Ore Geology Reviews 107 (2019) 41–57

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Ore Geology Reviews

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Fluid inclusion constraints on the hydrothermal evolution of the Dalucao T

Carbonatite-related REE deposit, Sichuan Province, China
⁎
Xiaochao Shua,b, Yan Liub,
a
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing 100083, People’s Republic of China
b
Key Laboratory of Deep-Earth Dynamics, Institute of Geology, Chinese Academy of Geological Sciences, Beijing 100037, People’s Republic of China

A R T I C LE I N FO A B S T R A C T

Keywords: Carbonatite-related rare-earth element (REE) deposits are the most important source of the world’s REE re-
Fluid inclusions sources. Hydrothermal fluids have been proposed to play a significant role in the transport and precipitation of
Hydrothermal evolution REEs, but fluid inclusion data on the hydrothermal processes in carbonatitic settings are relatively sparse. The
REE precipitation Dalucao deposit, located in the Mianning–Dechang (MD) REE belt, Sichuan, China, is a Cenozoic carbonatite-
Carbonatite
related REE deposit (c. 12 Ma) that offers an excellent opportunity to investigate the evolution of ore-forming
Dalucao deposit
Mianning–Dechang REE belt
fluids. Brecciated and weathered ores are common in this deposit. The former are characterized by mineral
assemblages comprising fluorite + barite + celestite + calcite + quartz + bastnäsite (No. 1 orebody) or
fluorite + celestite + pyrite + muscovite + calcite + quartz + bastnäsite (No. 3 orebody), whereas the latter
contain REE minerals, clay minerals, and minor gangue minerals. We present a comprehensive study of fluid
inclusions from the Dalucao deposit to constrain its hydrothermal evolution.
Magmatic, pegmatitic, hydrothermal, and supergene stages have been recognized. During the pegmatitic
stage, the main minerals that formed were coarse-grained fluorite, barite, celestite, calcite, and quartz, which
host melt inclusions, melt–fluid inclusions, and minor high-salinity fluid inclusions. The presence of melt and
melt–fluid inclusions suggests a magmatic origin for the ore-forming fluids. Hydrothermal processes included at
least two stages, characterized by hydrothermal veins that are developed in fractures within the carbonatite–-
syenite complex: (1) Fluid inclusions during the formation of the fluorite–quartz–barite veins in the pre-REE
stage were trapped under immiscible conditions, as evidenced by the presence of CO2-bearing inclusions co-
existing with aqueous ones. These immiscible CO2-bearing inclusions recorded a range of pressures from 1050 to
1600 bar. All of fluid inclusions in this stage exhibited homogenization temperatures varying from 278 to 442 °C,
with salinities ranging from 3.2 to 45.1 wt% NaCl equivalent (equiv.). (2) The REE-stage fluids were represented
by abundant aqueous inclusions, characterized by homogenization temperatures ranging from 147 to 323 °C and
salinities between 1.1 and 9.5 wt% NaCl equiv. These data suggest that the ore-forming fluids forming the
Dalucao deposit evolved from high-temperature, high-pressure, high-salinity, CO2-rich to low-temperature, low-
pressure, low-salinity, CO2-poor. Gas- and ion-chromatographic analyses combined with mineralogical features
indicate that the initial fluids were rich in REEs, (SO4)2−, Cl−, F−, Na+, K+, Ca2+, and volatile components
(e.g., H2O, CO2, N2, CH4, Ar, and C2H6). H–O isotope analyses of quartz suggest that the hydrothermal fluids had
a dominantly magmatic signature and were gradually diluted by meteoric waters. Hydrothermal REE transport
was probably controlled by F−, (SO4)2−, and Cl− as complexing ligands. We propose that fluid cooling and
mixing rather than immiscibility led to the precipitation of bastnäsite during the waning stage of hydrothermal
activity. Taken together, the inclusion data and observations of alteration, paragenesis and mineralization have
provided insights into the development of REE mineralization and the further exploration of carbonatite-related
REE resources.

1. Introduction Thomsen and Schmidt, 2008; Stoppa and Schiazza, 2013). Carbonatite
intrusions are mostly situated in anorogenic settings related to in-
Carbonatites are rare mantle-derived rocks produced by extremely tracontinental rifting (Woolley and Kjarsgaard, 2008) and frequently
low-degree partial melting of carbonated mantle (Sweeney, 1994; occur in ring-complexes associated with alkaline silicate rocks (Stoppa

⁎
Corresponding author.
E-mail address: ly@cags.ac.cn (Y. Liu).

https://doi.org/10.1016/j.oregeorev.2019.02.014
Received 14 March 2018; Received in revised form 7 December 2018; Accepted 13 February 2019
Available online 14 February 2019
0169-1368/ © 2019 Elsevier B.V. All rights reserved.
X. Shu and Y. Liu Ore Geology Reviews 107 (2019) 41–57

