LITHOS 432-433 (2022) 106898

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LITHOS
journal homepage: www.elsevier.com/locate/lithos

Petrogenesis and metal fertility of Yinzu pluton in the Daye district, eastern
China: Insights from whole-rock and mineral (zircon, apatite and
amphibolite) geochemistry
Run-Jie Zhou a, b, c, Guang Wen a, *, Jian-Wei Li a, Kang Cao a, Ke-Tao Wei d, e, Heng-An Cai d, e,
Shi-Chao Shang d, e, Yue Sun a, Liang Fan a, Bai-Cun Li d, e, Xu-Ke Dai f
a
State Key Laboratory of Geological Processes and Mineral Resources and School of Earth Resources, China University of Geosciences, Wuhan 430074, China
b
Hubei Geological Survey, Wuhan 430034, China
c
Hubei Geological Exploration Engineering Technology Research Center, Wuhan 40034, China
d
The First Geological Brigade of Hubei Geological Bureau, Daye 435100, China
e
Hubei Provincial Key Laboratory of Resource and Eco-geological Environment, Hubei Geological Bureau, Wuhan 430022, China
f
The Seventh Geological Brigade of Hubei Geological Bureau, Yichang 443000, China

A R T I C L E I N F O A B S T R A C T

Keywords: The Daye district in eastern China is featured by numerous granitoid intrusions of Early Cretaceous ages that
Daye district intrude Paleozoic to Early Triassic marine carbonate and clastic rocks. Several dozen skarn Cu-Fe-Au deposits
Yinzu pluton occur along the intrusive contact zones of the Echeng, Tieshan, Jinshandian, Lingxiang, Tongshankou and
Zircon
Tonglushan intrusions. However, no economic skarn mineralization has been recognized in other intrusions and
Apatite
Metal fertility
whether or not these intrusions are metal fertile remain unresolved. In this paper, we use whole-rock and mineral
(zircon, apatite and amphibole) geochemistry to provide significant new insights into the petrogenesis and metal
fertility of the Yinzu granitoid pluton.
The Yinzu pluton mainly consists of quartz diorite and diorite phases that have zircon U-Pb ages of 148.4 ± 1
Ma and 146.6 ± 1.6 Ma, respectively. Whole-rock Sr-Nd isotopic compositions ((87Sr/86Sr)i = 0.70635 to
0.70741; εNd(t) = − 8.74 to − 3.73) and zircon hafnium isotopes (εHf(t) = − 9.1 to − 4.8) overlap with values of the
Cu-fertile Tongshankou and Tonglushan granitoids, implying a common enriched lithospheric mantle source.
The whole-rock geochemical data suggest that both the diorite and quartz diorite have experienced variable
degrees of fractional crystallization of olivine, amphibole, titanite and magnetite. The Ce4+/Ce3+ ratios (16–445)
and oxygen fugacity (logfO2) calculated using trace element concentrations of zircon (ΔFMQ = +0.2 to +2.4)
suggest that both intrusive phases crystalized from oxidized melts similar to Cu-fertile magmas in the world, with
the quartz diorite being well comparable to the Tongshankou and Tonglushan granitoids. Based on available
melt-apatite partitioning models, the estimated S and Cl contents for the magmas parental to the Yinzu pluton are
akin to those of the Cu-fertile granitoids in the Daye district. Rocks of the Yinzu pluton display high apatite Sr/Y
(0.38–3.01) and Eu/Eu* (0.35–0.71) ratios as well as high zircon Eu/Eu* (0.51–0.86) and 10000*(Eu/Eu*)/Y
(2–27) ratios, indicating significant fractionation of amphibole with limited plagioclase fractionation and high
magmatic water contents (>4 wt% H2O). This view is consistent with the calculated melt H2O content of 4.3–6.1
wt% based on the amphibole compositions.
Collectively, results presented here indicate that magmas generating the Yinzu pluton are hydrous, oxidized
and S-rich, characters similar to the Cu-fertile granitoids in Daye and elsewhere. Thus, the Yinzu pluton is
considered to be Cu-(Au) fertile. This consideration is partially supported by occurrences of several vein-type Cu
prospects within and disseminated Au ores in Silurian clastic sedimentary rocks immediately to the southeast of
this pluton. Based on the regional metallogeny and results of this study, we suggest that the Yinzu pluton is a
promising target of future Cu-(Au) exploration.

* Corresponding author.
E-mail address: guangwen@cug.edu.cn (G. Wen).

