Ore Geology Reviews 80 (2017) 612622

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Ore Geology Reviews

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Pyrite Re-Os isotope systematics at the Zijinshan deposit of SW Fujian,

China: Constraints on the timing and source of Cu-Au mineralization
Si-Hong Jiang a,, Leon Bagas a,b, Qing-Ling Liang c
a
b
c

MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, CAGS, Beijing 100037, China
Centre for Exploration Targeting, The University of Western Australia, Crawley, WA 6009, Australia
Exploration Team 606 of the Sichuan Metallurgical and Geological Exploration Bureau, Chengdu 611730, China

a r t i c l e

i n f o

Article history:
Received 12 September 2015
Received in revised form 7 July 2016
Accepted 11 July 2016
Available online 13 August 2016
Keywords:
Re\
\Os isotopes
Pyrite
Cu-Au deposit
Zijinshan
Fujian
China

a b s t r a c t
Zijinshan is the largest high-suldation epithermal CuAu deposit on mainland China. The primary mineralization at the deposit is characterized by pyrite, digenite and covellite. Although some Rb\\Sr isochron ages of the
uid inclusions in quartz and the apparent K-Ar age of the Cu-bearing alunite alteration zone have been previously interpreted as the ore-forming age, the Rb-Sr and K-Ar dating systems are usually readily reset due to their closure temperature, and thus document the latest thermal event. In order to precisely determine the age of the Cu
mineralization, eight-pyrite separates were Re-Os dated, and seven yielded an isochron age of 103 4 Ma with
an initial 187Os/188Os ratio of 0.45 0.14. This date is interpreted as the age of Cu mineralization, which is in
agreement with geochronological data from molybdenite and the porphyritic granodiorite that hosts Cu-Mo
mineralization at Luoboling (located 2 km NE of Zijinshan), suggesting that these two deposits were formed during the same metallogenic event. The relatively low initial 187Os/188Os ratio indicates that the source of the Cu at
Zijinshan is predominantly the crust with input from the mantle.
2016 Elsevier B.V. All rights reserved.

1. Introduction
The Zijinshan Cu-Au deposit is the largest high-suldation
epithermal Cu-Au deposit hosted by the Middle- to Late Jurassic and
Early Cretaceous intrusives (monzogranite and dacitic porphyry) and
volcanic rocks on mainland China (So et al., 1998; Wang et al., 2009;
Zhang, 2013; Zhang et al., 2003). Zijinshan was discovered in 1988
with exploration continuing until 1994. This work included 92, 233 m
of drilling from over 200 drillholes and underground tunnel exploration
of 9431 m, which together were used to estimate a resources of 305 t
grading 0.58 g/t Au and 2.32 Mt. grading 0.36% Cu. Small-scale underground mining of high-grade auriferous took place during 19931997,
with annual productions reaching tens of thousands tonnes of ore.
Open-cut mining began in 1998, once advances were made in the area
exploiting low-grade auriferous ore with heap leaching. The annual
mined and processed ore increased from millions of tonnes to tens of
millions of tonnes from 1999 to 2007. Since 2008, 37.5 Mt of Au ore
and 6 Mt Cu ore were mined and processed annually at the deposit,
with the annual output of 16 tonnes of gold and 16,000 tonnes of
copper.
Since its discovery in 1988, many have investigated the geology, nature of the alteration, geochemistry and characteristics of the
Corresponding author at: Institute of Mineral Resources, CAGS, No.26 Baiwanzhuang
Rd., Beijing 100037, China.
E-mail address: jiangsihong1@163.com (S.-H. Jiang).

http://dx.doi.org/10.1016/j.oregeorev.2016.07.024
0169-1368/ 2016 Elsevier B.V. All rights reserved.

mineralizing uids at the deposit (e.g. Qiu et al., 2010; So et al., 1998;
Wang et al., 2009; Zhang, 2013; Zhang et al., 1991, 2003, 2005; Zhong
et al., 2011). These studies have recognized that the Au mineralization
is located in the upper zone of an ore-system with Cu mineralization
(principally digenite, enargite and covellite) present at deeper levels.
The alteration and mineral associations are characteristic of a highsuldation epithermal deposit related to the Early Cretaceous
magmatism, as proposed by Jiang et al. (2013); So et al. (1998), and
Zhang et al. (2003).
Some authors documented indirect age estimates for the Zijinshan
Cu-Au mineralization by dating the associated intrusions and alteration
minerals using U-Pb, Rb-Sr and KAr geochronology (Chen, 1996; Jiang
et al., 2013; Zhang et al., 2003). Laser-ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) zircon U-Pb dating shows that the dacitic porphyry hosting the mineralization is 111
1 Ma (Jiang et al., 2013), which constrains the lower limit of the age for
the Cu-Au mineralization. This is in agreement with the Rb\\Sr isochron
age of 100 3 Ma completed on uid inclusions in quartz from the silicic alteration zone at the deposit (Chen, 1996), and the apparent KAr age of 102 1 Ma for alunite from the Cu-bearing alunite alteration
zone (Zhang et al., 2003). The Rb-Sr and K-Ar isotopic system usually
document the last thermal events, due to their low closure temperatures. Given that volcanism continued in the area after the Cu-Au mineralizing event in the area (Jiang et al., 2015), it is doubted that the
Rb-Sr and K-Ar dates represent the mineralization age of the Zijinshan
Cu-Au deposit. Many have shown that pyrite is the second-most reliable

