Ore Geology Reviews 143 (2022) 104764

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Ore Geology Reviews

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Origin and evolution of W mineralization in the Tongshanling

Cu–polymetallic ore field, South China: Constraints from scheelite
microstructure, geochemistry, and Nd–O isotope evidence
Biao Liu, Hua Kong *, Qian-Hong Wu, She-Fa Chen, Huan Li, Xiao-Shuang Xi, Jing-Hua Wu,
Hua Jiang
Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitoring, Ministry of Education, School of Geosciences and Info-Physics,
Central South University, Changsha 410083, China

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

Keywords: Multistage, skarn-type W mineralization has recently been discovered in the Tongshanling Cu–polymetallic ore
Scheelite field, South China. This contribution reports new results from cathodoluminescence, trace element, and Nd–O
REE pattern isotopic analyses of scheelite samples from Tongshanling, designed to better constrain the W mineralization
Nd–O isotope
process and origin of associated metals and metallogenic fluids. Three generations of scheelite were identified
I-type granodiorite
that can be attributed to three paragenetic phases: (i) an early prograde skarn stage dominated by massive garnet
South China
and diopside intergrown with fine-grained scheelite, (ii) an intermediate retrograde skarn stage characterized by
an assemblage of abundant scheelite, medium-grained chlorite and epidote, and (iii) a late sulfide-quartz vein
stage typified by coarse-grained, subhedral scheelite grains that are typically intergrown with chalcopyrite,
sphalerite, and galena. Our data show that although WO3 and CaO concentrations are similar in scheelite of all
∑
three stages and rare earth element (REE) patterns vary, the REE + Y values of scheelite markedly and pro­
gressively decrease from the prograde skarn (mean = 901 ppm) to retrograde skarn (70.1 ppm) to the sulfide-
quartz vein (34.1 ppm) stages. This signature is consistent with either of the following scenarios: The copreci­
pitation of REE-enriched minerals (e.g., garnet and scheelite), a change in fluid oxygen fugacity change and/or
minor distortions in crystal texture. The δ18OH2O values of fluids linked to the prograde skarn and sulfide-quartz
vein stages (5.02‰–6.19‰) are consistent with a magmatic fluid input. The δ18OH2O values of fluids associated
with the retrograde skarn stage (2.85‰–3.45‰), on the other hand, are indicative of fluid mixing, possibly
reflecting dilution of magmatic fluids by meteoric waters. Interestingly, scheelite samples of the sulfide-quartz
vein stage returned low εNd(t) values (− 7.46 to − 7.07) and moderate two-stage Nd model ages (T2DM =
1526 –1557 Ma) that are identical to the whole rock Nd isotope composition of an adjacent Jurassic I-type
granodiorite porphyry pluton. Overall, the results of our study indicate a close genetic relationship between this
pluton and the W mineralization, a scenario that is at odds with the common association between I-type
granodiorites and Cu–Pb–Zn mineralization in South China.

1. Introduction
The Nanling Range, located in central South China, hosts to a number
of giant W-Sn deposits and several large Cu–Pb–Zn deposits (e.g.,
Shuikoushan, Baoshan and Tongshanling deposits), whose genesis can
be linked to magmatic hydrothermal mineralizing systems (Fig. 1a, b;
Chen et al., 2013; Li et al., 2013; Mao et al., 2013; Huang et al., 2017; Liu
et al., 2019b). Whilst W–Sn mineralization is associated with highly
evolved S-type or A-type granites that have low oxygen fugacity and flat
REE patterns (Chen et al., 2013), Cu–Pb–Zn mineralization is typically
linked to I-type granodiorites that are characterized by high oxygen
fugacity and LREE-enriched REE patterns (Li et al., 2013; Huang et al.,
2017; Huang et al., 2018). Recently, W mineralization has been identi­
fied in skarn-type Cu–Pb–Zn deposits where scheelite is intergrown with
chalcopyrite, sphalerite, and galena (Li et al., 2017; Mao et al., 2020; Nie
et al., 2020). However, the genesis and source of W mineralization in

* Corresponding author.
E-mail address: konghua@csu.edu.cn (H. Kong).

