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Ore Geology Reviews 110 (2019) 102932
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Mineralogical and geochemical characteristics of the Miaoya REE prospect, T

Qinling orogenic Belt, China: Insights from Sr-Nd-C-O isotopes and LA-ICP-
MS mineral chemistry
Dexian Zhanga,b, , Yan Liuc, , Junqing Pana,b, Tagen Daia,b, Richard C. Baylessa,b
⁎ ⁎
a
Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitor (Central South University), Ministry of Education, Changsha
410083, PR China
b
School of Geosciences & Info-physics, Central South University, Changsha 410083, PR China
c
Key Laboratory of Deep-Earth Dynamics, Institute of Geology, Chinese Academy of Geological Sciences, Beijing 100037, PR China
ARTICLE INFO ABSTRACT
Keywords: Most carbonatite-related REE (rare earth element) deposits record two stages of REE enrichment: magmatic and
Carbonatite–syenite complex magmatic–hydrothermal. It is generally accepted that the first stage of enrichment, which occurs in magmas
REE mineralization associated with carbonatite–syenite complexes, is a prerequisite to the formation of REE deposits. The mag-
Miaoya REE prospect matic–hydrothermal process is also important, as demonstrated by the fact that many fertile carbonatite–syenite
Low REE grade
complexes do not produce REE deposits.
Hubei Province
LA–ICP–MS
The Miaoya carbonatite–syenite complex is prospective for REE and is ideal for studies of the formation of
REE deposits. The Miaoya REE prospect lies in the western member of the Wudan Terrane of the Qinling Belt,
China, and is hosted by a carbonatite–syenite complex that was intruded along a fault zone between schist of the
lower Silurian Meiziya Group and adjacent Proterozoic quartzite. Mineralization at the Miaoya REE prospect
includes carbonatite-, syenite-, and mixed-type, all low grade (about 1%). Results of X-ray diffraction (XRD) and
electron probe micro-analyzer (EMPA) analyses reveal that modes of REE minerals are low in all samples
(< 5%), which is consistent with the fact that less monazite, bastnäsite and other REE minerals have been found
in the Miaoya REE prospect. REE mineralization is less likely to occur as an overprint on gangue minerals.
Results of Photon Laser Ablation Inductively-Coupled-Plasma Mass-Spectrometer (LA–ICP–MS) analyses reveal
that apatite and calcite in carbonatite have the highest REE concentrations which are responsible for the rela-
tively high concentration in carbonatite rather than because of the presence of REE minerals. The consistence of
Sr-Nd isotopes ratios between altered host rocks and fresh hosted rocks suggested REE mineralization originates
directly from the unmineralized carbonatite–syenite complex rather than other host rocks. Carbon and oxygen
isotope ratios of hydrothermal calcite are consistent with low-temperature alteration subsequent to ore.
Trace element ratios for the Miaoya carbonatite–syenite complex lie in the barren carbonatite field (REEs vs.
CaO/MgO, FeO/MgO, Ba and Sr/Ba) compared with those of other giant or large carbonatite–syenite complex
related REE deposits, just below the boundary between fields for fertile and barren carbonatites. This suggests
that the carbonatite–syenite complex at the Miaoya prospect did not have the potential to produce large or giant
REE deposits. The low REE of the Miaoya prospect compared with other carbonatite-syenite hosted deposits may
reflect: 1) as supported by petrography, minimal tectonic deformation in the area resulting in 2) restricted
cycling of hydrothermal solutions that led to 3) minimal fluid scavenging from REE-rich apatite and calcite for
local REE re-deposition and concentration.
1. Introduction worldwide (Woolley and Kjarsgaard, 2008), but only a few host large-
scale rare earth deposits (≥100 kT REO, where REO = total weight of
More than 530 occurrences of carbonatite have been documented rare earth oxides). Giant (> 1 Mt REO) deposits are even rarer. The
Corresponding authors at: Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitor (Central South University),
⁎
Ministry of Education, Changsha 410083, PR China (D. Zhang). Key Laboratory of Deep-Earth Dynamics, Institute of Geology, Chinese Academy of Geological
Sciences, Beijing 100037, PR China (Y. Liu).
E-mail addresses: [email protected] (D. Zhang), [email protected] (Y. Liu).
https://doi.org/10.1016/j.oregeorev.2019.05.018
Received 6 October 2018; Received in revised form 12 May 2019; Accepted 14 May 2019
Available online 17 May 2019
0169-1368/ © 2019 Elsevier B.V. All rights reserved.
D. Zhang, et al. Ore Geology Reviews 110 (2019) 102932
Fig. 1. (a) Tectonic belt and blocks in China; (b) Tectonic subdivision of the Qingling Belt; and (c) Schematic geological map of the Miaoya carbonatite-syenite
complex, Modified after Xu et al. (2010a,b).
term “rare earth elements” (REE) generally refers to the 14 naturally (Iron oxide-copper-gold)-related deposits (Yang and Woolley, 2006; Xu
occurring lanthanides plus Y, but not Sc. The REE are vital raw mate- et al., 2010a,b; Qiu and Yang, 2011; Xie et al., 2016; Li et al., 2017a),
rials for a variety of high-technology manufacturing applications (Yang with carbonatite deposits contributing more than 60% of global REE
and Woolley, 2006; Jordens et al., 2013; Hoshino et al., 2016; production. The less important secondary REE deposits are associated
Schønwandt et al., 2016; Smith et al., 2016). China is known for its with extensive weathering. Carbonatites are one of the most important
wide range of REE deposits, which have been producing since the mantle-derived host rocks for a variety of the REEs, Nb, and Zr, which
1980s, and these deposits have established China as a leader in the occur in apatite and fluorite. Carbonatites are temporally and spatially
global REE market (Chakhmouradian and Wall, 2012; Kynicky et al., associated with alkaline complexes composed of feldspar syenite,
2012; Xie et al., 2015, 2016; Pirajno, 2016; Liu and Hou, 2017; Behrens feldspathoidal syenite, lamprophyres, and kimberlite (Sweeney, 1994;
et al., 2018). Of the known economically significant reserves, 65% are Chakhmouradian, 2006; Yang and Woolley, 2006; Qiu and Yang, 2011;
related to intrusive carbonatites, including Bayan Obo in Inner Mon- Ling et al., 2013; Hou et al., 2015; Xie et al., 2016; Li et al., 2017a; Liu
golia (Yang et al., 2009; Ling et al., 2013; Lai et al., 2015; Lai et al., and Hou, 2017). Three main petrogenetic models have been proposed
2016) and those in the Mianning–Dechang (MD) belt of Sichuan (Hou for the origin of carbonatites: (1) low-degree partial melting of a me-
et al., 2009; Xie et al., 2009, 2015; Xu et al., 2010b; Liu et al., 2015b, tasomatized mantle source that is enriched in high field strength ele-
2018; Liu and Hou, 2017; Pirajno, 2016). The genesis of China’s giant ments (HFSE) (Sweeney, 1994; Chakhmouradian, 2006); (2) immiscible
carbonatite-hosted REE deposits involved a sequence of tectonic, melts separated from calc-alkaline silicate melts (Bodeving et al., 2017);
magmatic, and hydrothermal events that produced a complex assem- and (3) fractional crystallization (Zhu et al., 2017). Carbonatite-hosted
blage of rocks and mineralization styles (Hou et al., 2009, 2015; Xie REE deposits are generally high-grade, large-scale, and have a low Th
et al., 2009; Yang et al., 2009; Xu et al., 2010b; Kynicky et al., 2012; Lai content. Thus, REE deposits have attracted the attention of geologists in
and Yang, 2013; Lai et al., 2015; Xie et al., 2015; Lai et al., 2016; recent decades (Chakhmouradian, 2006; Yang and Woolley, 2006; Xu
Pirajno, 2016). et al., 2010b; Jordens et al., 2013; Smith et al., 2016; Xie et al., 2016; Li
The REE occur in primary and secondary deposits (Yang and et al., 2017a; Verplanck, 2017; Ying et al., 2017; Liu et al., 2018; Shu
Woolley, 2006; Hoshino et al., 2016; Schønwandt et al., 2016; Smith and Liu, 2019; Guo and Liu, 2019; Zheng and Liu, 2019). The existing
et al., 2016; Xie et al., 2016). Primary REE deposits are generally as- models for REE deposit formation include two important processes: REE
sociated with carbonatites, alkaline and phosphorite rocks and IOCG enrichment of carbonatite-syenite magma in the mantle is a
2
Fig. 2. A) Outcrop of biotitic carbonatite; B) Hand

specimen of biotitic carbonatite; (C) Outcrop of
syenite;(D) Hand specimen of syenite; note rock
hammer for scale in (A) and (C), the red Markings
for the placement of thin section cuts in (B) and (D).
