minor labradorite (Fig. 3). Some plagioclase crystals show composition- sheet-like and euhedral crystals (Fig. 2B–D, F), and displays weak
al zoning (Fig. 2B, D, F), from the core to rim, Na2O content increases chloritization (Fig. 2D). The major element compositions of the biotite
from 5.10% to 6.17% whereas CaO decreases from 11.03% to 9.06%. are listed in Table 3. SiO2 content ranges from 36.46 to 37.63 wt.%, aver-
aging 36.85 wt.%. The MgO contents varies from 12.15 to 13.55 wt.%,
averaging 12.63 wt.%. The FeO/MgO ratios vary from 1.21 to 1.51, aver-
5.1.2. K-feldspar aging 1.40, and are similar to biotites of calc-alkaline granitoids (1.76).
K-feldspar is another main rock-forming mineral of the Shilu grano- The Mg/(Mg + Fe) ratios range from 0.54 to 0.60 (average = 0.56),
diorite. Most of K-feldspars are generally prismatic (though some are which is higher than that of biotite of S-type granitoids (0.4; Liu and
Table 4
Electron microprobe analyses of selected hornblendes (wt.%) for the Shilu granodiorite. Calculations based on 8, 22, and 24 oxygen anions for plagioclace and K-feldspar, biotite, and horn-
blendes, respectively.
Sample SL-1 SL-2 SL-3 SL-4 SL-5 SL-6 SL-7 SL-8 SL-9 SL-10 SL-11 SL-12
SiO2 49.73 50.45 49.76 48.80 47.76 48.34 47.90 46.82 47.53 48.54 47.10 50.90
TiO2 0.83 0.54 0.61 0.66 0.71 0.65 0.90 1.07 0.79 0.62 0.97 0.71
Al2O3 5.53 4.78 4.89 5.06 5.68 6.02 6.54 7.59 6.97 5.60 7.86 4.76
FeO 13.43 12.27 12.10 12.19 12.49 13.11 12.93 13.54 13.11 12.86 14.26 12.28
MnO 0.34 0.53 0.48 0.60 0.51 0.50 0.46 0.56 0.48 0.54 0.47 0.47
MgO 14.51 15.61 14.82 15.15 14.37 14.29 14.94 13.46 13.82 14.23 13.20 15.58
CaO 11.94 11.72 11.86 11.83 11.77 11.73 11.75 11.47 11.60 11.95 11.74 11.84
Na2O 0.93 0.82 0.91 1.01 0.72 0.83 1.27 1.21 1.13 0.59 1.00 0.78
K2O 0.48 0.32 0.46 0.48 0.44 0.44 0.78 0.44 0.51 0.44 0.50 0.34
Total 98.05 97.22 96.26 96.06 94.75 96.06 97.75 96.32 96.22 97.82 95.70 97.41
T Si 7.256 7.358 7.356 7.252 7.202 7.190 7.040 6.980 7.081 7.250 6.970 7.371
AlIV 0.744 0.642 0.644 0.748 0.798 0.810 0.960 1.020 0.919 0.750 1.030 0.629
AlVI 0.208 0.180 0.207 0.137 0.212 0.245 0.173 0.313 0.304 0.235 0.341 0.182
Ti 0.091 0.059 0.068 0.073 0.080 0.072 0.099 0.120 0.088 0.070 0.108 0.077
C Al 0.208 0.180 0.207 0.137 0.212 0.245 0.173 0.313 0.304 0.235 0.341 0.182
Fe3+ 0.647 0.682 0.676 0.576 0.639 0.628 0.452 0.550 0.570 0.685 0.574 0.713
Ti 0.091 0.059 0.068 0.073 0.080 0.072 0.099 0.120 0.088 0.070 0.108 0.077
Mg 3.155 3.394 3.266 3.356 3.231 3.168 3.273 2.993 3.069 3.168 2.912 3.363
Fe2+ 0.899 0.684 0.783 0.857 0.837 0.886 1.004 1.025 0.969 0.843 1.065 0.664
B Fe2+ 0.093 0.130 0.037 0.081 0.099 0.116 0.134 0.114 0.095 0.079 0.126 0.110
Mn 0.042 0.065 0.061 0.075 0.065 0.063 0.057 0.070 0.061 0.069 0.059 0.057
Ca 1.866 1.805 1.879 1.843 1.837 1.821 1.809 1.816 1.844 1.852 1.815 1.832
A Ca 0.000 0.026 0.000 0.040 0.065 0.049 0.040 0.017 0.008 0.060 0.046 0.005
Na 0.264 0.233 0.239 0.292 0.212 0.240 0.362 0.348 0.326 0.171 0.285 0.218
K 0.090 0.059 0.086 0.091 0.084 0.083 0.146 0.084 0.096 0.084 0.095 0.063
Mg/Mg + Fe2+ 0.75 0.75 0.75 0.77 0.77 0.77 0.77 0.79 0.79 0.77 0.79 0.74
P/kbar 0.56 0.02 0.14 0.28 0.81 1.00 1.33 2.18 1.71 0.71 2.34 −0.03
H/km 1.86 0.05 0.46 0.94 2.68 3.31 4.40 7.19 5.66 2.34 7.71 −0.09
T/°C 703.0 700.7 705.4 727.1 746.3 724.5 784.0 785.4 685.8 725.8 781.1
Wang, 1994). Biotite tetrahedral AlVI average values (0.11) of the Shilu have oscillatory or planar zoning, which is typical of magmatic zircons.
granodiorite are also lower than corresponding values of S-type granites The cores are unzoned with strong luminescence, or have oscillatory
(0.353–0.561; Whalen and Chappell, 1988). In the biotite classification zones with medium CL brightness. The rims are of variable width and
diagram (Fig. 4a; Foster, 1960), when combined with electron micro- have oscillatory zoning with a euhedral shaped rim. Analyzed zircons
probe analyses and cation number (calculated on the basis of 11 oxygen exhibit low Th/U ratios (0.44–1.01), indicative of a magmatic origin