https://doi.org/10.1016/j.oregeorev.2022.104764
Received 5 August 2021; Received in revised form 30 January 2022; Accepted 8 February 2022
Available online 10 February 2022
0169-1368/© 2022 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
B. Liu et al.
many Cu–Pb–Zn mineralization systems are rarely involved in the
Nanling Range, which limits the study and exploration of the W in
Cu–Pb–Zn coupled mechanism and in those deposits of South China,
respectively.
Scheelite is a common mineral in magmatic-hydrothermal systems
worldwide, including porphyry-, skarn-, and greisen-type W–Sn deposits
(Bau and Moeller, 1992; Ghaderi et al., 1999; Brugger et al., 2008;
Poulin et al., 2018). Given the presence of the cations Ca2+ and W6+,
certain trace elements (e.g., REEs, Sr), where present in ore-forming
fluids, can enter the scheelite crystal lattice via a process known as
isomorphic substitution (Ghaderi et al., 1999; Poulin et al., 2016). The
redox environment change can be discriminated by the valence state of
variable elements (e.g., Mo, Eu and Ce) (Brugger et al., 2008; Song et al.,
2014; Xu et al., 2019). Although the REE patterns of scheelite in skarn
ores vary according to whether the scheelite precipitated early or later,
it is the various skarn minerals that typically govern the REE budget
(Ding et al., 2018; Liu et al., 2019a). Nevertheless, REE patterns of
scheelite in skarn ores can be useful for evaluating and fingerprinting
fluid evolution processes (Poulin et al., 2016; Poulin et al., 2018;
Brugger et al., 2000). Furthermore, because of its stable Sm–Nd and O
isotopic compositions, scheelite lends itself to the direct identification of
mineralization episodes and tracing of possible sources of ore-forming
fluids and ore components (Ghaderi et al., 1999; Brugger et al., 2002,
2008; Sun and Chen, 2017; Poulin et al., 2018).
In this study, scheelite grains from the early prograde skarn, inter­
mediate retrograde skarn, and late sulfide-quartz vein stages of the
Tongshanling Cu-polymetallic ore field were examined by using cath­
odoluminescence (CL) imaging, electron probe micro-analysis (EPMA),
laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-
MS), and Nd–O isotope compositional analyses to compare the internal
textures and compositional variations of different generations of
scheelite recorded at Tongshanling. Major and trace element composi­
tional analyses of garnets from the various paragenetic stages were used
Fig. 1. (a) A sketch map of plate tectonics in China. CAB: Cathaysian Block; NCB: North China Block; SCB: South China Block; TB: Tarim Block; YZB: Yangtze Block;
(b) simplified geological map of the Nanling Range, South China, showing the distribution of major W–Sn and W–Sn–Cu–Pb–Zn polymetallic deposits (modified from
Mao et al., 2007).
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Ore Geology Reviews 143 (2022) 104764
to correlate changes in REE patterns with fluid Eu anomalies, and to
identify ore-forming fluid sources. Overall, the results of this study
helped to better (i) constrain the W mineralization process and genesis
of the Cu–Pb–Zn mineralization systems, and (ii) document the genetic
relationships between multistage W mineralization and causative
granodiorite porphyry plutons.
2. Geological setting
The Tongshanling Cu-polymetallic ore field is located in the central
Nanling Range, an important element of the Nanling metallogenic belt
(Fig. 1). The central part of the ore field is occupied by a granodiorite
porphyry pluton that is exposed over an area of ~15 km2 and elongated
in a generally E-W direction (Fig. 2). Exposed sedimentary rocks are
dominated by Devonian, Carboniferous, Permian, and Jurassic strata.
The Devonian, Carboniferous, Permian strata are neritic sedimentary
rocks (e.g., limestone, dolomitic limestone, argillaceous limestone),
including Xikuangshan, Shentianqiao, Qiziqiao, etc. The Jurassic strata
are terrestrial sedimentary rocks and consists of conglomerate, sand­
stone and arenaceous shale. The wall rocks of the granodiorite porphyry
pluton consist of Upper Devonian and Lower Carboniferous limestones
with a marble and skarn alteration zone that ranges in width from 200 to
1000 m. The Jurassic strata (120–140 m thick) consists of continental
siltstone, sandstone, conglomerate, and arenaceous shale. Permian and
Jurassic clastic rocks, whilst present in the ore field, have not been
recorded near the granodiorite porphyry pluton and are nowhere hy­
drothermally altered (Fig. 2). Faults in the ore field can be subdivided
into two groups: NEN-SWS- and WNW-ESE-striking faults. The latter
postdate and cut the NEN-SWS-striking faults and are often filled by
felsic dykes (Quan et al., 2013). The Tongshanling Cu-polymetallic ore
field has a total combined Cu, Pb, and Zn reserve of 2.5 × 106 tons (Ding
et al., 2015). Widespread W mineralization has been identified in
numerous mining tunnels using a UV lamp, but the W reserves have not
B. Liu et al.
Fig. 2. Geological map of the Tongshanling Cu-polymetallic ore field (modified from Zhao et al., 2016).
been established.
The Cu–W–Pb–Zn mineralization at Tongshanling, which takes the
form of skarn- and sulfide-quartz vein-types ores, was primarily formed
in the Middle Jurassic (e.g., the Jianghua Cu–W–Pb–Zn deposit = 161.8
± 1.7 Ma: Huang et al., 2014). The skarn-type ores are distributed along
the contact zones between a Jurassic granodiorite porphyry pluton
(U–Pb zircon age = 160.7 ± 0.5 Ma: Huang et al., 2017) and the
Devonian and Carboniferous limestones (Fig. 3a, b). The sulfide-quartz
vein-type ores primarily occur along the WNW-ESE-striking faults cut­
ting the Devonian and Carboniferous strata (Fig. 3a, b). The δ34S values
of sulfide minerals (e.g., chalcopyrite, galena and sphalerite) from the
sulfide-quartz vein-type ores vary from –1.9‰ to 5.7‰ with an average
value of 2.6‰, indicating that the sulfur is mainly derived from magma
(Cai et al., 2015). The δ13CPDB and δ18OSMOW values of calcite from
garnet skarn was also overlapping with those of magmatic region. The
sulfide minerals have a similar Pb isotopic composition to that of the
granodiorite porphyry bulk-rock, both of which exhibit upper-crustal Pb
isotopic characteristics (Cai et al., 2015; Yu et al., 2018; Li et al., 2019).
The pear-shaped granodiorite porphyry pluton, which intruded the
Upper Devonian and Lower Carboniferous rocks (Fig. 2), is dominated
by porphyritic biotite-granodiorite containing ~40% of phenocrysts
(1.2–6 mm in size). The latter comprise of plagioclase (~60%), K-feld­
spar (~14%), quartz (~20%), and biotite (~6%), in a fine-grained
groundmass that is composed of plagioclase, quartz, and K-feldspar
with minor biotite and amphibole. The granitoid has high CaO/(Na2O +
K2O) ratios and light/heavy rare earth element (LREE/HREE) ratios, and
low Rb/Sr ratios, with an Eu anomaly, and weak Ba, Sr, P, and Ti
depletion, which indicates a low degree of fractionation (Jiang et al.,
2009; Huang et al., 2017). Later quartz porphyry cut both the pluton and
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Ore Geology Reviews 143 (2022) 104764
the Cu–W–Pb–Zn ore bodies (Fig. 3, Zhao et al., 2016).
3. Deposit geology
3.1. Jianghua Cu–W–Pb–Zn deposit
The Jianghua Cu–W–Pb–Zn deposit occurs along a concealed, NE-
SW-trending contact zone between the granodiorite porphyry pluton
and rocks of the Devonian Qiziqiao Formation below + 40 m above sea
level (Fig. 3b, Huang et al., 2014; Cai et al., 2015). Across the contact
zone from proximal to distal, the skarn mineralization can be divided
into prograde skarn and retrograde skarn zones (Fig. 4a, b, c, d). The
sulfide-quartz vein-type ore bodies are primarily controlled by WNW-
ESE-striking faults, cutting both Devonian carbonate rocks and skarn-
type ores (Fig. 4e). The contact zone skarns have strata-bound and
lenticular geometries and are composed of garnet (Fig. 4b), diopside
(Fig. 4b), and epidote (Fig. 4d). The diopside and epidote skarns host
major W-bearing ores with a width of 4–8 m and a length of >500 m.
Chalcopyrite and pyrite veinlets are reported from the granodiorite
porphyry pluton but have no economic value (Fig. 4a). Cu–Pb–Zn
mineralization is dominant in the sulfide-quartz vein-type ore bodies
with minor W mineralization also present (Fig. 4e, f; WO3 > 0.6 g/t).
The sulfide-quartz vein-type ore bodies are discontinuous. Their widths
range from 0.5 to 3 m whilst their lengths are typically >300 m (Fig. 3b
and 4e, f). Micritic, dolomitic and bioclastic limestones of the ~370 m
thick Qiziqiao Formation (Fig. 4i) are typically converted to marbles
that developed in proximity to the skarn type ore bodies.
Hydrothermal alteration associated with skarn mineralization occurs
primarily along the contact with the granodiorite porphyry pluton and
B. Liu et al.
Fig. 3. (a) Cross section along the exploration line 5 in the Jianghua Cu–W–Pb–Zn deposit with location of sample sites shown by a red box; (b) cross section along
the exploration line 32 in the Jiangyong Pb–Zn–W deposit with location of sample sites shown by a red box.
demonstrates a pronounced zonation (Fig. 4a–e). Five alteration zones
have been identified, including silicification-sericitization, garnet,
diopside, chloritization-epidotization, and marble zones (Fig. 4 a–e).
Alteration of the prograde skarn stage is characterized by the meta­
somatism of limestones to form garnet, diopside, and wollastonite-calc
silicate skarns (Fig. 4b, c). Alteration of the retrograde skarn stage is
characterized by replacement of most garnet and diopside by epidote,
chlorite, and quartz (Fig. 4d). Strong silicification and sulfide veinlets,
which formed during the sulfide-quartz vein stage, are superimposed on
the skarn zones (Fig. 4e, f).
3.2. Jiangyong Pb–Zn–W deposit
The Jiangyong Pb–Zn–W deposit is mainly distributed along the
contact zone between the granodiorite porphyry pluton and carbonate
rocks of the Carboniferous Shidengzi Formations (Fig. 3a). It contains
two major ore types: A skarn-type ore (Fig. 4g) that is dominated by
garnet, diopside, wollastonite, epidote, and chlorite, and a sulfide-
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Ore Geology Reviews 143 (2022) 104764
quartz vein-type (Fig. 4h). Skarn-type ore minerals are dominated by
scheelite with minor sphalerite and galena. The alteration zones of the
skarn-type mineralization are similar to those of at Jianghua although
smaller in width. Sulfide-quartz veins are distributed along WNW-ESE-
striking faults and fractures, and ore minerals in the veins are mainly
composed of pyrrhotite, pyrite, sphalerite, and galena (Fig. 4h). With
increasing distance from the granodiorite porphyry pluton, Pb and Zn
grades gradually increased. The Ag content is positively correlated with
the Pb content (Cai et al., 2015).
3.3. Skarn mineralogy
3.3.1. Prograde skarn stage
Mineral assemblages formed during this stage are dominated by
euhedral to subhedral garnet and diopside with subordinate scheelite
(Fig. 5a, b, c). According to mineral composition and spatial distribu­
tion, garnet can be subdivided into an early massive garnet in the
proximal zones of the granodiorite porphyry pluton (Fig. 4b and 5a), and
B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Fig. 4. Images showing the mineralization and alteration characteristics in the Tongshanling Cu-polymetallic ore field. (a) Granodiorite porphyry, with silicification
and disseminated sulfides on the right side of the yellow dashed line; (b) early garnet intergrown with diopside in the prograde, with late-stage sulfide veinlets in the
Jianghua Cu–W–Pb–Zn deposit; (c) late garnet intergrown with quartz and scheelite under UV lamp illumination in the Jianghua Cu–W–Pb–Zn deposit; (d) retrograde
stage epidote-chlorite-scheelite skarn in the Jianghua Cu–W–Pb–Zn deposit; (e) sulfide-quartz veins (chalcopyrite + pyrrhotite + pyrite + scheelite + quartz) cut
through the diopside skarn in the Jianghua Cu–W–Pb–Zn deposit; (f) scheelite is intergrown with galena, sphalerite and quartz under UV lamp illumination in the
Jianghua Cu–W–Pb–Zn deposit; (g) scheelite with a light blue color in the diopside skarns under UV lamp illumination in the Jiangyong Pb–Zn–W deposit; (h) sulfide-
quartz vein (galena + pyrrhotite + pyrite + quartz) and marbled zone in the Jiangyong Pb–Zn–W deposit; (i) bioclastic limestone of the Middle Devonian Qiziqiao
Formation in the Jiangyong Pb–Zn–W deposit. Cal, calcite; Chl, chlorite; Ccp, chalcopyrite; Di, diopside; Ep, epidote; Grt, garnet; Gn, galena; Pyh, pyrrhotite; Py,
pyrite; Qz, quartz; Sch, scheelite; and Sp, sphalerite.

a late garnet in the distal zones that is intergrown with quartz and minor
scheelite in the distal zones (Fig. 4c and 5b, c). Scheelite is associated
with the late garnet, and has a subhedral or anhedral shape (Fig. 5c). The
early massive garnet is coarse-grained, subhedral, or euhedral, and is
dominated by grossular (Adr22-25Gro68-71Pyr7-8) with minor andradite
also present (Table 2, Fig. 5a and 6a). The late garnet is typically
euhedral and coexists with diopside, quartz, and minor scheelite
(Fig. 5b, c). The modal abundance of grossular is increased from the
early garnet to the late garnet (Table 2, Fig. 6a, mean = 68.7%, 73.8%,
respectively). The skarns were formed in an oxidized environment
(Appendix 1; Meinert et al., 2005), as indicated by the presence of
abundant oxide minerals and the high SiO2 contents in garnet (>37%).
Furthermore, the abundance of diopside varies from the early skarns to
the late skarns(Fig. 4b and 5d, e). Large amounts of scheelite were
formed in the diopside skarns, and they replacing anhedral garnet and
diopside (Fig. 5d, e). Generally, scheelite grains formed in the prograde
skarn stage are relatively small in size (~500 μm). Fig. 7 summarizes the
paragenetic sequence of mineral formation based on the spa­
tial–temporal relationships and mineral assemblages formed in the three
stages within the Tongshanling Cu-polymetallic ore field.
3.3.2. Retrograde skarn stage
Mineral assemblages formed during the retrograde skarn stage pri­
marily comprise epidote and chlorite accompanied by minor dissemi­
nated scheelite and quartz (Fig. 5f); Rare fine-grained chlorite crystals
were still retained the pseudomorphs of garnet crystals. During the
prograde skarn stage, garnet may have been formed relatively early, as
indicated by dissolution of the early garnet and retrograde overprinting
of quartz, pyrrhotite, and scheelite. Furthermore, superposition of
silicification and sericitization, and identification of pyrite and chalco­
pyrite in the granodiorite porphyry pluton suggest formation of the
retrograde skarn in the contact zone of granodiorite porphyry pluton
(Fig. 4b). During the retrograde skarn stage, abundant scheelite crystals
coexisted with medium-grained and subhedral epidote and chlorite,
which is abundant (Fig. 5f).
3.3.3. Sulfide-quartz vein stage
Sulfide-quartz veins, which cut the massive skarns (Fig. 4e, h),
comprise chalcopyrite, galena, sphalerite, scheelite, and quartz, which
locally contains relict skarn inclusions (Figs, 5 g, h, i). Scheelite is
common in the sulfide-quartz veins and typically intergrown with
chalcopyrite, galena, and sphalerite (Fig. 5g, h, i). Scheelite grains of this
stage are relatively large (>5 mm) and subhedral, with microfractures