S.-H. Jiang et al. / Ore Geology Reviews 80 (2017) 612622

sulde for Re-Os dating after molybdenite, and can yield robust Re-Os
dates to constrain the timing of sulde mineralization (e.g. Brenan
et al., 2000; Feng et al., 2009; Huang et al., 2014a, 2014b; Lawley et al.,
2013; Morelli et al., 2004; Selby et al., 2009; Stein et al., 2000). In
order to obtain a more precise age and source of the metals at Zijinshan,
this study conducted Re-Os dating of pyrite. The Re-Os results presented
herein demonstrate that the Re-Os isotopic systematics remained
closed yielding a reliable isochron age, however one of the data was
found to be anomalous perhaps due to its low Os content or remobilization of Re or Os. This study will increase our understanding of the Re-Os
systematics of sulde minerals and highlights the caution needed in
interpreting Re-Os data.
2. Geological background
2.1. Geological setting
The porphyry-epithermal Cu-Au-Mo-Ag Zijinshan mineral eld
(ZMF) includes the Zijinshan Cu\\Au, Luoboling porphyry Cu-Mo,
Yueyang (or Bitian) low-suldation epithermal Ag-Au-Cu, Wuziqilong
mesothermal Cu, and Longjiangting mesothermal Cu deposits (Chen
et al., 2011; Cui et al., 2015; Lin, 2006; Ruan et al., 2009; Wang et al.,
2009; Xue and Ruan, 2008; Zhang et al., 1996, 2003; Zhong et al.,
2011, 2014). The ZMF is located at the intersection of the Xuanhe
Anticlinorium and Yunxiao-Shanghang Fault, and at the northeastern
margin of the Cretaceous (ca. 105 to 99 Ma) Shanghang Volcanic Basin
in the eastern part of the Cathaysia Fold Belt of southeastern China
(Fig. 1). The core of the anticlinorium consists of Neoproterozoic phyllite
and ne-grained metasandstone unconformably overlain by Devonian-

613

Carboniferous clastic rocks and limestone. Cretaceous volcanicsedimentary rocks crop out in the Shanghang Volcanic Basin (Jiang
et al., 2015; Fig. 1b).
Middle to Late Jurassic and Early Cretaceous intrusive rocks are common in the ZMF (Mao et al., 2002; Zhang et al., 2001a, 2001b; Zhao et al.,
2007). Based on the dating results and cross-cutting relations of all intrusive phases in the area, the intrusion sequence grading from the
old to young is: Jingmei pluton Wulongsi pluton Jinlongqiao
pluton Caixi pluton Sifang Granodiorite Luoboling porphyritic
granodiorite Zijinshan dacitic porphyry. Monzogranite, located in
the central-northern part of the region, characterizes the Middle to
Late Jurassic magmatic event represented by the Jingmei, Wulongsi,
Jinlongqiao, and Caixi plutons (Fig. 1b). The emplacement of the
monzogranitic plutons is controlled by deep-seated structures related
to the northeast-trending Lishui-Haifeng Fault (Fig. 1a; Zhang et al.,
2001a, 2001b). The Jingmei, Wulongsi, Jinlongqiao plutons have the
same mineral assemblages of K-feldspar (3540%), plagioclase (30
35%), quartz (2530%), biotite (35%), and accessory amounts of zircon,
apatite, titanite and allanite (Jiang et al., 2013). The textures of these
rocks, however, differ with the Jingmei pluton being commonly fractured and medium- to coarse-grained, the Wulongsi pluton being
ne- to medium-grained, and the Jinlongqiao pluton being negrained. These three plutons constitute the Zijinshan Granite with an
outcrop area covering some 28 km2. Available geochronological data indicate that the emplacement of the Zijinshan Granite and Caixi pluton
took place between 165 and 156 Ma and 150 4 Ma, respectively
(Jiang et al., 2013; Zhao et al., 2007). The Zijinshan Granite is intruded
by the Cretaceous Sifang Granodiorite, dacite porphyry, and cut by a
Cretaceous volcanic pipe. Located in the NE of the ore district, the Sifang

Fig. 1. Geological maps showing: (a) the location of the study area (after Chen et al., 2008); and (b) the Zijinshan mineral eld (modied from Jiang et al., 2013). The Shi-Hang Zone ()
and the Lishui-Haifeng Fault () divide the Cathaysia Block into the Cathaysia Interior, Cathaysia Fold Belt, and Southeast Coast Magmatic Belt.

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Granodiorite consists of ne- to medium-grained granodiorite, and is

intruded by the dacite porphyry at Zijinshan and porphyritic granodiorite at Luoboling.
The Sifang Granodiorite has a U-Pb zircon age of 112 1 Ma (Jiang
et al., 2013). It is a ne- to medium-grained granodiorite elongated in a
NNE-trending direction and covers ~10 km2 in area (Mao et al., 2002).
The pluton intrudes Neoproterozoic metamorphic rocks, DevonianCarboniferous clastic rocks and limestone, and the Zijinshan Granite.
The dacite porphyry, with a U-Pb age of 111 1 Ma (Jiang et al.,
2013), consists of plagioclase, K-feldspar, quartz and biotite phenocrysts
in a matrix composed of felsic aphanitic minerals. The volcanic pipe is
cut by dacite porphyry, dacitic phreatic breccia and marginal composite
phreatic breccia, overlain by tuff and surrounded by an 80200 m wide
shattered Jurassic granite. The phreatic breccia and dacite porphyry in
the NW and SE parts of the pipe form a vein-like zone hosted by NWtrending fractures, and constitute an area that is 1800 m long and
1200 m wide resembling a crab in shape (Fig. 2a). All of these Jurassic
and Cretaceous igneous rocks in the Zijinshan ore district have experienced intense hydrothermal alteration.
The Shanghang Basin is located 3 km SW of the Zijinshan Cu-Au deposit, covering ~100 km2 in area and hosts the Yueyang Ag-Au-Cu deposit. The basin contains Early Cretaceous mottled coarse-grained
clastic and volcanic rocks and Late Cretaceous clastic rocks. The volcanism in the basin was between 105 and 99 Ma, and included the deposition of a ~ 600 m thick intermediate to mac to felsic volcanic
succession (Jiang et al., 2015).