atoms; Table 3), the biotite of the Shilu granodiorite can be classified as (Belousova et al., 2002). Ten spot analyses of the granodiorite, yielded
magnesio-biotite, characterized by Mg-rich and low-AlVI, which is diag- a 206Pb/238U age of 107.02 ± 0.72 Ma, with a mean square weighted de-
nostic of I-type granitoids. viation (MSWD) of 0.25 (Table 5; Fig. 6).
5.1.4. Hornblende
5.3. Whole rock major and trace elements
Hornblende is the other main mafic mineral and is evenly
distributed in the Shilu granodiorite intrusion. Hornblende occurs as
Eight granodiorite samples from the Shilu intrusion were chosen for
subhedral to euhedral crystals (Fig. 2B, E, F) and is 0.05–1.0 mm in
major and trace element analyses, and the results are reported in
size. Length/width ratios of the hornblende vary from 1:1 to 3:1. This
Table 6. The results show a range of SiO2 contents from 63.43 to
amphibole displays different degrees of chloritization. It was analyzed
65.03 wt.%, the Al2O3 and MgO abundances range from 15.82 to
in polished thin sections by electron microprobe (Table 4). In the
16.36 wt.% and 2.07 to 2.28 wt.%, respectively. CaO, Na2O, and K2O con-
Shilu granodiorite intrusion, SiO2 contents of hornblende vary from
tents are 4.76 to 5.1 wt.%, 2.99 to 3.19 wt.%, and 2.46 to 2.86 wt.%, re-
48.82 to 50.90 wt.% (average = 49.64 wt.%), whereas CaO and MgO con-
spectively, and the contents of P2O5 and TiO2 are 0.157%–0.171% and
tents are 11.47–11.95 wt.% and 13.20–15.61 wt.%, respectively. The Mg/
0.453%–0.493%, respectively. Fe2O3 contents (3.94%–4.41%) exceed the
(Fe2 + + Mg) ratios are from 0.74 to 0.79 (average = 0.77), but the
FeO contents (2.05%–2.45%), and Na2O/K2O ratios are 1.06–1.30, falling
hornblendes are low in FeO (12.10–14.26 wt.%) and Ti-poor in
in the calc-alkaline series field on the SiO2 vs. K2O diagram (Fig. 7a). All
chemical formula (0.059–0.120) (Table 4). According to the amphi-
the calculated A/CNK values (molar Al2O3/(CaO + Na2O + K2O)) are
bole classification scheme of Leake et al. (1997), hornblende of the
from 0.94 to 0.98, indicating that these rocks are metaluminous
Shilu granodiorite is chiefly magnesiohornblende and tschermakite
(Fig. 7b). All samples have relatively low LOI (loss on ignition) values
(Fig. 4b). The chemistry of the Shilu hornblende is identical to the
of 1.0–2.93 wt.%, consistent with the relative lack of late hydrothermal
composition of amphibole generally formed in I-type granitoids
alteration.
(Clements and Wall, 1984).
Fig. 8a shows chondrite-normalized rare earth element (REE) distri-
bution patterns (Boynton, 1984; McDonough et al., 1992). Their ∑REE
5.2. U–Pb zircon chronology ranges from 111.9 to 134.0 ppm, characterized by a right-inclined shape
with more moderate LREE/HREE fractionation (light REE/heavy REE;
Zircon grains are colorless or yellow, occur as euhedral, elongate (La/Yb)N = 9.10–12.56) and small negative Eu anomalies (Eu/Eu* =
grains of 120–280 μm in size and have a length/width ratio of 1.5:1 to 0.83–0.90) (Table 6; Fig. 8a). In addition, the Yb contents (2.22–
3:1. In CL images (Fig. 5), most zircon grains are homogeneous or 2.65 ppm) are higher than 1.9 ppm.
Fig. 5. Representative cathodoluminescence (CL) images of zircons from the Shilu granodiorite. Circles indicate locations of analyzed sites, with numbers in the circles representing for spot
numbers. The 206Pb/238U age for each spot is given.
The trace element spider diagram (Fig. 8b) shows the relative en-
1σ
4
8
5
0
6
9
6
5
10
20
richment of large ion lithophile elements (LILE) such as Th, U, Rb, K,
Pb/232Th
and Pb with depleted high field strength elements (HFSE) such as Nb,
P, Ba, Ti, Zr, and Eu. High Rb and low Ba and Sr might suggest fractional
crystallization of orthoclase and plagioclase, whereas the moderate Eu
208
0
35
47
70
31
30
44
78
32
33
depletion is probably related to plagioclase fractionation. The depletion
1σ
in P and Ti indicates that the magma underwent fractional crystalliza-
1
1
1
1
2
1
2
2
1
1
tion of apatite, titanite, and Ti-rich minerals (Cao et al., 2014).
Pb/238U
5.4. Whole rock Sr–Nd isotopes