(For interpretation of the references to colour in
this figure legend, the reader is referred to the web
version of this article.)
prerequisite for the formation of large or giant REE deposits, and in (SS) zone (Fig. 1A and B). The South Qinling Belt has been interpreted
order for the concentrations of mineable REEs to form, hydrothermal as a Mesozoic Orogen developed along the Mianlue Suture (SS), and is a
fluids must circulate through the carbonatite-syenite rock (Hou et al., segment of South China Block (SCB). The North Qinling Belt (NQB) is
2015; Liu and Hou, 2017). considered a mid-Paleozoic Orogen feature with wide spread Paleozoic
A carbonatite–syenite complex in the Qinling Belt, China, hosts the island-arc type magmatism and metamorphism (Sun et al., 2002; Xu
Miaoya prospect. Concentrations of REE, Ba, Sr, and other elements in et al., 2015). The geological framework, magmatic activities and tec-
the prospect are relatively high, similar to concentrations at other large tonic settings of Qinling region have been systematically described in
REE deposits such as those at Maoniuping and Dalucao. However, the detail by several researchers (Meng and Zhang, 2000; Ratschbacher
Miaoya prospect is lower grade compared to these other deposits, et al., 2003; Xu et al., 2010b; Xu et al., 2015; Qiu and Deng, 2016; Geng
which suggests that not all fertile carbonatites produce viable REE de- et al., 2017; Ying et al., 2017; Zhu et al., 2017).
posits. Indeed, secondary processes are necessary to enrich the REE The Miaoya REE prospect is located in the western area of Wudan
contents of fertile carbonatites, without which large deposits of REE Terrane of the Qinling Belt (Fig. 1). Forty-five shows have been dis-
cannot form. This is demonstrated by the existence of only around a covered in 12 square kilometer area with a total resource of 1.3 Mt
dozen known large and giant carbonatite-related REE deposits globally. TR2O3 (Total weight in Metric tons of Rare Earth Element Oxides) and
In the past, low REE grades at the Miaoya prospect and other fertile 0.9 Mt Nb2O5 (Ma et al., 1981). The prospect is hosted in a carbonatite-
carbonatite–syenite complexes have attracted little attention of geos- syenite complex (Xu et al., 2010a,b) which intruded along the fault belt
cientists. As a result, not many studies are available on secondary between the schist of the Lower-Silurian (S1m) Meiziya group and the
processes of REE enrichment. Previous studies of the Miaoya area have Proterozoic meta-quartz keratophyre of the lower Sinian (Nh2y) Yao-
been limited to carbonatite petrogenesis, ore-forming ages, and geo- linghe group of Nahua formation (Fig. 1C). Carbonatite intruded the
chemical and isotopic characteristics of the Miaoya carbonatite–syenite syenite as stocks and minor dikes. Li and Zhou (2018) reported that a
complex (Xu et al., 2010b, 2015; Ying et al., 2017; Zhu et al., 2017). In biotite K-Ar age yielded an age of 278 Ma for carbonatite. The small
the present study, various samples from the prospect were subjected to oscillatory-zoned zircon crystals from the syenites give a concordant U-
X-ray powder diffraction (XRD), Laser Ablation–Inductively Coupled Pb age of 147 ± 0.5 Ma, while the large euhedral oscillatory-zone
Plasma–Mass Spectrometry (LA-ICP-MS), Electron Microprobe Analysis zircon crystal from syenite given age of 766 ± 25 Ma (Xu et al., 2012,
(EMPA), X Ray Fluorescence (XRF), Inductively Coupled Plasma – Mass 2015). Syenite predominantly consists of K-feldspar with minor albite,
Spectrometry (ICP-MS) analyses to examine trace element concentra- biotite, quartz, sericite, plagioclase, and calcite. Carbonatite consists of
tions and the ratios of Sr, Nd, C, and O isotopes. Based on these results fine to medium grain calcite and minor K-feldspar, albite, augite, bio-
and the interpreted geological setting, we identify the factors re- tite, fluorapatite, columbite, bastnäsite, ilmenite, pyrochlore, quartz,
sponsible for the low grade of the Miaoya REE prospect. monazite, aeschynite, ilmenorutile, rutile, and minor sulphides. The
REE minerals, dominated by monazite and bastnäsite, fill fractures in
calcite and feldspar. Compared with other carbonatite-related REE de-
2. Geological setting posits, the REE grade at the Miaoya prospect is relatively low (Liu and
Hou, 2017; Li and Zhou, 2018). The ranges and averages for REEs are:
The Qinling Belt (QB) is bounded by the South China Block (SCB) Nb2O5 (0.057–0.248%, ave. 0.1%), TR2O3 (0.070–2.277%, ave.1.0%),
and North China Block (NCB), and is subdivided into the South Qinling Ta2O5 (0.001–0.0061%, ave.0.001%), ZrO2 (0.015–0.031%, ave.
Belt (SQB) and North Qinling Belt (NQB) along the Shangdan Suture
3
0.03%), ThO2 (0.001–0.158%, ave. 0.005%) (Ma et al., 1981). (CAGS), in Beijing, China. The microprobe was operated at an accel-
erating voltage of 15 kV, a beam current of 20 nA, and beam size of
3. Sampling and analytical methods 5 μm. The following natural and synthetic standards, analytical lines
and detector types were used for electron-microprobe analysis (EMPA):
3.1. Sampling jadeite (NaKα, and AlKα on TAP, SiKα on PET); forsterite (MgKα, TAP);
topaz (FKα, TAP); K-feldspar (KKα, PET); wollastonite (CaKα), hema-
Samples come from a narrow, 1 km wide by 12 km long WNW- tite (FeKα, LIF); rutile (TiKα, LIF); MnO (MnKα, LIF); NaCl (ClKα, PET).
trending transect (covering ∼12 km2) (Fig. 1C). Eleven samples in- For bastnäsite, synthetic orthophosphate standards (La, Ce, Pr, Nd and
cluding one schist (My1), four carbonatites (My2, My3, My5 and My7), Sm) and natural thorite were employed to measure the abundances of
three syenites (My4, My6 and My8) and three mixed rocks (My9, My10 REE (La, Ce, Pr, Nd, Sm) and Th, respectively. Heavier lanthanides and
and My11) were collected at the Miaoya REE prospect, each with dis- Y were sought but not found at levels detectable by EMPA. Matrix
tinct lithology and spatial distribution (Fig. 1C and Fig. 2). All samples corrections were carried out using the ZAF correction program supplied
were fresh extracts from outcrops which were put into plastic bags, then by the manufacturer.
cut into several small slabs in the lab. All the slabs were subsequently
washed in water several times then dried in an oven at 105 °C for 8 h. 3.2.4. In situ LA-ICP-MS minerals analysis
One slab from each sample was sent to make polished thick sections for In situ trace element compositions of individual minerals (apatite,
microscopic observation and electron microprobe and LA-ICP-MS ana- biotite, augite, columbite, plagioclase, ilmenite and calcite) were
lyses, while the remaining 3 or 4 slabs from each sample were finely measured by a Photon Machines Excimer 193 nm laser ablation system,
ground in an agate ball mill. The ground powder was quartered for coupled to an Agilent 7700x at the FocuMS Laboratory, Nanjing. The
analyses of major elements, trace elements and rare earth elements, C-O detailed LA-ICP-MS parameters are similar to those used by Li et al.