https://doi.org/10.1016/j.lithos.2022.106898
Received 30 April 2022; Received in revised form 28 September 2022; Accepted 28 September 2022
Available online 4 October 2022
0024-4937/© 2022 Elsevier B.V. All rights reserved.
R.-J. Zhou et al.
1. Introduction
Magmas associated with porphyry-skarn Cu deposits are typically
characterized by high oxygen fugacity and high volatile (Cl, S and H2O)
contents (Burnham, 1979; Cao et al., 2018; Richards, 2011; Sillitoe,
2010). Tight constraints on magmatic oxidation state and volatile con­
tents of magmas are of critical importance in mineral exploration (Cao
et al., 2022a; Lu et al., 2016). Traditionally, magmatic oxidation state
and volatile contents can be estimated using geochemical signatures (e.
g., FeO/Fe2O3 and Sr/Y ratios) of whole-rocks, mineral-pairs (e.g.,
magnetite-ilmenite) and melt inclusions (Chang et al., 2018; Shu et al.,
2019; Wang et al., 2014). However, such traditional methods can be
questionable for rocks with hydrothermal alteration or weathering (Lu
et al., 2016; Shu et al., 2019; Zhong et al., 2019). Accessary minerals,
such as zircon and apatite, are ubiquitous in intermediate to felsic rocks
and relatively resistant to hydrothermal alteration. As such, those
minerals have been increasingly used to investigate compositional
evolution and variation in physicochemical conditions of their parental
magma (Ballard et al., 2002; Cao et al., 2018, 2022a; Lee et al., 2017; Li
et al., 2021a; Lu et al., 2016). For example, zircon Eu and Ce anomalies
have been used as proxies for magmatic water content and oxidation
state (Dilles et al., 2015; Lu et al., 2016), while apatite compositions
have been successfully applied to evaluate Cl and S budgets in a magma
Fig. 1. Geological map of the Daye district (modified from Shu et al., 1992; Li et al., 2009).
2
LITHOS 432-433 (2022) 106898
(Cao et al., 2012; Cao et al., 2022b; Xing et al., 2020, 2021; Xu et al.,
2021).
The Middle-Lower Yangtze River Valley metallogenic belt (MLYMB)
is one of the most important porphyry-skarn Cu-Au-Fe-(Mo-W) metal­
logenic belts in China (Chang et al., 2019; Mao et al., 2011). From west
to east, it consists of seven ore districts, including Daye, Jiurui, Anqing-
Guichi, Luzong, Tongling, Ningwu and Ningzhen. The Daye ore district
in the westernmost part of the MLYMB hosts >50 skarn-(porphyry)
deposits that are genetically related to the Early Cretaceous granitoid
intrusions (Fig. 1). Among these intrusions, the Echeng, Jinshandian and
Linxiang plutons are associated with several large- to medium-sized Fe
skarn deposits, whereas the Yangxin and Tieshan plutons are related to
large Cu-Au-(Fe) skarn deposits. No economically important deposit has
been recognized in association with the Yinzu pluton (Fig. 2a), but
several vein-type Cu prospects and small sediment-hosted Au deposits
occur in the northeastern margin of the pluton and Silurian clastic rocks
immediately to the southeast of this pluton (Fig. 2b). Based on whole-
rock major and trace element geochemistry, Wang et al. (2004) sug­
gested that Yinzu magma is resulted from partial melting of thickened
lower crust with garnet ± plagioclase ± hornblende as residual phases.
More recent studies have shown that Yinzu pluton is geochemically and
isotopically similar to the Cu-fertile granitoids in the Daye district,
which were derived from partial melting of an enriched lithospheric
R.-J. Zhou et al.
Fig. 2. (a) Geological map of the Yinzu pluton (modified from Shu et al., 1992; Ding et al., 2017). (b) Geological map of Xujiashan Au orefield in south Yinzu
(Modified from Yang et al., 2003).
mantle source following fractional crystallization of olivine, amphibole,
plagioclase, apatite, magnetite and variable crustal contamination (Ding
et al., 2017; Li et al., 2009; Li et al., 2013). However, whether or not the
Yinzu pluton is Cu-fertile remains unresolved.
In this paper, we present trace elements for zircon, major and trace
elements for apatite, major elements for amphibole, whole-rock
geochemistry and zircon Hf isotopes of the Yinzu pluton to constrain
the magma source, oxidization state and volatiles contents of the Yinzu
magma. Our results indicate that the Yinzu pluton is oxidized and hy­
drous with high contents of S, suggesting high Cu-(Au) fertility for the
pluton. Based on our results and the regional metallogeny, we propose
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LITHOS 432-433 (2022) 106898
that the Yinzu pluton is a promising target for future Cu-(Au)
exploration.
2. Geological background
The Daye district is located in the westernmost part of the MLYMB
and is confined by Tan-Lu, Xiangfan-Guangji and Ma-Tuan three major
Faults (Li et al., 2009; Shu et al., 1992). Stratigraphically, this district is
dominated by the Silurian and Permian to Middle Triassic marine car­
bonate and clastic rocks, with minor Cambrian to Ordovician and
Devonian sequences in its southern edge (Fig. 1). The lowermost
R.-J. Zhou et al.
stratigraphic member comprises >1000 m of Cambrian and Ordovician
dolomite limestones, argillaceous limestones and carbonaceous shale,
from the base upward, into the Loushanguan, Nanjinguan, Hon­
ghuayuan, Dawan, Guniutan and Baota Formations. The Silurian and
Devonian rocks are dominated by fine quartz sandstones and minor
amounts of shale and siltstones. The Carboniferous limestones, locally
intercalated with dolomites, are overlain by a 600-m-thick Permian
sequence of shales, cherts, coal beds, and limestones. The Triassic car­
bonate rocks are the most important wall rocks of skarn mineralization
throughout the district with 1000–1200 m marine limestones and do­
lomites (Li et al., 2014; Shu et al., 1992). During the Middle Triassic
period, the continental collision between the Yangtze and North China
cratons resulted in extensive fracture zone and the intensely strata fol­
ded (Li et al., 1993; Mao et al., 2011). The fracture zone formed in the
Neoproterozoic and reactivated during the Indosinian (Late Permian to
Triassic) and Yanshanian (Jurassic to Cretaceous) events, which resulted
in the development of extensive networks of faults and folds (Fig. 1; Shu
et al., 1992; Mao et al., 2011). These faults and folds provided favorable
sites for the emplacement of the magmas and the localization of the ore
bodies (Li et al., 2009; Mao et al., 2011).
Extensive early Cretaceous mafic to intermediate-felsic intrusive and
volcanic rocks are widespread in the region (Li et al., 2009; Xie et al.,
2011a, 2011b). There are six major granitoid plutons in this district.
From north to south, they are Echeng intrusive complex consisting of
diorite, quartz monzonite and granite, Tieshan intrusive complex
comprised of quartz diorite and minor gabbro-diorite, Jinshandian
diorite, Lingxiang diorite, Yinzu and Yangxin intrusive complex
composed of granodiorite, quartz diorite and gabbro-diorite (Fig. 1). The
Tieshan, Yangxin and Yinzu pluton contain abundant mafic magmatic
enclaves (MMEs) (Shu et al., 1992). In addition, there are >30 grano­
diorite stocks and dikes surrounding or intruding the plutons and most
of them crop out <1 km2. The volcanic rocks consisting of basalt,
basaltic andesite, trachyandesite, trachydacite, and rhyolite in western
part of the region (Xie et al., 2011a).
Zircon U-Pb dating showed that the magmatism associated with Cu
mineralization occurred at 150–138 Ma with a peak at 145–140 Ma
(Deng et al., 2015; Li et al., 2008, 2010a, 2014). Whereas the intrusions
related to Fe skarn deposits are generally younger, largely in the range of
135 to 128 Ma, concentrated at 133–130 Ma (Hu et al., 2017, 2020; Xie
et al., 2011a, 2012). Whole-rock geochemical studies suggested that the
ore-related granitoids are sourced from the enriched lithospheric
mantle, with the parent magmas having experienced variable degrees of
fractional crystallization of amphibole, plagioclase, magnetite, apatite
and crustal contamination during evolution (Li et al., 2009; Li et al.,
2013; Xie et al., 2015).
Several dozen skarn Fe, Cu or Cu-Au-(Fe-Mo-W) deposits have been
discovered in association with the major granitoid intrusions and
smaller porphyries. For example, the Yangxin pluton hosts the Ton­
glushan Cu-Au-Fe polymetallic skarn deposit with a total reserve of 1.08
Mt. Cu, 70 t Au and 60 Mt. Fe (Li et al., 2010a). In addition, many small
stocks also have important Cu deposits, for instance, the Tongshankou
granodiorite porphyry with a total outcrop of 0.4 km2 contains a
porphyry-skarn deposit with Cu reserve of ~0.5 Mt. (Li et al., 2009).
However, to date, no economically significant deposits have been found
in the Yinzu pluton and its periphery areas (Fig. 2a). There are only some
occurrences of small-scale Cu and Au mineralization in the southeast
margin of the pluton and its surrounding Silurian strata (Fig. 2b),
respectively.
3. Geology of the Yinzu Pluton
The Yinzu pluton is confined by the roughly EW-striking Maopu-
Liangduanqiao fault, NE-striking Jiangqiao fault and NEE-striking Yinzu
anticline (Shu et al., 1992). It crops out over an area of about 85 km2,
with length of 17 km and width of 9 km. The pluton mainly intruded the
Silurian quartz sandstone and is in contact with the Carboniferous to
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LITHOS 432-433 (2022) 106898
Triassic strata in the north (Fig. 2a). The pluton is in contact with the
Silurian clastic rock formed calc-silicate hornfels, whereas marble and
skarn were formed in contact with the Carboniferous and Permian car­
bonate rocks. The Yinzu pluton is dominantly composed of quartz diorite
with granodiorite porphyry intruding the quartz diorite in the center.
Minor diorite is distributed in the southwestern of the pluton (Fig. 2a).
The Yinzu quartz diorite is light to pale grey, medium- to coarse-
grained and consists of plagioclase (60–65 vol%), amphibole (10–15
vol%), quartz (10 vol%) and minor K-felspar and biotite (Fig. 3a-c).
Accessory minerals are mainly magnetite, apatite, titanite and zircon.
Most euhedral plagioclases show oscillatory zoning texture and some
were altered to sericite. Amphibole in the quartz diorite is generally
subhedral to anhedral with some magnetite enclosed in it (Fig. 3b).
Biotite is enhedral to subhedral and commonly contains apatite, zircon
and plagioclase as inclusions (Fig. 3b). Quartz is commonly anhedral
and is coexisting with plagioclase (Fig. 3c). Apatite is columnar with
subhexagonal shape, ranging in length from 50 to 300 μm (Fig. 3b).
Titanite presents as euhedral to subhedral crystal, with length of
200–600 μm (Fig. 3c). It occurs in the interstices between amphibole and
plagioclase.
The Yinzu diorite is greyish to dark-greyish, medium- to fine-grained
and is dominantly composed of plagioclase (65–70 vol%) and amphibole
(20–25 vol%) with apatite, magnetite, titanite and zircon as accessory
phases (Fig. 3d-f). Plagioclase crystals are generally euhedral to sub­
hedral and locally contain columnar apatite inclusions (Fig. 3e, f).
Amphibole is generally subhedral and coexists with plagioclase and
biotite. Biotite is subhedral to anhedral and is partly altered to chlorite
(Fig. 3e). Titanite is euhedral and generally occurs in the interstices
between major phases such as plagioclase, amphibole and biotite
(Fig. 3e). Apatite occurs as euhedral inclusions in amphibole and
plagioclase or is located along their grain boundaries (Fig. 3e, f). Locally
the diorite contains MMEs that are round to ovoid and 2–5 cm in
diameter (Fig. 3g). These MMEs are fine-grained and show sharp con­
tacts with the host diorite. They are dominantly composed of plagioclase
(60–65 vol%), amphibole (20–25 vol%) and biotite (5–10 vol%) with
accessory magnetite, titanite and apatite (Fig. 3h, i). Apatite crystals in
MMEs are typical acicular and have aspect ratios up to 50:1 (Fig. 3h, i).
The granodiorite has a porphyritic texture, consisting of phenocrysts
dominated by plagioclase (40 vol%), amphibole (8 vol%), biotite (8–10
vol%) and quartz (5 vol%), and fined-grained matrix mainly including
feldspars and quartz.
Zircon U-Pb dating yielded an age of 151.8 ± 2.7 Ma for the quartz
diorite, which is consistent with an 40Ar/39Ar plateau age of 151 ± 1.9
Ma for amphibole from the same phase (Li et al., 2014). Li et al. (2010b)
reported a zircon U-Pb age of 146 ± 1 Ma for Yinzu diorite. Previous
whole-rock geochemistry and Sr-Nd isotopic studies suggest that the
quartz diorite and diorite are derived from an enriched mantle source
following fractional crystallization of olivine, amphibole, plagioclase,
apatite, magnetite and variable crustal contamination (Ding et al., 2017;
Li et al., 2009; Li et al., 2013).
4. Samples and analytical methods
4.1. Sample descriptions
Ten samples were collected from the drill cores in this study. Three
quartz diorite samples were from the drill hole ZK01 (depth of 53 m,
112 m, 113 m) in Maduiyu (Fig. 3a-c). Seven diorite samples were from
the drill hole ZK501 (depth of 153 m, 222 m, 224 m, 294 m, 351 m, 450
m and 627 m) in Huanglongshan (Fig. 3d-i). All the samples were made
for thin sections used for petrographic observation. There is no signifi­
cant change of lithology in samples from the drill hole ZK01. In drill hole
ZK501, the diorite contains MMEs at depth of 224 m and it’s overprinted
by chlorite alteration and Cu mineralization at depth of 627 m.
Three quartz diorite (18MDY01, 18MDY02, 18MDY03) and two
diorite (18HLS02, 18HLS06) samples were sent for whole-rock chemical
R.-J. Zhou et al. LITHOS 432-433 (2022) 106898