107
107
107
107
108
108
108
107
107
106
206
1σ
13 The Sr–Nd isotope data are listed in Table 7. The initial 87Sr/86Sr ra-
1
3
3
2
3
4
5
2
2
tios and εNd(t) values were calculated at 107 Ma corresponding to the
Pb/235U
zircon U–Pb ages. The samples have high (87Sr/86Sr)i values, and show
little variability in initial 87Sr/86Sr ratios (0.70952–0.70971), with the
118
117
112
115
118
118
117
117
114
114
207
values being lower than the average continental crust values (0.719).
Apparent age (Ma)
The samples have slightly negative εNd(t) values of −8.4 to −0.8.

270
24
54
56
31
46
65
86
37
37
1σ
Pb/206Pb
6. Discussion
350
322
209
283
328
320
302
320
333
287
6.1. Age implications

207
0.00021
0.00040
0.00048
0.00024
0.00000
0.00031
0.00046
0.00100
0.00032
0.00023
As a typical skarn deposit, the orebodies of the Shilu deposit occur in

the contact zone of Carboniferous carbonates and the Shilu granodiorite
1σ
intrusion (Fig. 1c), indicating that they have a genetic relationship.

Pb/232Th
Therefore, the mineralization and the Shilu intrusion possibly formed

0.00172
0.00233
0.00345
0.00153
0.00000
0.00149
0.00217
0.00389
0.00161
0.00166
simultaneously. However, previous rock-forming Rb–Sr age (122 ±

1 Ma), single zircon evaporation dating method (126 Ma), and K–Ar
208
mineralization age (89 Ma) are not consistent each other (Zhai et al.,
0.00011
0.00017
0.00016
0.00017
0.00034
0.00022
0.00030
0.00024
0.00019
0.00016
1999; Zhao et al., 1985). Yu et al. (1988) obtained a consistent

39
Ar–40Ar plateau age (99–101 Ma) from three minerals K-feldspar,
1σ
biotite, and plagioclase in the Shilu granodiorite, indicating that ca.

Pb/238U
100 Ma represents the rock-forming age. However, Li et al. (2000)

0.01668
0.01680
0.01681
0.01677
0.01690
0.01687
0.01687
0.01678
0.01667
0.01660
proposed that the plateau age (100 Ma) represents the age of a late
206
thermal disturbance event. The LA-ICP-MS U–Pb age of 107 ± 0.72 Ma

for the Shilu granodiorite we obtained is quite consistent with molybde-
0.00153
0.00322
0.00284
0.00211
0.01465
0.00279
0.00390
0.00523
0.00242
0.00198
nite Re–Os isochron age of 104.1 ± 1.3 Ma, and the weighted average
1σ
model ages of 104.1 ± 1.3 Ma and 104.34 ± 0.66 Ma (Zhao et al.,

2012). Therefore, 107 ± 0.72 Ma can be considered as the best estimate
Pb/235U
of the emplacement age of the intrusion with the mineralization event

0.12295
0.12202
0.11654
0.12006
0.12270
0.12271
0.12173
0.12214
0.11872
0.11905
of the Shilu Cu–Mo deposit occurring at 104 Ma. These ages belong to
207
the Early Cretaceous and are compatible with the mineralization age
of the Tiantang skarn Cu–Pb–Zn deposit located to the northeast of
0.00056
0.00124
0.00121
0.00080
0.00694
0.00107
0.00149
0.00207
0.00084
0.00083
the Shilu deposit, which yields a sphalerite Rb–Sr isochron age of

1σ
97.87 ± 0.96 Ma (Zheng et al., 2013a).

Isotopic ratios
Pb/206Pb
0.05347
0.05266
0.05034
0.05193
0.05296
0.05284
0.05240
0.05276
0.05163
0.05208
207
LA-ICP-MS U–Pb results of zircons form the Shilu granodiorite.
Th/U
0.71
0.69
0.44
0.55
0.70
1.01
0.71
0.74
0.86
0.99
U238 (μg/g)
65
216
235
160
327
126
118
162
267
201
Th232 (μg/g)
71
89
48
153
161
181
120
115
229
199
Pb (μg/g)
60
43
55
31
22
81
91
3
5
124
SLH-1.10
Spot no.
SLH-1.1
SLH-1.2
SLH-1.3
SLH-1.4
SLH-1.5
SLH-1.6
SLH-1.7
SLH-1.8
SLH-1.9
Table 5
Fig. 6. LA-ICP-MS zircon U–Pb concordia diagram of the Shilu granodiorite.

The Yangchun basin is well endowed with polymetallic deposits Mao et al. (2004, 2007, 2008, 2013) and Yuan et al. (2008, 2011,
in the Yunkai area, western Guangdong Province. Except for the 2012) suggested that large-scale W–Sn mineralization of Nanling area,
porphyry–skarn Cu–Mo and Cu–Pb–Zn deposits there are also central part of South China, occurred in the Middle Jurassic (150–
numerous Cu–Fe and W–Sn deposits in the same basin. The W–Sn 160 Ma) (Mao et al., 2008, 2013). However, according to current infor-
deposits are closely related to felsic magmatism. mation, W–Sn deposits in the Yangchun basin and adjacent areas may
The hornblende 40Ar–39Ar plateau age of the Mashan intrusion is have formed in the Late Cretaceous. For example, the Yangchun vein-
163.6 ± 2.0 Ma (Li et al., 2000) and the SIMS U–Pb isotopic age of the type Sn deposit formed at 76 Ma (Yu et al., 1998); the Yinyan
Gangmei intrusion is 165.7 ± 1.3 Ma (Huang et al., 2013), Thus the porphyry Sn deposit formed at 90 Ma (Mao et al., 2008), and the molyb-
rock-forming ages of these intrusions are close to the mineralization denite Re–Os weighted average age of the Dajinshan quartz-vein-type
ages of the Mange'ling, Potoumian, Didougang and other skarn Cu–Fe W–Sn–Mo deposit at the northeastern edge of the Luoding basin is
deposits. We suggest that these Cu–Fe ores formed in the Mid-Late 82.5 ± 3.1 Ma (Yu et al., 2012). In addition, the molybdenite Re–Os
Jurassic and are associated with the Jurassic magmatism along the isochron age of the Yingwuling polymetallic W deposit is 83.0 ±
Qin–Hang belt in South China (170–155 Ma) (Mao et al., 2007, 1.7 Ma (Zheng et al., 2013b) and the zircon LA-ICP-MS U–Pb age of
2008, 2013). From the perspective of geochronology, the Shilu the host rocks associated with mineralization is 81.31 ± 0.55 Ma
Cu–Mo and the Tiantang Cu–Pb–Zn deposits are part of the Creta- (Zheng et al., 2013c).
ceous mineralization events of South China, and their formation Thus, the temporal order of the metal assemblages is as follows
ages are later than the Cu–Fe deposits in the Yangchun basin by (from oldest to youngest): copper–iron, copper (molybdenum), cop-
about 50 Ma. per–lead–zinc, and tungsten–tin.
Table 6
Major (in wt.%), trace and rare earth element (in ppm) compositions of the Shilu granodiorite.
Sample SL-YT-1 SL-YT-2 SL-YT-3 SL-YT-4 SL-YT-5 SL-YT-6 SL-YT-7 SL-YT-9
SiO2 64.77 64.75 65.01 63.43 64.64 64.23 65.03 63.53