isotopes and Sr-Nd isotopes. (2017b). In situ trace element measurements were made using the same
laser source and the same model ICP-MS to ensure consistency of re-
3.2. Analytical methods sults. The collected samples were first ground into thin slices, then
examined with a Leica-2700 microscope to determine detailed miner-
3.2.1. Bulk analysis of major and trace element alogy and, as far as possible to identify specific mineral crystals for
Whole-rock geochemical analyses of syenite were performed at the study. Then the thin sections were cleaned and placed into the chamfer
National Research Center of Geoanalysis, Chinese Academy of cell of the LA-ICP-MS for in situ trace element composition measure-
Geological Science. Pulverized whole-rock samples (0.7 g) were mixed ments. The detailed experimental procedures and processes used can be
with 5.3 g Li2B4O7, 0.4 g LiF, and 0.3 g NH4NO3 in a porcelain crucible. found in (Li et al., 2017b). The standard samples used were USGS GSD-
The powder mixture was transferred to a platinum alloy crucible, and 1G and GSE-1G. A laser beam of 25–40 µm was used. In addition, NIST
1 mL LiBr solution added to it. The fluxed sample was then dried and SRM610 was used as the system monitoring sample. USGS geochemical
melted in an automatic flame-fusion furnace and quenched to glass. The reference materials BCR-2, BHVO-2, AVG-2, and RGM-2 were used for
glass was analyzed by X-ray fluorescence (XRF) for major elements; quality control. The data were reduced by ICPMSDataCal 10.1 software
analytical errors were estimated to be < 2% relative. using 100%-normalization strategy without applying an internal stan-
The following suggested procedure (Liu et al., 2015a) was adopted dard (Liu et al., 2008).
for the analysis of REE and other trace elements in carbonatite, syenite,
and mixed syenite samples (national standard of the People’s Republic 3.2.5. High precision Sr-Nd isotope analysis
of China). Powder samples (50 mg) were dissolved in distilled 1 mL HF High precision Sr–Nd isotopic measurements were carried out at
and 0.5 mL HNO3 in 15 mL Savillex Teflon screw-cap capsules at 190 °C Nanjing FocuMS Technology Co. Ltd. Rock powder from samples was
for 1 day, and dried again, then digested with 0.5 mL HNO3, and then decomposed using high-pressure Poly Tetra Fluoroethylene (PTFE)
dried again. The capsule content was digested with 0.5 mL HNO3 and bombs. Strontium, Nd, and Pb were purified from the same digestion
dried a third time to ensure complete digestion. Then, the sample was solution using two-step column chemistry: The first exchange column
digested with 5 mL HNO3 and held at 130 °C in an oven for 3 h. After combined with BioRad AG50W × 8 and Sr Spec resin was used to se-
cooling, the solution was transferred to a plastic bottle and diluted to parate Sr, and REE from the sample matrix. The second column sepa-
50 mL before analysis. The sample solutions were analyzed by a Photon rated Nd from other REEs with Ln Spec-coated Teflon powder.
Inductively-Coupled-Plasma Mass-Spectrometer (ICP–MS). Standards The Sr-, Nd- bearing elutions were dried down and re-dissolved in
GBW07120, GBW 07103, GBW 07105, and GBW 07187 were measured 1.0 mL 2 wt% HNO3. Small aliquots of each were analyzed using an
together with the samples; a precision within 5% relative was achieved. Agilent Technologies 7700x quadrupole ICP-MS (Hachioji, Tokyo,
Japan) to determine the exact content of Sr, Nd available. Diluted so-
3.2.2. XRD bulk powder analysis lutions (50 ppb Sr and100 ppb Nd) were introduced into Nu
The XRD bulk analyses of samples were performed at the China Instruments Nu Plasma II MC-ICP-MS (Wrexham, Wales, UK) by
University of Geosciences, Beijing, using Rigaku D/Mac-RC and CuKα1 Teledyne Cetac Technologies Aridus II desolvating nebulizer system
radiation with a graphite monochromator and continuous scanning (Omaha, Nebraska, USA).
under the following operating conditions: voltage of 40 kV, beam cur- Isotopic ratio raw data were corrected for mass fractionation by
rent of 80 mA, scanning speed of 8°/min, slit of Geosciences, normalizing to 86Sr/88Sr = 0.1194 for Sr, 146Nd/144Nd = 0.7219 for
DS = SS = 1°, ambient temperature of 18 °C, and humidity of 30%. The Nd, with exponential law. International isotopic standards (NIST SRM
contents (mass%) of the primary mineral phases identified by the XRD 987 for Sr and JNdi-1 for Nd) were periodically analyzed to correct
were quantified using an internal standard, with corundum used as the instrumental drift. USGS geochemical reference materials BCR-2,
reference material (Liu et al., 2015a). All work followed the basic BHVO-2, AVG-2, and RGM-1 were used as quality controls.
principles and procedures of quantitative analysis using the internal-
standard method described in detail by Liu et al. (2015a,b). 3.2.6. C-O isotope analysis
Carbon–Oxygen isotopic compositions of carbonates were analyzed
3.2.3. Petrographic study using EMPA using a Thermo Finnigan GasBench II equipped with a CTC Combi-Pal
Back-scattered electron (BSE) images and major-element analyses of auto-sampler and linked to a Finnigan MAT 253 mass Spectrometer at
minerals were acquired using a JXA-8230 electron microprobe at the the Institute of Mineral Resources, CAGS, Beijing. Carbonate micro-
Institute of Mineral Resources, Chinese Academy of Geological Sciences samples were loaded manually into 12 mL round-bottomed borosilicate
4
exetainers and sealed using butyl rubber septa. Eighty-eight exetainers are fine grained (10–100 μm), and only rarely coarser-grained
including 18 aliquots of four national standards (GBW04405, (< 10 mm). BSE images reveal the schist is mainly composed of calcite,
GBW04406, GBW04416 and GBW04417) were routinely loaded for one quartz, muscovite and apatite (Fig. 4) and it contains few REE minerals
run. The exetainers were automatically flushed with grade 5 He by (Fig. 4A–B). Pyrite grains overgrow calcite and other minerals
penetrating the septa using a double-hole needle at a flow rate of (Fig. 4C–D). In carbonatite, large amounts of calcite, apatite and mus-
100 mL/min. Afterwards, 4–6 drops of phosphoric acid were deposited covite were found. The samples commonly contain monazite, which
in each exetainer. The exetainers were placed into an aluminum tray; surrounds or coexists with the apatite (Fig. 4E–F). Still some K-feldspar
calcite was kept for four hours at 72℃, while dolomite was kept for was found in carbonatite (Fig. 4F), while both monazite and bastnäsite
24 h. Subsequently, the sample gas was introduced ten times into the distributed randomly in the syenite and carbonatite. In typical samples
mass spectrometer, by sampling through the standard 100 μL sample at the Miaoya prospect, fewer generations of monazite can be found,
loop, which is a type of stable volume and stainless tube (Liu et al., and has relatively higher REE concentration (Table 3).
2015c). Carbon Dioxide was separated from other components using a As shown in Fig. 4E and F, carbonatite in this study contained a
gas chromatographic column (Poraplot Q with fused-silica tubing, significant amount of (less than 1.0 vol%) columbite with crystal dia-
25 mm × 0.32 mm, Thermo Fisher Scientific) heated to 70 °C, and the meters ranging from 100 to 500 μm. Some of these minerals show eu-
peak corresponding to this CO2 level was then passed via an open split hedral form but others were confined in fissures in apatite. Fig. 6 shows
into the mass spectrometer. The external precision calculated over 18 chondrite-normalized REE patterns and the spider diagram of carbo-
standards per run was typically 0.1‰ for δ13C and δ18O. The δ13C and natite and syenite and trace element patterns for carbonatite and sye-
δ18O results are reported in standard delta notation (‰ units) relative nite in western Sichuan, normalized to the abundance of chondrite
to the Vienna Pee Dee belemnite (V-PDB). concentrations in primitive mantle data as described by McDonough
and Sun (1995).