The dacitic porphyry and monzogranite host Cu-Au mineralization

at the Zijinshan deposit, and the porphyritic granodiorite hosts Cu-Mo
mineralization at the Luoboling deposit. Molybdenite from Luoboling
yields Re-Os isochron ages of 105 2 and 105 1 Ma (Liang et al.,
2012; Zhong et al., 2014), which are the same within error as the U-Pb
zircon date of 105 1 Ma for the porphyritic granodiorite (Jiang et al.,
2015). The Cretaceous porphyritic granodiorite intruding the Wulongsi
pluton hosts Cu at the Wuziqilong deposit (Zhang et al., 1996). Early
Cretaceous volcanic rocks host the Ag-Au-Cu mineralization at the
Yueyang deposit (Zhang et al., 2001a), where Liu and Hua (2005) report
a 40Ar/39Ar plateau age of 92 1 Ma for adularia, suggesting that this is
the latest mineralizing event in the mineral eld.
2.2. Zijinshan Cu-Au deposit
The Zijinshan Cu-Au deposit consists of an upper oxidized and
leached zone, and a lower primary zone, without secondary sulde enrichment in between. Suldes are intensely oxidized and leached to
form limonite and goethite in the upper oxidized and leached zone,
and a silica cap has developed at the top of the dacite porphyry and its
surrounding phreatic breccia. Gold has been supergene-enriched during
weathering forming a quartz-limonite-native gold assemblage.
Gold orebodies are concentrated between 650 and 1138 m above sea
level (ASL) at the highest peak of the Zijinshan Mountain, whereas the
primary Cu orebodies are located in the primary zone between 400
and 650 m ASL. This represents a vertical zonation with Au in the

Fig. 2. Simplied geological map (a) and prole of exploration line 3 (b) of the Zijinshan Cu\
\Au deposit. Abbreviations: Alu = alunite alteration, Di = dickite alteration, Phy = phyllic
alteration, and Q = silicic alteration.
Modied from Wang et al. (2009); K. Xue, pers. comm. (2010). The boundary of the hydrothermal alteration cited from Chen et al. (2013).

S.-H. Jiang et al. / Ore Geology Reviews 80 (2017) 612622

upper part and Cu in the lower part of the deposit and a transition zone
between 600 and 700 m ASL. All of the Cu and Au orebodies trend NW
and dip NE forming a dextral and lateral array, with steeper dips being
located in the upper part of the deposit (Fig. 2b).
2.2.1. Au mineralization
The Au mineralization at Zijinshan forms disseminations and impregnations localized in the silicic alteration zone, and tends to pinch
out above the current water table near the 650-m level (So et al.,
1998). Using a cut-off grade of 0.2 g/t Au, mineralization constitutes
huge lens with a combined length of ~ 1900 m, width of 900 m, and a
maximum depth of 940 m (Figs. 2 and 3a). The combined mineralization strikes 320 and dips 1525 NE, and is hosted by phreatic breccia
and dacite porphyry in the oxidized zone and surrounding a 80200 m
wide shattered granite with NW-trending extensional fractures. The
structurally controlled central silicied zone and intersecting extensional fractures usually contain higher grades of Au.
The Zijinshan deposit has a resource of 305 t Au and consists of
~ 35 vol.% metallic minerals including limonite and goethite, with
minor amounts of jarosite, native gold, covellite and oxidized pyrite
(Zhang, 2001). The gangue minerals constitutes over 93 vol.% of the
ore consisting of quartz, with minor amounts of dickite and other clay
minerals, and rare alunite and sericite. Native gold has a neness of
948991 and is found in cavities or fractures in granular to aky limonite (Zhang, 2001).
2.2.2. Cu mineralization
Zijinshan had a resource measured during 2011 of 2.32 Mt @ 0.36%
Cu with a cut-off grade of 0.2% Cu and 2389 t Ag (Zhang, 2013). The
Cu orebodies are between 380 and 926 m and usually b 600 m ASL,
and are predominantly hosted by the Wulongsi pluton as SW- to NEtrending en-echelon orebodies forming an overall NW-trending zone
that is 1200 m long and 1100 m wide (Figs. 2 and 3b). These Cu
orebodies consist of veins and stockworks lling NW-trending ssures.
The Cu veins typically are clustered, forming thick orebodies, which are
conformable with the alunite alteration zone and have a stratiform occurrence (So et al., 1998). The Cu orebodies dip 1020 NE at shallowmiddle depths, and ~ 1530 at deeper levels (Fig. 2), and contain 6
12 vol.% suldes including pyrite, digenite, covellite, enargite, and
minor amounts chalcocite, bornite, and chalcopyrite. Based on electron
microprobe and X-ray diffraction analyses, the copper suldes also include yarrowite, spionkopite, geerite, anilite and djurleite (Cui et al.,
2015; Huang et al., 2014a, 2014b). The gangue minerals constitute
~ 8894 vol.% of the ore and consist of quartz and secondarily dickite,