TiO2 0.464 0.453 0.461 0.493 0.491 0.486 0.469 0.483
Al2O3 16.22 16.27 16.08 15.82 16.21 16.36 16.2 16.05
TFe2O3 6.47 6.33 6.85 7.09 7.04 6.73 6.71 6.97
MnO 0.081 0.08 0.081 0.077 0.079 0.082 0.079 0.084
MgO 2.14 2.09 2.09 2.21 2.21 2.24 2.07 2.28
CaO 4.82 4.94 4.76 4.78 4.81 5.1 4.77 4.92
Na2O 2.99 3.15 3.02 3.02 3.15 3.19 3.09 3.04
K2O 2.58 2.71 2.78 2.66 2.55 2.46 2.85 2.86
P2O5 0.158 0.158 0.157 0.158 0.167 0.171 0.162 0.162
LOI 1.39 1.45 1.31 2.93 1.22 1.33 1 2.1
Total 102.08 102.38 102.60 102.67 102.56 102.38 102.43 102.47
TFeO 5.82 5.70 6.17 6.38 6.33 6.06 6.04 6.27
FeO 2.05 2.15 2.35 2.45 2.4 2.2 2.2 2.3
A/CNK 0.98 0.95 0.97 0.96 0.97 0.95 0.96 0.94
Mg# 0.40 0.40 0.38 0.38 0.38 0.40 0.38 0.39
La 27.9 27.6 27.4 27.7 26 28.1 28 22.2
Ce 51.7 51.3 51.2 51.5 49.3 53.2 52.3 42.9
Pr 6.04 6 5.99 6.01 5.72 6.27 6.18 5.2
Nd 22.9 22.9 22.3 22.2 22.1 23.9 22.9 20.6
Sm 4.44 4.32 4.35 4.24 4.25 4.76 4.29 4.26
Eu 1.17 1.13 1.11 1.1 1.17 1.23 1.17 1.2
Gd 3.95 3.96 3.82 3.76 3.75 4.21 3.79 4.1
Tb 0.709 0.732 0.709 0.688 0.691 0.782 0.697 0.765
Dy 4.19 4.14 4.14 3.99 3.89 4.65 3.92 4.22
Ho 0.775 0.775 0.777 0.762 0.743 0.856 0.735 0.809
Er 2.33 2.34 2.32 2.26 2.24 2.59 2.18 2.45
Tm 0.358 0.366 0.374 0.355 0.351 0.409 0.347 0.378
Yb 2.31 2.35 2.34 2.25 2.22 2.65 2.23 2.44
Lu 0.332 0.349 0.351 0.329 0.323 0.375 0.331 0.335
Y 22.9 22.8 22.4 20.9 21.3 24.7 21.4 23.5
Sc 12.7 12.1 11.8 12 12.3 12.7 11.7 13.7
V 102 91.2 93.2 97.7 98.2 100 98.8 104
Cr 23 20.2 21.5 21.5 21.8 21.9 21.9 24.3
Ni 7.37 7 6.76 7.06 7.22 7.58 6.89 7.59
Cu 4.95 19.1 33.7 6.67 4.21 3.93 3.42 40
Zn 43.4 37.5 42.2 44.1 48.3 43.2 41.9 42.8
Sr 475 456 438 431 455 467 424 445
Co 9.3 8.53 8.67 9.5 9.13 9.34 8.88 9.35
Rb 102 116 122 124 127 114 117 132
Zr 45.3 53.8 48.9 42 46.4 41.4 39.7 40
Nb 9.45 9.83 9.4 9.34 9.39 10.3 9.16 9.78
Ba 505 530 561 569 560 562 567 591
Hf 1.81 2 2.02 1.78 1.91 1.69 1.59 1.61
Ta 1.18 1.33 1.3 1.1 0.986 1.07 1 1.02
Pb 12.2 10.4 12.2 11 13.7 11.6 12.3 12.1
Th 10.6 12 13.2 11.6 9.92 9.91 11.9 9.45
U 3.8 4.97 4.03 3.63 3.28 2.31 5.98 2.7
Ga 19.2 18.7 19 18.6 19.4 19.5 18.2 19.1
Total REE 129.1 128.3 127.2 127.1 122.7 134.0 129.1 111.9
(La/Yb) N 8.67 8.43 8.40 8.83 8.40 7.61 9.01 6.53
Eu/Eu* 0.86 0.84 0.83 0.84 0.90 0.84 0.89 0.88
Fig. 7. (a) K2O versus SiO2 diagram for representative rocks from the Shilu granodioritic intrusion (fields in the plot are from Rickwood, 1989) (b) A/NK versus A/CNK{A/NK = molar ratio
of [Al2O3/(Na2O + K2O)]; A/CNK = molar ratio of [Al2O3/(CaO + Na2O + K2O)]}.
6.2. Petrogenesis that phlogopite was a more likely potassic phase than amphibole in
the source area (Fig. 10c).
The origin of high-K granites, particularly those classified as calc- Trace element and Sr isotope data can be used to trace the magma
alkaline I-type granites, remains a topic of debate (Liegeois et al., sources of the rocks. The REE patterns of rocks in the Shilu granodiorite
1998; Roberts and Clemens, 1993). Models for the generation of I-type exhibit light REE enrichment ([La/Yb]N N 9), but are low in total REE
granites range from mixing of mantle-derived magmas with crustal- (b200 ppm), and have moderately negative Eu anomalies (δEu =
derived materials (Dickinson, 1975; Hildreth and Moorbath, 1988), to 0.83–0.90, average = 0.86). These REE characteristics are different from
direct melting of intermediate meta-igneous rocks to hydrous those of crustal derived granitoids (Rudnick et al., 1985; Taylor and
medium- to high-K mafic rocks (Roberts and Clemens, 1993; Sisson Mclennan, 1995), suggesting that the Shilu granodiorite originated
et al., 2005). Various tectonic settings have also been proposed for from the mantle. Our geochemical data are shown on the Nb versus Y,
such rocks, ranging from lithospheric extension in a post-collisional set- Rb vs. (Y + Nb), Rb versus (Yb + Ta) and Ta vs. Yb diagrams (Fig. 11),
ting to subduction at an active continental margin (Roberts and in which it can be seen that all samples fall in the fields of volcanic arc
Clemens, 1993). granite (VAG) and syn-collision granite (Syn-COLG). These results
Harker diagrams for the Shilu granodiorite show that TiO2, MgO, indicate that the granitoids were generated in an arc setting. In the δEu
TFe2O3, CaO, K2O, Na2O and P2O5 partly have weak correlations with versus (La/Yb)N diagram (Fig. 12a), all samples fall into the crust–mantle
SiO2 (Fig. 9), suggesting that fractional crystallization probably has type field. Strontium isotope studies have indicated that the Shilu intru-
affected the rocks during their magmatic evolution. In the Shilu sion has (87Sr/86Sr)i ratios of 0.70952–0.70971, which also require contri-
intrusion, all of the samples fall into the OGT (non-fractionated M-, I- butions from a mix of mantle-derived and continental crust magmas.
and S-type granites) field in a plot of (K2O + Na2O)/CaO versus To some extent, the chemistry of hornblende and biotite can be used
Zr + Nb + Ce + Y (Fig. 10a). These results cannot be easily interpreted to identify magma sources. Almost all of the hornblende data fall into
as a fractional crystallization process. In the La/Yb vs. La diagram the mixed-source field of crust–mantle in a plot of TiO2 vs. Al2O3
(Fig. 10b), samples of the Shilu granodiorite are consistent with a partial (Fig. 12b). Similarly, all of the biotite compositions lie in the crust–man-
melting trend and lack the typical signs of fractional crystallization. This tle mixed-source field in the diagram ∑FeO/(∑FeO + MgO) versus
suggests that the effects of partial source melting had a greater effect on MgO (Fig. 12c). This implies that both the hornblende and biotite
the geochemical composition of the granodiorites than fractional crys- in the investigated intrusion are the products of crust–mantle mixed-
tallization. The absence of significant Eu anomalies eliminates K- source magmas, which is consistent with the trace element and Sr
feldspar as a potassic phase (Zhu et al., 2014). Melts in equilibrium isotopic results.
with phlogopite are expected to have relatively high Rb/Sr (N0.1) and The Shilu granodiorite has a relatively low εNd/t–t value (− 0.8 to
low Ba/Rb (b 20) ratios (Furman and Graham, 1999), which indicates − 8.4, average = − 5.93) and high n(87Sr)/n(86Sr)i value (0.70952–
Fig. 8. (a) Chondrite-normalized REE patterns. (b) Primitive-mantle-normalized spider diagrams.