4. Results
4.3. REE mineral characteristics measured using LA-ICP-MS
4.1. Chemical composition of syenite and carbonatite
Table 4 and Fig. 6A and B clearly provide evidence that the total
A total of 11 samples were analyzed, and the major and trace ele- REE concentrations are closely associated with apatite and minor cal-
ments of these samples are listed in Table 1. They show, together with cite (Fig. 6B red and pink lines) and calcite in carbonatite and minor
Fig. 3A and B, that the carbonatite at the Miaoya REE prospect has mixed rocks. Trace element data for apatite from the Miaoya REE
geochemical characteristics similar to those carbonatites from giant or prospect are shown in Table 4. In both the syenite and carbonatite,
large REE deposits(Niu et al., 2003; Woolley and Kjarsgaard, 2008; apatite is euhedral and it is common in both rock types (2.0–4.4 vol%
Yang et al., 2009; Hou et al., 2015; Liu et al., 2015a; Trofanenko et al., and 1.1–20.7 vol%; respectively). Ranges and averages of trace ele-
2016; Li and Zhou, 2018) as follows: (1) low SiO2, generally less than ments with high concentrations (Table 3) include Sr (5677–14659 ppm,
20%; and (2) low Al2O3 due to lacking of Al-silicates; and (3) high CO2 ave.11163 ppm), Y (234–967 ppm, ave. 442 ppm); Th (4.3–312 ppm,
content, generally 25–40%; and (4) CaO + MgO + Fe2O3 + FeO ran- ave. 65.9 ppm); U (0.05–30.3 ppm, ave. 6.4 ppm) while those with low
ging from 35% to 50%; and (5) higher TiO2, MnO, BaO, SrO, and P2O5, concentration include Rb (0.03–0.20 ppm, ave. 0.08 ppm), and HFSE
as compared to other igneous rocks. Samples My9, My10 and My 11 are (Zr:0.47–24.6 ppm, ave. 4.52 ppm; Hf: 0.01–0.18 ppm, ave. 0.07 ppm;
mixed rock, and they have characteristics of both syenite and carbo- Nb:0.35–5.67 ppm, ave. 1.37 ppm; Ta:0.00–0.10 ppm, ave.0.02 ppm).
natite. Mineralization at the Miaoya REE prospect is hosted by both Two types of calcite were identified at the Miaoya REE prospect
syenite and carbonatite. Typical samples of syenite and carbonatite ores based on total REE concentrations: calcite from schist and syenite (low
are enriched in large-ion-lithophile elements (Table 1). The light REE total REE concentration), and calcite from carbonatite (high total REE
(La, Ce, Pr, Nd, Sm, and Eu) content of the samples (335–19016 ppm) is concentration). The schist/syenite calcite also has high Rb
∼11 to ∼28.6 times those of the heavy REE (Gd, Tb, Dy, Ho, Er, Tm, (0.15–29.8 ppm) and lower HFSE (Zr, 0.01–75.7 ppm, Hf, 0.02–2.0 ppm,
Yb, Y, and Lu) (Table 1). Fig. 3 shows primitive-mantle-normalized REE Nb, 0.01–41.3 ppm, Ta: 0.01–0.15 ppm, Ti:1.2–1037 ppm) than the car-
patterns (Fig. 3A) and Fig. 3B shows a spider diagram of carbonatite bonatite calcite (Zr:0.01–272 ppm, Hf:0.02–4.7 ppm, Nb:0.01–377 ppm,
and syenite from the Miaoya prospect normalized to the abundance of Ta:0.01–7.1 ppm, Ti:0.1–110000 ppm).
primitive mantle reference concentrations as suggested by McDonough The REE patterns of these individual minerals using LA-ICP-MS
and Sun (1995). analysis are shown in Fig. 6. Apatite has the highest REE concentration,
both total REE (4400–14000 ppm, av. 7700 ppm) and individual ele-
4.2. REE minerals in the Miaoya prospect and petrographic studies ments, with range of (La)N/(Lu)N = 44.7–145. The chondrite-normal-
ized REE patterns for apatite exhibit negative slopes and lack a Eu
Analysis of both syenite and carbonatite samples using XRD and anomaly (Fig. 6A). The REE concentrations of calcite from the schist
EPMA reveal that they have different mineral assemblages (Tables 2 and syenite are relatively lower than those from carbonatite (Fig. 6B).
and 3, Figs. 4 and 5). Macroscopic and microscopic examination reveals The calcite from carbonatite has the highest REE concentration
that the carbonatite contains higher amounts of calcite (58.5–92.0 vol (126–35000 ppm, ave. 4100 ppm), and this type of calcite also has
%), mica (3.00–25.8 vol%), apatite (1.1–17.3 vol%), ankerite right-dip trend patterns with (La)N/(Lu)N = 0.24–322 (av. 57.1;
(2.0–13.9 vol%), and minor plagioclase (0–0.9%), K-feldspar Table 3), while the calcite from schist and syenite has low concentra-
(0.5–1.0 vol%), chlorite (0–3.0% vol.%), and quartz (0–5.0% vol.%), tion of all the trace elements, generally below 100 ppm and has flat REE
while the syenite samples are composed mainly of plagioclase patterns (Table 3 and Fig. 6B). The calcite from schist/syenite has a low
(16.0–25.9 vol%), mica (21.2–56.7 vol%), quartz (9.5–20.8 vol%), K- total REE concentration (38.0–88.8 ppm; av. 68.9 ppm), and low (La)N/
feldspar(0.3–7.5 vol%), calcite (0–27.0 vol%), ankerite (0–17.0 vol%), (Lu)N (0.03–0.59, ave. 0.12). Columbite and ilmenite have an average
and apatite (0–4.4 vol%). The most obvious characteristics are that REE up to 1000 ppm (Fig. 6C). The trace element concentrations in
syenite contains relatively high amount of plagioclase, mica and quartz augite, biotite, plagioclase, and quartz are low, below 10 ppm, and they
while carbonatite has more calcite and ankerite. Mineral concentrations show a positive Eu anomaly (Fig. 6D).
contained in mixed rocks are between syenite and carbonatite. Our
XRD, SEM, BSE imaging, and EMPA data indicate that monazite, rather 4.4. Sr-Nd and C-O isotopes
than bastnäsite, is the main primary REE mineral in the Miaoya pro-
spect (Table 3, Figs. 4 and 5). The REE minerals in the Miaoya prospect Table 5 show the Sr-Nb isotopic compositions of syenite and
5
Table 1
Major (oxide wt%) and trace element (ppm) content of carbonatite and syenite of the Miaoya REE prospect.