615

alunite, sericite, with minor amounts of barite, feldspar and sericite or

muscovite.
2.2.3. Hydrothermal alteration
Hydrothermal alteration is widespread at Zijinshan extending over
tens of square kilometres, and to a vertical depth of ~ 1100 m. The
major alteration minerals are silica, sericite, dickite and alunite. The silicied zone consisting of silicajarositelimonite alteration is closely
related to Au mineralization, and is located in the dacitic porphyry
along a volcanic vent in the centre of the hydrothermal alteration
zone, which extends outward and downward from an alunite-rich
zone containing Cu mineralization and characterized by the assemblage
alunitequartz to a dickite-rich zone characterized by dickitequartz,
and a phyllic zone characterized by sericitequartz (Fig. 2b; Zhang
et al., 2005).
3. Samples and analytical techniques
3.1. Sample description
Suldes present at Zijinshan include pyrite and covellite in the Au
orebodies, and the Cu orebodies include pyrite, digenite, covellite,
enargite, chalcocite, bornite and chalcopyrite. Of these, pyrite is a
major component associated with Au and Cu and alteration zones,
forming a progressive mineralizing event (Qiu et al., 2010; So et al.,
1998; Wang et al., 2009; Zhang, 2013; Zhang et al., 1991, 2003, 2005;
Zhong et al., 2011, 2014).
Since the pyrite within the Au-bearing ore is commonly oxidized to
limonite, we only sampled pyrite from Cu ore for paragenetic studies
and isotope systematics. Eight samples of Cu ore were collected from
mineralized diamond-drillhole core from the alunite alteration zone in
the centre of the Cu mineralization. Of these, Samples ZJ12-5, ZJ12-16,
ZJ12-17, ZJ12-27, ZJ12-30 and ZJ12-35 were taken from drillhole
DZK403 (MGA 2786657E, 39440259N and 330 m ASL), and Samples
ZJ12-43 and ZJ12-54 from drillhole DZK802 (MGA 2786525E,
39440306N and 525 m ASL) (Fig. 2a).
The samples collected from drillholes DZK403 and DZK802 are located in the alunite alteration zone, and pyrite in these samples is closely
associated with Cu mineralization. Fine- to medium-grained pyrite
was studied in hand specimen and under a microscope to determine
the paragenetic sequence with the Cu-bearing minerals. Photographs
of the vein assemblages and the paragenesis are shown in Fig. 4. The pyrite is commonly a solitary mineral or is associated with digenite or covellite in quartz veins (Fig. 5ad). Pyrite identied under a microscope
includes cataclastic anhedral, euhedral and colloform crystals (Fig. 5e

Fig. 3. Geological maps showing the occurrence of the Au orebodies at 700 m level (a) and Cu orebodies at 330 m level (b) of the Zijinshan Cu-Au deposit. Abbreviations are the same as in
Fig. 2.
Modied from Y. Y. Lu, pers. comm. (2014), S. Zhang and S. Li, pers. comm. (2014).

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S.-H. Jiang et al. / Ore Geology Reviews 80 (2017) 612622

Fig. 4. Photographs and reected light photomicrograph of samples showing the occurrence of main suldes from the Zijinshan Cu-Au deposit: (a) digenite and minor ne-grained pyrite
inll along a fracture; (b) parallel pyrite veins with minor locally concentrated digenite within quartz vein; (c) medium-grained pyrite within a quartz vein; (d) ne-grained pyrite and
digenite in a quartz veinlet; (e) colloform pyrite forming selvedges and digenite occupying the central part of a vein; (f) covellite inlling cataclastic anhedral pyrite grains; (g) pyrite
inlling and enclosing digenite; and (h) digenite lling a cavity in euhedral pyrite. Photomicrograph in (h) is the enlarged of the red box shown in (g), and (e)(h) are reected light
photomicrographs. The diameter of coin in the photographs is 20 mm. Abbreviations: Cov = covellite, Dig = digenite, Py = pyrite, and Qtz = quartz.

S.-H. Jiang et al. / Ore Geology Reviews 80 (2017) 612622

Fig. 5. Simplied paragenetic sequence of the Cu mineralization from the drillholes

DZK403 and DZK802 at the Zijinshan Cu-Au deposit.

617

0.54 ppb, Os = 16.23 0.17 ppb, and 187Os/188Os = 0.3363

0.0029; Yang et al., 2005).
Isochron regressions used Isoplot 3.00 (Ludwig, 2003), a 187Re decay
constant of 1.666 1011 (Smoliar et al., 1996), and an error correlation
factor (rho) (Schmitz and Schoene, 2007). All uncertainties are determined by error propagation of uncertainties in Re and Os mass spectrometer measurements, blank abundances and isotopic compositions,
spike calibrations, and reproducibility of standard Re and Os isotopic
values, and are reported in Table 1.
4. Results