Fig. 1. (a) Tectonic framework showing the spatial distribution of REE deposits in China (modified after Hou et al., 2015). (b) Sketch geological map showing the
Cenozoic carbonatite–syenite complexes with zircon U-Pb ages (Liu et al., 2015a) in the MD REE belt, which is controlled by Cenozoic strike-slip faults (modified
after Yuan et al., 1995). The Jinpingshan orogen was formed by subduction of the down going Proto-Tethyan oceanic lithosphere in the Proterozoic (Cong et al.,
1988; Luo et al., 1998). The Proterozoic metamorphic basement was locally covered by Paleozoic-Mesozoic sedimentary strata. Abbreviations: NCC = North China
Craton, TM = Tarim Block, YC = Yangtze Craton, CC = Cathaysia Craton, CAO = Central Asian Orogen, CCO = Central China Orogen, AHO = Alps-Himalayan
Orogen, SGO = Songpan-Ganzi Orogen.
42
X. Shu and Y. Liu
et al., 2005; Andersson et al., 2016; Song et al., 2016a). One of the
notable features of carbonatites is a strong enrichment in incompatible
lithophile elements such as rare-earth elements (REEs), Ba, Sr, and Nb
(Nelson et al. 1988; Chakhmouradian, 2006; Xu et al., 2015; Song et al.,
2016b). Rare-earth deposits associated with carbonatite intrusions are
the world’s most significant source of these elements (Chakhmouradian
and Wall, 2012; Weng et al., 2015; Liu et al., 2018). REEs are critical
materials because of their increasing importance in renewable energy
and high-technology applications (Xu et al., 2017). China supplies more
than 85% of the World’s REE resources (Goodenough et al., 2016) and
firmly established this country as a leader in the global REE market
(Chakhmouradian and Wall, 2012; Kynický et al., 2012, 2018; Pirajno,
2016), as represented by the largest world-class Bayan Obo deposit
(Smith et al., 2000; Smith and Henderson, 2000; Fan et al., 2006, 2016;
Yang et al., 2009, 2016) and Cenozoic Mianning-Dechang (MD) REE
belt (Xu et al., 2008, 2012; Hou et al., 2006, 2009, 2015; Liu et al.,
2015a–c, 2018; Liu and Hou, 2017).
Many carbonatite-related REE deposits are thought to have experi-
enced a continuous evolution from a magmatic setting to a hydro-
thermal setting (e.g., Xie et al., 2009, 2015), in which the hydrothermal
fluids played a significant role in the transport and precipitation of
REEs (Samson and Wood, 2005; Sheard, 2012; Pandur et al., 2014). As
summarized by Rankin (2005) and Williams-Jones et al. (2012), REE
precipitation in carbonatitic systems is hybrid, with an early magmatic
component that is overprinted by a later hydrothermal stage, the latter
being critical in producing economic concentrations. The potential
importance of REE mobility under hydrothermal conditions is sup-
ported by recent experimental researches (e.g., Migdisov et al., 2009;
Trofanenko et al., 2016). These studies now accommodate the fact that
REEs can be mobilized and transported by hydrothermal fluids in the
form of complexing ligands, such as fluoride, sulfate, chloride, or car-
bonate, depending on temperature, pressure, and the composition and
pH value of the fluids (Smith and Henderson, 2000; Williams-Jones
et al., 2012; Migdisov and Williams-Jones, 2014). Fluid inclusions have
long been considered as reliable recorders of primary fluids, which can
provide crucial constraints on hydrothermal processes and ore pre-
cipitation (Roedder, 1984, 1997). Thus, systematic fluid inclusion stu-
dies based on detailed petrographic observations are essential for de-
fining the mechanism of hydrothermal REE mineralization.
The Dalucao deposit in the MD REE belt offers an excellent oppor-
tunity for studying the genesis of carbonatite-related REE deposits
owing to its young age (c. 12 Ma; Liu et al., 2015a) and well-preserved
evidence for the magmatic–hydrothermal processes responsible for its
formation (Liu and Hou, 2017). Previous studies of the Dalucao deposit
have focused on geochronology (Liu et al., 2015a; Ling et al., 2016),
fluorite trace-element chemistry (Xu et al., 2012), ores (Liu et al.,
2015b, c), and isotopes (Liu and Hou, 2017). Some studies have noted
the complexity of the hydrothermal system related to the Dalucao de-
posit, as evidenced by the numerous types of inclusions that are trapped
within both REE (bastnäsite) and gangue minerals (e.g., fluorite and
quartz) (Yang et al., 1998; Hou et al., 2009). However, their conclu-
sions were based simply on limited microthermometric data and lacked
fluid-composition analyses and pressure estimations. Importantly, field
relations reported in these literatures provide a dearth of information
on the mineral assemblages, even though these assemblages host the
bulk of the REE mineralization. Thus far, the hydrothermal evolution
affecting REE transport and precipitation remain poorly understood.
In this contribution, we propose a detailed description of the
geology, alteration, paragenesis and mineralization in the Dalucao de-
posit based on field investigations and petrographic observations. We
further present a comprehensive study that incorporates fluid inclusion
petrography, microthermometry, laser Raman spectroscopy, gas- and
ion-chromatographic analyses, and stable isotope measurements (H, O)
of quartz. This new dataset allows us to better constrain the source(s)
and evolution of hydrothermal fluids and to further advance our un-
derstanding of REE precipitation in this deposit. Finally, the
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Ore Geology Reviews 107 (2019) 41–57
implications of studying these fluid inclusions for the exploration of
economic REE deposits in carbonatitic settings are explored.
2. Geological setting
The Cenozoic MD belt is located on the western margin of the
Yangtze Craton and measures about 270 km in length and 15 km in
width (Fig. 1; Hou et al., 2009). The belt contains a total estimated
resource in excess of 3 Mt of light rare-earth oxides (REOs), hosting one
giant (Maoniuping), one large (Dalucao), and two small–medium-sized
deposits (Muluozhai and Lizhuang), together with numerous other
mineralized carbonatite-syenite complexes (Hou et al., 2009; Liu and
Hou, 2017). The basement rocks of the Yangtze Craton are dominated
by high-grade Archean metamorphic rocks, Proterozoic metasedimen-
tary rocks, and overlying Phanerozoic clastic and carbonate sequences
(Cong, 1988; Luo et al., 1998). The Emeishan mantle plume produced
mid-Permian flood basalts, with minor picrites and picritic basalts,
which cover the western part of the Yangtze Craton, forming a large
igneous province over an area of ∼500,000 km2 (Lu, 1996; Xu et al.,
2001).
In eastern Tibet, late-collisional metallogenesis (c. 40–26 Ma)
during the Indo-Asian collision developed within a transform structure
dominated by Cenozoic strike-slip faulting, shearing, and thrusting,
thereby producing one of the most economically significant metallo-
genic provinces in China (Hou and Cook, 2009). This area hosts por-
phyry-type Cu–Mo–Au systems controlled by Cenozoic strike-slip faults,
orogenic Au systems related to sinistral ductile shearing, Pb–Zn–Ag–Cu
systems controlled by Cenozoic thrusting and subsequent strike-slip
faulting (Wang et al., 2014a, b, 2016; Deng et al., 2014a, b, 2017a–c;
Deng and Wang, 2016), and REE mineralization associated with car-
bonatite–alkaline complexes (Hou et al., 2006, 2009, 2015; Liu et al.,
2015a–c, 2018; Liu and Hou, 2017). The complexes intrude a Proter-
ozoic crystalline basement and an overlying Paleozoic–Mesozoic vol-
cano-sedimentary sequence, and constituted a narrow, NS-tending REE-
bearing belt (Fig. 1; Hou et al., 2009). Recent geochronological studies
have yielded concordant ages of 12.13 ± 0.19 and 11.32 ± 0.23 Ma
for the Dalucao deposit, 22.81 ± 0.31 and 21.3 ± 0.4 Ma for the
Maoniuping deposit, 26.77 ± 0.32 Ma for the Muluozhai deposit, and
27.41 ± 0.35 Ma for the Lizhuang deposit (Liu et al., 2015a). These
data indicate that the 27–22 Ma ages for syenites in the northern part of
the MD belt (Maoniuping, Lizhuang, and Muluozhai) are coeval with
strike-slip shearing along the Ailao Shan–Red River shear zone. How-
ever, the ages for syenites within the Dalucao deposit in the southern
part of the MD belt indicate that shearing along strike-slip faults in that
area continued until at least 12 Ma, and possibly longer (Liu et al.,
2015a). Strike-slip faulting along the MD belt in eastern Tibet is only
one of several structural responses to the Indo–Asia collision that
started at 60–55 Ma (Hou and Cook, 2009).
3. Ore deposit geology
3.1. General geology
The four REE deposits in the MD belt formed under similar geolo-
gical conditions but are characterized by different ore grades and ton-
nages and vary widely in the style of mineralization (Liu and Hou,
2017). The Dalucao REE deposit, which is controlled by the Dalucao
strike-slip fault, is the second largest in this belt (Fig. 2), and contains
about 0.76 Mt REO, grading 5.0% REO on average (Shi and Li, 1996).
Due to regional uplift, a Proterozoic quartz diorite pluton with a surface
exposure of 70 km2 was exhumed. The Cenozoic syenites intrude
mainly the quartz diorite pluton, and associated carbonatite sills in-
trude along fissures that formed by strike-slip faulting (Fig. 2). Two
breccia pipes associated with REE mineralization are developed in the
syenites, constituting the majority of the No. 1 (Fig. 3a, c) and No. 3
orebodies (Fig. 3b). The diameters of the long axes of these pipes vary
X. Shu and Y. Liu Ore Geology Reviews 107 (2019) 41–57

Fig. 2. (a) Schematic geological map showing the key features of the carbonatite–syenite complex and associated REE orebodies in the Dalucao REE deposit. (b-d).
Geological cross-sections along exploration lines 10 and 14 in the No. 1 orebody and line 30 in the No. 3 orebody (modified after Yang et al., 1998).

