TYPE Original Research

PUBLISHED 02 February 2023

DOI 10.3389/feart.2023.1121856

Melt- and fluid-inclusions studies in

OPEN ACCESS the Wunugetushan porphyry
EDITED BY
Fan Yang,
Lanzhou University, China
Cu–Mo deposit, NE China:
REVIEWED BY
Leilei Dong,
Constraints on the separation of Cu
University of Science and Technology
Beijing, China
Xiaoqiang Zhu,
and Mo
Anhui Normal University, China
Li Tang, Wei Lu 1, Yuecheng Zhang 2, Jingguo Du 1,2* and Zhiwei Song 3
China University of Geosciences, China
1
*CORRESPONDENCE
School of Earth Science and Resources, Chang’an University, Xi’an, China, 2School of Earth Sciences and
Jingguo Du, Resources, China University of Geosciences, Beijing, China, 3China Gold Inner Mongolia Mining Co Ltd,
[email protected] Manchuria, China

SPECIALTY SECTION
This article was submitted to
Economic Geology,
a section of the journal The Wunugetushan large porphyry Cu–Mo deposit in NE China is hosted by
Frontiers in Earth Science
Mesozoic quartz monzonite porphyry and has a Mo-rich core and Cu-rich rim in
RECEIVED 12 December 2022 space. In this paper, melt inclusions in porphyry intrusions and fluid inclusions in
ACCEPTED 19 January 2023
PUBLISHED 02 February 2023
different-stage quartz veins were studied to explore potential parameters leading to
Cu–Mo decoupling. Melt inclusions in porphyry intrusions have rhyolitic
CITATION
Lu W, Zhang Y, Du J and Song Z (2023),
compositions of 71.7–85.3 wt.% SiO2, 1.9–31.3 ppm Cu and 1.7–2.6 ppm Mo.
Melt- and fluid-inclusions studies in the Hydrothermal activity occurred over three stages: 1) Early Mo mineralization at
Wunugetushan porphyry Cu–Mo deposit, high temperatures (543°C–560°C) and CO2-rich fluids of intermediate salinity
NE China: Constraints on the separation of
Cu and Mo.
(11.0–17.3 wt.% NaCl equivalent), accompanied by biotitization and minor
Front. Earth Sci. 11:1121856. K-feldspathization; 2) Late Mo mineralization involving high-salinity (up to
doi: 10.3389/feart.2023.1121856 77.0 wt.% NaCl equiv.) oxidized fluids at intermediate temperatures
COPYRIGHT (400°C–454°C), with K-feldspathization and minor sericitization; 3) A Cu-
© 2023 Lu, Zhang, Du and Song. This is an mineralization stage with high-salinity (up to 45.6 wt.% NaCl equiv.) and CO2-
open-access article distributed under the
terms of the Creative Commons barren fluids characterized by temperature peaks at 250°C–300°C and
Attribution License (CC BY). The use, 400°C–450°C, accompanied by sericitization and illitization. Given possible
distribution or reproduction in other variations in melt Cu/Mo ratios during magmatic activity and redox conditions,
forums is permitted, provided the original
author(s) and the copyright owner(s) are pH, fluid composition, and temperature during the hydrothermal-fluid stage led
credited and that the original publication in to the separation of Cu and Mo, we found that integrated parameters including
this journal is cited, in accordance with increased Cu/Mo ratios in residual melt, variations in the redox state and more acidic
accepted academic practice. No use,
distribution or reproduction is permitted environment of hydrothermal fluids determine spatial separation of two metals.
which does not comply with these terms.
KEYWORDS

melt inclusion, fluid inclusion, Cu and Mo decoupling, wunugetushan, porphyry Cu-Mo

deposit

1 Introduction
Porphyry Cu–(Au–Mo) deposits are main suppliers for various metals and account for 75% of
global Cu reserves, 50% of Mo reserves, and 20% of Au reserves (Sillitoe, 2010). In general, the metals
Cu, Au, Mo, Ag, Pb, and Zn are temporospatially coupled in Cu–Au ± Mo, Cu–Mo, Zn–Pb ± Ag, and
Ag–Au deposits (Pak et al., 2004; Sillitoe, 2010). An understanding of the association and separation of
these metals is helpful in practical geological prospecting. In porphyry Cu–Mo deposits, Cu orebodies
are usually concentrated in shallow outer areas, and Mo orebodies occur at deeper levels in the core
(Redmond and Einaudi, 2010; Sillitoe, 2010; Li et al., 2012; Seo et al., 2012; Chang et al., 2018), but
mineralization time is not always consistent with their spatial distributions. In the Bingham Canyon
(USA; Seo et al., 2012), Hucunnan (eastern China; Cao et al., 2017), and Yulong (Tibet in

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FIGURE 1
(A) Geological map of NE China (after Safonova, 2009), showing (B) distribution of Mesozoic igneous rocks and ore deposits (modified from Wu et al.,
2014). Names of ore deposits: 1– Erentaolegai Ag deposit; 2–Chaganbulagen Ag–Pb–Zn deposit; 3–Jiawula Ag–Pb–Zn deposit; 4–Wunugetushan Cu–Mo
deposit; 5–Babayi Cu–Mo deposit; 6–Badaguan Cu–Mo deposit; 7–Xiaoyinuogaigou Au deposit; 8–Taipingchuan Cu–Mo deposit; 9–Chalukou Mo deposit;
10–Sandaowanzi Au (Sb)deposit; 11—Xinga Mo deposit; 12–Duobaoshan Cu–Mo deposit; 13–Tongshan Cu–Mo deposit; 14–Huojihe Mo deposit;
15–Cuiling Mo deposit; 16– Luming Mo deposit; 17–Laozhashan Au deposit; 18–Jinchanggou Mo deposit; 19–Dashihe Mo deposit; 20–Daheishan Mo
deposit; 21– Taipinggou Mo deposit; 22–Chagan’aobao Fe–Zn deposit; 23– Diyanqinamu Mo deposit; 24–Meng’entaolegai Pb–Zn–Ag deposit;
25—Xiaodonggou Mo deposit; 26–Jiguanshan Mo deposit; 27–Kulitu Mo–Cu deposit.