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Fig. 5. Photomicrographs of scheelite and garnet formed in different stages within the Tongshanling Cu-polymetallic ore field. (a) Early massive garnet in the
proximal zones of the granodiorite porphyry pluton in the Jianghua Cu–W–Pb–Zn deposit; (b) late garnet intergrown with quartz in the Jianghua Cu–W–Pb–Zn
deposit; (c) scheelite intergrown with garnet in the Jianghua Cu–W–Pb–Zn deposit; (d) scheelite intergrown with diopside in the Jianghua Cu–W–Pb–Zn deposit; (e)
scheelite intergrown with diopside in the Jiangyong Pb–Zn–W deposit; (f) scheelite intergrown with chlorite and epidote in the Jianghua Cu–W–Pb–Zn deposit; (g)
scheelite intergrown with chalcopyrite, sphalerite, and quartz in the Jianghua Cu–W–Pb–Zn deposit; (h) scheelite intergrown with chalcopyrite and quartz with
residual skarns in the Jianghua Cu–W–Pb–Zn deposit; (i) scheelite intergrown with sphalerite, galena, and quartz. Chl, chlorite; Cal, calcite; Ccp, chalcopyrite; Di,
diopside; Grt, garnet; Gn, galena; Qz, quartz; Sp, sphalerite; Sch, scheelite. Photomicrographs a and b taken under cross polarized light; c, g, and I taken under
catoptric light; d, e, f, and h taken under polarized light.

evident in places (Fig. 5i). MIRA-3 field-emission scanning electron microscope connected to a
GATAN MINI CL system under the electric conditions of 7.0–10.0 kV and
4. Sampling and analytical techniques 70–85 µA.

4.1. Sample collection and preparation
All samples were collected from the Jianghua Cu–W–Pb–Zn and
Jiangyong Pb–Zn–W deposits in the Tongshanling ore field. Table 1 lists
the detailed sample information. Most ore samples were obtained from
the underground mining tunnels at elevations of +120 m, +40 m, 0 m,
and − 15 m above or below sea level; only sample ZK501-420 was taken
from the drill cores of drill hole ZK501 at an elevation of − 200 m below
sea level. Thin sections with a thickness of 60–80 μm thickness were cut
from these samples for CL imaging, EPMA and LA-ICP-MS analyses.
Scheelite grains were then identified under UV lamp illumination and a
binocular microscope.
4.2. Analytical methods
4.2.1. Cathodoluminescence imaging
Cathodoluminescence (CL) imaging of scheelite was performed at
Zhongke Kuangyan Test Technology Co. Ltd., China, using a Tescan
4.2.2. Major and trace element analysis
Major element and trace element analyses of scheelite and garnet
were conducted at the Key Laboratory of Metallogenic Prediction of
Nonferrous Metals, Central South University. Major elements were
analyzed using an electron probe microanalyzer (EPMA-1720/1720H).
The analytical conditions for spot analysis were as follows: an acceler­
ating voltage of 15 kV, an electron beam current of 10 nA, and an
electron beam diameter of 5 μm (spot size). The standard reference
materials were natural scheelite and garnet, and the calibration method
was absorption and fluorescence (ZAF). Appendix 1lists the detection
limits of individual element.
A Teledyne Photon Machines Analyte HE Excimer 193 nm laser
ablation system coupled with an Analytic Jena Plasma Quant MS Elite
ICPMS was used to conduct in situ trace element compositions analysis
of individual scheelite grains at Central South University, China. The
selected thin sections were cleaned and placed in a HelEx II chamber cell
of the laser. The samples were placed in a sealed ablation cell that was
constantly flushed with a high purity Ar (13.5 L/min) and He (1.1 L/

6
B. Liu et al.
Fig. 6. (a) Ternary diagram showing the compositional variation of garnet. End-members: And, andradite; Gr, grossular; (b)–(d) ternary diagrams showing the REE
compositional variation of scheelite in the Tongshanling Cu-polymetallic ore field; Alm + Sp + Pr, almandine + spessartine + pyrope.
Fig. 7. Paragenetic associations of minerals formed in different stages in the
Tongshanling Cu-polymetallic deposit.
min) gas mixture. Spot sizes were 35 µm, the laser repetition rate was
typically 5 Hz, and the laser beam energy at the sample was maintained
at ~2.0 J/cm2. NIST610, BHVO, GSE-1, and BIR-1G were used as
external standards for garnet analyses, and Ca was used as the internal
standard. Furthermore, NIST SRM610 was used as the system moni­
toring sample. Data reduction was performed according to the standard
method using GLITTER 4.4.4 developed by GEMOC, and the Ca content
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Ore Geology Reviews 143 (2022) 104764
of scheelite was analyzed by EPMA (Griffin et al. 2008). Compared to
Agilent 7700X, the PQ MS Elite has higher sensitivity. The counts per
second are >90, 1500, and 1000 Mcps/ppm for low (e.g., Li), interme­
diate (e.g., In), and heavy (e.g., Th) mass number elements, respectively.
Appendix 2 and 3 show the limits of detection for the trace elements
analysis (ppm) of garnet and scheelite in this study, respectively.
4.2.3. Sm − Nd isotope analysis
Sm − Nd isotope analysis was performed at the Laboratory of Tianjin
Geological Survey Center, China using a thermoelectric ionization mass
spectrometer (TRITON08-100016sb, Thermo Fisher Scientific). The
powdered samples (≥100 mg) were dissolved in a mixed acid (HF +
HClO4), and Nd purification was performed by the HDEHP invert
chromatography method to ensure no interference of 144Sm to 144Nd.
The isotope dilution method was conducted to determine the Sm and Nd
contents, and the isotope ratio of Nd and Sr was directly determined on
the purified sample. The analysis error of Sm and Nd contents was better
than 0.5%, and the analysis error of 147Sm/144Nd (2δ) was ±0.5%.
4.2.4. Oxygen isotope analysis
The oxygen isotope compositions of scheelite grains were analyzed
using a Finnigan-MAT253 mass spectrometer at the Beijing Research
Institute of Uranium Geology, China. Firstly, the powdered sample
(≥100 mg) was completely reacted with BrF5 for 6 h in a vacuum (>2 ×
10− 3 Pa) and at a high temperature (550 ◦ C). O2 was then collected with
a sample tube containing a 5 Å molecular sieve. Its δ18O value was
measured on a Thermo Fisher 253 Plus gas isotope mass spectrometer.
B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Table 1 Table 2
Sample information of scheelite in the Tongshanling ore field. A summary of major element compositions (%) of garnet in the Tongshanling ore
Sample Deposit Location Stage Mineral Size of
field.
no. assemblages scheelite Sample no. 0527–4-5(core of early garnet) 0527–3-5 (late garnet)
0527–4- Jianghua 0 line, Prograde Garnet (early – Max Min Mean Max Min Mean
5 Level stage)
–15 m SiO2 38.2 36.8 37.5 39.4 38.5 39.0
0527–3- Jianghua 0 line, Prograde Garnet (late 50 to TiO2 2.74 2.32 2.57 0.11 bdl 0.05
5 Level stage) + 100 μm Al2O3 15.2 14.7 15.0 16.4 14.8 15.8
–15 m Scheelite FeO 7.00 5.95 6.59 10.1 8.17 8.91
ZK501- Jianghua 0 line, Prograde Garnet + 100 to MnO 0.05 0.01 0.03 2.03 1.36 1.69
420 Level Diopside + 300 μm MgO 1.81 1.53 1.74 0.00 0.00 0.00
–180 m Scheelite CaO 35.6 35.4 35.5 34.1 33.5 33.7
0602–8 Jianghua 0 line, Prograde Garnet + 200 to Na2O 0.05 0.01 0.03 bdl bdl bdl
s2 Level 0 m Diopside + 2000 μm K2O 0.00 0.00 0.00 0.02 bdl bdl
Scheelite BaO – – – – – –
0529–5 Jiangyong 31 line, Prograde Garnet + 300 to Rb2O – – – – – –
s6 Level + Diopside + 700 μm Cs2O – – – – – –
120 m Scheelite ZnO – – – – – –
0602–5 Jianghua 0 line, Retrograde Epidote + 2000 to F – – – – – –
s2 Level Chlorite + 5000 μm Cl 0.32 0.27 0.29 bdl bdl bdl
–15 m Scheelite Cr2O3 0.00 0.00 0.00 bdl bdl bdl
0527–3- Jianghua 0 line, Quartz- Chalcopyrite + 500 to NiO 0.00 0.00 0.00 – – –
12
2 Level sulfide vein Pyrrhotite + 2000 μm Formula based on O, apfo
–15 m Pyrite + Si 2.96 2.89 2.92 3.06 3.02 3.05
Scheelite Aliv 0.11 0.04 0.08 0.00 0.00 0.00
0602- Jianghua 0 line, Quartz- Chalcopyrite + 500 to Alvi 1.37 1.29 1.32 1.53 1.40 1.48
9S1 Level sulfide vein Pyrrhotite + 1000 μm Ti 0.16 0.14 0.15 0.01 0.00 0.00
–15 m Pyrite + Cr 0.00 0.00 0.00 0.00 0.00 0.00
Scheelite Fe3+ 0.45 0.39 0.43 0.48 0.39 0.41
2+
0602- Jianghua 0 line, Quartz- Chalcopyrite + 500 to Fe 0.00 0.00 0.00 0.19 0.13 0.17
10S1 Level sulfide vein Pyrrhotite + 1000 μm Mn 0.00 0.00 0.00 0.13 0.09 0.11
–15 m Pyrite + Mg 0.21 0.18 0.20 0.00 0.00 0.00
Scheelite Ni 0.00 0.00 0.00 0.00 0.00 0.00
0602- Jianghua 0 line, Quartz- Galena + 3000 to Zn 0.00 0.00 0.00 0.00 0.00 0.00
TSL Level + sulfide vein Sphalerite + 5000 μm Ca 2.99 2.93 2.96 2.85 2.79 2.82
25 m Scheelite Total 8.07 8.03 8.06 8.06 8.03 8.04
Calculated mol.% end-members
Almandine (Alm) 0.00 0.00 0.00 0.00 0.00 0.00
Andradite (And) 24.8 21.8 23.7 25.8 20.5 22.2
The external accuracy of the standard sample was better than ± 0.2‰,
Grossular (Gr) 70.7 67.6 68.7 75.2 71.0 73.8
and the relative standard was V-SMOW. The accuracy of individual test Pyrope (Pr) 7.97 6.56 7.47 0.00 0.00 0.00
samples was 0.05‰. Spessartine (Sp) 0.13 0.02 0.08 4.74 3.25 3.98
Alm + Sp + Pr 8.05 6.61 7.55 4.74 3.25 3.98
5. Analytical results Note: - = not analyzed; bdl = below detection limit.