from 200 to 400 m, and those of the short-axes between 180 and 200 m;
the pipes extend downwards for some 450 m (Hou et al., 2009). Clastic
rocks within the breccia-pipes consist predominately of magmatic det-
ritus and ore fragments hosted within a calcite-rich matrix with sub-
ordinate quartz and REE minerals. Sensitive high-resolution ion mi-
croprobe U-Pb dating results for zircon from syenites (Liu et al., 2015a)
and SIMS (secondary ion massspectrometry) data for bastnäsite (Ling
et al., 2016) have yielded a systematic and precise age of c. 12 Ma.
3.2. Alteration and mineralization
Fenitization is regarded as reflecting multiple pulses of fluids ex-
pelled from cooling and crystallizing carbonatitic or alkaline melt
(Morogan, 1994; Le Bas, 2008) and is the most significant style of al-
teration in the Dalucao deposit. Syenites in much of the deposit were
subjected to some degree of fenitization. However, the most intense
alteration occurs in and around the breccias, resulting in the formation
of a fenitization halo. The breccias are typically clast-supported, in
which the clasts are 4 to 17 cm in diameter and consist largely of an-
gular to rounded fragments (Fig. 4f). Field observations show that the
fenites are typically cut by calcite veins containing REE mineralization
(Fig. 4g), indicating that REE mineralization formed after fenitization.
Fenitization is marked by the replacement of albite by K-feldspar, the
replacement of primary aegirine–augite by biotite, and the develop-
ment of fine-grained assemblages of albite and biotite overprinting the
syenites (Fig. 5g, h). Late-stage alteration is dominated by intense
carbonatization, which overprinted the early-formed fenitization halo.
Despite multiple phases of brecciation (four events are recorded in
each of the pipes), mineralized veins are contained wholly within al-
tered syenite within the Dalucao deposit (Fig. 2; Liu et al., 2015c).
Tectonism and brecciation facilitated the circulation of ore-forming
fluids and provided the space for REE precipitation. The Dalucao de-
posit consists of two large ore lenses and comprises distinct two mi-
neralization systems (Fig. 2; Hou et al., 2009). The first mineralization
system occurs within the two breccia pipes. Ore veinlets are usually
transitional to mineralized breccia and brecciated ores, and are com-
monly enveloped by fine-veins and stringer zones with comparable
mineral assemblages. The second mineralization system occurs between
the two breccia pipes, and it has been displaced by the Mofanggou
strike-slip fault (Fig. 2). This system consists of swarms of ore-bearing
veins within syenite stocks and an underlying semi-layered mineralized
zone developed above the syenites (Hou et al., 2009).
The ores are weathered, brecciated, and dominated by fine-grained
REE minerals (Liu et al., 2015b, c). Brecciated ore is characterized by
mineral assemblages comprising fluorite + barite + celes-
tite + calcite + quartz + bastnäsite (No. 1 orebody; Fig. 4a, b) or
fluorite + celes-
tite + pyrite + muscovite + calcite + quartz + bastnäsite (No. 3 ore-
body; Fig. 4c), and it occurs as small lenses or veinlets. The second
significant type of mineralization is weathered ore, which is found

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X. Shu and Y. Liu
Fig. 3. (a) Field photograph of the No. 1 orebody. (b) Field photograph of the No. 3 orebody. (c) The cross section selected exhibiting the alteration, ore vein,
carbonatite and associated syenite in the Dalucao deposit (modified after Liu et al., 2015b).
predominantly in fissures within the No. 1 orebody but is rarely present
in other deposits of the MD belt (Fig. 4h). Weathered ore contains REE
minerals (including bastnäsite and monazite; Fig. 5e, f) together with
minor gangue minerals (e.g., fluorite; Fig. 5e) and abundant clay mi-
nerals (Liu et al., 2015c).
3.3. Paragenetic sequence
The paragenetic sequence of REE and gangue minerals in the
Dalucao deposit is similar to that in the Maoniuping deposit, although
the assemblages are somewhat simpler. Based on field observations,
petrographic examinations of typical ore specimens, and previous stu-
dies (e.g., Liu et al., 2015b), magmatic, pegmatitic, hydrothermal, and
supergene stages have been recognized (Fig. 6).
The magmatic stage was marked by the formation of the carbona-
tite–syenite complex. Many rock-forming minerals such as K-feldspar
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Ore Geology Reviews 107 (2019) 41–57
and albite, along with minor accessory minerals such as zircon and
apatite, formed in the carbonatite and associated syenite. The pegma-
titic stage is developed mainly within the No. 1 orebody. During this
stage, coarse-grained fluorite, barite, celestite, calcite, and quartz were
the main minerals that formed (Fig. 4d). Hydrothermal processes in-
clude at least two stages, characterized by the formation of hydro-
thermal veins in fractures within the carbonatite–syenite complex
(Fig. 4e): (1) The pre-REE stage was associated with the formation of
fine-grained gangue minerals. Typical gangue minerals are fluorite,
quartz, calcite, barite, and celestite. Only where fluorite occurs, as
opposed to the other gangue minerals (e.g., barite, calcite), can bast-
näsite be found. (2) The REE stage was characterized by the crystal-
lization of bastnäsite. Bastnäsite forms fractured or subhedral to eu-
hedral prismatic crystals that commonly overprint early-formed gangue
minerals (e.g., fluorite, calcite, quartz, and barite) or fill the cavities
between these minerals (Fig. 5a, b, d–f, i), indicating that REE
X. Shu and Y. Liu Ore Geology Reviews 107 (2019) 41–57

Fig. 4. Photographs showing various geologic features in the Dalucao deposit. (a) Representative ore sample from the No. 1 orebody. (b) Altered brecciated ore from
the No. 1 orebody (from Liu et al., 2015b). (c) Representative ore sample from the No. 3 orebody. (d) Coarse-grained mineral dikes in syenite (from Liu et al., 2015b).
(e) Hydrothermal ore vein cutting syenite. (f) Representative breccia in the No. 3 orebody. (g) Fenite containing calcite vein. (h) Silty gray-purple weathered sample
with a fluffy texture in altered syenite. (i) Supergene minerals from the No. 1 orebody. Abbreviations: Fl = fluorite, Ms = muscovite, Brt = barite, Cal = calcite,
Qtz = quartz, Py = pyrite. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

mineralization occurred during the late-stage of hydrothermal activity. 4.2. Methods

The supergene stage was marked by the occurrence of abundant clay
minerals (e.g., illite, kaolinite) (Fig. 4i).
4. Samples and analytical methods
4.1. Samples
The samples used in this study are all taken from representative
hydrothermal minerals within ore veins, and include: (1) the pegmatite-
stage fluorite; (2) the pre-REE-stage fluorite, quartz, and barite; (3) the
REE-stage bastnäsite, together with calcite and fluorite associated with
bastnäsite in a paragenesis. The locations of selected samples are
schematically shown in Fig. 2. More than 40 doubly polished thin
sections were prepared for optical examination, from which 20 re-
presentative ones were chosen for subsequent microthermometric
measurements and laser Raman spectroscopic analyses. In addition,
three samples from the same ore veins were prepared for gas- and ion-
chromatographic analyses to determine fluid compositions, and three
quartz samples were taken for stable isotope (H, O) analyses to con-
strain the source(s) of the fluids.
4.2.1. Microthermometry
Microthermometric measurements of fluid inclusions were per-
formed on a Linkam THMSG 600 heating–freezing stage attached to a
Leitz microscope at the State Key Laboratory of Geological Processes
and Mineral Resources, China University of Geosciences, Beijing, China.
The temperature calibration of the heating–freezing stage was carried
out by analyzing standard samples of synthetic fluid inclusions supplied
by Fluid Inc. (USA). The temperature accuracy of the heating–freezing
stage from −120 to −70 °C is ± 0.5 °C, from −70 to 100 °C is ± 0.2 °C,
and from 100 to 500 °C is ± 0.2 °C. The rate of heating–freezing was
generally 0.2 to 5.0 °C/min but was reduced to 0.2 °C/min close to the
phase transition temperature for CO2-bearing inclusions (such as CO2
clathrate melting temperature) and to 0.2–0.5 °C/min close to the
freezing point and homogenization temperature for aqueous inclusions,
in order to accurately record the phase transition temperatures. Heating
cycles of about 5 °C were used to determine the homogenization tem-
perature of vapor and solid phases in solid-bearing fluid inclusions.
Heating cycles also constrained the melting temperature of clathrate to
within ± 0.2 °C in most CO2-bearing inclusions. The salinities of aqu-
eous fluid inclusions were approximately calculated using the data of
Bodnar and Vityk (1994) for the NaCl–H2O system. Salinities of solid-

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X. Shu and Y. Liu Ore Geology Reviews 107 (2019) 41–57