Panel a is after Boynton (1984) and panel b is after Sun and McDonough (1989).
Table 7
Sr–Nd isotopic compositions of the Shilu granodiorite.
87
Sample Rb Sr Rb/86Sr 87
Sr/86Sr 2σ 87
Sr/86Sri Sm Nd 147
Sm/144Nd 143
Nd/144Nd 2σ 143
Nd/144Ndi εNd(t) t2DM
no. (ppm) (ppm) (ppm) (ppm) (Ga)
SL-YT-1 102 475 0.62083 0.710651 0.000014 0.70971 4.44 22.9 0.11715 0.512151 0.000008 0.512069 −8.4 1590
SL-YT-4 124 431 0.83179 0.710811 0.00001 0.70955 4.24 22.2 0.11540 0.512198 0.000012 0.512117 −7.5 1514
SL-YT-7 117 424 0.79779 0.710924 0.000013 0.70971 4.29 22.9 0.11319 0.512219 0.000012 0.512140 −7.0 1478
SL-YT-11 118 429 0.79523 0.710732 0.000009 0.70952 4.27 21.9 0.11780 0.512543 0.000015 0.512461 −0.8 969
Fig. 9. Harker diagrams for selected major and trace elements of the Shilu granodiorite.
0.70971, average = 0.70962), and Nd isotopes yield two-stage depleted where TAl is the total Al content in the hornblende estimated on the
mantle Nd model ages of 969–1590 Ma. When comparing the Shilu in- basis of 23 oxygens.
trusive rocks with other Late Yanshanian granites in South China on the The hornblende–plagioclase geothermometer proposed by Blundy
εNd/t–t diagram (Fig. 13a), nearly half of the Late Yanshanian granites and Holland (1990) was used to estimate the crystallization tempera-
are located within the field of Proterozoic crustal evolution region in ture. Temperatures were calculated as follows:
South China, close to the upper part of the evolution domain, showing
that they are derived mainly from Proterozoic crust with a low thermal 0:677P−48:98 þ Y Si−4 Plag
T¼ and K ¼ XAb
maturity, whereas the other half of the granites are located between the −0:0429−0:008314InK 8−Si
Proterozoic crustal evolution area of South China and the mantle evolu-
tion line of chondrite, indicating that they contain more mantle compo- where Si is the atomic number per unit of hornblende, P is pressure in
nents. In the εNd/t–t figure (Fig. 13a), the Shilu granodiorite is located kbar, T is the absolute temperature in K, and XPlag
Ab is the Ab value of
between the Proterozoic crustal evolution area of South China and the plagioclase (×10−2). When XAb b 0.5, Y = −0.806 + 25.5 (1 − XAb)2
mantle evolution line of chondrite. In the εNd/t–n(87Sr)/n(86Sr)i figure and when XAb N 0.5, Y = 0.
(Fig. 13b), the granodiorite is located in the lower right quadrant, The hornblende crystallization pressures and temperatures from
which is consistent with the distribution of I-type granites in South the Shilu intrusion are summarized in Table 4. For the granodiorite,
China, clearly indicating the characteristics of a mixed crust–mantle
source and illustrating the significant difference between the various
petrochemical evolution trends (Li et al., 2001).
Therefore, many geochemical features of the Shilu granodiorite, par-
ticularly the arc-like LREE patterns and trace element spidergrams, as
well as the initial Sr–Nd values, suggest the influence of crustal sources
and a geochemical affinity to I-type granites. These geochemical fea-
tures possibly suggest that the granodiorite was produced in an active
subduction system, as indicated by the arc-like features of the studied
granodiorite (Nb and Ta depletions relative to Th and La; Fig. 8b). The
characteristics of volcanic arc and syn-collision granite are well defined
in the Y–Nb, Y + Nb–Rb, Ta + Yb–Rb and Yb–Ta diagrams of tectonic
discrimination. However, there is a transitional regime from compres-
sion to extension in East China after 135 Ma (Dong et al., 2007; Li
et al., 2008; J.W. Mao et al., 2003; X.D. Mao et al., 2003; Mao et al.,
2005; Maruyama et al., 1997; Niu et al., 2003; Shu et al., 2006; Wang
et al., 2002), and the changing direction of the Paleo-Pacific plate from
oblique subduction to parallel to the continental margin (Mao et al.,
2013). It follows that the Shilu granodiorite was unlikely produced in
an active subduction system. Instead, the Cretaceous mafic dikes distrib-
uted east and west of the Wuyishan Mountain have different character-
istics, reflecting active continental margin and intraplate extensional
settings, respectively (Xie et al., 2006). The arc-like features were prob-
ably heritable and are associated with residual subducted slab frag-
ments of Jurassic rather than being indicative of an active arc
environment.
6.3. Physico-chemical crystallization conditions and significance for ore