southwestern China; Chang et al., 2018) deposits, molybdenite Neoproterozoic–Phanerozoic (Figures 1A,B). The CAOB
precipitation postdates chalcopyrite crystallization, whereas in the experienced complex tectonic events and extensive magmatism
Bangpu (Tibet in southwestern China; Wang et al., 2015) and during the Palaeozoic–Mesozoic, including evolution of the Palaeo-
Wunugetushan (northeastern China; Li et al., 2012) deposits, Mo Asian and Mongol–Okhotsk oceans and subduction of the Palaeo-
mineralization predates Cu mineralization. Numerous progresses have Pacific Plate (Xu et al., 2009; Metelkin et al., 2010; Tan et al., 2013; Xu
been made to explore possible drivers of Cu–Mo decoupling and mainly et al., 2013; Liu et al., 2014). As a consequence, a series of E–W- and
include 1) saturation temperatures of molybdenite and chalcopyrite in NE–NNE-trending faults developed, and massive
hydrothermal fluids (Li et al., 2012; Seo et al., 2012; Cao et al., 2017); 2) magmatic–hydrothermal ore deposits formed in NE China
vapour–brine immiscibility (Cao et al., 2017; Chang et al., 2018); 3) changes (Figure 1B). Most of these deposits are related to the Mesozoic
in fluid compositions (Seo et al., 2011; Kokh et al., 2017) including H2, S, Cl, subduction of the Palaeo-Pacific Plate (Metelkin et al., 2010; Wu
and CO2 contents; and 4) the degree of magmatic differentiation (Candela et al., 2011; Liu et al., 2014), and >20 ore deposits are hosted by
and Holland, 1986). Previous studies have focused on changes in physical Mesozoic magmatic rocks, including the Badaguan porphyry Cu–Mo
and chemical conditions during differentiation of metals in melt and the (Gao et al., 2016), Wunugetushan porphyry Cu–Mo (Qin et al., 1999;
evolution of hydrothermal fluids. Chen et al., 2011), Luming porphyry Mo (Hu et al., 2014), Erentaolegai
This study intends to explored the causes of Cu–Mo separation epithermal Ag (Chen et al., 1997), Jiawula hydrothermal vein-type
during both the magmatic and hydrothermal stages of mineralization, Pb–Zn–Ag (Zhai et al., 2013) and Chaganbulagen hydrothermal vein-
with a focus on melt inclusions in porphyry and fluid inclusions (FIs) type Ag–Pb–Zn (Pan and Sun, 1990; Wu et al., 2010) deposits. Other
in quartz veins in the Wunugetushan porphyry deposit, where Cu and ore deposits, such as the Duobaoshan and Tongshan Cu–Mo deposits
Mo orebodies are typically separated. (Zeng et al., 2014), are related to Palaeozoic magmatic activity.

2 Geological background 3 Ore deposit geology

Northeastern (NE) China lies in the southeastern Central Asian The Wunugetushan porphyry Cu–Mo deposit (Figure 2) has
Orogenic Belt (CAOB; Safonova, 2009; Xiao and Santosh, 2014), reserves of 1.27 million tonnes (Mt) Cu and 0.42 Mt Mo (Qin
which developed between the Siberian Craton in the north and the et al., 1999). The deposit was first discovered by the Inner
North China Craton in the south during the Mongolia Geological Survey Bureau in 1960 and has been explored

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FIGURE 2
Geological map of the Wunugetushan porphyry Cu–Mo deposit geological map (modified from Wang et al. (2015)) including sample locations.

by the Metallurgical and Geological Prospecting Company of The mining area includes a typical alteration halo of porphyry Cu
Heilongjiang Province and the China National Gold Group deposits comprising quartz–K-feldspar (QK), quartz–sericite (QS), and
Corporation. Exposed strata in the deposit are mainly Quaternary illite–hydromuscovite (IH) zones from core to rim (Qin et al., 1993; Li
sandstones, mudstones, and conglomerates. Magmatic activity was et al., 2012). The area of alteration in the northern section of the deposit
concentrated in two pulses, as indicated by Late Triassic biotite granite is 2,500–2,800 m long and 200–350 m wide; and that in the southern
that covers an area of ~110 km2 and yields a zircon U–Pb section is 2000–2,600 m long and 1,000–1800 m wide. The total area of
crystallization age of 210.0 ± 2.0 Ma (Mi et al., 2014), and Jurassic alteration is ~5 km2. Mo orebodies are 70–400 m thick and occur mainly
volcanic–subvolcanic stocks, including quartz monzonite porphyry, in the QK and QS zones; Cu orebodies occur mainly in the QS zone, and
rhyolite porphyry, and dacite porphyry (Figure 2). Quartz monzonite are up to 500 m thick in the northern section. Molybdenite-dominated
porphyry is the main host rock for Cu–Mo mineralization, and it quartz veins are commonly cut by chalcopyrite–pyrite-dominated
covers an area of ~0.42 km2 (Figure 3A) and intrudes earlier biotite quartz veins (Figure 3E), indicating earlier Mo mineralization.
granite. The crystallization age (180.4 ± 1.4 Ma) of the quartz Based on crosscutting relationships, alteration of mineral assemblages,
monzonite porphyry is consistent with the molybdenite ore Re–Os and the different mineralization types in quartz veins, the formation of
age of 180.5 ± 2.0 Ma (Wang et al., 2015). NE-trending faults and quartz veins is inferred to have involved three main stages (Figure 4): I)
volcanic ring fractures are the major structures in the Wunugetushan quartz + biotite ± molybdenite ± K-feldspar + magnetite (Figures 4A–C);
mining area, which shape the distribution of Cu–Mo orebodies. Late II) quartz + K-feldspar ± sericite + molybdenite (Figures 4B,D); and III)
NW-trending faults and associated rhyolite porphyry dikes (Figures quartz + sericite + chalcopyrite + pyrite (Figures 4E,F). Mo mineralization is
3B–D) represent post-mineralization events, cutting through or associated with Stage I and II, with alteration minerals including mainly
deforming the orebodies. biotite + magnetite ± K-feldspar + sericite. Biotite predated K-feldspar

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FIGURE 3
Field photographs of magmatic rocks and quartz veins in Wunugetushan porphyry Cu-Mo deposit. (A) quartz monzonite porphyry has a contact with
biotite granite by fault; late (B) rhyolite porphyry, (C) dacite porphyry and (D) diabase porphyry dikes distribute along the faults or cracks within biotite granite.
(E) Mo-dominated quartz vein is cut by late Cu-dominated quartz vein.