5.1. Cathodoluminescence images of scheelite 5.2. Major element compositions of scheelite

The CL image features of scheelite formed in different stages
considerably vary significantly. Scheelite grains intergrown with garnet
and formed in the prograde skarn stage have a relatively homogeneous
CL response, with certain brighter parts in the rim (Fig. 8a). Scheelite
grains intergrown with diopside and formed in the prograde skarn stage
have rather complicated zonation (Fig. 8b, c, d). Three scheelite grains
can be subdivided into three sub-types: the cores formed in the early
stage have a darker CL response (Sch I); the rims of Sch I have a rela­
tively brighter CL response (Sch II); the late cross-cutting veinlets have
different orientations and the brightest CL responses (Sch III). The CL
response of each subtype of scheelite is homogeneous; however, certain
weak oscillatory zonation is developed in the local area of Sch II (Fig. 8b,
c). Irregular microfracture is identified in scheelite grains intergrown
with diopside in the prograde skarn stage and cut through scheelite
grains, indicating brittle deformation events after the prograde skarn
stage (Fig. 8b, c, d). The scheelite grains formed in the retrograde stages
are composed of multiple subgrains with different CL zone (Fig. 8e, f).
The CL response of scheelite formed in the sulfide-quartz vein stage is
inhomogeneous, with multiple dark and bright areas in the same grain
(Fig. 8g, h, i). Furthermore, some scheelite grains formed in this stage
are broken into small irregular particles by various microfractures that
are not filled by late scheelite veinlets (Fig. 8i).
The compositions of major elements of scheelite grains are summa­
rized in Table 3, with detailed analytical data given in Appendix 4. All
scheelite grains formed in the prograde skarn, retrograde skarn, and
sulfide-quartz vein stages have similar WO3 (78.0%–82.4%, mean =
81.0%) and CaO contents (18.2%–19.7%, mean = 19.0%). The MoO3
contents of scheelite grains formed in the prograde skarn and retrograde
skarn stages are higher than those formed in the sulfide-quartz vein
stage (0.07%–2.67%, 0.10%–0.21%, and 0.04%–0.16%, respectively).
The FeO contents are only above the detection limit in certain scheelite
grains from the prograde stage (0%–0.06%), and below the detection
limit in almost all scheelite grains formed in the retrograde skarn and
sulfide-quartz vein stages.
5.3. Trace element compositions of garnet and scheelite
Tables 4 and 5 show the trace element analytical results of garnet and
scheelite, respectively, with detailed analytical data given in Appendix 5
and Appendix 6, respectively. Appendix 7 and Appendix 8 show the
analysis results of standard mineral (GSE-1).
The Mg, P, K, Ti, V, Cr, Ni, Zn, Ga, Sr, and Zr contents of garnet grains
are >10 ppm, whereas Sc, Co, Rb, Nb, Cd, and Pb contents range from 1
to 10 ppm. However, the prograde garnet grains have higher Mg, Sc, Ti,
Cr, Co, Ni, Zn, Sr, Zr, Pb, and REE contents and lower K and Ga contents
compared to the retrograde garnet. The REE patterns of prograde garnet

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B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Fig. 8. CL images of scheelite grains formed in the prograde, retrograde, and sulfide-quartz vein stages in the Tongshanling Cu-polymetallic ore field. (a) CL images
of the scheelite intergrown with garnet show a relatively homogeneous CL response in the Jianghua Cu–W–Pb–Zn deposit; (b) and (c) CL images of the scheelite
intergrown with diopside show a dark CL response in the cores and a bright CL response in the rims in the Jianghua Cu–W–Pb–Zn deposit; (d) CL images of the
scheelite intergrown with diopside reveal a core-rim texture and some late-stage cross-cutting veinlets with a brighter CL response in the Jiangyong Pb–Zn–W deposit;
(e) and (f) CL images of the scheelite formed in the retrograde stage exhibit a weak oscillatory zonation in the Jianghua Cu–W–Pb–Zn deposit; (h)–(i) CL images of the
scheelite formed in the sulfide-quartz vein stage have similar CL image characteristics to those of the scheelite formed in the retrograde stage in the Jianghua
Cu–W–Pb–Zn deposit.

are HREE-enriched with a negative Eu anomaly (Eu/Eu* = 0.25–0.81,
mean = 0.62) (Fig. 9a and 6b); however, the retrograde garnet is MREE-
enriched with a pronounced positive Eu anomaly (Eu/Eu* = 2.07–49.1,
mean = 11.2) (Fig. 9b and 6b). Moreover, the HREE contents gradually
decrease from the cores to the rims of the late garnet (Fig. 9b).
Scheelite grains formed in the prograde skarn, retrograde skarn, and
sulfide-quartz vein stages have relatively similar contents of trace ele­
ments (Appendix 6). The Si, Fe, Cu, Zn, As, Sr, Zr, Nb, Mo, Sn, and Pb
contents of scheelite grains are > 10 ppm, and their Ti, Rb, Ba, Ba, and Bi
contents range from 1 to 10 ppm. Furthermore, scheelite grains formed
in the prograde skarn stage have higher Cu, Zn, As, Mo, Sn, Pb, and Sr
contents and lower Ti contents than scheelite formed in the retrograde
skarn and sulfide-quartz vein stages.
In the prograde skarn stage, scheelite grains intergrown with garnet
have variable ΣREE + Y contents (473–1503 ppm, mean = 901 ppm).
Their LREE (La–Nd), MREE (Sm–Ho), and HREE (Er–Y) contents are
429–1346 ppm (mean = 793 ppm), 44.8–159 ppm (mean = 105 ppm),
and 2.75–35.1 ppm (mean = 14.7 ppm), respectively. Their REE pat­
terns demonstrate an increasing slope from La to Nd and a decreasing
slope from Nd to Lu, with a significant positive Eu anomaly (Eu/Eu* =
1.32–2.62, mean = 2.06) along with no Ce anomaly (Ce/Ce* =
0.91–1.02, mean = 0.96) (Fig. 9c), respectively. Scheelite grains inter­
grown with diopside show variable ΣREE + Y contents (116–509 ppm,
mean = 222 ppm). The LREE (La–Nd), MREE (Sm–Ho), and HREE (Er–Y)
contents are 96.4–480 (mean = 185 ppm), 4.09–50.1 (mean = 18.9
ppm), and 2.82–63.2 ppm (mean = 17.9 ppm), respectively. The REE
patterns of scheelite are relatively flat in LREE but are significantly
HREE-depleted with a negative Eu anomaly (Eu/Eu* = 0.36–0.65, mean
= 0.47) and without a Ce anomaly (Ce/Ce* = 0.76–1.07, mean = 0.97)
(Fig. 9e and 6c), respectively.
In the retrograde stage, scheelite grains intergrown with epidote and
chlorite have considerably lower ΣREE + Y contents (14.6–241 ppm,
mean = 70.1 ppm) with a variable Eu anomaly (Eu/Eu* = 0.17–14.4,
mean = 2.47) and without Ce anomaly (Ce/Ce* = 0.93–1.10, mean =
1.00) (Fig. 9f), respectively. Note that the late cross-cutting scheelite
veinlets in the prograde stage (Fig. 8d and 9e) have similar REE patterns
to scheelite in the retrograde stage (Fig. 9f).
In the sulfide-quartz vein stage, scheelite grains intergrown with
chalcopyrite, galena, and sphalerite have the lowest ΣREE + Y contents
(5.12–250 ppm, mean = 84.9 ppm; 6.35–73.4 ppm, mean = 34.1 ppm,
respectively). From the cores to the rims of scheelite grains intergrown
with chalcopyrite, the ΣREE + Y contents, particularly the HREE