Fig. 3. Hand specimens and photomicrographs of Yinzu pluton. (a) Fresh quartz diorite mainly composed of plagioclase, amphibole, K-feldspar, biotite and quartz.
(b) Quartz diorite mainly composed of plagioclase, amphibole, quartz, and biotite; (c) Euhedral titanite coexisting with plagioclase and anhedral quartz. (d) Fresh
diorite dominantly composed of plagioclase, amphibole and biotite. (e) Euhedral-subhedral apatite and titanite coexisting with the amphibole and biotite. (f)
Columnar apatite occurring as inclusions in subhedral-anhedral amphibole. (g) Ellipsoidal mafic enclaves in the diorite. (h) Acicular apatite and subhedral amphibole
coexisting with plagioclase; (i) Acicular apatite coexisting with plagioclase. Abbreviations: Amp = amphibole, Ap = apatite, Bt = biotite, Kfs = K-feldspar, Mag =
magnetite, Pl = plagioclase, Qz = quartz, Ttn = Titanite.

analysis and the samples of 18MDY02 and 18HLS02 were further used
for the zircon separation. Zircon was separated using standard heavy-
liquid and magnetic methods, then choose the appeared clear and free
of inclusion grains under a binocular microscope. Next, these selected
zircon grains were mounted in epoxy, polished to the core center. Zircon
grains were examined under a microscope with transmitted and re­
flected light, and most of the grains were transparent euhedral ranging
in size from 50 to 200 μm. Before analytical work, cathodoluminescence
images were taken using a scanning electron microscope (CL-SEM) to
reveal these zircon grains internal structures. The apatite grains were
imaged petrographically by cold optical cathodoluminescence (OP-CL)
microscopy to reveal these apatite grains textures. Apatite and amphi­
bole were identified on the thin sections, imaged by backscattered
election microscopy and then used to analysis.
4.2. Analytical methods
4.2.1. Whole-rock geochemistry
The samples used for whole-rock compositional analysis were first
cleaned with deionized, subsequently crushed and milled to 200 meshes.
Both major and trace elements were measured at the ALS Mineral
(Guangzhou) Co. Ltd. The major oxides were determined by the X-ray
fluorescence (XRF) spectrometer. The lithium borate fusion method was
used to detect them and the accuracy of the data is better than 5%. Trace
elements, including REEs, were measured with inductively coupled
plasma mass spectrometry (ICP-MS) and the accuracy and precision
were better than 5–10%.
4.2.2. Electron microprobe analysis of apatite and amphibole
Major element compositions of apatite and amphibole were
measured by electron microprobe (EMP) at the Center for Material
Research and Analysis, Wuhan University of Technology, with a JEOL
JXA-8100 Microprobe. The analysis was performed using an acceler­
ating voltage of 15 kV, 20 nA beam current, and beam diameter of 5 μm.
Counting times on the peak positions were 40 s for La, Ce, and S; 20 s for
P, As, V, Si, Ti, Al, Ca, Mg, Mn, Fe, and K; and 10 s for Na, Cl, and 5 s for
F. The standard materials used were fluorapatite for P and Ca, barite for
S, tugtupite for Cl, K-feldspar for K, rutile for Ti, olivine for Mg, synthetic
LaPO4 for La, synthetic CePO4 for Ce, rhodonite for Mn, and hematite for
Fe. Only apatite crystals oriented with their c-axis perpendicular to the
electron beam were selected for analysis to minimize halogen migration
and improve the analytical accuracy (Goldoff et al., 2012). F, Cl, and Ca
were measured first using relatively shorter analysis times on a peak/
background of 10/5 s, and the remain stable elements were analyzed
subsequently on a peak/background of 30/15 s (Pyle et al., 2002).
Durango and Madagascar apatite were analyzed as a secondary standard
during the apatite analysis, and the data agree well with the recom­
mended values and the precision was better than 5% for most of the
elements.