(biotite ± K-feldspar + quartz veins are cut by K-feldspar + molybdenite + thin sections (70–100 µm thick) from each sample were polished and
quartz veins; Figure 4B). Stage III was the main period of Cu mineralization, studied by optical microscopy. Because fluid inclusions may be
with Cu sulphides (e.g., chalcopyrite and bornite) being precipitated modified during fracturing to form secondary inclusions, only
together with pyrite, sericite, and minor illite (Figures 4E,F). primary inclusions could represent the physical and chemical
conditions of the hydrothermal fluid. Petrographic observations
were undertaken at the China University of Geosciences, Beijing,
4 Samples and analytical methods China, using an Olympus BX51 microscope to identify primary FIs.
Identification of primary FIs was based on their being isolated and
4.1 FI petrography and microthermometry completely enclosed by the quartz host, or growing along quartz
growth zones or c axes (Figure 5). Only primary inclusions or
Representative quartz veins were sampled in the Cu and Mo inclusion assemblages exhibiting consistent phase proportions at
orebodies (16 and 32 samples, respectively; Figure 2). Up to seven room temperature (Figure 5) were selected for further

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FIGURE 4
Alteration and mineralization hosted in various quartz veins. (A) bio + qtz + moly vein, accompanied with biotitization. (B) early bio + qtz + kfs± moly vein
is cut by kfs + qtz + moly vein, early K-feldspathization alteration is overprinted by sericitization. (C) kfs + qtz + moly vein, feldspar is replaced by illite. (D)
sericite and illite distribute symmetrically on the two sides of kfs + qtz + moly vein. (E, F) ser+qtz+py±ccp vein. Abbreviations: kfs–K-feldspar;
plag–plagioclase; qtz–quartz; ser–sericite; bio–biotite; py–pyrite; moly–molybdenite; ccp–chalcopyrite.

microthermometric study at the MLR Key Laboratory of 4.3 LA–ICP–MS analysis of melt inclusions
Metallogeny and Mineral Assessment, Institute of Mineral
Resources, Chinese Academy of Geological Sciences (CAGS), Laser ablation–inductively coupled plasma–mass spectrometry
Beijing, China. The analyses employed a Linkham (LA–ICP–MS) analyses of melt inclusions were undertaken at the State
(United Kingdom) THMS600 temperature-control stage with a Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry,
range of −180°C–580°C (precision ±0.1°C for cooling and ±2°C for China Academy of Science (CAS), Guiyang, using an Agilent
heating). Ice melting temperatures were observed at a heating rate of 7900 ICP–MS system coupled to a GeoLasPro 193 nm ArF excimer
0.1°C min–1, and homogenization temperatures at 1°C min–1. LA system (Lan et al., 2017a; Lan et al., 2017b). Details of instrumental
Salinities (wt.% NaCl equivalent) of aqueous FIs and those operating conditions can be found in Lan et al. (2017a), Lan et al. (2017b).
containing halite daughter minerals were calculated from ice The sample chamber was flushed with He gas at 0.5 L min–1. A laser spot of
melting (Bodnar, 1993) and halite dissolution (Sterner et al., diameter of 30–50 μm was applied with repetition rates of 4–10 Hz and
1988) temperatures, respectively. energy densities of 8–10 J cm–2, depending on melt-inclusion size.
Inclusions connected to micro-cracks or surrounded by late FI trails
were excluded. Only entire, isolated, unexposed melt inclusions being
4.2 Laser Raman microspectroscopy drilled out of the host quartz. Signals associated with excess ablated host
were subtracted from sample signals following Halter et al. (2004).
Laser Raman spectroscopic analysis of FIs employed a LabRAM Elements were quantified against the US National Institute of
HR800 (Horiba, Japan) microspectrometer at the Beijing Research Standards and Technology Standard Reference Material (SRM) 610 as
Institute of Uranium Geology, Beijing, China. An Ar+ ion laser with a an external standard, and the constant Al2O3 content (~14 wt.%) of whole-
wavelength of 532 nm and a source power of 25 mW were used, with a rock quartz monzonite porphyry was used as an internal standard. A
spectral resolution of ±1 cm−1. typical LA–ICP–MS signal of melt inclusions ablated through host quartz

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FIGURE 5
The criteria for identifying primary fluid inclusions. (A, B) isolated, totally enclosed by quartz; (C, D) fluid inclusions growing along the growth zoning of
quartz; (E) primary fluid inclusion assemblages with the consistent phase ratios.

is provided in Supplementary Figure S1. Melt compositions were finally 5 Results

calculated by subtracting the host until the results fit on whole-rock
composition trends (see in Supplementary Figure S2). This approach 5.1 Fluid inclusion petrography
irreversibly will cause the compositional change that leads to misfits with
regard to whole-rock trends (Heinrich et al. 2003). The major elements FIs are hosted in quartz at Wunugetushan deposit, with four
results from Wunugetushan agree well with trends defined by the whole- types identified on the basis of phase types and ratios at room
rock data (see in Supplementary Figure S2). temperatures (22.5°C), as follows. 1) C-type FIs contain either pure

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FIGURE 6
Representative fluid inclusion types in Wunugetushan porphyry Cu-Mo deposit. (A) C-type inclusions in early Mo mineralization stage and (B) late Mo
mineralization stage. (C) S-type inclusions in late Mo mineralization stage and (D) Cu mineralization stage. (E) V-type inclusions in early Mo mineralization
stage and (F) L-type inclusions in Cu mineralization. Abbreviations: LH2O- liquid H2O, LCO2- liquid CO2, VCO2- vapor CO2, VH2O- vapor H2O, hal-halite, hem-
hematite, anh-anhydrite, op-opaque mineral.

CO2 vapour or an aqueous phase plus one or two carbonic phases hematite, halite, anhydrite, sylvite, and other opaque minerals
(Figures 6A,B). They are generally small (<12 µm diameter) with a (Figures 6C,D). During heating, sylvite disappear first, then
subhedral to irregular crystal morphology (Figure 6A). Most are halite crystals, the bubbles, and finally the anhydrite. Most
hosted in early molybdenite + K-feldspar + quartz veins. In the S-type inclusions homogenize to a liquid phase. 3) Vapour-
two- and three-phase FIs, CO2-bearing vapour accounts for dominated V-type FIs (Figure 6E) contain 60–100 vol.% vapour
10–30 vol.% and 40–60 vol.% of the total inclusion, respectively and coexist with other types of FIs. They are round or subhedral in
(Figure 6B). C-type FIs usually homogenize into liquid or shape with diameters of 7–13 µm (Figure 6E), and usually grow
occasionally vapour-phase inclusions, while some pure CO2 together with S-type FIs in quartz growth zones. V-type fluid
vapour inclusions are transformed into two- or three-phase CO2 inclusions are more abundant in early Stage I and II quartz
inclusions at room temperatures (23°C–25°C). 2) Solid-bearing veins than in later veins. 4) Liquid-rich L-type FIs (Figure 6F)
S-type FIs contain one or more daughter minerals, an aqueous contain 10–30 vol.% vapour and >60 vol.% liquid. They are
liquid, and a relatively small vapour bubble (Figures 6C,D). They irregular in shape with diameters of 5–15 µm (Figure 6F). L-type
include negative crystal clusters or isolated individuals hosted in FIs occur mainly in Stage III quartz veins, and commonly coexist
late Stage II and III quartz veins. Daughter minerals include with V-type FIs and occasionally S- and C-type FIs.