h). Digenite often lls the centre of quartz and colloform pyrite veins
(Fig. 5e), envelopes cataclastic anhedral and euhedral pyrite (Fig. 5g),
or lls cavities in euhedral pyrite (Fig. 5h). Covellite also lls cavities
in early cataclastic anhedral pyrite grains (Fig. 5f). This suggests that
the digenite and covellite are coeval and probably slightly younger
than the pyrite and, by inference, the superjacent gold mineralization
is younger than the early pyrite.
3.2. Analytical method
Sample preparation and inductively coupled plasma mass spectrometry (ICP-MS) measurements were performed in the National Research
Center of Geoanalysis (NRCG), Chinese Academy of Geological Sciences
in Beijing. The details of the sample preparation and chemical procedure
including sample digestion, distillation for extraction, spikes and ICPMS measurement are described in Du et al. (2001, 2004) and Yang
et al. (2008). Re and Os isotopic ratios were measured with a Thermo
Fisher Scientic Triton-plus. The total procedural blanks were about
3.5 pg for Re, 0.23 pg for Os and 0.007 pg for 187Os based on blank
runs analyzed together with the samples. Corrections from Os blanks
were more signicant than that from Re blanks, as the blank Os on average was 459% of the total sample Os whereas the blank Re on average
was 111% of the total sample Re. Osmium blank corrections for most of
the samples were signicant with 187Os/188Os = 0.2190 0.0330 used
to correct the Os concentration and isotopic composition of the sample.
The national standard material, GBW04477 (JCBY, suldes from the
Jinchuan Cu-Ni deposit in China), was used to monitor the accuracy of
the measurements. Re and Os contents and 187Os/188Os of the JCBY suldes determined during the course of this work are 38.799 0.115 ppb,
16.27 0.05 ppb, and 0.3358 0.0017, respectively, which coincide
within the uncertainties levels of the reference values (Re = 38.61

The blank-corrected Re and Os data for eight pyrite samples from

Zijinshan are presented in Table 1. These samples contain
0.03240.3628 ppb Re, 0.395.92 ppt common Os, and 0.057
0.631 ppt 187Os, with low 187Re/188Os ratios ranging from 230 to 4167
and 187Os/188Os ratios from 0.812 to 7.742. The 187Os isotope makes
up 10 to 50% of the total Os in these samples, with most being b 50%
(Table 1). This indicates that the pyrite is not the low-level and highly
radiogenic sulde (LLHR) dened by Stein et al. (2000), and is similar
to the suldes at the Jiama Cu-Mo deposit reported by Ying et al.
(2014). We thus use the traditional 187Re/188Os versus 187Os/188Os
plots to determine Re-Os ages (Fig. 6).
Regression of the Re-Os data for all eight pyrite separates analyses
yields a model 3 isochron age of 113 25 Ma with initial 187Os/188Os
of 0.44 0.90 with a large degree of scatter (MSWD = 654; Fig. 6a),
and the seven pyrite analyses except for Sample ZJ1243 yield a
model 3 isochron age of 103 4 Ma with initial 187Os/188Os of
0.45 0.14 and MSWD of 222 (Fig. 6b).
5. Discussion
5.1. Age constraints
The isochron age of 113 25 Ma (Fig. 6a) obtained from all the eight
pyrite samples not only has a large age error, but also has a very large
mean square weighted deviation (MSWD) of 654. Clearly, this age
from Sample ZJ12-43 is an imprecise isochron caused obviously by deviates in the regression.
Pyrite from seven samples (excluding Sample ZJ12-43) yields a ReOs isochron age of 103 4 Ma with a large MSWD value of 222
(Fig. 6a). If the sample with a low Os content is excluded, the MSWD

Table 1
ReOs data for pyrite from the Zijinshan Cu-Au deposit.
187

Os
(ppt)

187

116.3 0.2 0.39 0.01

0.149 0.003

1429 16

0.7167

351.7 0.3 0.40 0.01

0.407 0.006

0.6979

346.7 0.2 0.54 0.01

0.403 0.003

Sample

Location

Wt.
(g)

Re
(ppt)

ZJ12-5

Drill hole DZK403

at 25 m
Drill hole DZK403
at 778.6 m
Drill hole DZK403
at 815.5 m
Drill hole DZK403
at 641.9 m
Drill hole DZK403
at 594 m
Drill hole DZK802
at 609.7 m
Drill hole DZK403
at 630 m
Drill hole DZK802
at 128.5 m

0.7000

ZJ12-16
ZJ12-17
ZJ12-35
ZJ12-30
ZJ12-54
ZJ12-27
ZJ12-43

0.7069

32.4 0.2

Os
(ppt)

0.49 0.01

0.057 0.001

Re/188Os

Rho

187

Os/total
Os (%)

187

2.904 0.043

0.274

28

0.45 0.14a 122

103

4167 35

7.673 0.088

0.247

50

0.45 0.14a 110

104

3087 15

5.715 0.037

0.231

43

0.45 0.14a 111

102

315.1 4.6

187

Os/188Os

0.8796 0.0139

0.161

10

Os/188Os
initial

Model
Model
age (Ma)c age (Ma)d

0.45 0.14

167

82

211

94

0.4145

284.7 1.4 5.92 0.06

0.631 0.010

230.3 2.2

0.8120 0.0139

0.176

10

0.45 0.14

0.7025

33.6 0.4

0.66 0.01

0.076 0.001

242.2 2.4

0.8711 0.0102

0.263

10

0.45 0.14a 216

104

0.6972

40.8 0.4

0.53 0.01

0.088 0.001

368.9 2.5

1.266 0.012

0.241

14

0.45 0.14a 206

133

0.7068

362.8 0.4 0.56 0.01

0.574 0.005

3077 24

7.742 0.071

0.412

50

2.46

151

142

Notes: Uncertainties reported at the 2 level, 187Os/188Os uncertainties reported at 2SE; all data are blank corrected, blanks for Re, Os and 187Os were 3.5 0.3 pg, 0.23 0.01 pg, and 0.007
0.001 pg, respectively.
a
Initial derived from isochron (Fig. 6b).
b
Initial ratios calculated with an age of 103 Ma.
c
Model age calculated without removing common Os.
d
Model age calculated after removing common Os using initial 187Os/188Os ratio of 0.45.