Fig. 5. (a) Needle-like bastnäsite aggregates overprinting fluorite, barite, celestite and phlogopite. (b) Bastnäsite filling in the spaces of celestite. (c) Typical mag-
matic minerals (e.g., zircon). (d) Typical brecciated ore in the No. 3 orebody, with bastnäsite overprinting fluorite, celestite and phlogopite. (e) Weathered ore in the
No. 1 orebody, with bastnäsite overprinting fluorite. (f) Monazite and bastnäsite overprinting early-formed gangue minerals. (g) The fenitization in the No. 3
orebody, with the occurrence of K-feldspar, albite and muscovite. (h) Celestite-bearing calcite vein cutting altered syenite. (i) Sulfide filling in the spaces of celestite.
Abbreviations: Fl = fluorite, Bsn = bastnäsite, Ms = muscovite, Cls = Celestite, Ap = apatite, Kfs = K-feldspar, Ab = albite, Phl = phlogopite, Bt = biotite,
Cal = calcite, Py = pyrite, Zrn = zircon, Gn = galena, Mnz = monazite.

bearing inclusions were estimated according to the formula of Bodnar
and Vityk (1994). For inclusions that homogenized by solid phase dis-
solution, this method might underestimate salinity by up to 3 wt% NaCl
equiv. (Bodnar and Vityk, 1994). The salinities of CO2-bearing inclu-
sions were determined using the equations of Collins (1979). The
densities of fluid inclusions were calculated using the Flincor program
(Brown, 1989), according to the calculation method of Brown and Lamb
(1989).
4.2.2. Laser Raman spectroscopy
The compositions of individual inclusions from different minerals
were analyzed at room temperature using a Renishaw System-2000
Raman microspectrometer according to the method of Burke (2001) at
the Institute of Mineral Resources, Chinese Academy of Geological
Science, Beijing, China. The excitation wavelength was the 514.53 nm
line of an Ar-ion laser operating at 20 mW. The spectra were recorded
with counting time of 30 s and spot size of 1 μm, and ranged from 10 to
4000 cm−1, 1 accumulation, and the spectral resolution was 1–2 cm−1.
4.2.3. Gas- and ion-chromatographic analyses
The gas- and ion-chromatographic analyses of fluid inclusions were
performed at the Institute of Geology and Geophysics, Chinese
Academy of Sciences, Beijing, China. The gaseous compositions of the
fluids were determined using a Prisma TM QMS200 Quadrupole Mass
Spectrometer using the method of Zhu and Wang (2000). The dried
washed sample weighing 2 g was put in a clean quartz tube and heated
to 100 °C. Then, the valve was turned on, and the gas pipe was va-
cuumed. When the pressure in the quartz tube was less than
6 × 10−6 Pa, the burst stove was heated to 550 °C at a rate of 0.333 °C/
s. The vacuum valve was turned on to determine gas composition.
A Shimadzu HIC-SP instrument was used to analyze the ionic
composition of the fluid inclusions. After cleaning and drying, crushed
samples were decrepitated at 500 °C in a vacuum and then leached
repeatedly using millipure water in an ultrasonic cleaning bath at room
temperature until the electrical conductivity of the leachate was the
same as the millipure water. All the collected leachates were volume-
trically fixed to 30 ml and then analyzed.
4.2.4. Hydrogen and oxygen isotopes
Hydrogen and oxygen isotopic analyses were conducted at Beijing
Createch Testing Technology Co., Ltd, Beijing, China. Hydrogen iso-
topic ratios of decrepitated quartz-hosted fluid inclusions were mea-
sured by mechanically crushing quartz grains according to the method
of Gong et al. (2007). Samples were first degassed by heating under a

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X. Shu and Y. Liu
Fig. 6. Paragenetic sequence of REE and gangue minerals in the Dalucao deposit (modified after Liu et al., 2015b).
vacuum at 120 °C for 3 h. The water was then released from the fluid
inclusions by heating the samples to ∼1000 °C in an induction furnace.
The subsequently released water was trapped, reduced to H2 by zinc at
410 °C (Friedman, 1953), then analyzed using a MAT-253 mass spec-
trometer, with a precision for δD of ± 1‰. Oxygen was liberated from
quartz by reaction with BrF5 (Clayton and Mayeda, 1963) and con-
verted to CO2 on a platinum-coated carbon rod. The δ18O determina-
tions were made using a MAT-253 mass spectrometer, with a precision
for δ18O of ± 0.2‰. The isotope data are expressed in the delta (δ)
notation as the per mil (‰) deviation relative to the Vienna Standard
Mean Ocean Water (V-SMOW).
5. Results
5.1. Inclusion petrography
Based on phase associations at room temperature and phase tran-
sitions upon heating, the inclusions from the Dalucao deposit were
grouped into melt inclusions, melt–fluid inclusions, and fluid inclu-
sions. The fluid inclusions were further classified as aqueous (H-type),
pure CO2 (PC-type), CO2-bearing (HC-type), solid-bearing (HS-type),
and solid-bearing inclusions containing CO2 (CS-type). In this
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Ore Geology Reviews 107 (2019) 41–57
classification system, the letters H, C, and S denote liquid phase, car-
bonic phase, and solid phase, respectively. Inclusion petrography and
classification strictly concentrated on fluid inclusion assemblages
(Goldstein and Reynolds, 1994).
Melt inclusions were trapped in fluorite during the pegmatite stage.
At room temperature, these inclusions are typically composed of a
molten glass phase, in some cases containing a small number of bubbles
(Fig. 7a). On cooling, the melt inclusions convert into melt–fluid in-
clusions containing CO2, an aqueous solution, and a melt phase.
Melt–fluid inclusions with different phase ratios are commonly
found in clusters and in some cases are associated with melt inclusions
or CO2-bearing fluid inclusions. Most of these inclusions contain several
solids, liquid CO2, aqueous solutions, and in some cases glass phase
(Fig. 7b), in which the solids occupy most of the inclusion volume.
Most H-type inclusions show two visible phases at room tempera-
ture, namely, liquid H2O and vapor H2O (LH2O + VH2O), and occur as
elliptical or negative shapes 4 to 27 μm in size (Fig. 7c). In general, the
vapors are relatively small, with filling degrees ranging from 10 to
40 vol%. In REE-stage bastnäsite, most of them are densely scattered or
grouped in clusters, and thus, are considered to be primary (Fig. 7i).
The PC-type inclusions are pure CO2 inclusions and contain two
phases (LCO2 + VCO2) (Fig. 7d) or one phase (LCO2) (Fig. 7j) at room
X. Shu and Y. Liu Ore Geology Reviews 107 (2019) 41–57

Fig. 7. Photomicrographs of individual fluid inclusions (a-h) and fluid inclusion assemblages (i-l) from the Dalucao deposit. (a) Melt inclusion in fluorite. (b)
Melt–fluid inclusion in fluorite. (c) H-type inclusion in fluorite. (d) PC-type inclusion in fluorite. (e) HC-type inclusion in fluorite. (f) HS-type inclusion in fluorite. (g)
CS-type inclusion in fluorite. (h) HS-type inclusion comprising multi-solids in fluorite. (i) Abundant H-type inclusions with constant bubble fractions in bastnäsite. (j)
Coexistence of PC- and HC-type inclusions in quartz. (k) Coexistence of HC- and H-type inclusions in fluorite. (l) HC inclusions are closely spatially associated with CS
inclusions in quartz. Abbreviations: Fl = fluorite, Bsn = bastnäsite, Qtz = quartz, V = vapor phase, L = liquid phase, S = solid phase.

temperature. The latter are transformed into two-phase inclusions
(LCO2 + VCO2) during freezing, indicating that the PC-type inclusions
are liquid at room temperature (Roedder, 1984). These inclusions are
small (2–15 µm in diameter) and generally occur in pre-REE-stage
quartz and barite.
The HC-type inclusions have been widely observed in gangue mi-
nerals of the pre-REE stage. These inclusions contain three phases
(LH2O + LCO2 + VCO2) (Fig. 7e) or two phases (LH2O + LCO2) (Fig. 7j) at
room temperature. For the latter type, the liquid CO2 may separate CO2
bubbles (LCO2 → LCO2 + VCO2) during freezing. The inclusions are
4–26 µm in diameter and the volume fraction of the CO2 phase varies
from 20 to 80 vol% at room temperature.
The HS-type inclusions comprise one or several solids, aqueous and
vapor phases (LH2O + VH2O + S) (Fig. 7f, h), in which the volume
fraction of the solid phase varies from 10 to 40 vol%. These inclusions
are usually present in the pre-REE stage and are generally 6–25 µm in
diameter. Sulfate with irregular crystal shapes is the dominant daughter
mineral for most of these inclusions (Fig. 9a, b), although minor halite
crystals are also observed in fluorite and quartz as regular prismatic or
cubic shapes.
The CS-type inclusions contain solid, aqueous, and CO2 phases
(LH2O + LCO2 + S or LH2O + LCO2 + VCO2 + S) (Fig. 7g). These

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Table 1
Microthermometric data of fluid inclusions from the pre-REE stage and the REE stage in the Dalucao deposit.
Host mineral Inclusion type N CO2-bearing inclusions Tm, s (°C) Th, tot (°C) Tm, ice (°C) Salinity (wt% NaCl equiv.)