sample No. My1 My2 My3 My5 My7 My4 My6 My8 My9 My10 My11
rock types schist carbonatite syenite mixed rock
SiO2 50.4 3.70 2.46 13.5 3.15 36.0 49.4 60.6 31.4 27.9 26.2
TiO2 2.61 0.54 0.15 1.04 0.26 0.79 0.37 0.36 1.25 1.00 0.83
Al2O3 11.1 0.60 0.72 5.77 1.30 12.5 11.8 20.2 8.94 13.2 6.25
Fe2O3 4.41 1.19 0.92 1.28 1.07 4.35 2.58 3.05 2.67 1.88 3.25
FeO 7.76 3.94 1.25 4.68 2.53 4.38 1.24 0.37 5.03 4.37 2.40
MnO 0.19 1.04 0.59 0.56 0.60 0.29 0.72 0.15 0.50 0.54 0.42
MgO 5.09 2.80 0.42 1.69 1.14 1.29 2.31 0.99 5.27 3.02 2.48
CaO 5.96 46.2 51.9 36.3 48.8 16.8 10.6 0.71 18.9 20.8 28.9
Na2O 0.67 0.06 0.11 0.11 0.11 0.28 4.28 3.32 1.70 0.65 0.59
K2O 5.38 0.17 0.34 2.18 0.45 8.40 4.09 6.67 2.53 4.65 2.04
P2O5 0.44 2.22 4.17 1.92 8.38 1.13 1.30 0.13 3.87 2.04 16.0
BaO 0.27 0.04 0.04 0.09 0.04 0.86 0.09 0.37 0.10 0.13 0.06
SrO 0.05 0.36 0.48 0.63 0.59 0.13 0.10 0.01 0.21 0.24 0.53
CO2 5.51 36.9 36.0 30.0 31.2 12.9 10.7 2.81 17.8 19.5 9.52
H2O− 0.08 0.08 0.04 0.05 0.11 0.02 0.07 0.04 0.08 0.04 0.03
Total 99.9 99.8 99.5 99.7 99.8 100 99.7 99.8 100 99.9 99.6
Fe2O3 + FeO 12.2 5.12 2.17 5.97 3.60 8.73 3.82 3.42 7.70 6.25 5.65
FCM 23.2 54.1 54.4 44.0 53.6 26.8 16.8 5.11 31.9 30.1 37.1
K2O + Na2O 6.05 0.23 0.45 2.28 0.56 8.68 8.37 9.99 4.23 5.30 2.63
Trace element (ppm)

Rb 127 13.5 6.16 56.7 15.2 133 52.5 146 71.4 110 56.6
K 57,239 1411 2821 18,089 3734 69,702 33,938 55,347 20,994 38,585 16,928
Ba 2457 355 292 787 245 7851 755 3384 886 1056 487
Th 5.57 8.01 27.4 21.3 34.0 26.4 39.1 117 44.6 32.7 72.7
U 1.87 2.25 45.9 57.4 3.56 14.4 4.61 13.6 40.5 3.06 16.9
Nb 83.5 323 144 307 60.1 474 318 571 2182 350 8269
La 33.3 1038 415 330 619 186 6433 94.4 416 310 662
Ce 68.1 2487 833 674 1559 387 9749 155 1113 631 1786
Sr 404 3260 3958 5734 5319 1157 988 128 2002 2212 4983
Nd 42.7 755 249 200 440 132 1913 60.5 298 199 537
P 192 969 1821 838 3659 493 568 57.0 1690 891 6986
Zr 145 61.1 80.1 332 151 81.8 182 1634 108 541 354
Hf 4.10 0.76 0.77 4.53 2.15 1.19 3.73 33.7 2.32 7.45 4.45
Sm 8.54 131 46.6 38.2 80.1 24.9 185 6.02 51.7 36.2 97.0
Ti 15,233 2034 1173 6600 1807 4728 2587 2296 7653 6336 5338
Y 29.8 236 206 89.0 179 113 74.4 20.3 66.5 81.4 218
Yb 2.80 15.8 14.8 6.54 11.1 7.76 7.24 2.77 3.76 5.64 13.2
Lu 0.55 1.98 2.10 1.07 1.57 1.18 1.18 0.56 0.59 0.95 1.80
Cr 36.2 24.1 8.74 6.56 6.01 10.8 34.1 3.09 200 4.87 6.14
Sn 2.46 0.45 0.70 1.22 0.37 1.49 4.44 4.32 3.25 2.27 1.95
Sb 0.12 0.17 0.89 0.17 0.15 0.16 0.36 0.12 0.30 0.17 0.20
Li 52.4 6.06 1.28 16.2 4.62 26.8 16.3 40.1 21.3 42.1 18.8
Be 2.49 0.28 0.14 1.45 0.64 2.48 1.01 14.0 3.04 5.25 2.29
Mn 1426 6803 4506 4537 4730 2307 8782 1174 3932 4401 3320
Co 35.5 4.67 5.28 6.15 4.45 2.84 4.80 0.76 16.6 7.27 3.72
Ni 44.3 4.49 7.00 3.91 6.44 10.3 9.97 3.17 103 6.82 5.12
Cu 139 2.57 3.66 2.56 3.14 5.25 6.01 1.20 20.4 5.73 6.85
Zn 136 72.6 52.0 157 93.6 134 163 205 349 165 200
Ga 19.3 10.7 5.10 12.3 9.07 24.8 47.0 62.4 21.4 25.1 15.0
Mo 1.47 0.37 4.89 6.93 7.85 4.85 712 10.5 5.78 16.7 7.86
Cd 0.09 0.90 0.40 0.42 0.40 0.22 2.24 0.35 1.45 0.36 0.45
In 0.09 0.05 0.12 0.05 0.08 0.05 0.39 0.12 0.18 0.17 0.06
Cs 9.94 0.62 0.10 2.10 0.57 1.95 0.86 2.18 1.56 4.66 1.84
Tl 0.75 0.08 0.05 0.19 0.09 0.56 0.34 0.63 0.45 0.60 0.31
Pb 6.74 19.5 19.4 30.9 43.2 10.3 13.8 22.0 22.0 22.1 11.0
Bi 0.09 0.05 0.12 0.06 0.08 0.05 0.27 0.22 0.05 0.05 0.11
Ta 1.72 1.37 6.64 44.6 1.75 13.8 2.32 21.2 29.2 20.6 51.0
W 3.91 1.74 1.46 2.12 2.05 2.17 1.51 3.44 7.23 6.73 21.7
As 0.43 4.96 5.55 1.92 2.90 1.87 8.55 0.29 8.45 1.21 3.07
V 233 94.1 101 157 109 152 176 73.6 208 205 141
Sc 26.9 1.33 3.37 1.21 2.15 1.10 9.72 2.38 8.71 1.94 1.16
Rare Earth Elements (ppm)

La 33.3 1038 505 330 619 186 6433 94.4 416 310 662
Ce 68.1 2487 908 674 1559 387 9749 155 1113 631 1786
Pr 9.94 233 97.2 64.5 137 47.6 694 17.3 93.8 63.5 160
Nd 42.7 755 332 200 440 132 1913 60.5 298 199 537
Sm 8.54 131 50.3 38.2 80.1 24.9 185 6.02 51.7 36.2 97.0
Eu 2.58 35.9 15.6 11.2 23.2 7.94 41.8 1.77 13.9 10.5 30.9
Gd 8.66 89.4 45.8 31.4 66.4 21.9 91.1 4.28 34.6 29.3 77.9
Tb 1.27 10.9 7.14 3.94 8.24 3.41 6.73 0.60 3.83 3.71 10.2
Dy 6.78 54.0 43.6 19.6 40.9 20.7 22.0 3.58 17.0 18.4 51.4
(continued on next page)
6
Table 1 (continued)
sample No. My1 My2 My3 My5 My7 My4 My6 My8 My9 My10 My11
rock types schist carbonatite syenite mixed rock
Ho 1.17 9.59 8.68 3.40 6.94 4.00 3.19 0.75 2.70 3.22 8.42
Er 3.14 25.4 23.3 8.74 17.0 11.0 10.5 2.42 6.33 8.35 20.8
Tm 0.43 3.02 3.02 1.08 2.00 1.39 1.04 0.40 0.68 0.99 2.41
Yb 2.80 15.8 16.5 6.54 11.1 7.76 7.24 2.77 3.76 5.64 13.2
Lu 0.55 1.98 2.16 1.07 1.57 1.18 1.18 0.56 0.59 0.95 1.80
Y 29.8 236 263 89.0 179 113 74.4 20.3 66.5 81.4 218
ΣREE 190 4890 2058 1394 3012 857 19,159 350 2056 1321 3459
LREE 165 4680 1908 1318 2858 785 19,016 335 1986 1250 3273
HREE 24.8 210 150 75.8 154 71.3 143 15.4 69.5 70.6 186
LREE/HREE 6.66 22.3 12.7 17.4 18.5 11.0 133 21.8 28.6 17.7 17.6
(La)N/(Yb)N 8.53 47.1 22 36.2 40.0 17.2 637 24.4 79.4 39.4 36.0
δEu 0.92 1.01 0.99 0.99 0.97 1.04 0.98 1.07 1.00 0.99 1.09
δCe 0.92 1.24 1 1.13 1.31 1.01 1.13 0.94 1.38 1.10 1.35
Fig. 3. (A) and (B) Plots of Primitive Mantle-normalized REE patterns and spider diagrams for carbonatite, syenite and schist from the Miaoya REE prospect
(normalization values are from McDonough and Sun, 1995).
Table 2
Mineralogy and modes for carbonatite and syenite samples as determined from XRD data. Mineral percentages are in vol.%.