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and mineralization type indicate that mineralization stages can be

further subdivided into Mo mineralization and Cu mineralization
stages, with the former including early and late Mo stages based on
alteration type.
In the early Mo mineralization stage, FIs are mainly of the C- and
V-types, with minor L-type FIs. The C-type FIs yield homogenization
temperatures of 543°C–560°C and clathrate-melting temperatures of
4.1°C–6.4°C (two yielded carbonic-phase homogenization
temperatures of 21.5°C–25.5°C). L-type FIs have homogenization
temperatures of 560°C–570°C (Figure 7A) and ice-melting
temperatures of −7.4°C to −13.5°C (corresponding to salinities of
11.0–17.3 wt.% NaCl equiv.). V-type FIs of this stage are usually
difficult to observe during heating because of their limited liquid
content.
In the late Mo mineralization stage, the abundance of FIs follows
the order V-type > S-type > L-type. Homogenization temperatures of
FIs are clustered at 340°C–460°C (Figure 7B) with peaks at 400°C and
450°C. V-type FIs have homogenization temperatures of 302°C–512°C,
ice-melting temperatures of −6.2°C to −19.7°C, and salinities of
9.5–22.5 wt.% NaCl equiv. During heating, the vapour bubbles
disappear before dissolution of the daughter-mineral crystal. This is
opposite that of other S-type FIs, possibly due to the fluid system being
heterogeneously saturated or oversaturated. Homogenization
temperatures of S-type FIs are in the range of 291°C–503°C, with
salinities of 42.4–77.0 wt.% NaCl equiv.
In the Cu mineralization stage, FI abundance follows the order:
L-type > V-type > S-type. Homogenization temperatures are in the
range 230°C–500°C with peaks at 250°C–300°C and 400°C–450°C; the
latter is similar to that of FIs of the late Mo mineralization stages
(Figure 7C). The L-type FIs have homogenization-temperature peaks
at 300°C–350°C and 400°C–450°C, and ice-melting temperatures
of −7.1°C to −15.4°C (corresponding to salinities of 11.2–19.0 wt.%
NaCl equiv.). V-type FIs have homogenization temperatures of
400°C–450°C and ice-melting temperatures of −7.5°C to −16.9°C,
with salinities of 7.2–20.1 wt.% NaCl equiv. Vapour bubbles within
S-type FIs disappear earlier than the halite (except for two outliers)
during heating. The S-type FIs have homogenization temperatures of
244°C–319°C, daughter-mineral melting temperatures of
244°C–315°C, and salinities of 32.9–45.6 wt.% NaCl equiv.

5.3 Laser Raman microspectroscopy

Laser Raman microspectroscopy results (Figure 8) indicate that

CO2 is detectable only in FIs from early molybdenite-bearing quartz
veins (Figures 8A,B). The red-coloured daughter mineral in FIs from
Cu- and Mo-dominated quartz veins is hematite (Figure 8C). H2O is
the major liquid phase in all FIs (Figure 8D).
FIGURE 7
Frequency histograms of total homogenization temperatures (Th)
for fluid inclusions in different stages. (A) early Mo mineralization stage; 5.4 Melt inclusion composition
(B) late Mo mineralization stage; (C) Cu mineralization stage.

Melt inclusions in quartz from the monzonite porphyry are

completely crystallized, and those in dacite porphyry are crystallized or
partly glassy (Figure 9). Melt inclusions from monzonite porphyry and
5.2 Microthermometry dacite porphyry have similar major- and trace-element compositions,
including 71.7–85.3 wt.% SiO2, ~14.0 wt.% Al2O3, <0.7 wt.% FeOt,
Microthermometric data for FIs are summarized in Table S1 and 3.8–6.1 wt.% K2O, 0.1–0.2 wt.% Na2O, 0.3–1.0 wt.% CaO, 67–79 ppm
Figure 7. Relationships between different generations of quartz vein Rb, 1.4–2.0 ppm Cs, 1.9–41.5 ppm Cu, and 1.0–2.6 ppm Mo (Table S2).

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FIGURE 8
Laser Raman spectra of fluid inclusions. (A, B) CO2 in vapor phase of V-type inclusion. (C) hematite daughter mineral in S-type inclusion. (D) H2O in vapor
phase of L-type inclusion. Abbreviations: hem-hematite, qtz-quartz.

FIGURE 9
Representative hand specimen of quart monzonite porphyry and dacite porphyry and photomicrographs of melt inclusions within them. (A) quart
monzonite porphyry comprising of plag (45%), qtz (10%), and matrix (45%). (B) totally isolated crystalline melt inclusion hosted in quartz of monzonite
porphyry. (C) dacite porphyry consisting of plag + quartz (10%) and matrix (90%). (D) quartz-hosted melt inclusions in dacite porphyry. Abbreviations: qtz-
quartz, plag–plagioclase, melt inclusion–MI, fluid inclusion–FI.

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FIGURE 10
Plot of homogenization temperatures (Th) and salinity of individual fluid inclusion in different stages.

6 Discussion 1989; Tan et al., 2013). A high H+ activity may also promote CO2
escape through reactions such as 2H+ + CO32− → H2O+ CO2↑. With
6.1 Fluid evolution in the wunugetushan ore the gradual assumption of alkali cations and OH−, crystallization of
deposit anhydrite and hematite, and escape of CO2, the activity of H+ in fluids
would have increased while fO2 decreased (Hu et al., 2002; Ulrich et al.,
The physicochemical evolution of magmatic–hydrothermal fluids 2001; Heinrich, 2005; Seo et al., 2012). Acidic alteration minerals
depends strongly on emplacement depth. Fluids exsolved from deep (sericite and illite) and sulphides (mainly molybdenite) would then
granitic intrusions under conditions of high temperature and pressure have precipitated.
approximate the granite solidus, and lithostatic initial fluids are In the late Cu mineralization stage, fluids became more acidic with
typically single-phase, of intermediate salinity, and CO2-rich, as in low fO2, and were CO2-barren after the crystallization of alkali cations
most porphyry-mineralized systems (Williams-Jones and Heinrich, (K+) and OH-bearing minerals (e.g., biotite and K-feldspar), anhydrite
2005; Audétat et al., 2008; Kouzmanov and Pokrovski, 2012; Audétat and hematite, and loss of CO2 (Heinrich, 2005). The low fO2 and high
and Li, 2017; Audétat, 2019). H+ activity of fluids led to extensive deposition of acidic alteration
In the early Mo mineralization stage of the Wunugetushan minerals (sericite and illite) and sulphides (mainly chalcopyrite). In
porphyry Cu–Mo deposit, a high-temperature (>550°C), CO2-rich the Cu mineralization stages, S-type FIs coexisting with V-type FIs in
fluid was first exsolved from the magmatic–hydrothermal system. This single quartz grains homogenized to a liquid phase, and the latter
fluid evolved near the interior of the porphyry host and was similar to homogenized to a vapour phase at similar homogenization
the intermediate-density-type fluid of Audétat. (2019), having a temperatures, indicating a boiling-fluid system. Fluid mixing is
variable and relatively low salinity (4.1–17.3 wt.% NaCl equiv.; represented by the two temperature peaks (Figure 7C) with the hot
Figure 10). During this stage, alteration involved strong alkali magmatic-hydrothermal fluid adding by cold meteoric water.
metasomatism, as indicated by the abundance of biotite and
K-feldspar resulting from interaction between hydrothermal fluid
and wall rock. The preservation of magnetite coexisting with biotite 6.2 Factors controlling the separation of Cu
indicates the high oxygen fugacity (fO2) of the primary fluids and Mo
(Figure 4C). This resulted in limited sulphur activity, and little
molybdenite and pyrite were precipitated. Temporospatial decoupling of Cu and Mo has been documented
Fluids of the late Mo mineralization stage were highly oxidized, in many porphyry Cu–(Mo–Au) deposits (Sillitoe, 2010 and reference
alkali-rich and of high salinity, resulting in the growth of high-fO2 therein) but the causative factors remain elusive. The Cu content of
minerals (anhydrite and hematite), many daughter minerals within magma is strongly influenced by early sulphide saturation (Audétat
FIs, and strong potassic alteration. In contrast to the early et al., 2011). Because of the high partition coefficient for Cu between
mineralization stage, fluids were depleted in CO2, possibly because sulphide and silicate melt (Dsulphide/melt Cu= 250–900; Audétat
of fluid boiling or mixing during local depressurization and the et al., 2011) and general sulphide saturation in mantle sources or
addition of meteoric water into the open hydrothermal system, as during early crystal fractionation (Lee et al., 2012; Lee and Tang, 2020),
indicated by previously published FI δD and δ18O data (Ye and Wang, the Cu content of the melt will decrease as magma evolves (e.g., Du