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B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Table 3 variations in 147Sm/144Nd (0.173278–0.218343) and 143Nd/144Nd ra­

A summary of major element compositions (ppm) of scheelite in the Tong­ tios (0.512235 to 0.512297). Although the 147Sm/144Nd versus
143
shanling ore field. Nd/144Nd isochron diagram contains seven points from the scheelite
Stage Sample WO3 MnO MoO3 FeO CaO samples with a linear trend on, it cannot yield an isochron age (Fig. 10a).
no. Mass Mass Mass Mass Mass Using the Re–Os isochron age of molybdenite that is intergrown with
% % % % % scheelite (161.8 ± 1.7 Ma, Huang et al., 2014), the calculated εNd(t)
Prograde 0527–3-5 Max 82.3 0.01 0.17 0.06 19.3 values of the scheelite vary in a small range of − 7.46 to − 7.07, with an
(garnet, Min 81.8 bdl 0.10 0.03 18.9 average value of − 7.28, and the T2DM values vary from 1526 to 1557 Ma
− 15 m) Mean 82.1 0.01 0.13 0.05 19.1
with an average value of 1542 Ma (Fig. 10b).
Prograde ZK501 Max 82.5 0.03 0.18 0.27 19.3
(garnet, Min 79.3 bdl 0.10 bdl 18.5
− 200 m) Mean 81.2 0.01 0.14 0.12 18.9 5.5. Oxygen isotope compositions of scheelite
Prograde 0529- Max 81.6 0.03 2.67 0.08 19.3
(diopside) 5S60602- Min 78.0 bdl 0.07 bdl 18.5 Table 7 shows the δ18O values of scheelite grains formed in the
8S2 Mean 80.4 0.01 1.15 0.02 18.9
prograde skarn, retrograde skarn, and sulfide-quartz vein stages and the
Retrograde 0602–5 s2 Max 82.4 0.02 0.39 0.01 19.2
Min 80.8 bdl 0.10 bdl 18.2 corresponding δ18OH2O values of fluids. The mean homogenization
Mean 81.7 0.01 0.21 0.01 18.9 temperatures of fluid inclusions in quartz and garnet intergrown with
Quartz- 0527–3-2 Max 81.2 0.025 0.16 0.09 19.7 scheelite are 240 ◦ C, 220 ◦ C, and 210 ◦ C, respectively (Wang et al.,
sulfide Min 80.2 bdl 0.04 bdl 19.4
2017), that were used to calculate the δ18OH2O values of fluids based on
vein Mean 80.7 0.005 0.08 0.02 19.5
Quartz- 0602-TSL- Max 81.7 0.04 0.08 0.03 19.4 the scheelite-H2O fractionation equilibrium (Wesolowski and Ohmoto,
sulfide 15 Min 81.0 bdl 0.04 bdl 18.7 1983). The results are summarized in the plot of δ18OH2O for the cor­
vein Mean 81.4 0.01 0.06 0.01 19.2 responding homogenization temperature of fluid inclusions (Fig. 11b),
Note: bdl = below detection limit. and in the plot of δ18O versus temperature contoured with δ18OH2O
values (Fig. 11a). From the prograde to retrograde stage, the calculated
δ18OH2O values are decreased from + 6.19‰ to + 2.85‰. In the sulfide-
Table 4 quartz vein stage, they range from + 5.02% to + 5.42% (Table 7).
A summary of rare earth element compositions (ppm) of garnet in the Tong­ Moreover, Fig. 11b shows the δ18OH2O values of certain other typical
shanling ore field. skarns, greisen, and porphyry W deposits related to magmatic fluids
Early garnet Late garnet (Poulin et al., 2018). The detailed comparisons and implications of these
Max Min Mean Max Min Mean
plots will be discussed later.

La 0.02 0.01 0.01 0.02 bdl 0.01

6. Discussion
Ce 0.02 0.01 0.01 0.35 0.01 0.09
Pr 0.01 0.01 0.01 0.21 0.01 0.07
Nd 0.12 0.04 0.08 3.75 0.11 1.24 6.1. Element substitution mechanisms and fluid evolution
Sm 0.14 0.07 0.10 5.13 0.08 1.60
Eu 0.07 0.03 0.06 6.38 0.65 2.65 6.1.1. Trace elements and REE substitution mechanisms
Gd 0.69 0.45 0.54 7.86 0.01 1.63
Tb 0.24 0.19 0.22 1.23 bdl 0.19
The crystal structure of scheelite is prone to infiltration by trace el­
Dy 3.32 2.41 2.88 6.89 0.01 0.86 ements that can then substitute either the eight-coordinated ionic Ca
Ho 1.16 0.86 0.97 0.99 bdl 0.11 ions (e.g., Sr2+, Pb2+, and Ba2+) or the four-coordinated W6+ ions (e.g.,
Er 4.83 3.19 3.87 2.08 bdl 0.21 Mo, Mn, Ga, and Nb) ions (Kontak and Smith, 1993). The LA-ICP-MS
Tm 0.76 0.51 0.64 0.19 bdl 0.02
trace elements analysis undertaken as part of this study confirmed
Yb 6.21 4.15 5.07 1.01 bdl 0.11
Lu 1.06 0.68 0.82 0.10 bdl 0.01 that certain trace elements were incorporated in the scheelite, particu­
Y 38.5 28.9 32.7 33.3 0.01 4.41 larly Sr, Mo, and REE + Y. The contents of ore-forming elements of
ΣREE 18.3 13.1 15.3 32.6 1.02 8.80 scheelite (e.g., Cu, Zn, Pb, Mo, and As) are drastically decreased from the
ΣREE + Y 56.8 42.0 48.0 65.9 1.05 13.2 early prograde stage to the intermediate retrograde stage, and the late
LREE 0.33 0.23 0.27 15.8 0.96 5.65
HREE 18.1 12.8 15.0 20.4 0.02 3.15
sulfide-quartz vein stage, indicating that the ore-forming concentrations
LREE/HREE 0.02 0.01 0.02 41.8 0.60 8.26 of elements in fluids significantly changed with fluid evolution.
LaN/YbN bdl bdl bdl 1.24 0.01 0.21 Incorporation of REE + Y in scheelite occurs via the following three
δEu 0.81 0.25 0.62 49.1 2.07 11.2 substitution mechanisms: (1) 2Ca2+ ↔ Na+ + REE3+ (M1); (2)
0.48 0.19 0.30 0.61 0.24 0.39
δCe
Ca2++W6+ ↔ REE3++Nb5+ (M2); and (3) 3Ca2+ ↔ 2REE3+ + □ (where
Note: bdl = below detection limit; Eu* = (Sm/SmN + Gd/GdN)/2; Ce* = (La/LaN □ is a site vacancy) (M3) (Ghaderi et al., 1999). The M3 mechanism is
+ Pr/PrN)/2. isomorphic substitution and has greater flexibility in the radius of the
substituting REE without strong REE fractionation, whereas M1 and M2
contents, are gradually decreased (Fig. 9g and 6d). The REE patterns of require a coupled substitution with charge balance compensation (Na+
scheelite change from flat to LREE-enriched with a prominent positive or Nb5+) controlled by the ionic radius (Ghaderi et al., 1999; Brugger
Eu anomaly (1.17–20.6, mean = 6.96) and a subtle negative Ce anomaly et al., 2000). In this study, although only a small amount (0–106 ppm) of
(Ce/Ce* = 0.80–1.02, mean = 0.91). The scheelite grains intergrown Nb was detected in the analyzed scheelite grains, Nb was shown to be
with galena and sphalerite has identical REE patterns to those formed in positively correlated with REE + Y–Eu but only in scheelite grains that
the prograde skarn and retrograde skarn stages (Fig. 9h and 6d). are intergrown with diopside (i.e., sample 0529–5 s6). There is no co-
variance with REE + Y–Eu evident in other samples (Fig. 12a, b). This
5.4. Sm–Nd isotopic compositions of scheelite result that the M2 substitution mechanism occurred only in sample
0529–5 s6 from the Jiangyong Pb–Zn–W deposit. The Na2O contents of
Table 6 lists the Sm and Nd compositions and isotopic compositions the analyzed scheelite grains are below the limit of detection in all
of scheelite grains intergrown with chalcopyrite, galena, and sphalerite samples, indicating that REEs were not substituted via the M1 mecha­
and formed in the sulfide-quartz vein stage with the Jianghua nism, and M3 is possibly the dominant substitution mechanism.
Cu–W–Pb–Zn deposit. Their Sm and Nd contents of scheelite vary from
6.70 to 10.6 ppm and from 20.0 to 32.9 ppm, respectively, with limited

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B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Table 5
A summary of rare earth element compositions (ppm) of scheelite in the Tongshanling ore field.
Prograde (garnet) Prograde (diopside) Retrograde Quartz-sulfide vein