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R.-J. Zhou et al.
4.2.3. LA-ICP-MS trace element analysis of apatite
Trace elements in apatite were measured by laser ablation induc­
tively coupled-plasma mass spectrometry (LA-ICP-MS) in Wuhan Sam­
pleSolution Analytical Technology Co., Ltd., using an Agilent 7700e ICP-
MS instrument coupled to a laser-ablation system. Detailed operating
conditions for the laser ablation system and the ICP-MS instrument were
same as described by Zong et al. (2017). Each analysis incorporated a
background acquisition of approximately 20–30 s followed by 50 s of
data acquisition with a constant repetition rate of 10 Hz, 44 μm laser
beam aperture. Argon was used as the make-up gas and mix with helium
as the carrier gas to acquire ion-signal intensities. The external standards
include NIST SRM 610, NIST BCR-2G, BHVO-2G and BIR-1G. Element
concentrations were calibrated against multiple-reference materials
without applying internal standardization (Liu et al., 2008). Madagascar
and Durango apatite were analyzed as a secondary standard during the
apatite analysis, and the data agree well with the recommended values.
Data reduction was performed using the in-house software ICPMSDa­
taCal (Liu et al., 2008).
4.2.4. Zircon U-Pb isotope and trace element analysis
Zircon U-Pb isotopes and trace elements were simultaneously
analyzed at the State Key Laboratory of Geological Processes and Min­
eral Resources (GPMR), with an Agilent 7500a ICP-MS instrument. The
laser was operated at a constant repetition rate of 10 Hz with spot size of
32 μm beam. Each analysis included a background acquisition of
approximately 20 s followed by 60 s of data acquisition. The zircon
91500 and NIST SRM610 standards were used as the primary reference
materials, while standard GJ-1 and PLE were used for data quality
assessment. Zircon 91500 was used as primary reference materials to
correct instrumental mass discrimination and elemental fractionation
during the ablation. Zircon GJ-1 and PLE were used as quality control for
geochronology. Each block of eight samples were bracketed by analyses
of two zircon 91500. Calibration trace elements were achieved using
standard procedures that included use of NIST 610 glass reference ma­
terial for external standardization and the stoichiometric zircon SiO2
content for internal standardization. The time-drift correction and
quantitative calibration for U-Pb dates and trace element analyses were
conducted using in-house software ICPMSDataCal (Liu et al., 2010).
Concordia diagrams and weighted mean 206Pb/238U age calculation
were calculated using Isoplot.
Fig. 4. Geochemical characteristics of Yinzu pluton. (a) SiO2 vs. (K2O + Na2O) diagram (after Middlemost, 1994); (b) SiO2 vs. K2O diagram (after Rickwood, 1989).
Data sources of Yinzu quartz diorite and diorite are from Wang et al. (2004), Li et al. (2009), Li et al. (2013), Ding et al. (2017) and Li et al. (2021b).
6
LITHOS 432-433 (2022) 106898
4.2.5. Zircon Hf isotope analysis
In situ zircon Hf isotopic analyses were acquired with a Nu Plasma
HR MC-ICP-MS instrument coupled with an excimer laser ablation sys­
tem (GeoLas 2005) at GPMR. A stationary spot was used for analyses
with a beam diameter of 44 μm at 10 Hz repetition rate for 40 s and
performed on the same locations that were used for the U-Pb isotopic
analysis. Analyses were carried out using He as carrier gas to efficiently
transport aerosol to MC-ICP-MS. Zircon standard 91500 was used as an
external standard and the zircon GJ-1 was treated as quality control.
Every ten samples analyses were followed by two analyses of 91500. The
εHf(t) values were calculated by the chondritic values of 176Hf/177Hf and
176
Lu/177Hf. Off-line selection, integration of background, analyses
signals, interference, mass fractionation correction and external cali­
bration of Lu-Hf isotopic ratios were conducted using in-house software
ICPMSDataCal (Liu et al., 2010).
5. Results
5.1. Whole-rock geochemistry
Major and trace element compositions of the quartz diorite and
diorite are listed in Supplementary Table S1 and shown in Figs. 4, 5. The
quartz diorite has relatively homogenous SiO2 (63.05–63.91 wt%),
Na2O (3.92–3.98 wt%) and K2O (2.08–2.34 wt%) contents with A/CNK
values of 0.91–0.93 (Fig. 4a, b). These values are 53.67–57.56 wt%,
3.19–3.93 wt%, 2.58–3.22 wt% and 0.73–0.77 for the diorite (Fig. 4a,
b). In the SiO2-K2O diagram, both the quartz diorite and diorite plot in
the calc-alkaline to high-K calc-alkaline field (Fig. 4b). The quartz dio­
rite contains 73–81 ppm Rb, 698–739 ppm Sr, 16–19 ppm Y, 79–101
ppm V, whereas the diorite has 80–99 ppm Rb, 620–960 ppm Sr, 19–25
ppm Y, 142–229 ppm V. Both the quartz diorite and diorite are char­
acterized by enrichments in light rare earth elements (LREEs) and de­
pletions in heavy rare earth elements (HREEs), with (La/Yb)N ratios of
10–20 and no obvious Eu anomalies (Fig. 5h, i).
5.2. Zircon U-Pb isotopes and trace element compositions
Zircon U-Pb dating results for the quartz diorite and diorite are
provided in Supplementary Table S2. Zircon crystals are generally
prismatic, with diameter from 100 to 230 μm and aspect ratios ranging
from 1:1 to 3:1. Under CL imaging, zircon from the quartz diorite and
diorite commonly displays typical magmatic oscillatory zoning (Fig. 6a).
R.-J. Zhou et al. LITHOS 432-433 (2022) 106898

Fig. 5. The element compositions and ratios plot for the Yinzu pluton. a-f. Harker variation diagrams showing the major and trace element compositions of the Yinzu
pluton. (g) Sr/Y vs. SiO2 plot. h. (La/Yb)N vs. SiO2 plot. (i) Eu/Eu* vs. SiO2 plot (Data sources of Yinzu quartz diorite and diorite after Fig. 4).

Fig. 6. Representative CL images of zircon and the Concordia diagrams of LA-ICP-MS zircon U-Pb data for Yinzu quartz diorite (a) and diorite (b). Scale bar is
100 μm.