formation
The main conditions of magma melting, temperature and pressure,

can constrain the origin and evolution of magmatic rocks, and the
depth of the source can be investigated by establishing the formation
temperature and pressure of the magma. Currently, estimations of the
original temperature and pressure of granitic magma are based mainly
on experimental petrology information. However, other means are
required to obtain this information for the Shilu intrusion, due to
the various granites presenting limited experimental petrology
information.
Here, we use biotite and hornblende thermobarometry to calculate
the temperature and pressure conditions during the crystallization
of the Shilu grandiorite intrusion. The total Al content of hornblende
(AlIV + AlVI) can be used to calculate the crystallization pressure. The
following equation proposed by Johnson and Rutherford (1989) was
used to estimate the crystallization depth and pressure, with the crystal-
lization depth calculated from a pressure–depth relationship of
1 kbar ≈ 3.3 km: Fig. 10. (a) Plots of (K2O + Na2O)/CaO versus Zr + Nb + Ce + Y, (b) plots of La/Yb vs. La
of the Shilu granodiorite and (c) plots of Ba/Rb vs. Rb/Sr of the Shilu granodiorite. FG =
Fractionated M-, I- and S-type felsic granites; OGT = non-fractionated M-, I- and S-type
T granites.
P ðkbarÞ ¼ –3:46 þ 4:23 Al ð0:5 kbarÞ Panel a is after Whalen et al. (1987) and panel c is after Furman and Graham (1999).
pressures fall into two ranges of 0.02–0.81 and 1.00–2.34 kbar, corre- in the biotite. The high Ti contents and low AlVI in biotite corresponds to
sponding to depths of 0.05–2.68 and 3.31–7.71 km, respectively. high temperature of crystallization and high-oxygen fugacities
Etsuo et al. (2007) suggested that the total aluminum content of (Albuquerque, 1973; Buddington and Lindsley, 1964). The co-
biotite in granites is related to the crystallization pressure. Application existence of magnesio-biotite and accessory minerals such as primary
of a hornblende–biotite geothermometer to the Shilu Cu–Mo deposit magnetite and titanite in the Shilu intrusion also indicates that
yields a pressure of 0.8–2 kbar (Fig. 14a), corresponding to depths of the magmas have a high oxygen fugacity. The chemical compositions
2.64–6.6 km. of biotite are displayed in a Fe3 +–Fe2 +–Mg diagram (Wones and
A Ti vs. Mg/(Mg + Fe) temperature diagram was used to calculate Eugeter, 1965), and all plot between the Ni–NiO and Fe2O3–Fe3O4 buffer
the crystallization temperature of biotite (Fig. 14b), values for the lines (Fig. 15). Based on empirical mineral associations, the link be-
granodiorite of 680–780 °C. tween oxidized felsic magmas and mineralization is well-known
Therefore, the hornblende and biotite thermobarometry constrain (Ballard et al., 2002; Hedenquist and Lowenstern, 1994; Mungall,
the temperature and pressure conditions for the formation of the grano- 2002). Previous studies have demonstrated that mantle-derived
diorite to 686–780 °C and 1.00–2 kbar (depth = 3.31–6.6 km). The magmas with high oxygen fugacity are consistent with the inclusion
granite formed at low temperatures, and as these temperatures are of ore-forming elements in the magma (Silltoe, 1997). Cu porphyries
lower than the average temperature of I-type granites (781 °C; King or Mo-bearing granites are usually related to oxidized melt systems
et al., 1997), its formation may have been related to the addition of (Li et al., 2012; Meinert et al., 2005; Qiu et al., 2013; Zhang et al.,
fluid, which also indicates that it was probably inherited from its paren- 2011). Moreover, copper in a magma with high oxygen fugacity will
tal magmas. become enriched during differentiation and partition into a magmat-
Ishihara (1977) defined two series of granites based on their Fe–Ti ic–hydrothermal fluid (Ballard et al., 2002; Pasteris, 1996; Sun et al.,
oxide mineralogy: (1) The more reduced ilmenite-series granites con- 2004; Urich et al., 1999). Oxygen fugacity not only affects the melt sulfur
tain ilmenite as the only Fe–Ti oxide and may also contain pyrrhotite, abundance, but also fluid–melt differentiation, the metal content of the
and (2) the more oxidized magnetite-series granites contain magnetite related skarns (Simon et al., 2003), and mineral composition and stabil-
and ilmenite and may also contain pyrite or pyrrhotite plus titanite. In ity (Einaudi et al., 2003). Therefore, fluid–rock interactions occurred
the Shilu intrusion, the TiO2 and AlVI abundances range from 3.61% to readily between the magmatic fluids and carbonate country rocks to
4% and 0 to 0.1, respectively. According to Albuquerque (1973), higher form Cu-bearing skarn particularly at the retrograde alteration stage
temperatures favor accommodation of Ti instead of AlVI which is higher (Zhang et al., 2010).
Fig. 11. (a) Nb versus Y, (b) Rb vs. (Y + Nb), (c) Rb versus (Yb + Ta) and (d) Ta vs. Yb diagrams. ORG = oceanic ridge granite; VAG = volcanic arc granite; syn-COLG = syn-collision
granite. WPG = within plate granites.
After Pearce et al. (1984).
lithosphere in this area was controlled by interaction between these