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Fig. 6. Isochron of pyrite samples: (a) eight points yielding an age of 113 25 Ma (MSWD = 654) and an initial 187Os/188Os ratio of 0.44 0.90; (b) using seven points without Sample
ZJ1243 yielding an age of 103 4 Ma (MSWD = 222), and an initial ratio of 0.45 0.14; (c) six points from Samples ZJ12-5, ZJ12-16, ZJ12-17, ZJ12-54, ZJ12-30 and ZJ12-35 dening a
model 3 isochron age of 104 3 Ma (MSWD = 44, initial 187Os/188Os ratio of 0.40 0.08); and (d) six points from Samples ZJ12-5, ZJ12-16, ZJ12-17 and ZJ12-54 yielding an isochron age
of 103 1 Ma with initial 187Os/188Os of 0.46 0.01 and MSWD of 2.5.

value will be signicantly lowered. For example, Six samples (ZJ12-5,

ZJ12-16, ZJ12-17, ZJ12-54, ZJ12-30 and ZJ12-35) yield a Model 3 isochron age of 104 3 Ma with the MSWD value of 44 and initial
187
Os/188Os ratio of 0.40 0.08 (Fig. 6c), ve samples (ZJ12-5, ZJ1216, ZJ12-17, ZJ12-54 and ZJ12-30) yield an isochron age of 103
2 Ma with the MSWD value of 8.5 and initial 187Os/188Os ratio of
0.43 0.07 (not shown in Fig. 6), and four samples (ZJ12-5, ZJ12-16,
ZJ12-17 and ZJ12-54) dene a more accurate Model 1 isochron age of
103 1 with the MSWD value of 2.5 and initial 187Os/188Os ratio of
0.46 0.01 (Fig. 6d). These isochron ages are consistent within errors,
indicating that there is only one metallogenic event indicated by the
Re-Os data of the pyrite samples, and the large MSWD values are mainly
caused by the analytical error associated with a low Os content. Therefore, the Re-Os isochron age of 103 4 Ma obtained from pyrite from
the seven samples (except for Sample ZJ12-43) is interpreted as the reasonable and reliable age for the sulde mineralization at Zijinshan. This
date is similar within error to the Rb-Sr isochron age of 100 3 Ma for
uid inclusions in quartz (Chen, 1996), and the K-Ar apparent age of
102 1 Ma for alunite from Zijinshan (Zhang et al., 2003). Furthermore,
the date is the same as the Re-Os molybdenite isochron dates of 105
2 Ma and 105 1 Ma and the LA-MC-ICP U-Pb zircon age of 105 1 Ma
for the porphyritic granodiorite at Luoboling (Jiang et al., 2015; Liang
et al., 2012; Zhong et al., 2014).
Although the Cu minerals and Au orebodies were formed relatively
later than the pyrite indicated by the paragenesis, the age of the CuAu mineralization would not be 0.8 million years younger than the
date of the pyrite in a single intrusive event (Cathles et al., 1997). Therefore, the pyrite Re-Os isochron date of 103 4 Ma approximately represents the age of Cu-Au mineralization at Zijinshan. This shows that

the Cu-Au mineralization at Zijinshan is coeval with the Luoboling CuMo mineralization and both represent a signicant ca. 105 Ma mineralizing event in the region.
5.2. Initial Os isotope compositions and the source of metals
Osmium is a compatible element with high Re/Os ratios and radiogenic Os isotopic compositions in the continental crust, and its
187
Os/188Os ratios have an estimated average upper crustal value of
1.9256 (Esser and Turekian, 1993). Relative to the upper crust, the
lower crust has one to two times as much Os with about half of the
Re, is less radiogenic, and has one-half to one-third the 187Os/188Os
ratio of between 0.64 and 0.96 of the upper crust (Saal et al., 1998). Furthermore, since Os and Cu are chalcophile elements, they should have
similar geochemical behaviour. Osmium is therefore used to trace the
source of metals associated with Cu.
The initial 187Os/188Os ratio from the pyrite samples from Zijinshan
with an isochron age of 103 4 Ma is 0.45 0.14 (Fig. 6d), and is
more radiogenic than the chondritic 187Os/188Os ratio of 0.126 at
103 Ma, but less than the crustal value for 187Os/188Os inferred by
Esser and Turekian (1993) and Saal et al. (1998). This indicates a significant mantle component for the source of osmium in the pyrite samples.
We therefore infer that the source of the copper at Zijinshan is at least
partly derived from the mantle with input from a crustal source. This inference is consistent with the origin of the Early Cretaceous granodiorite
and volcanic rocks, which are regarded as mixed mantle-derived and
crustal melts suggested by their Nd-Sr-Hf isotopes (Jiang et al., 2013,
2015; Wu et al., 2013). This indicates that both the metals and magma
have a signicant mantle component.