Sample no. Rock types Mineral components
My1 schist quartz:6.5%; calcite:2.9%; mica:89.1%; Chlorite:1.5%

My2 carbonatite quartz:5.0%, K-feldspar:0.6%, calcite:58.5%, ankerite:13.9%, mica:14.5%, apatite:7.5%
My3 carbonatite quartz:0.6%, plagioclase:0.9%, K-feldspar:0.5%, calcite:92.0%, mica:3.0%, apatite:3.0%
My5 carbonatite K-feldspar:1.0%, calcite:62.5%, ankerite:9.6%, mica:25.8%, apatite:1.1%
My7 carbonatite calcite:66.4%, ankerite:2.0%, mica11.3%, Chlorite:3.0%, apatite:17.3%
My4 syenite K-feldspar:22.6%, calcite:27.0%, mica:46.0%, apatite:4.4%
My6 syenite quartz:9.5%, plagioclase:25.9%, K-feldspar:7.5%, calcite:16.9%, ankerite:17.0%, mica:21.2%, apatite:2.0%
My8 syenite quartz:20.8%, plagioclase:18.6%, K-feldspar:3.9%, mica:56.7%
My9 mixed rock quartz:11.5%, plagioclase:16.0%, K-feldspar:0.6%, calcite:9.0%, ankerite:34.5%, mica:19.5%, apatite:8.9%
My10 mixed rock quartz:4.2%, plagioclase:9.0%, K-feldspar:1.2%, calcite:22.6%, ankerite:16.7%, mica:41.5%, apatite:4.8%
My11 mixed rock quartz:8.4%, plagioclase:7.4%, K-feldspar:0.2%, ankerite:24.1%, mica:39.2%, apatite:20.7%
carbonatite. Most samples have high Sr content, 3200 ppm to 5700 ppm highly variable δ18OV-SMOW indicate the rock-forming process lies in a
in carbonatite, 2000 ppm to 2200 pp in mixed rocks and 4900 ppm in low temperature environment rather than resulting from contamina-
mixed carbonatite. The Sr in syenite (128–11000 ppm) and schist tion.
(404 ppm) are relatively low. Samarium and Nd concentrations are
variable and do not have a consistent trend (Fig. 7; Table 5). The initial 5. Discussion
87
Sr/86Sr (0.7038 to 0.7095) and 143Nd/144Nd (0.512269 to 0.512439)
isotope ratios of different samples remain constant. 5.1. REE enrichment at the Miaoya prospect
The C and O isotopic compositions of the carbonatite are listed in
Table 6 and plotted in Fig. 8. The carbonatite in the syenite–carbonatite A number of petrogenetic models have been proposed to explain the
complexes exhibit δ18O values of 11.1‰ to 13.8‰ and δ13C values of generation of carbonatite magmas. Some models invoke a parental si-
–5.4‰ to –3.1‰ (Table 6); these compositions fall outside of the field licate melt to explain the close spatial association of carbonatites with
of the typical primary mantle-derived carbonatite on a δ18OV-SMOW vs. silica-undersaturated alkaline rocks. In the case of carbonatite complex-
δ13CV-PDB diagram (Fig. 8) where the consistency δ13CV-PDB value and related REE deposits, the preferred petrogenetic model is that of
7
Table 3
EMPA analysis of REE minerals (wt%) from the carbonatite and syenite of the Miaoya REE prospect.
Analyses No. Mineral Na2O MgO Al2O3 SiO2 F K2 O P2O5 FeO MnO UO2 ZrO2 ThO2 Nb2O5 Ta2O5 CaO BaO NiO SO3 TiO2
My10-3-2 apatite 0.21 0.00 0.00 0.31 2.05 0.01 40.6 0.07 0.02 0.00 0.00 0.01 0.04 0.00 55.2 0.00 0.00 0.07 0.00
My11-1-10 apatite 0.11 0.00 0.01 0.00 2.11 0.00 40.7 0.01 0.06 0.00 0.13 0.00 0.00 0.00 55.6 0.00 0.00 0.00 0.00
My11-1-11 apatite 0.18 0.01 0.00 0.00 2.76 0.00 39.7 0.08 0.11 0.00 0.04 0.04 0.03 0.00 55.8 0.00 0.00 0.02 0.00
My11-1-6 apatite 0.20 0.00 0.00 0.00 1.47 0.00 41.4 0.14 0.01 0.00 0.03 0.00 0.01 0.03 54.0 0.00 0.01 0.02 0.00
My11-1-7 apatite 0.22 0.01 0.00 0.00 1.52 0.00 40.5 0.03 0.10 0.00 0.11 0.02 0.00 0.03 55.1 0.02 0.00 0.01 0.05
My11-2-1 apatite 0.20 0.01 0.00 0.05 1.81 0.01 40.5 0.00 0.06 0.00 0.10 0.05 0.00 0.00 55.0 0.00 0.02 0.02 0.00
My11-2-2 apatite 0.13 0.02 0.00 0.05 2.44 0.00 40.7 0.00 0.06 0.01 0.09 0.06 0.01 0.06 55.3 0.08 0.00 0.02 0.00
My2-1-1 apatite 0.08 0.00 0.01 0.00 2.27 0.00 40.7 0.00 0.06 – – – – – 55.6 0.00 0.00 0.01 0.00
My2-1-2 apatite 0.06 0.02 0.00 0.00 2.64 0.00 40.8 0.06 0.01 – – – – – 55.6 0.06 0.01 0.02 0.04
My2-2-3 apatite 0.04 0.02 0.00 0.01 2.49 0.01 41.1 0.00 0.00 – – – – – 55.3 0.00 0.03 0.01 0.00
My2-2-4 apatite 0.00 0.00 0.01 0.00 3.00 0.01 41.6 0.01 0.00 – – – – – 55.9 0.00 0.00 0.02 0.00
My4-1-1 apatite 0.00 0.01 0.00 0.04 1.36 0.00 41.6 0.05 0.00 0.01 0.04 0.00 0.00 0.03 55.1 0.00 0.00 0.00 0.02
My4-1-2 apatite 0.24 0.02 0.00 0.17 2.20 0.00 39.7 0.01 0.09 0.03 0.12 0.03 0.02 0.00 55.8 0.00 0.00 0.06 0.00
My4-1-3 apatite 0.21 0.01 0.00 0.03 2.81 0.00 40.6 0.05 0.04 0.00 0.05 0.00 0.00 0.00 55.2 0.01 0.00 0.01 0.02
My4-1-6 apatite 0.16 0.00 0.00 0.13 1.66 0.00 40.5 0.10 0.06 0.00 0.08 0.00 0.00 0.00 55.3 0.06 0.01 0.01 0.00
My4-2-2 apatite 0.01 0.00 0.00 0.00 2.96 0.00 40.5 0.05 0.05 0.00 0.03 0.00 0.03 0.00 55.7 0.00 0.01 0.02 0.01
My4-2-4 apatite 0.17 0.00 0.01 0.14 1.90 0.00 39.4 0.01 0.00 0.01 0.09 0.00 0.01 0.03 55.1 0.03 0.06 0.02 0.01
My7-2-1 apatite 0.01 0.00 0.00 0.03 1.33 0.00 41.7 0.05 0.06 0.00 0.14 0.00 0.00 0.06 55.0 0.00 0.00 0.00 0.01
My10-1-1 monazite 0.00 0.00 0.02 0.19 0.27 0.04 31.4 0.02 0.00 0.04 0.08 1.15 0.11 0.00 0.15 0.00 0.03 0.00 0.00
My10-3-1 monazite 0.00 0.00 0.00 0.12 0.35 0.00 30.3 0.00 0.00 0.07 0.14 1.39 0.00 0.09 0.13 0.00 0.06 0.00 0.00
My2-3-1 monazite 0.00 0.00 0.00 0.05 – – 31.7 – – 0.05 0.07 0.05 0.02 0.01 – – – – –
My2-3-2 monazite 0.00 0.00 0.00 0.02 – – 31.3 – – 0.00 0.03 0.09 0.00 0.00 – – – – –
My4-1-4 monazite 0.00 0.00 0.00 0.08 0.30 0.00 30.9 0.02 0.00 0.11 0.14 0.13 0.02 0.00 0.24 0.00 0.00 0.00 0.00
My4-1-5 monazite 0.00 0.07 0.02 0.21 0.22 0.02 30.7 0.05 0.00 0.12 0.03 0.79 0.02 0.09 0.36 0.00 0.00 0.00 0.00
My4-2-1 monazite 0.00 0.00 0.00 0.16 0.27 0.01 31.3 0.01 0.00 0.04 0.00 0.28 0.00 0.05 0.43 0.00 0.00 0.00 0.00