Max Min Mean Max Min Mean Max Min Mean Max Min Mean

La 158 42.2 91.9 125 18.7 43.5 47.1 2.49 13.6 9.62 0.48 4.03
Ce 509 160 297 245 45.2 87.9 113 7.51 31.3 19.1 1.53 8.45
Pr 102 33.38 59.3 25.3 4.94 10.5 14.0 0.81 4.10 5.05 0.39 2.24
Nd 583 193 345 84.5 18.9 43.2 41.6 1.09 12.5 25.0 2.28 11.6
Sm 91.3 24.6 54.3 16.6 1.94 6.93 6.49 0.02 1.73 3.07 0.28 1.48
Eu 31.2 13.7 25.1 2.81 0.32 1.02 2.76 0.03 0.59 1.62 0.09 0.42
Gd 33.3 5.18 19.9 15.5 0.99 5.91 6.27 0.02 1.64 2.49 0.15 1.22
Tb 2.44 0.44 1.27 1.95 0.10 0.68 0.69 bdl 0.17 0.27 0.02 0.12
Dy 9.07 0.74 4.28 11.1 0.60 3.64 3.44 bdl 0.88 1.87 0.06 0.60
Ho 1.10 0.13 0.51 2.08 0.09 0.67 0.60 bdl 0.14 0.36 0.01 0.11
Er 4.26 0.16 1.51 4.72 0.15 1.27 1.02 bdl 0.21 0.73 0.01 0.19
Tm 0.17 bdl 0.10 0.63 0.01 0.13 0.09 bdl 0.02 0.07 0.00 0.02
Yb 2.35 bdl 0.57 2.50 0.04 0.47 0.36 bdl 0.06 0.28 0.00 0.06
Lu 0.11 bdl 0.02 0.22 bdl 0.04 0.03 bdl 0.01 0.02 bdl 0.01
Y 28.3 2.51 12.5 55.2 2.62 16.0 14.7 0.01 3.20 8.76 0.20 3.57
ΣREE + Y 1518 476 913 509 116 222 241 14.6 70.1 250 5.12 60.7
LREE 1463 467 873 490 101 193 221 14.5 63.8 62.2 5.88 28.2
HREE 48.8 6.74 28.1 38.7 2.02 12.8 12.0 0.03 3.10 5.85 0.27 2.31
LREE/HREE 69.3 17.6 37.1 76.1 7.53 21.6 455 2.43 96.8 28.4 4.26 14.0
LaN/YbN 411 27.6 187 1116 20.7 199 1132 8.17 377 631 6.07 94.1
δEu 2.62 1.32 2.06 0.65 0.36 0.47 14.4 0.17 2.47 4.46 0.30 1.36
δCe 1.02 0.91 0.96 1.07 0.76 0.97 1.10 0.93 1.00 0.82 0.64 0.71

Note: bdl = below detection limit; Eu* = (Sm/SmN + Gd/GdN)/2; Ce* = (La/LaN + Pr/PrN)/2.

6.1.2. Redox environment changes
The trace element Eu has two ionic valences: Eu2+ and Eu3+
(Shannon et al., 1976). Similar to other REE3+, Eu3+ can be substituted
in the eight-coordinated site (i.e., Ca2+) through M1, M2, and M3 sub­
stitution mechanisms (Blundy and Wood, 1994; Ghaderi et al., 1999).
Eu2+ can enter the scheelite lattice via M3 substitution mechanisms
(Blundy and Wood, 1994). Scheelite preferentially incorporates Eu3+
with maximum compatibility in the ionic radius (Shannon et al., 1976;
Brugger et al., 2000; Brugger et al., 2008). The valency state of Eu in
scheelite is expressed in the correlation diagram of EuN and Eu*N (Eu*N
= (SmN × GdN)1/2) (Fig. 12c, d; Ghaderi et al., 1999). In this study, the
EuN versus Eu*N diagram shows a positive correlation for the scheelite
intergrown with garnet and diopside and formed in the prograde stage,
suggesting that Eu3+ dominates (Fig. 12c). However, EuN does not co-
vary with Eu*N for most analysis points of the scheelite intergrown
with epidote, chlorite, and chalcopyrite and formed in the retrograde
and sulfide-quartz vein stages, which indicates that Eu2+ was primarily
concentrated in fluids (Fig. 12d). To summarize, Eu3+ is dominant in the
scheelite formed in the prograde stage, and Eu2+ is present in the
scheelite formed in the retrograde stage and sulfide-quartz vein stage.
Scheelite is highly sensitive to the precipitation environment, and its
composition is directly influenced by the physico-chemical environment
of formation (Ghaderi et al., 1999; Brugger et al., 2000; Poulin et al.,
2018). The Mo-W substitutions in scheelite are redox-sensitive, and high
Mo contents suggest the formation of scheelite for highly oxidizing en­
vironments (Brugger et al., 2008; Song et al., 2014; Poulin et al., 2018;
Xu et al., 2019). The scheelite formed in the prograde stage has a
significantly higher Mo content than that formed in the retrograde and
sulfide-quartz vein stages, thus suggesting a transition from an oxidizing
environment in the prograde stage to a reducing environment in the
retrograde and sulfide-quartz vein stages (Fig. 13).
The physico-chemical environment of scheelite precipitation is
significantly changed as per the stability field of specific mineral as­
semblages (Hsu, 1977). The W and Mo substitutions form powellite
(CaMoO4) as a complete solid solution in scheelite in an oxidizing
environment because powellite contains oxidized Mo6+ and requires a
higher oxidation state for its stability (Fig. 14; Hsu and Galli, 1973; Hsu,
1977; Tyson et al., 1988). Experiments demonstrate that the logfO2
values of coexisting scheelite and powellite are greater than –20 under
the condition of 580 ◦ C and 1 kbar, whereas the logfO2 values of
scheelite, molybdenite, and pyrrhotite formed in the sulfide-quartz vein
stage range from − 28 to − 18 (Hsu, 1977). The temperature (240 ◦ C) and
pressure (0.2 kbar) of fluid are lower than the experimental values in the
Tongshanling deposit (Wang et al., 2017). Previous studies demonstrate
that the change of logfO2 value is positively correlated with tempera­
ture, and is insignificantly influenced by pressure on (McBride et al.,
1993; Barin, 1995). Therefore, the overall fluid oxygen fugacity of the
Tongshanling deposit is lower than the experimental value. However,
the fluid logfO2 value of fluid is gradually declined from the prograde
stage to the retrograde skarn and sulfide-quartz vein stages.
The REE analysis results demonstrate that the ΣREE + Y contents of
garnet are substantially decreased from the early garnet to the late
garnet (mean = 1743 ppm, 48.0 ppm, and 13.2 ppm, respectively,
Table 4). The ΣREE + Y contents of scheelite have a similar trend and
decreased from the prograde to the retrograde stage and sulfide-quartz
vein stage (mean = 452 ppm, 129 ppm, and 60.68 ppm, respectively;
Table 5), indicating the gradual decrease in REE + Y contents of ore-
forming fluids with time. The physico-chemical environment changes
may affect the REE + Y elements in the fluids entering the scheelite
lattice (Wood et al., 1990; Haas et al., 1995). However, a change in
redox conditions has little effect on the partition coefficient of most
REEs, particularly MREE (Green and Pearson, 1983; Ghaderi et al.,
1999; Wood and Samson, 2000; Hazarika et al., 2016). Furthermore, the
REE concentration in fluids will decrease with increasing pH values
(Michard et al., 1989; Henley and Ellis, 1983) and decreasing fluid
temperatures (Wood et al., 1990; Zhai et al., 2014; Liu et al., 2019b).
From the retrograde to sulfide-quartz vein stages, the homogenization
temperature of quartz fluid inclusions does not show a significant
decreasing trend (Wang, 2017). Possibly, the change is primarily
attributed to the precipitation of skarn minerals enriched in ΣREE + Y
(e.g., garnet, diopside, and wollastonite) and the early stage precipita­
tion of scheelite that captured large amounts of REE (especially LREEs)
in the ore-forming fluids (Fig. 9; Van Orman et al., 2001; Roniza et al.,
2014; Liu et al., 2019b). In addition to a dramatic decrease in the total
amount of REEs, REEs are also continuously fractionated, and the REE
patterns are gradually changed with time (Fig. 9a, b). From the early to
the late garnets, the REE patterns are gradually changed from the HREE-
enriched patterns with a weak negative Eu anomaly to the MREE-
enriched patterns with a prominent positive Eu anomaly (Fig. 9a, b).
HREEs are gradually depleted from the early garnet to the late garnet,

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B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Fig. 9. Chondrite-normalized REE patterns of scheelite and garnet in the Tongshanling Cu-polymetallic ore field. (a) REE patterns of the early garnet in the Jianghua
Cu–W–Pb–Zn deposit and REE patterns of granodiorite porphyry bulk-rock (after Jiang et al., 2009); (b) REE patterns of the late garnet in the Jianghua Cu–W–Pb–Zn
deposit; (c) REE patterns of the scheelite intergrown with garnet in the Jianghua Cu–W–Pb–Zn deposit; (d) REE patterns of the scheelite intergrown with diopside in
the Jianghua Cu–W–Pb–Zn deposit; (e) REE patterns of the scheelite intergrown with diopside and scheelite from the late-stage cross-cutting veinlets in the Jiangyong
Pb–Zn–W deposit; (f) REE patterns of the scheelite formed in the retrograde stage in the Jianghua Cu–W–Pb–Zn deposit; (g) REE patterns of the scheelite intergrown
with chalcopyrite in the Jianghua Cu–W–Pb–Zn deposit; and (h) REE patterns of the scheelite intergrown with galena and sphalerite in the Jianghua Cu–W–Pb–Zn
deposit. Chondrite values are after Sun and McDonough (1989).