Tm, CO2 (°C) Tm, cla (°C) Th, CO2 (°C)

Pre-REE stage
Fl HS 20 220 to 378 331 to 440 32.9 to 45.1
HC 29 −61.4 to −60.4 −4.8 to 8.2 22.2 to 27.0 305 to 402 3.5 to 19.6
H 37 278 to 364 −8.5 to −4.7 7.4 to 12.3
Qtz HS 5 202 to 330 286 to 360 32.0 to 40.6
PC 5 −60.4 to −60.3 13.3 to 27.7
HC 8 −60.4 to −60.0 −5.9 to 8.4 12.1 to 29.6 300 to 442 3.2 to 23.4
H 7 302 to 404 −9.2 to −6.7 10.1 to 13.1
Brt HS 5 216 to 290 305 to 363 30.1 to 32.9
PC 4 −60.7 to −60.2 22.2 to 24.0
HC 5 −60.7 to −60.2 −9.6 to 7.8 24.1 to 27.1 308 to 390 20.9 to 21.4
H 6 310 to 360 −6.5 to −4.2 6.7 to 9.9

REE stage
Fl H 51 162 to 323 −5.8 to −0.6 1.1 to 8.9
Bsn H 30 163 to 301 −4.3 to −0.8 1.4 to 6.9
Cal H 8 147 to 248 −6.2 to −3.5 5.7 to 9.5

Notes: N = number of fluid inclusions analyzed, Tm, CO2 = melting temperature of solid CO2, Tm, ice = melting temperature of final ice, Tm, cla = melting temperature
of CO2 clathrate, Th, CO2 = partial homogenization temperature of CO2 phase, Tm, s = melting temperature of solid phase, Th, tot = temperature of total homo-
genization; Mineral abbreviations: Fl = fluorite, Qtz = quartz, Brt = barite, Cal = calcite, Bsn = bastnäsite; Fluid inclusion type: H = Aqueous inclusion, PC = pure
CO2 inclusion, HC = CO2-bearing inclusion, HS = solid-bearing inclusion.

inclusions range in size from < 10 to 25 μm and typically show ellip-
tical shapes, although some irregular inclusions with intermediate-sized
bubbles (10–50 vol% at room temperature) are also recognized. They
are generally found in quartz and fluorite from the pre-REE stage and
are closely spatially associated with HC-type inclusions.
5.2. Microthermometry
Microthermometric studies were conducted on H-, PC-, HC-, and
HS-type inclusions from the pre-REE stage and on H-type inclusions
from the REE stage. Microthermometric measurements were performed
based on the concept of fluid inclusion assemblages, that is, closely
associated groups of inclusions with visually identical phase ratios and
similar shapes (Goldstein and Reynolds, 1994). The microthermometric
data and calculated parameters for fluid inclusions are summarized in
Table 1 and graphically illustrated in Fig. 8.
5.2.1. Pre-REE stage
A total of 131 fluid inclusions in fluorite, quartz, and barite yielded
homogenization temperatures varying from 278 to 442 °C. The PC- and
HC-type inclusions exhibited melting temperatures of solid CO2 ranging
from −61.4 to −60.0 °C. The temperatures are lower than the triple
point for pure CO2 (−56.6 °C), indicating the presence of a subordinate
amount of other gases. This is consistent with ion-chromatographic
analyses indicating minor amounts of other gases (e.g., N2, CH4) occur
in fluid inclusions (see below). Two different modes of partial homo-
genization of CO2 phase, viz. to liquid and to vapor, can be observed
within the fluid inclusion assemblages. More than 60% of the analyzed
LC-type inclusions showed partial homogenization to liquid, whereas
the others to vapor. All of these inclusions displayed partial homo-
genization temperatures ranging from 12.1 to 29.6 °C, with total
homogenization temperatures exhibiting a wide range from 300 to
442 °C. The melting of CO2 clathrate in the presence of CO2 liquid oc-
curred between −9.6 and 8.4 °C, with the calculated salinities ranging
from 3.2 to 23.4 wt% NaCl equiv. These measurements for H-type in-
clusions constrained a salinity range of 6.7 to 13.1 wt% NaCl equiv.
based on freezing points of −9.2 to −4.2 °C. Total homogenization was
observed at temperatures between 252 and 370 °C, with two modes of
homogenization to liquid or vapor phases. In all LVS inclusions, the
liquid–vapor homogenization occurred at temperatures from 286 to
440 °C, and the solid dissolution occurred at temperatures from 202 to
378 °C, corresponding to salinities from 30.1 to 45.1 wt% NaCl equiv.
5.2.2. REE stage
H-type inclusions are abundant and constitute primary inclusion
assemblages. All calculated H-type inclusions in the REE-stage minerals
showed consistent microthermometric mode, i.e., homogenization to a
liquid phase, with total homogenization temperatures ranging from 147
to 323 °C. These inclusions had ice-melting temperatures ranging from
−6.2 to −0.6 °C, corresponding to salinities ranging from 1.1 to 9.5 wt
% NaCl equiv.
5.3. Laser Raman spectroscopy
Laser Raman spectrograms of selected fluid inclusions are shown in
Fig. 9. The spectrograms show that the daughter minerals in HS-type
inclusions are dominated by sulfates (e.g., anhydrite, Fig. 9a; celestite;
Fig. 9b). Attempts to analyze the compositions of the carbonic phase
within HC-type inclusions in fluorite were unsuccessful because of the
strong fluorescence of fluorite that obscured the CO2 peaks. Thus, the
HC-type inclusions in quartz were chosen with the purpose of analyzing
the compositions of the vapor bubbles (Fig. 9c, d). In contrast, CO2 was
absent in the vapor phase of H-type inclusions hosted by bastnäsite
(Fig. 9e, f). In addition, the peak at 982 cm−1 suggests that (SO4)2− is
the dominant anion in the liquid phase (Fig. 9e).
5.4. Gas- and ion-chromatographic analyses
The gas-chromatographic analyses (Table 2) reveal the common
presence of H2O, CO2, N2, CH4, Ar, and C2H6 in the fluids, in which H2O
and CO2 are the dominant gas components. The ion-chromatographic
analyses (Table 3) show that the ions consist of (SO4)2−, Cl−, F−, Na+,
K+, and Ca2+. Ions of (CO3)2− were not analyzed, as an Na2CO3 so-
lution was used as the flow phase during analysis. Charge imbalance
between anions and cations in these data is because some cations, in
particular REE3+, were not analyzed.
5.5. Hydrogen and oxygen isotopes
Oxygen and hydrogen isotopic results are listed in Table 4, which
includes the data of Liu et al. (2015b). The δ18OV-SMOW values of six
quartz samples range from 3.0‰ to 8.5‰. The δ18Ofluid values were