two plates (Dong et al., 2007; Mao et al., 2004, 2005, 2007, 2008; Shu
et al., 2006), which probably resulted from the oblique subduction of
the Izanagi plate on the Pacific margin (Maruyama et al., 1997). As the
subduction of the Izanagi plate continued, continental crust gradually
thickened and developed a series of NE-trending lithospheric exten-
sional belts and deep faults in a back-arc setting (Mao et al., 2007,
2008, 2011a,b, 2013). After 135 Ma, the movement direction of the
Paleo-Pacific plate changed from oblique subduction to one parallel to
the continental margin (Mao et al., 2013). Lithospheric extension of
South China took place and the majority of the related ore systems are
therefore located in volcanic basins and rift basins (Mao et al., 2011a,b),
which can be ascribed to regional large-scale lithospheric thinning and
delamination of the thickened lithosphere and thermal erosion (Mao
et al., 2013).
The various mineral systems that are concentrated in the Yangchun
basin may indicate that the area experienced a strong crust–mantle in-
teraction and that the granite associated with mineralization has
evolved from felsic to intermediate during this process. Therefore, we
propose that, as part of the Jurassic and Cretaceous granites in South
China, copper–iron, copper–molybdenum or copper–lead–zinc, and
tungsten–tin deposits, as well as granite associated with the
polymetallic mineralization, have different geochemical characteristics
and tectonic settings.
There are some differences in the age, magma source, and composi-
tion of the Jurassic–Cretaceous igneous activity of the Yangchun basin in
western Guangdong (Huang et al., 2013; Li et al., 2001; Zheng et al.,
2013c). Shilu, Mashan, Gangmei and Yingwuling are located in the
Hunan–Guangxi–Guangdong belt, which is one of four late Mesozoic
belts with low Nd model ages (Zhou et al., 2007), which are distributed
along the southern end of the Wuchuan–Sihui Fault. The low Nd-model
ages of granite are caused mainly by the addition of mantle material. All
of the above factors may be related to subduction of the Pacific plate,
which would have caused back-arc extension, crustal thinning, and as-
thenospheric mantle upwelling (Zhou et al., 2007). However, the pre-
Jurassic granites formed by the melting of crustal material, as implied
by their older Nd-model ages (Zhou et al., 2007). Li et al. (1999) sug-
gested that from the Early to Late Jurassic, the lithosphere in the
Yangchun area stretched and thinned, while further increases in the
temperature gradient led to extensive remelting of the crust. The source
of the Late Jurassic shoshonitic intrusive rocks was probably shallower
than that of the Early Jurassic shoshonitic rocks, and much closer to
Fig. 12. (a) Plots of (La/Yb)N vs. δEu of the Shilu intrusion, (b) plot of TiO2 versus Al2O3 for the upper part of the lithospheric mantle. However, the source of the
hornblendes and (c) plot of ∑FeO/(∑FeO + MgO) versus MgO for biotites. Cretaceous calc-alkaline magma area was further upward in the lower
Panel b is after Jiang and An (1984) and panel c is after Zhou (1986).
crust, indicating that the lithosphere stretched and thinned evenmore.
From the above, the East China continent, including the western
6.4. Tectonic implications Guangdong, was in continuing extension after 135 Ma (Goldfarbl
et al., 2007; Mao et al., 2007). Regionally, Cretaceous rift basins devel-
Although western Guangdong is far from the subduction zone of the oped, including the Luoding, Yangchun, and Huaiji basins, all of which
Pacific and Eurasian plates, the geodynamic evolution of the Mesozoic are the sites of multi-metal mineral resources. Stratigraphically, nappe
Fig. 13. Diagrams of (a) εNd(t) versus age (b) n(87Sr)/n(86Sr)i versus εNd(t).
After Zhou (2007) and references herein.
mafic dikes of northern Guangdong reflect a tensional regime for the

southeast area in the late Early Cretaceous (105 ± 5 Ma). In addition
to the granodiorite of the Shilu deposit, the U–Pb zircon age of the
Deqing monzogranite is 99 ± 2 Ma, the U–Pb age of the Diaocun grano-
diorite is 104 ± 3 Ma (Geng et al., 2006), and the zircon U–Pb age of the
Baigang granite is 106.4 ± 0.7 Ma (Gao et al., 2005). At this time, felsic
volcanic rocks also formed, including the Ma'anshan and Zhougongding
rhyolites, which yield a zircon U–Pb isotope age of 100 ± 1 Ma. The geo-
chemical signsatures of these intrusive–extrusive rocks are similar to
those of the intermediate-felsic igneous rocks along the coast of
Zhejiang and Fujian, suggesting that they both formed in a continuously
extensional environment (Gao et al., 2005). Therefore, a lithospheric ex-
tensional regime was the Cretaceous geodynamic setting of South
China, including western Guangdong (Hu et al., 2007; Mao et al., 2004,
2007, 2008), and the Yangchun–Shilu copper deposit is the product of
this tectonic setting.
7. Conclusions
(1) LA-ICP-MS U–Pb zircon dating of the Shilu granodiorite associat-