7
R.-J. Zhou et al.
The patchy or weakly zoned zircon grains are mostly found in the diorite
(Fig. 6b). Zircon from the quartz diorite contains variable U (103–359
ppm), Th (50–403 ppm) with Th/U ratios of 0.4–1.1. A total of 19 an­
alyses on 19 zircon grains from sample 18MDY02 yield concordant U-Pb
ages, with a weighted mean 206Pb/238U age of 148.4 ± 1.0 Ma (MSWD
= 0.54; n = 19) (Fig. 6a). Zircon grains from the diorite have 55–400
ppm U, 46–568 ppm Th with Th/U ratios of 0.6–1.4. A total of 18 zircon
grains from sample 18HLS02 yield concordant U-Pb ages, with a
weighted mean 206Pb/238U age of 146.6 ± 1.6 Ma (MSWD = 0.36; n =
18) (Fig. 6b).
Zircon trace element data with La > 1 ppm and Ti > 50 ppm are
likely affected by tiny LREE-rich mineral inclusions, Ti-(Fe-)oxides and
fluid inclusions (Lu et al., 2016; Zou et al., 2019), thus are discarded.
The rest data are listed in Supplementary Table S3. Zircon from the
quartz diorite and diorite is characterized by HREE enrichments and
LREE depletions, with strong positive Ce and negative Eu anomalies
(Fig. 7). Zircon from quartz diorite and diorite has total REE concen­
trations of 302–1254 ppm and 205–1770 ppm, respectively. The
calculated zircon Eu/Eu* ((Eu/Eu* = EuN/sqrt (SmN*GdN), where ‘N’
donates to chondrite-normalized value) values are 0.51–0.69 and
0.47–0.86 for the quartz diorite and diorite, respectively. Zircon from
the quartz diorite has Dy/Yb, (Ce/Nd)/Y and 10000*(Eu/Eu*)/Y ratios
of 0.12–0.22, 0.01–0.14 and 3.6–21.4, respectively (Fig. 8). For the
diorite, these ratios are 0.14–0.28, 0.004–0.058 and 2–27, respectively
(Fig. 8).
The Ti-in-zircon thermometer were calculated following the method
of Ferry and Watson (2007). The presence of magmatic quartz in all
samples indicates that the activity of SiO2 can be assumed to be 1 (Ferry
and Watson, 2007). The aTiO2 has been assumed to be 0.7 because
titanite occurs but rutile is absent in the samples (Ferry and Watson,
2007). The crystallization temperatures are calculated at 634–756 ◦ C
(mean = 679 ◦ C) and 715–820 ◦ C (mean = 784 ◦ C) for the quartz diorite
and diorite, respectively (Fig. 9a). Using the lattice-strain model
described in Ballard et al. (2002) and the whole-rock chemistry as the
approximate for melt compositions, zircon Ce4+/Ce3+ values are
calculated to range from 116 to 445 (mean = 305) and 16 to 150 (mean
= 74) for the quartz diorite and diorite, respectively (Fig. 9b).
5.3. Apatite textures and trace element compositions
Primary magmatic apatite grains are enhedral and commonly
enclosed within major silicate minerals (e.g., amphibole, biotite,
Fig. 7. Chondrite-normalized REE patterns of zircon and whole-rock from
Yinzu quartz diorite and diorite; Normalizing values are from McDonough and
Sun (1995). Data sources of fertile and barren magmas are from Lu
et al. (2016).
8
LITHOS 432-433 (2022) 106898
plagioclase) in the quartz diorite and diorite (Fig. 3b, e, f). Represen­
tative BSE and OP-CL images of apatite from the quartz diorite and
diorite are presented in Fig. 10. The apatite grains from quartz diorite
are mostly columnar crystals with aspect ratios ranging from 5:1 to 1:1
and size of 100–300 μm (Figs. 3b, 10a-c). They are homogenous under
BSE but are yellow-brown and show oscillatory zoning textures in OP-CL
images (Fig. 10a-c). Apatite from the diorite is prismatic and 50 to 150
μm in size with aspect ratio ranging from 6:1 to 2:1 (Figs. 3e, f; 10d-f).
The apatite crystals show homogenous texture in the BSE images and
green-yellow color and oscillatory zoning textures in OP-CL images
(Fig. 10d-f).
Major and trace element compositions of apatite from the quartz
diorite and diorite are listed in Supplementary Tables S4-S5. Apatite
from the quartz diorite has P2O5 contents of 40.39–42.75 wt%, CaO
contents of 54.9–56.2 wt%, MnO contents of 0.04–0.23 wt%, FeO con­
tents of 0–0.49 wt% and SO3 contents of 0.07–0.24 wt% (Fig. 11a). It
contains high F concentrations ranging from 2.63 to 3.82 wt% and Cl
contents ranging from 0.09 to 0.39 wt%. The P2O5 and CaO contents in
apatite grains from the diorite are 54.82–56.67 wt% and 40.40–42.70 wt
%, respectively. The SO3, Cl and F contents of apatite from the diorite are
in the range of 0.13–0.48 wt%, 0.06–0.28 wt%, and 1.92–3.15 wt%,
respectively (Fig. 11a). All the apatite grains from the quartz diorite and
diorite are fluorapatite (Fig. 11b).
Apatite in both the quartz diorite and diorite shows moderate LREE
enrichment and HREE depletion, with weakly positive Ce and negative
Eu anomalies (Fig. 12a). Apatite from the quartz diorite contains vari­
able Sr (279–701 ppm), Y (137–505 ppm), La (423–985 ppm), Ce
(941–2038 ppm), Yb (9–33 ppm) and total REE concentrations
(2148–4882 ppm), with Eu/Eu* and Ce/Ce* ((Ce/Ce* = CeN/sqrt
(LaN*PrN), where ‘N’ donates to chondrite-normalized value) values of
0.35–0.67 and 0.97–1.12, respectively. It has Sr/Y and La/Yb ratios of
0.61–2.4 and 12.59–49.45, respectively (Fig. 12b). Apatite from the
diorite has Sr, Y, La, Ce, Yb and total REE concentrations of 309–789
ppm, 136–968 ppm, 300–1859 ppm, 551–3319 ppm, 11–64 ppm and
1256–7915 ppm, respectively, with Eu/Eu*, Ce/Ce*, Sr/Y and La/Yb
ratios of 0.38–0.74, 0.92–1.28, 0.38–3.01 and 10.03–43.30, respectively
(Fig. 12b).
5.4. Amphibole compositions
Major and trace element compositions of amphibole from the quartz
diorite and diorite are listed in Supplementary Table S6. Based on the
classification of Leake et al. (1997), amphiboles from both the quartz
diorite and diorite are calcic amphibole with (Ca + Na)B (on the occu­
pancy of the B sites) > 1.8, NaB < 0.3, and CaB > 1.7. These calcic
amphiboles can be further classified as Mg-amphibole (Fig. 13a). Am­
phiboles from the quartz diorite have SiO2 contents of 44.36–51.63 wt%,
Al2O3 contents of 4.29–9.69 wt%, MgO contents of 10.76–14.89 wt%,
CaO contents of 11.05–12.20 wt%, FeOtot contents of 12.44–16.81 wt%
and Cl contents of 0.02–0.10 wt% (Supplementary Table S6). The SiO2
and Al2O3 contents of amphiboles from the diorite exhibit relatively
large variation ranging from 42.79 to 53.06 wt% and 2.84 to 10.41 wt%,
respectively. The MgO and FeOtot contents of amphiboles from the
diorite are in the range of 11.56–15.62 wt% and 12.04–15.29 wt%,
respectively. They have a wide range of Cl concentrations (0.01–0.14 wt
%). The Excel spreadsheets (Ridolfi et al., 2010; Ridolfi and Renzulli,
2012) were used to calculate the amphibole chemical formula and es­
timate the magma crystallization temperatures and water content. The
crystallization temperatures range between 700–850 ◦ C and 750–900 ◦ C
for the quartz diorite and diorite, respectively (Fig. 13b). The calculated
water content ranges from 4.78 to 6.09 wt% (mean = 5.62 wt%) for the
quartz diorite and from 4.30 to 5.94 wt% (mean = 4.87 wt%) for the
diorite (Fig. 13b).
R.-J. Zhou et al. LITHOS 432-433 (2022) 106898

Fig. 8. (a) Zircon Dy/Yb vs. Eu/Eu* plot. Zircons from Yinzu quartz diorite and diorite have similar Dy/Yb and Eu/Eu* ratios with the fertile magmas; (b) Zircon
(Ce/Nd)/Y vs 10000*(Eu/Eu*)/Y plots. Yinzu quartz diorite has much higher zircon 10000*(Eu/Eu*)/Y ratios (>1) and (Ce/Nd)/Y ratios (>0.01) than the barren
magmas. Data of fertile and barren magmas are from Lu et al. (2016); Data sources of Tongshankou and Tonglushan are from Wen et al., 2020.

Fig. 9. (a) Calculated zircon ΔFMQ vs. temperature; (b) Zircon Ce/Ce* vs. Ce4+/Ce3+ (Data sources of Tongshankou and Tonglushan are from Wen et al. (2020)).