My4-2-3 monazite 0.00 0.00 0.00 0.09 0.37 0.00 29.7 0.00 0.00 0.07 0.12 0.24 0.04 0.00 0.24 0.00 0.00 0.00 0.00
My7-1-1 monazite 0.00 0.00 0.00 0.75 0.35 0.00 30.1 0.12 0.00 0.03 0.00 3.89 0.00 0.15 0.18 0.00 0.00 0.00 0.00
My10-3-3 muscovite 0.26 2.36 31.8 50.7 0.45 8.33 0.00 2.6 0.02 0.05 0.00 0.00 0.00 0.00 0.00 0.22 0.00 0.01 0.20
My10-3-4 muscovite 0.19 2.39 31.6 50.7 0.72 8.34 0.01 2.47 0.05 0.05 0.00 0.00 0.06 0.00 0.02 0.25 0.00 0.00 0.87
My10-3-5 muscovite 0.22 2.36 31.5 50.1 0.56 8.43 0.05 2.75 0.05 0.00 0.03 0.00 0.01 0.00 0.05 0.22 0.00 0.01 0.81
My10-3-6 muscovite 0.18 2.24 31.7 50.4 0.59 9.06 0.01 2.55 0.03 0.00 0.01 0.01 0.06 0.00 0.04 0.20 0.03 0.00 0.73
My10-3-7 muscovite 0.17 2.67 30.9 51.6 0.70 8.04 0.00 2.59 0.02 0.02 0.04 0.00 0.00 0.00 0.00 0.28 0.03 0.00 0.61
My10-3-8 muscovite 0.18 2.34 31.9 51.1 0.66 8.29 0.00 2.70 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.25 0.00 0.00 0.79
My7-2-2 muscovite 0.13 1.99 28.1 50.1 0.42 9.49 0.03 4.81 0.03 0.00 0.01 0.00 0.05 0.00 0.03 0.38 0.01 0.00 0.87
My7-2-3 muscovite 0.07 1.94 28.0 50.6 0.46 9.51 0.03 4.85 0.06 0.00 0.00 0.00 0.11 0.00 0.01 0.43 0.02 0.00 0.87
My7-2-4 muscovite 0.11 2.04 28.7 50.3 0.44 8.36 0.00 5.02 0.06 0.02 0.01 0.00 0.00 0.00 0.00 0.54 0.05 0.00 0.86
My11-1-1 columbite 0.00 0.45 0.00 0.01 0.00 0.00 0.04 14.7 1.81 0.16 0.00 0.09 75.3 0.32 0.11 0.00 0.00 0.00 4.67
My11-1-2 columbite 0.00 0.34 0.00 0.05 0.00 0.00 0.02 14.8 1.49 0.19 0.00 0.22 75.4 0.40 0.21 0.10 0.04 0.00 4.64
My11-1-4 columbite 0.00 0.03 0.01 0.00 0.00 0.00 0.02 15.2 1.38 0.00 0.38 0.09 75.3 0.00 0.00 0.04 0.01 0.00 5.94
My11-1-5 columbite 0.00 0.39 0.06 0.36 0.01 0.02 0.04 15.7 1.36 0.00 0.11 0.36 75.7 0.12 0.08 0.00 0.00 0.00 4.37
My11-1-8 columbite 0.00 0.38 0.01 0.07 0.03 0.00 0.03 11.1 1.48 0.08 0.02 0.09 73.1 0.14 0.12 0.13 0.06 0.00 11.6
My11-1-9 columbite 0.00 0.45 0.00 0.02 0.00 0.00 0.00 13.4 1.54 0.11 0.13 0.15 75.2 0.41 0.10 0.00 0.00 0.00 6.81
My11-1-12 phlogopite 0.23 2.64 30.3 53.8 0.60 9.09 0.01 2.02 0.03 0.00 0.05 0.00 0.04 0.00 0.04 0.28 0.00 0.00 0.81
My11-1-3 phlogopite 0.20 2.68 31.3 50.1 0.72 9.55 0.00 2.16 0.01 0.00 0.06 0.00 0.06 0.00 0.00 0.16 0.02 0.03 0.46
Analyses No. mineral Y2O3 La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Tb2O3 Dy2O3 Ho2O3 Er2O3 Tm2O3 Yb2O3 Lu2O3 Total
My10-3-2 apatite 0.00 0.00 0.14 0.15 0.09 0.03 0.04 0.07 0.00 0.11 0.25 0.00 0.00 0.00 0.00 99.46
My11-1-10 apatite 0.03 0.20 0.11 0.15 0.14 0.00 0.04 0.19 0.05 0.11 0.00 0.00 0.00 0.00 0.00 99.79
My11-1-11 apatite 0.00 0.00 0.14 0.07 0.29 0.40 0.00 0.00 0.01 0.23 0.10 0.00 0.00 0.08 0.16 100.19
My11-1-6 apatite 0.00 0.14 0.16 0.17 0.06 0.00 0.00 0.00 0.03 0.17 0.00 0.00 0.03 0.00 0.11 98.14
My11-1-7 apatite 0.00 0.03 0.09 0.17 0.22 0.14 0.07 0.15 0.04 0.00 0.01 0.00 0.04 0.00 0.00 98.65
My11-2-1 apatite 0.00 0.00 0.16 0.10 0.15 0.00 0.00 0.19 0.03 0.03 0.18 0.00 0.08 0.00 0.00 98.78
My11-2-2 apatite 0.00 0.37 0.05 0.07 0.09 0.06 0.00 0.00 0.00 0.41 0.00 0.10 0.00 0.00 0.12 100.31
My2-1-1 apatite – – – – – – – – – – – – – – – 98.67
My2-1-2 apatite – – – – – – – – – – – – – – – 99.34
My2-2-3 apatite – – – – – – – – – – – – – – – 98.95
My2-2-4 apatite – – – – – – – – – – – – – – – 100.42
My4-1-1 apatite 0.00 0.17 0.04 0.06 0.00 0.00 0.00 0.00 0.02 0.00 0.22 0.00 0.26 0.00 0.06 99.08
My4-1-2 apatite 0.00 0.41 0.16 0.15 0.00 0.00 0.00 0.19 0.02 0.13 0.00 0.03 0.04 0.00 0.00 99.67
My4-1-3 apatite 0.00 0.44 0.18 0.24 0.03 0.16 0.00 0.09 0.01 0.17 0.00 0.00 0.00 0.00 0.11 100.48
My4-1-6 apatite 0.00 0.00 0.15 0.10 0.20 0.13 0.00 0.21 0.01 0.03 0.05 0.00 0.11 0.00 0.00 99.04
My4-2-2 apatite 0.00 0.14 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.05 0.02 0.00 0.00 0.00 99.61
My4-2-4 apatite 0.00 0.17 0.13 0.16 0.35 0.00 0.01 0.12 0.02 0.17 0.00 0.00 0.06 0.00 0.02 98.19
My7-2-1 apatite 0.00 0.24 0.02 0.03 0.03 0.16 0.01 0.05 0.01 0.00 0.32 0.00 0.02 0.05 0.00 99.27
My10-1-1 monazite 0.10 10.5 27.3 11.3 6.20 2.45 0.00 5.74 0.00 0.26 0.52 0.00 0.00 0.00 0.00 97.82
My10-3-1 monazite 0.09 9.77 28.3 11.1 5.99 2.42 0.00 6.06 0.00 0.03 0.53 0.00 0.00 0.00 0.00 96.93
My2-3-1 monazite – 10.5 30.8 12.4 7.13 1.73 0.00 6.04 0.00 0.09 0.21 0.00 0.00 0.00 0.20 101.08
My2-3-2 monazite – 10.4 30.6 12.8 7.22 1.61 0.00 6.03 0.00 0.41 0.33 0.02 0.00 0.00 0.00 100.86
My4-1-4 monazite 0.08 10.1 30.3 12.9 4.24 2.02 0.00 6.20 0.00 0.00 0.69 0.00 0.00 0.00 0.00 98.36
My4-1-5 monazite 0.23 10.9 29.0 12.8 3.91 2.15 0.00 6.65 0.00 0.00 0.50 0.00 0.00 0.00 0.21 99.02
My4-2-1 monazite 0.11 12.3 30.4 10.0 5.59 1.59 0.00 6.39 0.00 0.00 0.49 0.00 0.00 0.08 0.11 99.69
8
Table 3 (continued)
Analyses No. mineral Y2O3 La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Tb2O3 Dy2O3 Ho2O3 Er2O3 Tm2O3 Yb2O3 Lu2O3 Total
My4-2-3 monazite 0.06 11.5 30.1 12.3 6.25 1.22 0.00 6.03 0.00 0.00 0.29 0.03 0.21 0.00 0.13 99.04
My7-1-1 monazite 0.05 10.8 28.2 10.9 5.75 1.74 0.00 6.05 0.00 0.00 0.28 0.00 0.00 0.00 0.00 99.35
My10-3-3 muscovite 0.00 0.00 0.06 0.03 0.00 0.16 0.00 0.00 0.01 0.00 0.16 0.00 0.00 0.00 0.02 97.48
My10-3-4 muscovite 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.03 0.02 0.00 0.09 0.06 0.00 0.00 0.00 97.94
My10-3-5 muscovite 0.00 0.16 0.00 0.00 0.02 0.08 0.06 0.12 0.00 0.00 0.00 0.04 0.08 0.18 0.10 97.95
My10-3-6 muscovite 0.00 0.03 0.07 0.00 0.03 0.11 0.00 0.35 0.07 0.00 0.00 0.00 0.00 0.00 0.09 98.58
My10-3-7 muscovite 0.00 0.16 0.00 0.09 0.00 0.00 0.00 0.08 0.00 0.16 0.00 0.02 0.06 0.00 0.00 98.20