S.-H. Jiang et al. / Ore Geology Reviews 80 (2017) 612622

5.3. Pyrite Re-Os systematics

As the pyrite contains more or less common Os ranging from 0.39 to
5.92 ppt (Table 1), their model ages spread from 110 to 216 Ma. If we
remove the common Os using the initial 187Os/188Os ratio of 0.45 (obtained from the pyrite Re-Os isochron; Fig. 6b), much younger model
ages are obtained from these pyrite samples, with four samples (ZJ125, ZJ12-16, ZJ12-17 and ZJ12-54) having very close model ages of 102
104 Ma (Table 1). In contrast, two samples (ZJ12-30 and ZJ12-35) give
much younger model ages of 8294 Ma, while Samples ZJ12-27 and
ZJ12-43 gave much older model ages of 133142 Ma, indicative of Re
loss or Os gain. However, the 187Os/188Os and 187Re/188Os ratios for
Samples ZJ12-30, ZJ12-35 and ZJ12-27 plot very close to the 103
4 Ma pyrite regression isochron in Fig. 7, thus their younger or older
model ages could due to a combination of analytical error, and Re loss
or Os gain.
Furthermore, the Re-Os analysis of Sample ZJ1243 shows a high degree of scatter relative to the 103 4 Ma regression (Fig. 7), and its
187
Os content of 0.574 0.005 ppt is 82,000 times higher than
0.007 0.001 pg for the blank sample. Thus the deviation in the sample
from the 103 4 Ma pyrite regression isochron in Fig. 7 is not only
caused by analytical error, but also includes open system disturbances
of Re and Os subsequent to the crystallization of the pyrite. Therefore,
the initial 187Os/188Os ratio of 2.46 for Sample ZJ12-43, as calculated
by using the 103 Ma date, has no geological signicance (Table 1).
As discussed above, one of the pyrite separates shows open system
Re-Os isotope behaviour due to Re loss or Os gain (Fig. 7). Re-Os isotopic
system can be perturbed by a variety of processes such as hydrothermal
or supergene alteration, deformation, and metamorphism (e.g. Lambert
et al., 1998; Morelli et al., 2004; Ruiz and Mathur, 1999; Trist-Aguilera
et al., 2006; Xiong and Wood, 1999, 2001; Xiong et al., 2006). Given that
no obvious metamorphism or intense deformation took place in the
ZMF during the Mesozoic, the effects of the metamorphism and deformation on the Re-Os isotopic system can be excluded. Furthermore, all
the samples in this study are taken from the primary sulde orebodies,
and have not been supergene altered. Therefore, the open-system behaviour of the Re-Os isotopes for the pyrite separates from Sample
ZJ12-43 is most likely due to high-temperature hydrothermal alteration
following ore formation.
Experimental studies have demonstrated that Re can be remobilized
by very oxidized hydrothermal uids under high-temperatures of above
400 C (Xiong and Wood, 1999; Xiong et al., 2006). In addition, Re-Os
isotopes are not affected by hydrothermal alteration at temperatures
of 100200 C with oxygen levels under which suldes are stable

619

(Xiong et al., 2006). As mentioned above, the volcanic activity in the

Shanghang Basin took place between 105 and 99 Ma, following the formation of hypogene suldes at Zijinshan (Jiang et al., 2015). The most
plausible explanation, therefore, for the open Re-Os isotopic system
for the pyrite from Sample ZJ12-43 is due to intensive volcanism in
the basin, which requires further investigation to conrm.
5.4. Implications to the genetic model
According to the model proposed by Sillitoe (1999, 2000, 2010),
high-suldation Cu-Au mineralization is intimately associated with porphyry Cu deposits, such as the Far Southeast-Lepanto deposit in the
Philippines and Yanacocha deposit in Peru (Hedenquist et al., 1998;
Longo et al., 2010). Therefore, given that the depth limit of drilling at
Zijinshan is 400 m ASL, there is signicant potential for porphyry Cu
mineralization and associated porphyritic intrusions beneath the
known Cu-Au mineralization. In addition, Wang et al. (2014) recently
discovered roquesite (CuInS2) at Zijinshan, which is a mineral that is
present in mesothermal and hypothermal deposits (e.g. Cook et al.,
2011; Shimizu and Kato, 1991). This further points to the potential for
porphyry-type mineralization at depth in the area (also see Qiu et al.,
2010; Wang et al., 2014; Zhang et al., 1991, 2001a, 2001b).
The ca 103 Ma Re-Os date for the Cu mineralization at Zijinshan adds
further support to the above hypothesis, because the date indicates a
close temporal association with the porphyry-type Cu-Mo mineralization at Luoboling. It is therefore suggested that these two deposits
share a common parental magma chamber, as supported by geophysical
data (Zhang et al., 2001a, 2001b). However, it has been recently proposed that the Zijinshan Cu-Au and Luoboling Cu-Mo deposits belong
to two different mineralization systems (e.g. Qiu et al., 2010; Wang
et al., 2009, 2014; Zhang, 2013). It is interesting to note that the Au
and Cu orebodies at Zijinshan plunge towards the Luoboling Cu-Mo deposit, which structurally suggests continuity between both deposits at
depth (Fig. 8a). In addition, the Cu-Mo orebodies and porphyritic granodiorite host rocks have been uplifted by ~400 m during faulting along
the NE-trending normal fault between the two deposits (Zhang et al.,
2001a, 2001b). Combined with the Re-Os date obtained in this study,
it is considered likely that the Au-Cu mineralization at Zijinshan and
Cu-Mo mineralization at Luoboling are part of a single zoned ore system
(Fig. 8b), with the Cu-Mo mineralization located in the top of the mineralized intrusion, while the Cu-Au mineralization enriched laterally
away from the Cu-Mo orebodies. This model is similar to the Cu-Au mineralization style at the Far Southeast-Lepanto deposit in the Philippines
(Hedenquist et al., 1998).
5.5. Contributions to the understanding of metallogeny in ZMF

Fig. 7. ReOs analyses from all pyrite samples. The isochron from Fig. 6b is also plotted as a
reference (see text for discussion).