5.5. Zircon Hf isotopes
The Hf isotopic compositions of zircon from the quartz diorite and
diorite are listed in Supplementary Table S7. The εHf(t) values were
calculated using the zircon U-Pb ages determined in this study. The
(176Hf/177Hf)t and εHf(t) of zircon from the quartz diorite are 0.282454
to 0.282551 and − 8.1 to − 4.8 (Fig. 14a), respectively, corresponding to
two-stage model ages of 0.994 to 1.111 Ga, and 1.327 to 1.514 Ga,
respectively. Zircon from the diorite has (176Hf/177Hf)t and εHf(t) values
of 0.282427 to 0.282534 and − 9.1 to − 5.4 (Fig. 14a), respectively,
corresponding to two-stage model ages of 1.002 to 1.150 Ga, and 1.358
to 1.567 Ga, respectively.
6. Discussion
6.1. Petrogenesis of the Yinzu pluton
Zircon Hf isotopes have been used as a powerful tracer for magma
source (Wu et al., 2007). The εHf(t) values of the zircon from the Yinzu
quartz diorite and diorite are relatively homogeneous ranging between
− 8.1 to − 4.8 (mean = − 6.5) and − 9.1 to − 5.4 (mean = − 7.3),
respectively (Supplementary Table S7; Fig. 14a). These values are
broadly comparable to the contemporary basaltic andesite and gabbro in
the Daye district (εHf(t) values of − 13.7 to − 5.8; Fig. 14a), which have
been interpreted to have derived from an enriched lithospheric mantle
source (Hou and Yuan, 2010; Xie et al., 2011b). Rocks of the Yinzu
pluton are also similar in zircon Hf isotopes to those of the Cu-fertile
granodiorite porphyry at Tongshankou (εHf(t)(144Ma) = − 9.9 to − 1.4
with a mean of − 5.1) and quartz diorite at Tonglushan (εHf(t)(138.8Ma) =
− 14.4 to − 7.7 with a mean of − 9.6) in the Daye district (Fig. 14a). In
addition, the Yinzu quartz diorite has εNd(t) and (87Sr/86Sr)i values of
− 8.3 to − 5.9 and 0.7063 to 0.7074, respectively (Ding et al., 2017; Li
et al., 2009; Li et al., 2013), which resemble those of the Cu-fertile
Tongshankou granodiorite and Tonglushan quartz diorite, as well as
those of the contemporaneous basaltic andesite and mafic dike in the
Daye district and adjacent areas in the eastern Yangtze craton (Fig. 14b).
Taken together, the Yinzu pluton likely shares a common magma source
to the Cu-fertile granitoids in Daye district and the coeval basaltic and
gabbroic rocks over the eastern Yangtze craton.
Andesitic to dacitic magmas represented by the Yinzu diorite and
quartz diorite cannot be directly generated by partial melting of an
enrichened lithospheric mantle source (Green, 1973). Selected Harker
plots indicate that fractional crystallization could have been an impor­
tant process in the formation of the Yinzu pluton, with removal of Mg-,
Fe-, Ca-, Ti- and V-rich phases such as olivine, amphibole, titanite and
magnetite (Fig. 5a-f). Previous geochemical modeling suggests that the
Yinzu diorite has experienced 35% fractional crystallization of olivine
from basaltic melts derived from an enrichened mantle source (Li et al.,

9
R.-J. Zhou et al. LITHOS 432-433 (2022) 106898

Fig. 10. Representative BSE and optical microscopic CL (OP-CL) images of apatite grains from Yinzu quartz diorite (a-c) and diorite (d-f). (a) BSE image of prismatic
apatite hosted in amphibole. (b) Euhedral apatite displaying zoning textures under OP-CL. (c) Prismatic apatite showing oscillatory zoning with yellow-brown
luminescence. (d) Euhedral apatite hosted in amphibole is homogeneous under BSE. (e) BSE image showing zoning texture of apatite. (f) Prismatic apatite
showing green-luminescent and oscillatory zoning texture. (For interpretation of the references to color in this figure legend, the reader is referred to the web version
of this article.)

Fig. 11. Apatite SO3 vs. Cl diagram (a) and F-Cl-OH (b) plot. Apatite F-Cl-OH chemical formula is calculated using the method in Ketcham (2015).

2009). This view is consistent with relatively low Mg# ratios, Cr and Ni
contents in the Yinzu diorite (Supplementary Table S1). The Yinzu
quartz diorite has geochemical features comparable with Cu-fertile
granitoids at Tongshankou and Tonglushan such as LREE enrichments
and HREE depletions, lack of obvious Eu anomalies, and high Sr/Y and
La/Yb ratios, features akin to adakites (Figs. 4, 5, 7; Li et al., 2009). In
Harker diagrams, the linear or sub-linear trends of P2O5, TiO2, TFeO,
MgO, CaO and V with increasing SiO2 demonstrate that Yinzu quartz
diorite was likely formed via fractional crystallization of magmas rep­
resented by the Yinzu diorite (Fig. 5a-f). The correlations between P2O5,
TiO2, TFeO, MgO, CaO and V and SiO2 indicate that the quartz dioritic
magma may have experienced fractional crystallization of amphibole,
titanite, magnetite and apatite (Fig. 5a-f). In addition, the Yinzu quartz
diorite defines trends of increasing Sr/Y and La/Yb ratios and roughly
constant Eu/Eu* ratios with increasing SiO2 content (Fig. 5g-i), indi­
cating significant amphibole fractionation but limited plagioclase
differentiation.
6.2. Magmatic redox state
Cu-fertile magma is typically characterized by high magmatic
oxidation state (Ballard et al., 2002; Richards, 2015; Richards and
Kerrich, 2007; Wang et al., 2014). Under oxidized conditions, sulfate
would have been the dominant sulfur species (Field et al., 2005; Rye,
2005), thereby significant sulfide separation would be less likely and Cu
can be largely retained in the evolved melt, favoring subsequent
porphyry-skarn Cu mineralization (Carroll and Rutherford, 1985;
Richards, 2015).
Zircon is a sensitive indicator for magmatic oxidation state (Ballard
et al., 2002; Burnham and Berry, 2012; Trail et al., 2012). Compared
with other trivalent REE cations and Ce3+, Ce4+ is preferentially parti­
tioned into zircon because it has identical charge and similar ionic size

10
R.-J. Zhou et al. LITHOS 432-433 (2022) 106898

Fig. 12. Chondrite-normalized rare earth element patterns of the apatite and whole-rocks (a) and apatite Sr/Y vs. Eu/Eu* plot (b) for Yinzu quartz diorite and diorite.
Normalizing values are from McDonough and Sun (1995). Data sources of the fertile magmas are collected from Pan et al. (2016), Xie et al. (2018), Nathwani et al.
(2020), Cao et al. (2021), and Zhou et al. (2022).

Fig. 13. (a) Classification of amphiboles according to nomenclatures of Leake et al. (1997); (b) H2O content vs. temperature diagram of amphiboles.

to Zr4+. Consequently, zircons crystalizing from oxidized magmas
generally have high Ce4+/Ce3+ ratios (Ballard et al., 2002; Shu et al.,
2019; Wen et al., 2020). The Ce anomalies are traditionally calculated
using the equation Ce/Ce* = CeN/sqrt(LaN*PrN), however, it is difficult
to obtain reliable zircon Ce/Ce* values due to the very low La and/or Pr
concentrations in zircons (Ballard et al., 2002; Lu et al., 2016; Zhong
et al., 2019). Alternatively, we calculate zircon Ce anomalies using the
method of Zhong et al. (2019) based on reliable MREEs and HREEs data.
Zircon Ce4+/Ce3+ ratios were calculated using the method of Ballard
et al. (2002). The calculated zircon Ce anomalies and Ce4+/Ce3+ ratios
for the Yinzu quartz diorite are 781–3683 (mean = 2060) and 116–445
(mean = 305), respectively. These values resemble those of the Cu-
fertile Tongshankou granodiorite and Tonglushan quartz diorite in the
Daye district (Fig. 9b). Zircon from the Yinzu diorite has calculated Ce
anomalies and Ce4+/Ce3+ ratios of 27–696 (mean = 372) and 16–149
(mean = 74), respectively. Recently, Loucks et al. (2020) proposed a
new method to calculate magmatic oxidation state via zircon chemistry,
which is based on the equation:
log ƒO2 (sample)–log ƒO2(FMQ) = 3.998 ( ± 0.124) × log [Ce/sqrt (Ui × Ti) ]
+ 2.284 ( ± 0.101)
Where the Ce, Ti, and Ui are the contents of Ce Ti and initial U in
zircon. Using this method, the calculated ƒO2 values are ΔFMQ = +1.2
to +2.3 (mean = + 1.8) for the Yinzu quartz diorite, similar to the Cu-
fertile Tongshankou granodiorite and Tonglushan quartz diorite in the
Daye district (Fig. 9a) and Cu-fertile granitoids globally (with ƒO2 close
to ΔFMQ = +1 to +2; Richards, 2015). The Yinzu diorite have