suggesting that HREEs are fractionated more significantly than LREEs.
The gradual depletion of HREEs in fluids is primarily attributed to the
precipitation of HREE-enriched minerals (Brugger et al., 2000; Peng
et al., 2005). The ionic radii of REEs and their substitutes may be the
important factors controlling the REE patterns of enriched HREEs or
depleted LREEs in scheelite and garnet (Onuma et al. 1968; Shannon
et al., 1976; Ding et al., 2018). The ideal calculated radius of REE3+ for
eight-coordination Ca2+ in the scheelite is considerably closer to those of
LREEs (Shannon et al., 1976), whereas the ideal theoretical radius of
REE3+ in Al-enriched garnet (e.g., almandine and grossular) is closer to
those of HREEs (Shannon et al., 1976, Dahlquist et al., 2007; Ding et al.,
2018). Therefore, precipitation of the early garnet led to the reduction of

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B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Table 6
Sm − Nd isotope compositions of scheelite from the Jianghua Cu–W–Pb–Zn deposit in the Tongshanling ore field.
147
Sample Stage Sm (ppm) Nd (ppm) Sm/144Nd 143
Nd/144Nd 2σ εNd(t) T2DM

20200825-2S2 Sulfide-quartz vein stage 10.57 29.25 0.2183 0.512297 0.000002 − 7.10 1527
20200825-2S3 Sulfide-quartz vein stage 7.496 22.88 0.1981 0.512269 0.000004 − 7.24 1538
20200825-2S4 Sulfide-quartz vein stage 9.776 32.88 0.1797 0.512238 0.000004 − 7.45 1556
20200825-2S5 Sulfide-quartz vein stage 8.010 26.99 0.1794 0.512247 0.000008 − 7.27 1542
20200825-2S6 Sulfide-quartz vein stage 6.699 19.98 0.2027 0.512282 0.000002 − 7.08 1525
20200825-2S7 Sulfide-quartz vein stage 8.301 24.01 0.2090 0.512271 0.000005 − 7.41 1553

Note: εNd(t) is calculated by the Re–Os isochron age of molybdenite; 1000lnOscheelite-H2O = 1.39 × 106/T2-5.87 (Huang and Lu, 2014).

Fig. 10. (a) Sm–Nd isotope isochron diagram of scheelite in the Jianghua Cu–W–Pb–Zn deposit; (b) age versus εNd(t) plot for scheelite, and granodiorite porphyry
and quartz porphyry in the Tongshanling ore field. The εNd(t) of basement rocks of SCB are from Sun et al., 2003. The εNd(t) of granodiorite and quartz porphyry is
from Huang et al., 2017. DMM, depleted end-member; CHUR, chondritic uniform reservoir.

Table 7
Oxygen isotope composition (‰) of scheelite in the Tongshanling ore field.
Sample no. Deposit Stage Mineral assemblages Oscheelite (‰) T (℃) δ18OH2O (‰)

0529–5 s6 Jiangyong Prograde Garnet + Diopside + Scheelite 5.6 240 6.19

0602–8 s2 Jianghua Retrograde Epidote + Chlorite + Scheelite 3.3 220 3.45
0602–5 s2 Jianghua Retrograde Epidote + Chlorite + Scheelite 2.7 220 2.85
0527–3-2 Jianghua Quartz-sulfide vein Chalcopyrite + Pyrrhotite + Pyrite + Scheelite 5.1 210 5.02
0602-9S1 Jianghua Quartz-sulfide vein Chalcopyrite + Pyrrhotite + Pyrite + Scheelite 5.5 210 5.42
0602-10S1 Jianghua Quartz-sulfide vein Chalcopyrite + Pyrrhotite + Pyrite + Scheelite 5.3 210 5.22

Note: T(℃) is the homogeneous temperature of fluid inclusion (Wang, 2017); 1000lnOscheelite-H2O = 1.39 × 106/T2-5.87 (Wesolowski and Ohmoto, 1983).

HREEs in the fluid, and the late garnet inherited the HREE character­
istics in the fluid.
The REE patterns and Eu anomaly of scheelite grains intergrown with
garnet are similar to those of the late garnet, with a prominent HREE
depletion and a positive Eu anomaly, whereas the LREE patterns are
opposite (Fig. 9b, c). Although the CL images of scheelite grains inter­
grown with diopside are heterogeneous, with a distinct core-rim texture,
their REE patterns have similar LREE enrichment and negative Eu
anomaly (Fig. 8b–d and 9d, e). However, the REE patterns of scheelite
grains from the late-stage cross-cutting veinlets demonstrate additional
intense LREE enrichment similar to those of scheelite grains formed in
the retrograde stage (Fig. 8d and 9e, f), suggesting that scheelite grains
of prograde stage is overprinted by the ore-forming fluid in the retro­
grade skarn stage (Fig. 8d).
Scheelite grains in sulfide-quartz veins have distinct REE patterns
from those within skarns (Fig. 9g, h). In the same scheelite grains
intergrown with chalcopyrite, the REE patterns are changed from MREE-
enriched to LREE-enriched, and the HREEs are gradually depleted from
the cores to rims of scheelite grains (Fig. 9g). The crystal lattice of
paragenetic minerals (e.g., quartz and chalcopyrite) can not incorporate
REEs with low REE contents (ΣREE is often <10 ppm) (Li et al., 2015;
Liu et al., 2019a). Therefore, in the sulfide-quartz vein stage, the para­
genetic minerals are not a primary control on REE fractionation. The
REE substitution is associated with the Ca2+ site and a minor distortion
may result in a decrease of the Ca2+ site (i.e., 1.12 Å → 1.06 Å), which
can lead to the local maximum in the REE patterns from La to Sm (Poulin
et al., 2018). In most of the reported world’s W deposits that have been
reported, scheelite intergrown with quartz is either enriched or depleted
in MREEs (convex or concave type), whereas scheelite in skarn is pri­
marily enriched by LREE (Ghaderi et al., 1999, Brugger et al., 2000;
Poulin et al., 2018; Ding et al., 2018; Li et al., 2019; Liu et al., 2019a).
Initially, scheelite with the convex REE pattern was considered to pri­
marily develop in a metamorphic environment (Ghaderi et al., 1999,
Brugger et al., 2000), but it has been extensively recognized in the
sulfide-quartz vein-type W deposits related to magmatic hydrothermal
fluids. The convex REE pattern is more likely to be caused by the dif­
ference in the crystal structure, and a minor distortion will result from a
change in the relative size of the crystallographic site from light to heavy
REE (i.e., 1.12 Å–1.00 Å, Poulin et al., 2018), which will effectively shift
the local maximum in the REE patterns from La-Nd to Er-Tm. Therefore,
the crystal structure of scheelite intergrown with quartz may differ from
that of scheelite in skarn, and its fluid dynamics is more complex and

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B. Liu et al. Ore Geology Reviews 143 (2022) 104764

Fig. 11. Plots of temperature (◦ C) versus δ18Oscheelite with isopleths of δ18OH2O as calculated using the scheelite-H2O fractionation equation (Wesolowski and
Ohmoto, 1983; a) and compared with the world’s typical W deposits related to magmatic-hydrothermal fluids (modified from Sheppard et al., 1977 and Poulin et al.,
2018; b). Gr - greisen, PR - porphyry-related, S - skarn.

∑
Fig. 12. (a)–(b) Nb (atom) versus REE + Y–Eu (atom) plots of scheelite in the Tongshanling Cu-polymetallic ore field; (c)–(d) REE plots of scheelite in the
∑
Tongshanling Cu-polymetallic ore field. The solid line is the 1:1 correlation line, indicating a perfect correlation of REE + Y–Eu (atom) with Nb (atom) (modified
from Ghaderi et al., 1999); atom number = m/M (m = mass, M = molar mass).

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B. Liu et al. Ore Geology Reviews 143 (2022) 104764

∑
Fig. 13. Mo versus REE + Y plot of scheelite in the Tongshanling Cu-polymetallic ore field.

Fig. 14. Plot of Y/Ho ratios versus La/Lu ratios for four types of scheelite in the Tongshanling Cu-polymetallic ore field. The horizontal distribution of the Y/Ho
ratios indicates that they are derived from the same source fluid (diagram modified from Irber et al., 1999).

variable (Brugger et al., 2000; Peng et al., 2005; Poulin et al., 2018; Liu
et al., 2019a).
6.2. Genesis and sources of W mineralization
Dating of molybdenite formed in the sulfide-quartz vein stage yiel­
ded a Re − Os isotope isochron age of 161.8 ± 1.7 Ma for the Jianghua
Cu–W–Pb–Zn deposit (Huang et al., 2014), which is consistent with the
zircon U–Pb age of the adjacent granodiorite porphyry pluton (160.7 ±
0.5 Ma; Zhao et al., 2016; Huang et al., 2017). This temporal affinity is
consistent with the pluton and sulfide-quartz veins having formed in the
same magmatic-hydrothermal event. The isotope compositions of S and
Pb in sulfides (e.g., pyrite, pyrrhotite, and chalcopyrite) indicate that the
sulfide-quartz vein ores were derived from the Jurassic granodiorite
porphyry (Cai et al., 2015; Yu et al., 2018; Li et al., 2019). In this study,
the δ18OH2O values of fluids in the sulfide-quartz vein stage range from
6.88% to 7.28 ‰. They are similar to those of scheelite in the prograde
stage (Fig. 10), which broadly overlaps with the magmatic fluid
composition (5.50 to 13.2 ‰, Sheppard, 1977). The fluids have lower
δ18OH2O values in the retrograde stage than in the prograde and sulfide-
quartz vein stages (Fig. 11a, b), which may be attributed to the extensive
fluid-rock interaction or the addition of a small amount of meteoric
water during the retrograde stage (Chacko et al., 2001; Meinert et al.,
2005). The addition of meteoric water was also confirmed in other
porphyry-, skarn-, and greisen-type W–Sn deposits (e.g., Hermosillo,
Guadalupana, Traversella, San Alberto, Fig. 11b, Poulin et al., 2018).
The εNd(t) values of scheelite in the sulfide-quartz vein stage from
the Jianghua Cu–W–Pb–Zn deposit varied from − 7.46 to − 7.07, which is
similar to the Jurassic granodiorite porphyry (Fig. 10b, εNd(t) = − 7.90
to − 7.42, Wu et al., 2021) and lower than the late quartz porphyry
filling in WNW-ESE-striking faults (Fig. 10b, εNd(t) = − 5.30 to − 2.72,
Wu et al., 2021). These negative εNd(t) values suggest that Nd was
derived from crustal material with a weak influence of mantle material,
and the two-stage Nd model ages (T2DM = 1526–1557 Ma) demonstrate
that it was produced by partial melting of Mesoproterozoic crustal rocks.
In the age versus εNd(t) diagram, the Nd isotope signature in the sulfide-