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X. Shu and Y. Liu
Fig. 8. Histograms of homogenization temperature and salinity for fluid inclusions from the Dalucao deposit.
calculated using the quartz–water equilibrium function (Clayton et al.,
1972): 1000lnαquartz-water = 3.38 × 106 × T−2 − 3.40, with the
average homogenization temperature of all fluid inclusions. The mea-
sured δDV-SMOW values for the pre-REE and REE stages are −80.2‰ to
−71.0‰ and −105.1‰ to −88.4‰, respectively. The calculated
δ18Ofluid values for the pre-REE and REE stages are 1.3‰ to 1.6‰ and
−7.5‰ to −5.0‰, respectively.
6. Discussion
6.1. Source of the ore-forming fluids
The Sr–Nd–Pb isotopes for the Dalucao deposit, published by Hou
et al. (2015) and Liu and Hou (2017), require a shared origin for both
host rocks and hydrothermal minerals. The H–O isotopic data provide
further constraints on the source of the ore-forming fluids. The early-
formed quartz samples in fluorite–quartz–barite hydrothermal veins
from the pre-REE stage show relatively high δ18Ofluid (1.3‰ to 1.6‰)
and δDV-SMOW (−80.2‰ to −71.0‰) values, consistent with those
reported from other carbonatite-related REE deposits within the MD
belt (e.g., Maoniuping, Hou et al., 2009; Liu and Hou, 2017). These data
are plotted in the region between the primary magmatic water box and
the meteoric water line but still dominated by magmatic water (Fig. 10;
Taylor, 1974). The magmatic signature is also supported by the petro-
graphic features of the inclusions. These inclusions, varying from melt
inclusions, melt–fluid inclusions, and fluid inclusions, suggest a mag-
matic origin for the ore-forming fluids and record a continuous evolu-
tion from a magmatic setting to a hydrothermal setting. Combined with
the close spatial and temporal association between the carbonatite–-
syenite complex and REE mineralization, it is assumed that the ore-
forming fluids in the Dalucao deposit were derived from the carbona-
tite–syenite magmas.
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Ore Geology Reviews 107 (2019) 41–57
In comparison, the quartz samples from the REE stage yield lower
δ18Ofluid (−7.5‰ to −5.0‰) and δDV-SMOW (−105.1‰ to −88.4‰)
values than those from the pre-REE stage, strongly implying the in-
volvement of meteoric waters (Fig. 10), consistent with the low mea-
sured homogenization temperatures (147 to 323 °C) and salinities (1.1
to 9.5 wt% NaCl equiv.) of fluid inclusions. These inclusions are inter-
preted to have resulted from the mixing of primary fluids with meteoric
waters during the late-stage circulation of low-temperature and low-
salinity fluids. A similar scenario is inferred for the mineralization at
Bayan Obo (Smith and Henderson, 2000) and in the Gallinas Mountains
(Williams-Jones et al., 2000).
In conclusion, all H–O isotopic values in quartz gradually decrease
from the pre-REE stage to the REE stage, indicating that the ore-forming
fluids in the Dalucao deposit have a dominantly magmatic signature
and were gradually diluted by meteoric waters during hydrothermal
processes.
6.2. Estimation of the minimum trapping pressure
Pressures can be approximately estimated according to micro-
thermometric data of fluid inclusions (Driesner and Heinrich, 2007).
The homogenization temperature determined by fluid inclusions on
immiscibility or boiling traits will represent absolutely fluid trapping
temperature (Roedder and Bodnar, 1980; Brown and Hagemann, 1995).
In contrast, fluid inclusions trapped without immiscibility or boiling
traits will give the minimum homogenization temperature, yielding the
minimum trapping pressure (Roedder and Bodnar, 1980; Rusk et al.,
2008). The estimation of P–T conditions in (SO4)2−-related fluid sys-
tems is extremely difficult but can be attempted if the fluids are treated
as similar to those in NaCl-related systems.
Petrographic observations and microthermometry of fluid inclu-
sions indicate that the fluids in the pre-REE stage experienced intense
X. Shu and Y. Liu Ore Geology Reviews 107 (2019) 41–57

Fig. 9. Laser Raman spectroscopy spectrograms for individual inclusions in the Dalucao deposit. (a) Anhydrite spectrum in the solid phase of a solid-bearing
inclusion. (b) Celestite spectrum in the solid phase of a solid-bearing inclusion. (c) CO2 spectrum in the vapor phase of a CO2-bearing inclusion. (d) CO2 and H2O
spectrums of a CO2-bearing inclusion. (e) (SO4)2− spectrum in the liquid phase of an aqueous inclusion. (f) H2O spectrum in the liquid phase of an aqueous inclusion.
Abbreviations: Fl = fluorite, Qtz = quartz, Bsn = bastnäsite.

Table 2
Proportions of gases (mol%) in the gas-chromatographic analyses of fluid inclusions in hydrothermal minerals from the Dalucao deposit.
Sample number1 Mineral2 Host inclusions3 H2O CO2 N2 CH4 Ar C2H6 H2S

DLC13-1–15(3) Fl H, HS, HC, CS 44.3 50.0 3.35 1.24 0.76 0.33 0.00
DLC11-28(2) Fl H, HS, HC 87.0 11.6 0.76 0.38 0.17 0.03 0.00
DLC13-1–15(2) Brt H, PC, HC 81.3 16.9 0.89 0.49 0.32 0.09 0.01

Notes:
1
These samples for gas-chromatographic analyses were collected in the same ore vein.
2
Mineral abbreviations: Fl = fluorite, Brt = barite.
3
Fluid inclusion type: H = Aqueous inclusion, HS = solid-bearing inclusion, PC = pure CO2 inclusion, HC = CO2-bearing inclusion, CS = solid-bearing inclusion
contain CO2.

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Table 3
Ion compositions (μg/g) in the ion-chromatographic analyses of fluid inclusions in hydrothermal minerals from the Dalucao deposit.
Sample number1 Mineral2 Host inclusions3 (SO4)2− Cl− F− Na+ K+ Ca2+

DLC13-1-15(3) Fl H, HS, HC, CS 15.9 0.19 N.O.4 0.28 N.O. N.O.

DLC11-28(2) Fl H, HS, HC 3.90 0.38 N.O. 0.60 0.21 N.O.
DLC13-1-15(2) Brt H, PC, HC 2.53 1.18 3.90 0.70 0.27 1.39

Notes: Charge imbalance between anions and cations in these data is because some cations, in particular REE3+, were not analyzed.
1
Samples as in Table 2.
2
Mineral abbreviations as in Table 2.
3
Fluid inclusion type as in Table 2.
4
The detection result was not obtained.

Table 4 resulting in such immiscibility.

Hydrogen and oxygen isotope data of selected quartz in the Dalucao deposit. Not all homogenization temperatures of HC-type inclusions can be
Sample Mineral Th (°C) δ18OV- δ18Ofluid δDV-SMOW Reference used to constrain the conditions of fluid immiscibility, as the different
number SMOW sizes of inclusions may influence homogenization temperatures.
(‰) (‰) (‰) Inclusions with greater volume and larger surface area may deform
during heating such that the measured homogenization temperatures
DLC185-01 Quartz 300 8.3 1.4 −79.6 This study
DLC185-02 Quartz 300 8.5 1.6 −80.2 This study
are unreliable. Similar difficulties arise from the fact that a phase may
DLC185-04 Quartz 300 8.2 1.3 −71.0 This study not be seen owing to its shape and small volume (Mao et al., 2015).
DL13-1-6Qz Quartz 215 5.8 −5.0 −92.8 Liu et al. In view of these factors, immiscible HC-type inclusions with moderate
(2015b) sizes, CO2 volume fractions of 20% to 80%, homogenization tempera-
DL11-28Qz Quartz 215 3.0 −7.5 −88.4 Liu et al.
tures of 310 to 350 °C, and densities of 0.75 to 0.92 g/cm3 were used to
(2015b)
DL11-33Qz Quartz 215 5.5 −5.3 −105.1 Liu et al. evaluate the pressures of immiscibility. The trapping pressures are es-
(2015b) timated to range from 1050 to 1600 bar, with the isochores calculated
by the Flincor program (Brown, 1989) and the formula of Bowers and
Notes: Th is the approximate average homogenization temperature of all in- Helgeson (1983) (Fig. 11a). If the fluid system is assumed to be a simple
clusions hosted in selected quartz; δ18Ofluid values are calculated according to water–salt system, the formula given by Driesner and Heinrich (2007)
the quartz-water equilibrium temperature formula provided by Clayton et al.
can be used to estimate the minimum trapping pressure during the REE
(1972).
stage. Fig. 11b gives the trapping pressures of < 100 bar in homo-
genization temperature versus salinity. The low pressure reflects a
shallow and open mineralizing environment in which little CO2 was
present. The well-developed tensile fractures and the tectonism that
resulted in the formation of fissures and/or breccias throughout the
hydrothermal processes appear to have been the main causes of de-
creasing pressure.