11
R.-J. Zhou et al. LITHOS 432-433 (2022) 106898

Fig. 14. (a) Box plot for zircon εHf(t) of the intrusive rocks in Daye district. For comparison, the 127–137 Ma basaltic andesites, gabbros and pyroxene diorites in
Daye are also shown. (b) Whole rock initial 87Sr/86Sr versus εNd(t) plot. Data sources for the zircon Hf isotopes are from Li et al. (2008); Xie et al. (2011a); Li et al.
(2013) and Wen et al. (2020). Data source of mafic rocks from Xie et al. (2011a); Chu et al. (2020); Zhang et al. (2021). Date sources for the whole-rocks Sr-Nd
isotopes are from Li et al. (2009, and references therein), Xie et al. (2015, and references therein) and Ding et al. (2017).

calculated fO2 values of ΔFMQ = +0.2 to +1.4 (mean = 0.6) slightly 76.8–264.8 ppm and 89.4–298.9 ppm, respectively (Table 1). However,
lower than the quartz diorite (Fig. 9a). Collectively, zircon compositions the estimated magma sulfur contents based on the equation of Parat
indicate that the Yinzu pluton are relatively oxidized with ƒO2 values et al. (2011) are generally lower (Table 1). The reason for this discrep­
comparable with Cu-fertile intrusions in the Daye district and elsewhere ancy is not quite clear. Nevertheless, the calculated melt S contents using
(Richards, 2015). both methods are broadly comparable to the Cu-fertile granitoids in
Daye district (15–354 ppm S; Zhou et al., 2022) and Cu porphyries in the
Tethyan metallogenic belt (8–510 ppm S; Xu et al., 2021; Cao et al.,
6.3. Magmatic volatile contents (S, Cl and H2O)
2022b).
Using the method of Piccoli and Candela (1994), the Yinzu quartz
Volatiles such as S, Cl and H2O in magmas are fundamental for the
diorite and diorite have apatite saturation temperatures of 882 to 936 ◦ C
generation of porphyry-skarn Cu-(Au) deposits (Lu et al., 2016;
(Table 1), similar to the temperature for the experiments of Webster
Richards, 2011; Richards and Kerrich, 2007). Sulfur and Cl can facilitate
et al. (2009). Thus, we calculate melt Cl concentrations using the
hydrothermal mobilization and concentration of ore metals due to their
apatite-melt Cl partition coefficients experimentally determined by
capacity to form ligands with these metals (Cao et al., 2022b; Chelle-
Webster et al. (2009) at 200 MPa and 900 ◦ C. The calculated melt Cl
Michou and Chiaradia, 2017; Richards and Kerrich, 2007). Magma with
concentrations for the Yinzu quartz diorite and diorite are 870–3850
high H2O contents tend to exsolve hydrothermal fluids to a larger degree
ppm and 610–4790 ppm, respectively, comparable to Cu-fertile granit­
and at relatively early stage of magma solidification in the upper crust
oids in the Daye district (430–5990 ppm; Zhou et al., 2022) as well as
(Burnham, 1979; Richards, 2011), so that the metals in the magma can
that of the arc basalts (100 to 4100 ppm; Wallace, 2005).
be sufficiently extracted by its exsolved fluids.
Magmas associated with porphyry-skarn Cu deposits commonly have
Apatite incorporates significant amounts of S and Cl and can be used
high water content (>4 wt% H2O; Richards, 2011; Richards et al., 2012;
to investigate S and Cl budget of the melt from which it crystalized.
Loucks, 2014). Estimated magmatic water contents based on amphibole
Under oxidized conditions, sulfur in the magmas occurs mainly as S6+,
chemistry for the Yinzu quartz diorite and diorite are 4.78–6.09 wt%
allowing S to be incorporated into apatite as SO2− 4 (Konecke et al.,
and 4.29–5.94 wt%, respectively (Fig. 13b). The hydrous characteristic
2017). The Yinzu quartz diorite and diorite crystalized from the oxidized
of magmas can suppress early plagioclase crystallization and increase
melts (see above), which have zircon ΔFMQ = +1.2 to +2.3 and +0.2 to
amphibole crystallization (Davidson et al., 2007; Loucks, 2014).
+1.4. Thus, SO3 contents of apatite can be used as proxy for sulfur
Compared to the heavy REEs, amphibole preferentially incorporates
contents of magma forming the Yinzu quartz diorite and diorite (Parat
middle REEs (Davidson et al., 2007) and thus amphibole fractionation
et al., 2011; Peng et al., 1997). Using method from Peng et al. (1997),
would decrease Dy/Yb ratios and deplete Y for the residual melt. In
the quartz diorite and diorite have calculated melt S concentrations of

Table 1
Apatite Cl and S compositions and the calculated melt Cl and S contents for the Yinzu quartz diorite and diorite.
Sample Apatite Cl (wt%) Apatite S (ppm) AST(◦ C)1 Cl in melts (ppm) 2 S in melts (ppm) 3 S in melts (ppm) 4
(average) [median] (average) [median] (average) [median] (average) [median] (average) [median]

quartz diorite 0.087–0.385 276–953 870–3850 76.8–264.8 11.8–34.7

934
(n = 28) (0.208) [0.182] (540) [485] (2075) [1815] (149.2) [134.6] (18.8) [16.5]
diorite 0.061–0.479 500–1674 610–4790 89.4–298.9 16.9–109.3
893
(n = 17) (0.169) [0.145] (1021) [997] (1687) [1450] (182.4) [178.1] (44.9) [37.2]
1
. Apatite saturation temperature (AST) calculated from whole-rock SiO2 and P2O5 concentrations using the equation of Piccoli and Candela (1994).
2
. Melt Cl is calculated based on Dapatite/melt
Cl = 1 from Webster et al. (2009), where Dapatite/melt
Cl is apatite-melt partition coefficients for Cl.
3
. Estimated from apatite SO3 contents using the apatite-melt partition coefficient formula of Peng et al. (1997).
4
. Estimated from apatite SO3 contents using the equation: SO3 apatite (wt%) = 0.157 × ln SO3 glass (wt%) + 0.9834 from Parat et al. (2011) based on nature and
experimental apatite/melt partitioning data.