15
B. Liu et al.
quartz vein stage is similar to those of the granodiorite porphyry
(Fig. 10b, Jiang et al., 2009; Zhao et al., 2016; Huang et al., 2017). This
indicates that the W mineralization in the sulfide-quartz vein stage were
primarily derived from the granodiorite porphyry pluton (Fig. 10b).
Y and Ho have similar ionic radii, and the Y/Ho ratios have remained
constant in a single hydrothermal system, and therefore, they can be
used to reveal the source of fluids (Irber et al., 1999; Bau and Moeller,
1992; Liu et al., 2019). The Y/Ho versus La/Ho diagram (Fig. 14) shows
that the Y/Ho ratios of the early garnet are similar to those of scheelite
grains formed in the prograde and retrograde skarn stages, which in­
dicates that they were derived from the same fluid source. Although the
Y/Ho ratios of the late garnet and scheelite grains formed in the sulfide-
quartz vein stage have a greater range of 19.5–75.0 (Fig. 14), this range
is less than one order of magnitude (17.6–75.0). Therefore, their fluid
sources are similar and may have originated from the granodiorite
porphyry pluton. The small increase in the Y/Ho ratios is possibly
caused by fluid evolution (Bau, 1996).
6.3. Implications for regional W mineralization
In the Nanling metallogenic belt there are many large and super-
large W-Sn deposits, such as the Tongshanling Cu-Pb-Zn-W (Cai et al.,
Fig. 15. Diagenesis and mineralization model diagram of W polymetallic mineralization in the Nanling metallogenic belt, South China.
16
Ore Geology Reviews 143 (2022) 104764
2015; Huang et al., 2018), Shizhuyuan Sn-W (Liao et al., 2021), and
Yaogangxian W-Sn deposits (Peng et al., 2006; Dong et al., 2014; Fig. 1).
Generally, the ore-forming granitoids associated with these deposits can
be subdivided into the S-type, A-type, and I-type with the emplacement
of the I-type granodiorites commonly ~5 Ma earlier than that of the A-
type and S-type granites (160 ~ 165 Ma; 150 ~ 160 Ma, Chen et al.,
2013; Li et al., 2013; Mao et al., 2013; Huang et al., 2017, Fig. 5). The A-
type and S-type granites have higher differentiation index values than
that of the I-type and are related to the large-scale W-Sn and Cu
mineralization in Nanling metallogenic belt respectively (Cao et al.,
2020; Fig. 15c, d). The A-type and S-type granites have similar T2DMNd
values (0.94 ~ 1.49 Ga, and 1.6 ~ 2.0 Ga), indicating that they are
derived from Mesoproterozoic strata remelting (Guo et al., 2014).
Moreover, the T2DMNd value of Tongshanling granodiorite and scheelite
(1.53 ~ 1.56 Ga) confirms that they are primarily originated from the
Mesoproterozoic strata (Wu et al., 2021; Fig. 10). Therefore, the Meso­
proterozoic metamorphic strata are more complex and composed of Cu-
enriched and W-enriched in the South China plate, and the W-enrich­
ment occurs more extensively in Mesoproterozoic metamorphic strata
(Yang et al., 2016; Zhang et al., 2017; Fig. 15). Therefore, the I-type
granodiorite has a certain potential for W mineralization in the Nanling
metallogenic belt. However, the metallogenic scale of the latter may be
B. Liu et al.
lesser than that of S-type and A-type granites.
The W-polymetallic deposits in the Nanling metallogenic belt are
dominated by the skarn-type (e.g., Huangshaping; Ding et al., 2018),
sulfide-quartz vein-type (e.g., Yaogangxian; Peng et al., 2006; Dong
et al., 2014), and greisen-type (e.g., Shizhuyuan; Liao et al., 2021). The
oxygen isotope of scheelite and the H-O isotope of symbiotic quartz
confirmed indicate that the three types of W-polymetallic deposits are
originated from magmatic-hydrothermal fluids, with a small amount of
meteoric input (δ18Ofluid = 4.0‰–8.0‰; Lu et al., 2003; Yang et al.,
2019), which is agreed with the W mineralization related to magmatic-
hydrothermal fluids of the world (Fig. 11; Poulin et al., 2018). However,
the CL images and REE patterns of scheelite grains from the three types
of deposits are different. The CL images of scheelite grains from the
skarn-type deposits are heterogeneous, with a core-rim zonation and
cross-cutting texture (Fig. 8b), and their REE patterns are LREE-enriched
(Chen et al., 2013; Poulin et al., 2018). The CL images of scheelite grains
from the sulfide-quartz vein-type deposits are homogeneous, and their
REE patterns are MREE-enriched or MREE-depleted (Li et al., 2013;
Huang et al., 2017; Huang et al., 2018); the greisen-type scheelite has
plate REE patterns and a weak zonation CL image (Wu et al., 2019).
Various CL images features and different REE patterns of scheelite grains
from the three types of deposits indicate that their fluid characteristics
and evolution processes are different, which is consistent with those in
the Tongshanling Cu-polymetallic ore field (Figs. 8 and 9). Therefore,
the CL images, REE patterns, and O isotopic compositions of scheelite
grains in the Nanling metallogenic belt can be used to trace the source
and evolution of ore-forming fluids.
Except for the Tongshanling Cu-W-Pb-Zn deposit, similar deposits
related to the I-type granodiorite have been reported in the Nanling
metallogenic belt (Cai et al., 2015; Huang et al., 2018), such as the
Shuikoushan deposit in the north and the Baoshan and Jiaoli deposits in
the east (Feng et al., 2012; Chen et al., 2013; Li et al., 2013; Mao et al.,
2013). Their metallogenic ages and mineralization types are similar to
those of the Tongshanling ore field, and they are also dominated by the
skarn and quartz vein-types of mineralization (Feng et al., 2012; Chen
et al., 2013; Li et al., 2013; Mao et al., 2013). Furthermore, several
medium-large W deposits related to the I-type granodiorite have been
discovered on the northern margin of the Yangtze plate (Mao et al.,
2020), such as the Xiaoyao (Su et al., 2018), Matou (Zhao et al.,2015),
and Gaojiabang deposits (Xiao et al., 2017), which indicates that W
mineralization related to the I-type granodiorite is extensively devel­
oped in South China. This may be attributed to the ubiquity of the W-
rich source strata, which are ubiquitous in South China (Shen et al.,
2008; Guo et al., 2014; Jiang et al., 2020; Cao et al., 2020), and to the
fact that different types of granites (i.e., S-, A-, and I-type) have different
degrees of potential for W mineralization. Therefore, the genesis
research and ore prospecting of W in the Cu-polymetallic ore field
related to the I-type granodiorite should be focused further on in the
Nanling metallogenic belt.
7. Conclusions
1) The CL images, major element and trace element compositions,
and REE patterns of scheelite grains formed in the prograde, retrograde,
and sulfide-quartz vein stages reveal multistage W mineralization in the
Tongshanling Cu-polymetallic ore field. Precipitation of the early garnet
resulted in a strong HREE depletion in fluids, and a gradual decrease in
the ΣREE + Y contents of late scheelite was caused by the precipitation
of the early scheelite.
2) The mechanism responsible for REE substitution in scheelite is
dominated by M3, i.e., 3Ca2+ ↔ 2REE3+ + □ (in where □ represents a
site vacancy). The high Mo contents and Eu3+ in scheelite indicate a high
oxygen fugacity in the prograde stage, whereas the low Mo contents and
Eu2+ in scheelite indicate a low oxygen fugacity in the retrograde and
sulfide-quartz vein stages.
3) The δ18OH2O values of fluids in the prograde and sulfide-quartz
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Ore Geology Reviews 143 (2022) 104764
vein stages are similar to those of the magmatic fluid, but are slightly
lower than those of the magmatic fluid, but are slightly lower than those
of the magmatic fluid in the retrograde skarn stage. Thus, the ore-
forming fluids were primarily originated from the magmatic-
hydrothermal fluid, and a small amount of meteoric water was mixed
in the ore-forming fluids in the retrograde stage via intense fluid-rock
interaction.
4) Scheelite grains and the Jurassic granodiorite porphyry pluton in
the Tongshanling ore field have identical εNd(t) and T2DM values,
indicating that the metals were primarily derived from crustal sources
and produced by the partial melting of Mesoproterozoic rocks. Thus, the
genesis research and ore prospecting of W mineralization related to the
I-type granodiorite in Cu-polymetallic ore fields should be evaluated,
particularly for deposits located in the W–Sn metallogenic belt.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by the National Key Research
and Development Plan (Grant No. 2018YFC0603901 and
2018YFC0603902) and Natural Science Foundation of Hunan Province
(Grant No. 2021JJ40722).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.oregeorev.2022.104764.
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