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rhyolite (75–85 wt.% SiO2) worldwide (Audétat et al., 2011).

Therefore, for a highly acidic intrusive phase, as in the
Wunugetushan example, selective precipitation of two metals with
contrasting crystallization temperatures could lead to the separation of
Cu and Mo.
Molybdenum orebodies in the Wunugetushan deposit are
concentrated in the deep interior of the porphyry host, while Cu
orebodies occur more towards the exterior, with their spatial
distribution being similar to that in many other porphyry
Cu–Mo deposits (e.g., the Yulong deposit; Chang et al., 2018).
However, the Wunugetushan case differs in the timing of
molybdenite and chalcopyrite, with molybdenite precipitating
earlier than chalcopyrite, contrary to the situation in other ore
FIGURE 11 deposits. Oxidized fluids generally promote metal transport
Cu/Mo ratios in melt vs. SiO2 in melt.
because the high solubility, but deposition requires a reducing
environment, as achieved by the breakdown of oxidized minerals
such as anhydrite and magnetite. Chalcopyrite precipitation is
promoted by neutral or oxidized fluids, contrasting with
and Audétat, 2020). In comparison with the strongly chalcophilic molybdenite, which tends to precipitate from more reduced and
behaviour of Cu, the melt Mo content increases during magma acidic fluids (Seo et al., 2012). Small changes in the redox state or
evolution and is less affected by early molybdenite saturation pH of hydrothermal fluids may thus be responsible for spatial
(Audétat et al., 2011) because of the low partition coefficient for separation of Cu and Mo. In the early molybdenite–quartz veins,
Mo between sulphide and silicate melt (Dsulphide/melt Mo= 0.2–10; molybdenite was first precipitated from alkaline and high-fO2
Audétat et al., 2011). Progressive magma differentiation should fluids, but amounts of molybdenite are small due to the high
therefore lower the Cu/Mo ratio of residual melt in multi-phase fO2 of the initial fluids. Molybdenite precipitation occurred
porphyry intrusion stocks (Candela and Holland, 1986), and in mainly during the late mineralization stage, when oxidizing
such a scenario molybdenite-bearing quartz veins are hosted by minerals were consumed and fluids became more acidic and less
late porphyry intrusions and molybdenite precipitation generally oxidized. Chalcopyrite precipitation was accompanied by strong
postdating chalcopyrite crystallization. This is observed in most acidic alteration (sericitization and illitization) and the formation
porphyry Cu–Mo deposits, as in the Bingham Canyon (USA; Seo of more oxidized minerals such as hematite (Figure 5D). Increasing
et al., 2012), Hucunnan (E China; Cao et al., 2017), and Yulong (Tibet fluid fO2 and acidity, from the Mo to Cu mineralization stages, thus
in southwestern China; Chang et al., 2018) deposits, where early played a positive role in the spatial separation of the two metals.
chalcopyrite precipitation is accompanied with widespread potassic Higher CO2 concentrations in aqueous fluids may reduce the
alteration. As a consequence, the contrasting behaviours of Cu and Mo solubility of Mo (Kokh et al., 2017). Decompression during
during sulphide saturation will reduce the Cu/Mo ratio in melt, emplacement, condensation of magma bodies and CO2 escape
leading to Cu behaving compatibly and Mo incompatibly, with may thus cause the early precipitation of molybdenite, but
spatial Cu–Mo decoupling. However, early sulphide saturation is variations in CO2 concentration from the Mo to Cu
limited in relatively basic to intermediate melts with SiO2 contents mineralization stages would merely affect the molybdenite
of 50–65 wt.%, and as magma evolves to more acidic compositions saturation of initial fluids, whether causing the separation of Cu
(SiO2 content >70 wt.%) the decrease of melt Cu/Mo ratio will be and Mo is not clear. Ascent and decompression of porphyry
depressed (Audétat et al., 2011) and a high Cu/Mo ratio might be intrusions would lead to the original single-phase fluids entering
expected due to the high saturation temperature of molybdenite (close brine and vapour phases, which are immiscible in many porphyry
to the granite solidus at >550°C; Audétat and Li, 2017) relative to Cu systems (Williams-Jones and Heinrich, 2005; Audétat et al.,
chalcopyrite. 2008; Kouzmanov and Pokrovski, 2012; Audétat, 2019).
In the Wunugetushan deposit, the effect of early sulphide Experimental studies have shown that brine inclusions generally
saturation is weak and Cu–Mo orebodies tend to be simple, host higher Mo concentrations than vapour-rich inclusions (Klemm
featuring a single orebody related to a single acidic intrusion phase. et al., 2008; Zajacz et al., 2017; Chang et al., 2018), whereas Cu also
Early sulphide saturation and the possible injection of mafic magma preferentially be transported by hypersaline brines than vapour-
pulses have negligible effects on the Cu and Mo contents of the dominated FIs (Lerchbaumer and Audétat, 2012). Both Mo- and
magma. This inference is supported by the lack of significant Mo or Cu Cu-rich brine phases could have condensed from fluids and
mineralization in late diabase porphyry at Wunugetushan. Melt- accumulated deep in the ore deposit due to their high densities.
inclusion data indicate that causative magmas of the Chang et al. (2018) reported local Cu–Mo decoupling in the Yulong
Wunugetushan deposit have a rhyolitic composition Cu–Mo deposit caused by the sequential deposition of Mo and Cu
(71.7–83.6 wt.% SiO2), relatively more acidic than other porphyry from a condensed brine phase, but whether vapour/brine
Cu(–Mo) deposits. The melt Cu/Mo ratio increases with SiO2 content immiscibility could be a dominant factor in Cu–Mo separation
(Figure 11), possibly due to early molybdenite crystallization at high in an ore-deposit scale is still need explored. In the case of
temperatures of 560°C–570°C (approximating the granite solidus) Wunugetushan, vapor-brine immiscibility of FI is not popular
leading to a decrease in Mo content of the evolved melt. The and whether such a process affect the Cu/Mo decoupling still
molybdenite saturation also has been observed in many high-silica need to be explored in the future.