6.3. Fluid evolution

The petrographic and microthermometric data from the fluid in-

Fig. 10. Plot of δDV-SMOW versus δ18Ofluid of the fluids in the Daluaco deposit.
Metamorphic water field, magmatic water field, and meteoric water line are
from Taylor (1974); SMOW = standard mean ocean water.
immiscibility caused by aqueous–carbonic phase separation, as evi-
denced by: (1) HC-type inclusions with variable CO2 volume fractions
coexist with PC-type inclusions (Fig. 7j); (2) H- and HC-type inclusions
have intimate spatial relationship, and exhibit similar homogenization
temperature ranges but contrasting salinities (Fig. 7k) (Fig. 7k); and (3)
HC-type inclusions identified in pre-REE-stage quartz are closely spa-
tially associated with CS-type inclusions (Fig. 7l). Fournier (1992,
1999) argued that when lithostatic conditions translated into to hy-
drostatic conditions due to the change from ductile to brittle behavior
of the hydrothermal system, the fluid pressure would drop rapidly,
clusions indicate that different types of fluids were present during dif-
ferent stages in the Dalucao deposit. The evolution of hydrothermal
fluids in terms of salinity, temperature, and pressure has been re-
constructed on the basis of fluid inclusion microthermometry, and used
to establish a model for fluid evolution in such carbonatite-related REE
deposits.
It is assumed that the carbonatite–syenite magmas would release
highly oxidized, high-flux, and REE-rich fluids during stress relaxation
(Hou et al.,2015). The gas- and ion-chromatographic analyses com-
bined with the observed mineralogical features indicate that the initial
fluids were rich in REEs, (SO4)2−, Cl−, F−, Na+, K+, Ca2+, and volatile
components (e.g., H2O, CO2, N2, CH4, Ar, and C2H6), similar to those in
other carbonatite-related REE deposits, such as Maoniuping (Xie et al.,
2009, 2015) and Hoidas Lake (Pandur et al., 2014). As the initial fluids
were enriched in Na+ and K+, fenitization occurred as metasomatism
in this mining area. At depth, where the country rocks are hottest, little
cooling of fluids occurred and the pressure approximated lithostatic
pressure. Such fluids had an appreciable capacity to transport REEs
owing to the high temperature of the hydrothermal system and, con-
sequently, no major REE mineralization developed.
The further evolution of the hydrothermal system was marked by
the formation of ore veins, the widespread precipitation of gangue
minerals, and the onset of bastnäsite crystallization. All of the fluid
inclusion types identified in the pre-REE stage, including aqueous, CO2-
bearing, and solid-bearing inclusions, record homogenization

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Fig. 11. Pressure–temperature conditions for fluid inclusions in different stages. (a) Pressure estimation for fluid immiscibility in pre-REE stage based on intersections
(shaded area) between isochores constructed with the minimum and maximum densities of immiscible HC-type inclusions, and minimum and maximum homo-
genization temperatures. The isochores are calculated using the Flincor program (Brown, 1989) and the formula of Bowers and Helgeson (1983). (b) P-T-X phase
diagram of H-type inclusions in NaCl-H2O system (modified after Driesner and Heinrich, 2007). The two-phase surface separates the single-phase field at high
pressure from the two-phase fluid stability field at lower pressure and is contoured for composition and temperature with the critical curve on its crest. The halite-
liquid–vapor surface is contoured for temperature. The liquid-halite coexistence surface is omitted for clarity.

temperatures verying from 278 to 442 °C and salinities ranging from 3.2
to 45.1 wt% NaCl equiv., in an fluid system of NaCl-H2O-CO2 (Table 1,
Fig. 8). The temperatures of the pre-REE-stage fluids are significantly
lower than those of any plausible magmatic source and must have
originated at depth and cooled thereafter. As mentioned above, CO2-
and solid-bearing inclusion assemblages are common and, importantly,
strong immiscibility caused by aqueous–carbonic phase separation took
place during this stage. Immiscibility, which characterizes the pre-REE
stage, resulted in a dramatic decrease in the CO2 content of the fluids,
as indicated by the presence of CO2-bearing inclusions coexisting with
aqueous ones. Along with immiscibility and the progressive cooling of
ascending fluids, the fluids reached the limits of solubility for CaF2,
BaSO4, and CaCO3, triggering the precipitation of fluorite, barite, and
calcite in hydrothermal veins that had not yet been blocked by earlier-
crystallized material.
The REE stage was characterized by the crystallization of bastnäsite,
representing the waning stage of hydrothermal activity. Abundant
aqueous inclusions that developed during the REE stage constitute the
primary inclusion assemblages and record homogenization tempera-
tures ranging from 147 to 323 °C and salinities varying from 1.1 to
9.5 wt% NaCl equiv. in a fluid system approximating binary NaCl–H2O
(Table 1, Fig. 8). The prevalence of aqueous inclusions in bastnäsite, as
well as the scarcity of CO2-bearing inclusions, indicates that REEs are
most likely to have been precipitated from low- to medium-saline
aqueous fluids with minor amounts of CO2. Fluid mixing was the major
event during this stage, as evidenced by the H–O isotopic data from
quartz, and appears to be the most plausible explanation for the re-
corded decrease in temperature. With an inflow of more meteoric wa-
ters and the termination of immiscibility, the fluids gradually became
predominantly meteoric, cooled and diluted, as reflected by the absence
of CO2-bearing and high-salinity fluid inclusions in the minerals that
grew during the REE stage.
6.4. REE precipitation
Generally, hydrothermal REE precipitation may be triggered by one
or several of the following parameters: (1) a decrease in temperature
(Trofanenko et al., 2016); (2) a change in the pH value (Williams-Jones
et al., 2010; Chiaradia, 2014); (3) immiscibility or boiling of the ore-
forming fluids (Smith and Henderson, 2000; Xie et al., 2009, 2015); and
(4) the mixing of various fluids (Williams-Jones et al., 2000; Gultekin
et al., 2003). Experimental studies have pointed to the importance of
the presence of available ligands for high REE solubility (e.g., Wood,
1990; Haas et al., 1995). The initial fluids in the Dalucao deposit were
rich in (SO4)2−, Cl−, and F−, as mentioned above, suggesting that REEs
can form strongly associated complexes with complexing ligands in-
cluding sulfate, chloride, and, in particular, fluoride, consistent with the
case studies of REE deposits (e.g., Li et al., 2017; Li and Zhou, 2018)
and experimental petrography work (e.g., Migdisov et al., 2009). The
mineralogical signal in which fluorite, barite, calcite, and bastnäsite
typically form stable mineral assemblages in the Dalucao deposit also
supports this view.
Trofanenko et al. (2016) noted that owing to the high content of
CO2 in hydrothermal fluids, fluid–rock interaction does not cause the
precipitation of REE-bearing complexes by increasing the activity of
carbonic species and pH. Rather, precipitation of bastnäsite will occur
spontaneously once the temperature falls below the limit of its thermal
stability. Similarly, there is a clear trend of markedly decreasing tem-
peratures from the pre-REE stage to the REE stage during hydrothermal
activity in the Dalucao deposit (Table 1, Fig. 8). This suggests that a
simple cooling process might have played a key role in REE precipita-
tion. The possible effects of fluid mixing on REE precipitation also ap-
pear to be reasonable since characteristics of fluid mixing were com-
monly observed in bastnäsite-host inclusions. One plausible explanation
is that fluid mixing further lowered the temperature of hydrothermal
system and promoted the mineralization process. In contrast, fluid
immiscibility is unlikely to have been responsible for bastnäsite crys-
tallization because of its occurrence during the pre-REE stage. To -
say the least, fluid immiscibility is not a direct factor or a dominant
mechanism resulting in REE precipitation.
Obviously, the schematic diagram shown in Fig. 12 does not reflect
the three-dimensional character of ore veins or the apparent continuity
of vein development. As discussed above, with changes in the physi-
cochemical properties of the hydrothermal system, the fluids during the
pre-REE stage experienced intense immiscibility, causing the escape of
most of the CO2 (Fig. 12a). We propose that the precipitation of bast-
näsite did not occur until the immiscibility ended, and there were
massive inflows of external fluids. As fluids ascended to the near sur-
face, they were diluted by the inflow of meteoric waters that further -
reduced the temperature of the hydrothermal system. These changes,
followed by an increase in the pH value of the hydrothermal system,
destabilized the REE-bearing complexes and triggered the precipitation
of bastnäsite (Trofanenko et al., 2016). Such mechanism of hydro-
thermal REE precipitation has parallels with the suggestions of others