12
R.-J. Zhou et al.
addition, plagioclase preferentially incorporates Eu relative to other
REEs and diminish of plagioclase crystallization would minimize nega­
tive Eu anomalies for the melt (Chiaradia et al., 2012; Richards and
Kerrich, 2007). The combined effects of reducing plagioclase crystalli­
zation and enhancing amphibole production would result in high
magma (Eu/Eu*)/Y ratios. Therefore, Dy/Yb ratios, Eu anomalies and
(Eu/Eu*)/Y ratios of melt and those melt-equilibrated zircons can be
used as proxies for magmatic hydration state (Lu et al., 2016). Previous
studies showed that zircons from the Cu fertile magmas commonly have
high Eu/Eu* (>0.4) and low Dy/Yb ratios (<0.3), whereas zircon from
the barren magmas commonly have low Eu/Eu* (<0.3) and high Dy/Yb
ratios (>0.3; Ballard et al., 2002; Lu et al., 2016; Cao et al., 2022a).
Zircons from both the quartz diorite and diorite have low Dy/Yb
(0.12–0.28) ratios, weakly negative Eu anomalies (Eu/Eu* =
0.47–0.86), and high 10000*(Eu/Eu*)/Y ratios (2–27), which are
comparable with zircons from Cu-fertile granitoids in the Daye district
and fertile porphyries in the world (Fig. 8a). Lu et al. (2016) suggested
that zircon (Ce/Nd)/Y ratio may also be a potential proxy for the hy­
dration state of melt. In the zircon (Ce/Nd)/Y versus 10000*(Eu/Eu*)/Y
diagram, zircons from the Yinzu quartz diorite and diorite overlap with
those from fertile magmas and are distinct with barren magmas in the
world (Fig. 8b).
Apatite from the Yinzu intermediate rocks displays Sr/Y ratios of
0.38 to 3.01 and Eu/Eu* values of 0.35–0.71 (Fig. 12b), comparable to
those of the Cu-fertile granitoids (e.g., Tongshankou, Ruanjiawan and
Tonglushan) in Daye district (Fig. 12b) as well as those from fertile
magmas in the Sanjiang metallogenic belt in southwestern China,
Xiongcun district in southern Tibet and Baguio district of the Philippines
(Fig. 12b). The high apatite Sr/Y and Eu/Eu* ratios are indicative of
high ratios of amphibole fractionation for the magma (Nathwani et al.,
2020), which suggests high water content of the melt. The high hydra­
tion state of the Yinzu pluton is consistent with the high whole-rock Sr/Y
and Eu/Eu* ratios as discussed above (Fig. 5h, i). The amphibole, zircon,
apatite and whole-rock geochemistry indicate that the Yinzu pluton is
hydrous, comparable with the Cu-fertile intrusions in the Daye district
and those in the world.
6.4. Metal fertility of the Yinzu pluton and implications for exploration
Whole-rock geochemical and Sr-Nd-Hf isotope data from this study
and previous investigations indicate that the Yinzu quartz diorite likely
resulted from fractional crystallization of parental magmas represented
by the Yinzu diorite which were in turn generated by partial melting of
an enriched lithospheric mantle source, followed with significant
olivine, amphibole, apatite fractionation at mantle depth (Li et al.,
2009). The Yinzu quartz diorite has a common magma source and
similarly high H2O, S and Cl contents and oxidation state to Cu-fertile
granitoids in Daye and elsewhere, which suggests that the Yinzu
quartz diorite may have high fertility in generating porphyry-skarn Cu
deposits. To date, however, no economically significant Cu deposits
have been found in the contact zone between the Yinzu pluton and its
wall rock. One possible reason is that the wall rock surrounding the
Yinzu pluton is dominated by the quartz sandstone/shale rather than
carbonate (Fig. 2), making unlikely to form extensive skarn Cu miner­
alization. Alternatively, the lack of economically significant Cu miner­
alization may reflect post-ore erosion of shallow-seated Cu deposits. This
consideration is partly evidenced by the predominance of Silurian strata
around the Yinzu pluton, in contrast to the existing Cu-mineralized
major plutons that intrude extensive Triassic carbonates strati­
graphically above the Silurian strata (Figs. 1, 2). Nevertheless, potential
Cu skarn mineralization may present at depth where the pluton is in
contact with carbonate rocks, which are abundant (over 1000 m thick)
in the Cambrian-Ordovician strata underling the Silurian sediments (Shu
et al., 1992).
Recent exploration has discovered several sediment-hosted Au de­
posits on the periphery of the Yinzu pluton, such as the Xujiashan ore
13
LITHOS 432-433 (2022) 106898
field consisting of four Au deposits (Zhanghai, Xishan, Meirenjian and
Chenjiazhai) within 1.5 km to the southeast margin of Yinzu pluton
(Fig. 2b). The ore field is hosted by carbonaceous shale of Late Silurian
Gaojiabian group and fine-grained quartz sandstones of the Middle
Silurian strata (Fig. 2b). The Au deposits are mainly controlled by NW-
striking fault. The main Au-bearing mineral is pyrite, and wall-rock
alteration consists of silicification, sericitization, carbonation, chloriti­
zation and kaolinization. Gold mineralization is closely related to silic­
ification, and a positive correlation between the intensity of Au
mineralization and silicification is observed (Yang et al., 2003). Located
to southeast of the Daye district, the Fengshandong ore field in the Jiurui
district of MLYMB contains both Cu-Au skarn deposits and sediment-
hosted Au deposits. Based on geological, mineralogical, chronological
and sulfur isotopic investigations, Xie et al. (2019) suggested that the
Cu-Au skarn deposits and sediment-hosted Au deposits are genetically
linked and represent the proximal and distal products of a magmatic-
hydrothermal system. Although the age of the sediment-hosted Au de­
posits to the south Yinzu pluton has not been well constrained yet, they
show mineral assemblages and alteration patterns similar to those
carbonate-hosted Au deposits in the Fengshandong ore field (Yang et al.,
2003; Xie et al., 2019). Thus, the Au deposits hosted in the Silurian shale
are probably the distal products of the Yinzu magmatic-hydrothermal
system.
Collectively, based on the regional metallogeny and the geochemical
data discussed above, we suggest that Yinzu pluton has high Cu-(Au)
fertility and is a promising target of future Cu-(Au) exploration. Possible
targets may include skarn Cu-(Au) mineralization in the contact zone of
pluton and carbonate rocks of the Ordovician at depth and sediment-
hosted Au deposits in the periphery area of this pluton.
7. Conclusions
The Yinzu intermediate rocks have zircon εHf(t) values identical to
those of Cu-fertile intrusions in the Daye district and were likely sourced
from the enriched lithospheric mantle. The whole-rocks geochemistry
data demonstrate that Yinzu diorite and quartz diorite has experienced
variable degrees of fractional crystallization of olivine, amphibole,
titanite, apatite and magnetite. Based on zircon and apatite geochem­
istry, the estimated magmatic oxidation state, melt Cl and S contents of
the Yinzu intermediate rocks are similar to Cu-fertile magmas world­
wide. The apatite Sr/Y (0.38–3.01) and Eu/Eu ratios (0.35–0.71) com­
bined with zircon Dy/Yb ratios (0.1–0.28), 10000*(Eu/Eu*)/Y (2–27)
and Eu/Eu* values (0.5–0.86) from the Yinzu intermediate rocks indi­
cate significant amphibole and limited plagioclase fractionation, sug­
gesting high hydration state of the magma. The Yinzu pluton is akin to
Cu-fertile granitoids worldwide regrading oxidation state and volatile
concentrations, indicating high Cu-(Au) fertility for the Yinzu pluton.
Based on the regional metallogeny and results of this study, we propose
that the Yinzu pluton is a promising target of future Cu-(Au) exploration,
with potential skarn Cu-(Au) mineralization in the contact zone at depth
and sediment-hosted Au deposits in the periphery area of this pluton.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.lithos.2022.106898.
Declaration of Competing Interest
The authors declare that they have no known competing interests or
personal relationships that could have appeared to influence the work
reported in this manuscript.
Acknowledgements
This study was financially supported by National Natural Science
Foundation of China (42172101) and Hubei Geological Bureau (grants
KJ2019-5, KJ2021-9). We thank Dong-Qin Liu, Guo-Fei Yu, and Ying-
Kun Qi for their help during the field work, and Xiao-Lei Nie and Mei-
R.-J. Zhou et al.
Jun Yang for assistance with electron microprobe analyses, and Shi-
Guang Du and Liang Pan for assistance with the LA-ICP-MS minerals
analyses. The manuscript benefited from reviews by two anonymous
reviewers, which are gratefully appreciated. Our thanks extend to Prof.
Di-Cheng Zhu for handling the manuscript. This is contribution 66 from
CUG Center for Research in Economic Geology and Exploration Tar­
geting (CREGET).
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