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Lu et al. 10.3389/feart.2023.1121856

Taken together, the spatial separation of Cu and Mo in the Funding

Wunugetushan deposit resulted from the combined effects of
multiple factors, including melt Cu/Mo ratios, and the redox state This study was supported financially by the National Natural Science
and pH variations of the hydrothermal fluid. It is unclear whether Foundation of China (No. 42002072), Fundamental Research Funds for
vapor-brine immiscibility predominates in causing Cu–Mo the Central Universities (Grant 300102271304), Natural Science Basic
separation, especially on the scale of an ore deposit. Research Program of Shaanxi (Program No. 2023-JC-QN-0336).

7 Conclusion Acknowledgments
Field surveys and melt- and fluid-inclusion studies of the We also want to thank associate editor Fan Yang and three
Wunugetushan porphyry Cu–Mo deposit have led to the following reviewers for their constructive suggestions.
conclusions. The Cu and Mo orebodies are hosted by a single
monzonite porphyry, with Mo orebodies tending to be
concentrated within the porphyry host and Cu orebodies Conflict of interest
externally. The hydrothermal fluid evolved through three main
stages: early and late Mo mineralization and Cu mineralization. ZS was employed by China Gold Inner Mongolia Mining Co Ltd.
Across these stages, fluids changed from initially being of The remaining authors declare that the research was conducted in
intermediate salinity, CO2-rich, oxidized, and high temperature, to the absence of any commercial or financial relationships that could be
being of high salinity and CO2-depleted, and finally to again being of construed as a potential conflict of interest.
intermediate salinity but highly oxidized. The separation of Cu and The reviewer LT declared a shared affiliation with the author YZ to
Mo was promoted by a combination of factors including increased Cu/ the handling editor at time of review.
Mo ratios in residual melt, and the changing redox state and acidity of
ore-forming fluids.
Publisher’s note
Data availability statement All claims expressed in this article are solely those of the
authors and do not necessarily represent those of their affiliated
The datasets presented in this study can be found in online organizations, or those of the publisher, the editors and the
repositories. The names of the repository/repositories and reviewers. Any product that may be evaluated in this article, or
accession number(s) can be found in the article/Supplementary claim that may be made by its manufacturer, is not guaranteed or
Material. endorsed by the publisher.

Author contributions Supplementary material

JD designed the project and collected the samples; WL wrote the The Supplementary Material for this article can be found online at:
first manuscript and studies the melt inclusions; YZ anticipated the https://www.frontiersin.org/articles/10.3389/feart.2023.1121856/
field work and fluid inclusion studies; ZS did the field work. full#supplementary-material

References
Audétat, A., Dolejs, D., and Lowenstern, J. B. (2011). Molybdenite saturation in silicic Implications for the separation of copper and molybdenum in skarn deposits. Ore.
magmas: Occurrence and petrological implications. J. Pet. 52, 891–904. doi:10.1093/ Geol. Rev. 81, 925–939. doi:10.1016/j.oregeorev.2016.04.013
petrology/egr008
Chang, J., Li, J. W., and Audétat, A. (2018). Formation and evolution of multistage
Audétat, A., and Li, W. T. (2017). The Genesis of Climax-type porphyry Mo deposits: magmatic-hydrothermal fluids at the Yulong porphyry Cu-Mo deposit, eastern Tibet:
Insights from fluid inclusions and melt inclusions. Ore. Geol. Rev. 88, 436–460. doi:10. Insights from LA-ICP-MS analysis of fluid inclusions. Geochim. Cosmochim. Acta. 232,
1016/j.oregeorev.2017.05.018 181–205. doi:10.1016/j.gca.2018.04.009
Audétat, A., Pettke, T., Heinrich, C. A., and Bodnar, R. J. (2008). Special paper: The Chen, X., Li, H. N., and Duan, G. Z. (1997). Origin of the Erentaolegai granite and its
composition of magmatic-hydrothermal fluids in barren and mineralized intrusions. Econ. relations with silver deposit, Inner Mongolia. Min. Resour. Geol. 11, 91–98.
Geol. 103, 877–908. doi:10.2113/gsecongeo.103.5.877
Chen, Z. G., Zhang, L. C., Wan, B., Wu, H. Y., and Cleven, N. (2011).
Audétat, A. (2019). The metal content of magmatic-hydrothermal fluids and its Geochronology and geochemistry of the Wunugetushan porphyry Cu–Mo deposit
relationship to mineralization potential. Econ. Geol. 114 (6), 1033–1056. doi:10.5382/ in NE China, and their geological significance. Ore Geol. Rev. 43, 92–105. doi:10.
econgeo.4673 1016/j.oregeorev.2011.08.007
Bodnar, R. J. (1993). Revised equation and table for determining the freezing point Du, J. G., and Audétat, A. (2020). Early sulfide saturation is not detrimental to porphyry
depression of H2O–NaCl solutions. Geochim Cosmochim. Acta. 57, 683–684. doi:10.1016/ Cu-Au formation. Geology 48, 519–524. doi:10.1130/G47169.17
0016-7037(93)90378-a
Gao, B. Y., Zhang, L. C., Jin, X. D., Li, W. J., Chen, Z. G., and Zhu, M. T. (2016).
Candela, P. A., and Holland, H. D. (1986). A mass transfer model for copper and Geochronology and geochemistry of the Badaguan porphyry Cu–Mo deposit in Derbugan
molybdenum in magmatic hydrothermal systems:the origin of porphyry-type ore deposits. metallogenic belt of the NE China, and their geological significances. Int. J. Earth Sci. Geol.
Econ. Geol. 81, 1–19. doi:10.2113/gsecongeo.81.1.1 Rundsch) 105, 507–519. doi:10.1007/s00531-015-1261-4
Cao, Y., Zheng, Z. J., Du, Y. L., Gao, F. P., Qin, X. L., Yang, H. M., et al. (2017). Ore Halter, W. E., Pettke, T., and Heinrich, C. A. (2004). Laser-ablation ICP-ms
geology and fluid inclusions of the Hucunnan deposit, Tongling, Eastern China: analysis of silicate and sulfide melt inclusions in an andesitic complex I:

Frontiers in Earth Science 12 frontiersin.org

Lu et al. 10.3389/feart.2023.1121856

Analytical approach and data evaluation. Contrib. Mineral. Pet. 147, 385–396. doi:10. Safonova, I. Y. (2009). Intraplate magmatism and oceanic plate stratigraphy of the paleo-
1007/s00410-004-0562-6 asian and paleo-pacific oceans from 600 to 140 Ma. Ore. Geol. Rev. 35, 137–154. doi:10.
1016/j.oregeorev.2008.09.002
Heinrich, C. A., Pettke, T., Halter, W. E., Aigner-Torres, M., Audétat, A., Gunther, D.,
et al. (2003). Quantitative multi-element analysis of minerals, fluid and melt inclusions by Seo, J. H., Guillong, M., Aerts, M., Zajacz, Z., and Heinrich, C. A. (2011). Microanalysis
laser-ablation inductively-coupled-plasma mass-spectrometry. Geochim. Cosmochim. of S, Cl, and Br in fluid inclusions by LA-ICP-MS. Chem. Geol. 284, 35–44. doi:10.1016/j.
Acta. 67, 3473–3497. doi:10.1016/s0016-7037(03)00084-x chemgeo.2011.02.003
Heinrich, C. A. (2005). The physical and chemical evolution of low-salinity magmatic Seo, J. H., Guillong, M., and Heinrich, C. A. (2012). Separation of molybdenum
fluids at the porphyry to epithermal transition: A thermodynamic study. Min. Deposita. 39, and copper in porphyry deposits: The roles of sulfur, redox, and pH in ore mineral
864–889. doi:10.1007/s00126-004-0461-9 deposition at Bingham Canyon. Econ. Geol. 107, 333–356. doi:10.2113/econgeo.
107.2.333
Hu, S. X., Zhao, Y. Y., Sun, J. G., Ling, H. F., Ye, Y., Lu, B., et al. (2002). Fluids and their
sources for gold mineralization in the north China platform. J. Nanjing Univ. Nat. Sci. 38, Sillitoe, R. H. (2010). Porphyry copper systems. Econ. Geol. 105, 3–41. doi:10.2113/
381–391. gsecongeo.105.1.3
Hu, X. L., Ding, Z. J., Yao, S. Z., He, M. C., Shen, J., Zhu, B. P., et al. (2014). Sterner, S. M., Hall, D. L., and Bodnar, R. J. (1988). Synthetic fluid inclusions. V.
Geochronology and Sr–Nd–Hf isotopes of the mesozoic granitoids from the great Solubility relations in the system NaCl–KCl–H 2 O under vapor–saturated
xing’an and lesser xing’an ranges: Implications for petrogenesis and tectonic evolution conditions. Geochim.Cosmochim. Acta 52, 989–1005. doi:10.1016/0016-7037(88)
in NE China. Geol. J. 51, 1–20. doi:10.1002/gj.2576 90254-2
Klemm, L. M., Pettke, T., and Heinrich, C. A. (2008). Fluid and source magma evolution Tan, G., She, H. Q., Yin, J. P., Yang, Y. C., Li, J. W., Xiang, A. P., et al. (2013). Source and
of the Questa porphyry Mo deposit, New Mexico, USA. Min. Deposita 43, 533–552. doi:10. evolution of ore-fluid in wunugetushan large Cu-Mo deposit, inner Mongolia: Evidence
1007/s00126-008-0181-7 from fluid inclusions and hydrogen and oxygen isotopic geochemistry. Glob. Geol. 32 (3),
463–482 in Chinese with English abstract.
Kokh, M. A., Akinfiev, N. N., Pokrovski, G. S., Salvi, S., and Guillaume, D. (2017). The
role of carbon dioxide in the transport and fractionation of metals by geological fluids. Ulrich, T., Gunther, D., and Heinrich, C. A. (2001). The evolution of a porphyry Cu–Au
Geochim. Cosmochim. Acta. 197, 433–466. doi:10.1016/j.gca.2016.11.007 deposit, based on LA-ICP-MS analysis of fluid inclusions: Bajo de la Alumbrera,
Argentina. Econ. Geol. 97, 1889–1920. doi:10.2113/gsecongeo.97.8.1889
Kouzmanov, K., and Pokrovski, G. S. (2012). Hydrothermal controls on metal
distribution in porphyry Cu (-Mo-Au) systems. Soc. Econ. Geol. Special Publ. 16, Wang, L. Q., Tang, J. X., Chen, W. B., Chen, W., Zhang, Z., Lin, X., et al. (2015a). Origin
573–618. doi:10.5382/SP.16.22 of the ore-forming fluids and metals of the Bangpu porphyry Mo–Cu deposit of tibet,
China: Constraints from He–Ar, H–O, S and Pb isotopes. J. Asian Earth Sci. 103, 276–287.
Lan, T. G., Hu, R. Z., Bi, X. W., Mao, G. J., Wen, B. J., Liu, L., et al. (2017b).
doi:10.1016/j.jseaes.2014.07.041
Metasomatized asthenospheric mantle contributing to the generation of Cu-Mo
deposits within an intracontinental setting: A case study of the ~128 Ma Wang, Y. H., Zhao, C. B., Zhang, F. F., Liu, J. J., Wang, J. P., Peng, R. M., et al. (2015b).
wangjiazhuang Cu-Mo deposit, eastern north China Craton. J. Asian Earth Sci. 160, SIMS zircon U–Pb and molybdenite Re–Os geochronology, Hf isotope, and whole-rock
460–489. doi:10.1016/j.jseaes.2017.07.014 geochemistry of the Wunugetushan porphyry Cu–Mo deposit and granitoids in NE China
and their geological significance. Gondwana Res. 28, 1228–1245. doi:10.1016/j.gr.2014.
Lan, T. G., Hu, R. Z., Fan, H. R., Bi, X. W., Tang, Y. W., Zhou, L., et al. (2017a). In-situ
10.001
analysis of major and trace elements in fluid inclusion and quartz: LA-ICP-MS method
and applications to ore deposits. Acta Pet. Sin. 33, 3239–3262 in Chinese with English Williams-Jones, A. E., and Heinrich, C. A. (2005). 100th anniversary special paper:
abstract. Vapor transport of metals and the formation of magmatic-hydrothermal ore deposits.
Econ. Geol. 100, 1287–1312. doi:10.2113/gsecongeo.100.7.1287
Lee, C.-T., Luffi, P., Chin, E. J., Bouchet, R., Dasgupta, R., Morton, D. M., et al. (2012).