ed with porphyry–skarn copper deposit yields an age of 107 ±
0.72 Ma, which is consistent with molybdenites Re–Os age of
104.1 ± 1.3 Ma, suggesting that the magmatism was coeval
with the timing of mineralization in Early Yanshanian period.
(2) The Shilu granodiorite is calc-alkaline and characterized by en-
richment in silica, alkalis, calcium, light REEs, and large ion
lithophile elements, and depleted in heavy REEs and high field
strength elements. The Shilu granodiorite fits the I type granit-
oids, with both mantle and crustal contributions.
(3) Plagioclase in the Shilu granodiorite is primarily andesine–labra-
dorite (An = 44–54 wt.%), whereas biotite is magnesio-biotite
and hornblende is Mg-rich calcic hornblende. These, imply that
the Shilu intrusion is the product of crust–mantle mixed-source
melts, which is consistent with the trace element and Sr–Nd iso-
topic results. Hornblende and biotite thermobarometry constrain
Fig. 14. (a) Plot of coexisting amphibole–biotite to pressure, (b) Plot of Ti versus Mg/
(Mg + Fe) for biotites. the crystallization pressure and temperature of the granodioritic
Panel a is after Lin and Yin (1998) and panel b is after Henry et al. (2005). magma at 686–780 °C and 1.0–2 kbar (depth = 3.31–6.6 km), re-
spectively. The chemical compositions of rock-forming minerals
indicate that the parent magma formed in a high oxygen fugacity
structures generally occur along the basement in Cretaceous continental
environment.
sedimentary sequences. For example, the Lower Cretaceous rocks in the
(4) The Shilu Cu–Mo deposit was formed in a consistently extension-
Luoding basin moved from south to north along the basement contact
al environment and closely related to remelting of residual
(Zhao et al., 2012). Li et al. (1997) suggested that the 103–110 Ma
subducted slab fragments in the Jurassic.
Acknowledgments
The geological workers from the Shilu Cu–Mo Mine and Engineer
Weipeng Lin, Zhixia Ouyang and Yun Tian from Geology Bureau for
Nonferrous Metals of Guangdong Province are thanked for their help dur-
ing the field geological investigation. We would like to thank associate
Professor Kejun Hou and Zhenyu Chen from the State Key Laboratory
for Continental Tectonics and Dynamics, Institute of Geology, Chinese
Academy of Geological Sciences for his advice and assistance during
electron microprobe analyses and LA-ICP-MS zircon U–Pb dating. We
thank research assistant Qintao Zeng and Hegen Ouyang from the
Chinese Academy of Geological Sciences, and Dongyang Zhang, Bikang
Xiong, Xinming Zhao and Weiwei Zhou from the China University of
Geosciences (Beijing) for her help during data analyses. We also thank
Senior Engineer Mu Liu from the CNNC Beijing Research Institute of
Uranium Geology for her help during Sr–Nd isotope analyses. The work
was financially supported by the National Basic Research Program
of China (Grant No. 2012CB416704), Open Research Project of key labora-
Fig. 15. Ternary Fe3+–Fe2+–Mg2+ plot for biotites. tory of Metallogeny and Mineral Assessment (Grant No. ZS1306), and the
After Wones and Eugeter (1965). National Natural Science Foundation of China (Grant No. 41203036).
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Ore Geology Reviews 67 (2015) 382–398

Contents lists available at ScienceDirect

Ore Geology Reviews

Geochronology and geochemistry of the Shilu Cu–Mo deposit in the

5.4. Whole rock Sr–Nd isotopes

The samples have slightly negative εNd(t) values of −8.4 to −0.8.

6.1. Age implications

As a typical skarn deposit, the orebodies of the Shilu deposit occur in

intrusion (Fig. 1c), indicating that they have a genetic relationship.

Therefore, the mineralization and the Shilu intrusion possibly formed

simultaneously. However, previous rock-forming Rb–Sr age (122 ±

1999; Zhao et al., 1985). Yu et al. (1988) obtained a consistent

biotite, and plagioclase in the Shilu granodiorite, indicating that ca.

100 Ma represents the rock-forming age. However, Li et al. (2000)

thermal disturbance event. The LA-ICP-MS U–Pb age of 107 ± 0.72 Ma

model ages of 104.1 ± 1.3 Ma and 104.34 ± 0.66 Ma (Zhao et al.,

of the emplacement age of the intrusion with the mineralization event

the Shilu deposit, which yields a sphalerite Rb–Sr isochron age of

97.87 ± 0.96 Ma (Zheng et al., 2013a).

Fig. 6. LA-ICP-MS zircon U–Pb concordia diagram of the Shilu granodiorite.

Sample SL-YT-1 SL-YT-2 SL-YT-3 SL-YT-4 SL-YT-5 SL-YT-6 SL-YT-7 SL-YT-9

SiO2 64.77 64.75 65.01 63.43 64.64 64.23 65.03 63.53

Fig. 8. (a) Chondrite-normalized REE patterns. (b) Primitive-mantle-normalized spider diagrams.

6.3. Physico-chemical crystallization conditions and signiﬁcance for ore

The main conditions of magma melting, temperature and pressure,

lithosphere in this area was controlled by interaction between these

maﬁc dikes of northern Guangdong reﬂect a tensional regime for the

(1) LA-ICP-MS U–Pb zircon dating of the Shilu granodiorite associat-

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