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Fig. 12. Schematic diagram depicting the evolution of the hydrothermal system in the Dalucao deposit. In this model, the carbonatite–syenite magmas exsolved high-
flux and REE-rich fluids. (A) Pre-REE stage: The fluids experienced intense immiscibility and, consequently, caused most CO2 escape. Accompanied with the im-
miscibility and the progressively cooling of ascending fluids, they reached the limits of solubility for CaF2, BaSO4 and CaCO3, triggering the precipitation of fluorite,
barite and calcite in fractures. (B) REE stage: With fluids ascending to near surface, massive meteoric waters mixed with the cooler hydrothermal fluids and,
consequently, the isotherms retreated downward and hydrostatic pressure dominated in this hydrothermal system. Fluid cooling and mixing severely diminished the
stability of REE-bearing complexes and led to the precipitation of bastnäsite (Williams-Jones et al., 2000, 2010; Trofanenko et al., 2016).

regarding carbonatite-related REE deposits, such as the Gallinas that may aid in REE exploration. First, the pegmatite containing melt
Mountains fluorite–REE deposits in the USA (Williams-Jones et al., and melt-fluid inclusions is prominent in the No. 1 orebody of the
2000) and the Kizilcaören fluorite–barite–REE deposit in Turkey Dalucao deposit, which is also reported in the giant Maoniuping REE
(Gultekin et al., 2003). As a result, bastnäsite crystallized at low tem- deposit, but does not occur within small–medium-sized Muluozhai and
peratures (mostly below 300 °C) and overprinted, or filled the cavities Lizhuang deposits (Liu and Hou, 2017). The occurrence of such peg-
between, early-formed gangue minerals (Fig. 12b). matite implies that the magmas exsolved high-flux fluids. Thus, peg-
matite appears to be one of the signs for potential large REE deposits.
Second, extensive fenitization occurs as metasomatism on wall-rocks in
7. Implications for REE exploration
the Dalucao deposit, suggesting that the fluids derived from carbona-
tite-syenite magmas experienced multi-stage activities. Therefore, fe-
Previous studies have shown that the formation of carbonatite-re-
nitization is potentially an exploration indicator of REE mineralized
lated REE deposits involves two processes of REE enrichment: REE
system, as in the giant Bayan Obo deposit (Le Bas, 2008). Third, field
enriched in the magmatic source of fertile carbonatites is the pre-
and petrographic observations both reveal that hydrothermal fluorite,
requisite, and the secondary process for REE precipitation under hy-
barite, and calcite have a close genetic relationship with bastnäsite in
drothermal conditions is also vital (Hou et al., 2015; Liu and Hou,
the ore veins of the Dalucao deposit. This is consistent with ion-chro-
2017). Thus, discovering REE resources related to carbonatite intru-
matographic analyses indicating that the fluids were rich in (SO4)2−,
sions requires geochemical analyses of primary carbonatites and a
Cl− and F−, which are critical in forming complexes with REEs
meticulous study of fluid inclusions.
(Williams-Jones et al., 2012; Migdisov and Williams-Jones, 2014). In
More than 500 carbonatite localities have been documented
contrast, similar mineral assemblages are not found in low-grade REE
worldwide (Woolley and Kjarsgaard, 2008), but only a few of these host
prospects, such as Qieganbulake (Ye et al., 2013) and Miaoya (Xu et al.,
significant REE deposits (≥100-kt REO). The fact that most large REE
2010), even although both areas have experienced REE enrichment in
deposits are located along cratonic margins implies that areas of me-
the magmatic source, similar to that inferred for the MD belt. Hence, a
tamorphic basement that are bounded, or cut by, translithospheric
stable mineral assemblage comprising fluorite, barite, and calcite is an
faults along cratonic margins have significant potential for generating
effective exploration guide. Finally, a large number of CO2-bearing and
REE deposits. It is accepted that fertile carbonatites generally tend to be
high-salinity fluid inclusion assemblages, the most characteristic in-
extremely enriched in Ba, Sr, and REEs compared with most barren
clusion types of carbonatitic fluids (Rankin, 2005), are widely observed
carbonatites (Hou et al., 2015; Liu and Hou, 2017). Furthermore, Hou
in hydrothermal gangue minerals (e.g., fluorite, quartz) within the
et al. (2015) noted that fertile Cenozoic carbonatites within the MD belt
Dalucao deposit. Thus, ore veins that contain fluid inclusions that are
formed by the partial melting of subcontinental lithospheric mantle
characterized by bearing CO2 and high salinity are suggested to be a
(SCLM) that had been metasomatized by REE- and CO2-rich fluids de-
preferred prospecting target area.
rived from subducted marine sediments. The metasomatism, a process
that introduces abundant REEs into SCLM, is critical to REE enrichment
8. Conclusions
in magmatic source of fertile carbonatites.
Our fluid inclusion study on the basis of alteration, paragenesis, and
1. The presence of melt and melt–fluid inclusions in pegmatite stage
mineralization in the Dalucao deposit has provided several indicators

55
X. Shu and Y. Liu
suggests a magmatic origin for the ore-forming fluids, which were
derived from carbonatite–syenite magmas. Gas- and ion-chromato-
graphic analyses indicate that the initial fluids formed in an
SO4–Cl–F–Na–K–Ca–REE hydrothermal system in which H2O and
CO2 were the dominant volatile components.
2. As indicated by microthermometric data and the estimated
minimum trapping pressures of the fluid inclusions, as well as H–O
isotope systematics, the ore-forming fluids evolved from high-tem-
perature, high-pressure, high-salinity and CO2-bearing to low-tem-
perature, low-pressure, low-salinity and CO2-poor via immiscibility,
cooing and mixing. Cooling of the fluids and the inflow of meteoric
waters were the key factors resulting in hydrothermal REE pre-
cipitation.
3. From an exploration viewpoint, primary carbonatites located along
cratonic margins that are enriched in Sr, Ba, and REEs are a pre-
requisite for regional REE-searching. In addition, several indicators
reflecting hydrothermal processes, including the occurrence of
pegmatite and fenitization, and the development of stable mineral
assemblages comprising fluorite–barite–calcite and containing CO2-
bearing and high-salinity inclusion assemblages, appear to be ex-
cellent exploration guides for REE mineralized systems.
Acknowledgments
The present study was funded by the Major State Basic Research
Program of China (2015CB452600), the Strategic Priority Research
Program of Chinese Academy of Sciences (Grant No. XDA20070304),
the Natural Sciences Foundation of China (Grant No. 41772044),
Chinese State Key Research and Development Program
(2016YFE0203000), Fundamental Research Funds for the Chinese
Academy of Geological Sciences (YYWF201705), and China Geological
Survey (1212011020000150011-03).
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