Based on the pyrite Re-Os date reported here and the genetic model
for the Zijinshan Cu-Au and Luoboling Cu-Mo deposits (Fig. 8b), a mineralization centre can be proposed at ZMF located beneath Luoboling.
Obviously, the Cu-Au mineralization at Zijinshan and Cu-Mo mineralization at Luoboling, and even the Cu mineralization at Wuziqilong, are
closely related to the emplacement of the ca. 105 Ma porphyritic granodiorite at this centre. Other deposits in the ZMF, including the Yueyang
Ag-Au-Cu and Longjiangting Cu deposits, however, are 56 km away
from the mineralization centre at Luoboling, which are considered too
far to be directly related to the porphyritic granodiorite; although
some authors suggested that the low-suldation epithermal Ag-Au-Cu
mineralization at Yueyang is intimately connected to the highsuldation epithermal Cu-Au mineralization at Zijinshan (e.g. Qiu
et al., 2010; Wang et al., 2009; Zhang et al., 2003, 2005). Therefore, another synchronous mineralization centre may be located near the
Yueyang Ag-Au-Cu and Longjiangting Cu deposits, similar to the
Luoboling mineralization centre. Of course, a different metallogenic
event subsequent to the Cu-Mo-Au mineralization at Zijinshan and
Luoboling cannot be excluded, as the 40Ar/39Ar plateau age for adularia

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S.-H. Jiang et al. / Ore Geology Reviews 80 (2017) 612622

Fig. 8. (a) Spatial relationship between the Zijinshan Cu\

\Au deposit and Luoboling Cu\
\Mo deposit (after Zhang, 2013); (b) Proposed model showing the relationship between these two
deposits, which are probably controlled by a single ore system. The inferred depth of the intrusions beneath the Zijinshan and Luoboling ore districts and the alteration zones in Luoboling
Cu-Mo deposit are cited from Zhang et al. (2003, 2005); Zhong et al. (2011, 2014) and Zhang (2013). Note that the Cu-Mo mineralization and hosting porphyritic granodiorite in Fig. 7a is
400 m higher than that in Fig. 7b due to the subsequent uplift caused by normal faulting (see text for discussion). Abbreviations are the same as in Fig. 2.

at Yueyang deposit is 92 1 Ma (Liu and Hua, 2005), which is signicantly younger than the ore-forming age of ca. 105 Ma at Zijinshan
and Luoboling. Alternatively, the 40Ar/39Ar age of adularia at Yueyang
deposit only records the time of the latest thermal event, and thus cannot represent the ore-forming age of the Yueyang deposit. Therefore,
more work should be carried out on these two deposits located far
from the Luoboling mineralization centre, and it is possible to nd
concealed porphyry Cu-Mo deposits or a new metallogenic centre.
6. Conclusions
Seven pyrite separates from the Zijinshan Cu-Au deposit yield a ReOs isochron age of 103 4 Ma. This date is coeval with the molybdenite
Re-Os and the porphyritic granodiorite U-Pb ages for the Luoboling CuMo deposit, indicating that these two deposits were formed during the
same metallogenic event. The initial Os isotope composition of 0.45

0.14 suggests that the Os in the hydrothermal uids may be derived

from the crust with input from the mantle. The Re-Os date of ca.
103 Ma for the Cu mineralization at Zijinshan is signicant for the genetic model that the Au-Cu mineralization at Zijinshan and the Cu-Mo mineralization at Luoboling are evolved by a single ore system, while there
maybe another ore system responsible for the formation of the Yueyang
Ag-Au-Cu and Longjiangting Cu deposits.
Although pyrite can yield robust Re-Os data to constrain the timing
of suldes in a deposit, analysis of one pyrite from the Zijinshan deposit
shows a disturbance of the Re-Os system and, hence, clearly highlights
the necessity to be cautious in the interpretation of such data.
Acknowledgements
The Chinese Ministry of Land and Resources (Project No.
200911007-26) and the Basic Work Programme for Science and

S.-H. Jiang et al. / Ore Geology Reviews 80 (2017) 612622

Technology (Project No.2014FY121000) nancially support this study.

Prof. Shao-Huai Wang from Zijin College of Mining at Fuzhou University
is thanked for his assistance during eldwork. We are grateful to Zijin
Mining Group Co. Ltd. for permission to work and collect samples
from the Zijinshan Cu-Au mine. We are also grateful to Prof. Andao
Du, Dr. Wenjun Qu, Dr. Chao Li and Dr. Liming Zhou for their assistance
with the Re-Os isotopic analyses at the National Research Center of
Geoanalysis, Chinese Academy of Geological Sciences in Beijing. One
anonymous reviewer, editor-in-chief Prof. Franco Pirajno and Prof.
Jingwen Mao are thanked for their constructive comments and reviews,
which have signicantly improved this manuscript.

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