Copper systematics in arc magmas and implications for crust–mantle differentiation. Wu, C., Tian, J., Chang, F., Liu, C., and Liu, W. (2014). Early cretaceous A-type granites
Science 336 (6077), 64–68. doi:10.1126/science.121731 and Mo mineralization, aershan area, eastern inner Mongolia, northeast China:
Geochemical and isotopic constraints. Int. Geol. Rev. 56, 1357–1376. doi:10.1080/
Lee, C.-T.-A., and Tang, M. (2020). How to make porphyry copper deposits. Earth
00206814.2014.935965
Planet. Sci. Lett. 529, 1–11. doi:10.1016/j.epsl.2019.115868
Wu, F. Y., Sun, D. Y., Ge, W. C., Zhang, Y. B., Grant, M. L., Wilde, S. A., et al. (2011).
Lerchbaumer, L., and Audétat, A. (2012). The metal content of silicate melts and
Geochronology of the Phanerozoic granitoids in northeastern China. J. Asian Earth Sci. 41,
aqueous fluidsin subeconomically Mo-mineralized granites: Implications for porphyry Mo
1–30. doi:10.1016/j.jseaes.2010.11.014
genesis. Econ. Geol. 108, 987–1013. doi:10.2113/econgeo.108.5.987
Wu, G., Mei, M., and Gao, F. J. (2010). Ore-forming fluid characteristics and Genesis of
Li, N., Chen, Y. J., Ulrich, T., and Lai, Y. (2012). Fluid inclusion study of the Wunugetu
silver–lead–zinc deposits in the Manzhouli area, Inner Mongolia, China. Earth Sci. Front.
Cu–Mo deposit, Inner Mongolia, China. Min. Deposita 47, 467–482. doi:10.1007/s00126-
17, 239–255 in Chinese with English abstract.
011-0384-1
Xiao, W. J., and Santosh, M. (2014). The Western central asian orogenic belt: A window
Liu, J., Mao, J. W., Wu, G., Wang, F., Luo, D. F., Hu, Y. Q., et al. (2014). Fluid inclusions
to accretionary orogenesis and continental growth. Gondwana. Res. 25, 1429–1444. doi:10.
and H–O–S–Pb isotope systematics of the Chalukou giant porphyry Mo deposit,
1016/j.gr.2014.01.008
Heilongjiang Province, China. Ore Geol. Rev. 59, 83–96. doi:10.1016/j.oregeorev.2013.
12.006 Xu, W. L., Ji, W. Q., Pei, F. P., Meng, E., Yu, Y., Yang, D. B., et al. (2009). Triassic
volcanism in eastern Heilongjiang and Jilin Provinces,NE China: Chronology,
Metelkin, D. V., Vernikovsky, V. A., Kazansky, A. Y., and Wingate, M. T. D. (2010). Late
geochemistry, and tectonic implications. J. Asian Earth Sci. 34, 392–402. doi:10.1016/j.
Mesozoic tectonics of Central Asia based on paleomagnetic evidence. Gondwana Res. 18,
jseaes.2008.07.001
400–419. doi:10.1016/j.gr.2009.12.008
Xu, W. L., Pei, F. P., Wang, F., Meng, E., Ji, W. Q., Yang, D. B., et al. (2013).
Mi, K. F., Liu, Z. J., Li, C. F., Liu, R. B., and Wang, J. P. (2014). U-Pb ages and Hf isotopes
Spatial–temporal relationships of Mesozoic volcanic rocks in NEChina: Constraints on
of Zircon in biotite granite from Wunugeshan porphyry Cu-Mo deposit. Geol. J. 33,
tectonic overprinting and transformationsbetween multiple tectonic regimes. J. Asian
113–114 in Chinese with English abstract.
Earth Sci. 74, 167–193. doi:10.1016/j.jseaes.2013.04.003
Pak, S. J., Choi, S. G., and Choi, S. H. (2004). Systematic mineralogy and chemistry of
Ye, X., and Wang, L. J. (1989). A study on fluid inclusion and metallogenesis of a
gold-silver vein deposits in the Taebaeksan district, Korea: Distal relatives of a porphyry
porphyry Cu–Mo deposit, Urugetu Hill, Inner Mongolia, China. Sci. Geol. Sin. 33,
system. Mineral. Mag. 68 (3), 467–487. doi:10.1180/0026461046830199
84–92.
Pan, L. J., and Sun, E. Y. (1990). Geological characteristics of the Chaganbulagen
Zajacz, Z., Candela, P. A., and Piccoli, P. M. (2017). The partitioning of Cu, Au and Mo
silver–lead–zinc deposit, Inner Mongolia. Min. Explor. 5, 1–9.
between liquid and vapor at magmatic temperatures and its implications for the Genesis of
Qin, K. Z., Li, H. M., Li, W. S., and Ishihara, S. (1999). Intrusion and mineralization ages magmatic-hydrothermal ore deposits. Geochim. Cosmochim. Acta. 207, 81–101. doi:10.
of the Wunugetushan porphyry Cu–Mo deposit, Inner Mongolia, Northwestern China. 1016/j.gca.2017.03.015
Geol. Rev. 45, 181–185.
Zeng, Q. D., Liu, J. M., Chu, S. X., Wang, Y. B., Sun, Y., Duan, X. X., et al. (2014). Re–Os
Qin, K. Z., Wang, Z. T., Wang, L. J., Bao, Y. H., and Li, Y. M. (1993). Studies on and U–Pb geochronology of the Duobaoshan porphyry Cu–Mo–(Au)deposit, northeast
hydrothermal convection, alteration superimposition and ore-forming processes of the China, and its geological significance. J. Asian Earth Sci. 79, 895–909. doi:10.1016/j.jseaes.
Wunugetushan porphyry copper molybdenum deposit, Inner Mongolia. Geol. Explor. 2013.02.007
Non-Ferrous Metals 2, 136–143.
Zhai, D. G., Liu, J. J., Wang, J. P., Yao, M. J., Wu, S. H., Fu, C., et al. (2013). Fluid
Redmond, P. B., and Einaudi, M. T. (2010). The Bingham Canyon porphyry Cu-Mo-Au evolution of the Jiawula Ag–Pb–Zn deposit, inner Mongolia: Mineralogical, fluid
deposit. I. Sequence of intrusions, vein formation, and sulfide deposition. Econ. Geol. 105, inclusion, and stable isotopic evidence. Int. Geol. Rev. 55, 204–224. doi:10.1080/
43–68. doi:10.2113/gsecongeo.105.1.43 00206814.2012.692905

Frontiers in Earth Science 13 frontiersin.org