My10-3-8 muscovite 0.00 0.00 0.00 0.03 0.11 0.03 0.01 0.00 0.01 0.04 0.00 0.00 0.00 0.00 0.00 98.35
My7-2-2 muscovite 0.02 0.07 0.08 0.00 0.09 0.00 0.00 0.00 0.03 0.13 0.00 0.23 0.00 0.00 0.00 97.13
My7-2-3 muscovite 0.00 0.07 0.04 0.06 0.00 0.00 0.00 0.09 0.04 0.00 0.00 0.00 0.00 0.00 0.00 97.24
My7-2-4 muscovite 0.00 0.00 0.07 0.05 0.31 0.13 0.11 0.00 0.02 0.25 0.00 0.00 0.00 0.00 0.00 97.45
My11-1-1 Columbite 0.23 0.00 0.00 0.00 0.00 0.00 0.13 0.20 0.09 1.65 0.00 0.25 0.00 0.00 0.00 100.24
My11-1-2 Columbite 0.32 0.00 0.00 0.00 0.00 0.17 0.00 0.25 0.00 1.03 0.12 0.45 0.00 0.00 0.06 100.35
My11-1-4 Columbite 0.07 0.00 0.00 0.00 0.00 0.09 0.00 0.23 0.07 1.00 0.00 0.14 0.00 0.00 0.00 100.02
My11-1-5 Columbite 0.17 0.00 0.01 0.08 0.00 0.17 0.09 0.00 0.00 1.27 0.00 0.37 0.00 0.00 0.00 100.86
My11-1-8 Columbite 0.12 0.18 0.00 0.06 0.00 0.00 0.05 0.00 0.02 1.14 0.00 0.08 0.00 0.00 0.12 100.24
My11-1-9 Columbite 0.22 0.00 0.00 0.06 0.17 0.00 0.00 0.11 0.00 1.30 0.00 0.14 0.00 0.00 0.08 100.42
My11-1-12 phlogopite 0.00 0.13 0.03 0.03 0.00 0.05 0.18 0.07 0.00 0.04 0.00 0.06 0.04 0.00 0.04 100.59
My11-1-3 phlogopite 0.00 0.00 0.04 0.00 0.00 0.00 0.17 0.11 0.00 0.00 0.00 0.17 0.00 0.07 0.02 98.02
Note: in this table analyses No. expressed by (sample No.) − (analyses region) − (EMPA spot numbers).
Fig. 4. Selected back-scattered electron images showing the typical textural and mineralogical characteristic of schist, syenite and carbonatite at the Miaoya REE
prospect. (A) and (B) Disseminated apatite and calcite distributed along the foliation of muscovite (Ms), quartz (Qtz) and calcite in schist (sample My1); (C) and (D)
Euhedral apatite (Ap) intergrown with monazite (Mnz) in a calcite matrix in syenite (sample My4); (E) and (F) Sub-euhedral apatite intergrown with muscovite (Ms),
monazite (Mnz) and calcite (Cal) in mixed ore (sample My10).
9
Fig. 5. Selected back-scattered electron images show typical characteristics of the two types of ore and mineral associations at the Miaoya REE prospect. (A)
Bastnäsite (Bsn) intergrown with apatite and calcite in carbonatite (sample My2); and (B) Euhedral apatite (Ap) and monazite (Mnz) intergrown with K-feldspar (Kf)
in carbonatite (sample My2); (C) and (D) Euhedral apatite (Ap) distributed in the calcite (Cal) matrix of syenite (sample My4). (E) and (F) Euhedral columbite
residing in a fracture filled with calcite (Cc), phlogopite (Phl) apatite (Ap) in mixed ore (My11).
carbonatite and syenite formed by unmixing of a silicate magma carbonates. Thus, the formation of carbonatites at the Miaoya prospect
(Kjarsgaard, 1988; K., 1989; Kjarsgaard B. A., 1989; Hou et al., 2009). might have involved deep recycling of sediment and consequent en-
Three lines of evidence suggest that the Miaoya carbonatite–syenite richment of REE of the mantle source rock of the parent silicate magma
complex formed by unmixing of silicate magma: the syenites and car- (Song et al., 2016b).
bonatites are spatially co-located (Fig. 2), carbonatite and syenite yield At the Miaoya prospect, measured Sr–Nd isotopic ratios for REE-
similar Sr–Nd isotopic ratios (Table 5), and trace element concentra- mineralized carbonatites and syenites are similar to Sr–Nd ratios for
tions in syenite and carbonatite produce similar patterns on spider fresh carbonatites and syenites (Fig. 7; Table 5). The Sr–Nd isotope
diagrams and REE plots (Fig. 3). High concentrations of REE in the ratios define isotopic arrays that deviate from the mantle array in way a
carbonatite are likely to have been produced by partitioning of the REE similar to the EACL (East African Carbonatite Line), which was derived
into the carbonatite phase on unmixing. A similar co-genesis of syenite directly from the mantle without the involvement of REE-rich sedi-
and carbonatite has been proposed for other areas in the Mianning–- mentary material (Hou et al., 2015). Sr–Nd ratios can be used to classify
Dechang REE belt (Hou et al., 2009). carbonatites as fertile or barren. Barren carbonatites follow the evolu-
It has been proposed that initial enrichment of REE in carbonatite tion trend of HIMU and EMI, while fertile carbonatites such as those at
complex magmas is a consequence of the subduction and recycling of Bayan Obo, Weishan, and Mianning–Dechang deviate from this trend,
sediment (Tian et al., 2008; Hou et al., 2015). The results of previous as discussed by Hou et al. (2015) (see Fig. 8).
work on the petrogenesis of the Miaoya carbonatite–syenite complex Carbonatites from the Miaoyo prospect have high total REE con-
are consistent with this model (Xu et al., 2010a, 2015; Ying et al., 2017; centrations (1300–4800 ppm) relative to the majority of the syenites
Zhu et al., 2017). Carbonatites from the Miaoya prospect show low (350–857 ppm REE), although one syenite sample contains 19,000 ppm
δ26Mg values (−1.89‰ to −1.07‰) that are typical of sedimentary REE. These concentrations, in combination with the genetic model
10
Fig. 6. Plots of Primitive Mantle-normalized REE patterns for individual minerals from the Miaoya REE prospect. (A) REE patterns of apatite; (B) Calcite from schist,
syenite, and carbonatite has different patterns; (C) REE patterns of columbite and ilmenite; (D) REE patterns of augite, biotite, plagioclase and quartz. (normalization
values from Mcdonough and Sun, 1989).
inferred from the geological setting, suggest that carbonatites from the and rare (Fig. 5). Taken together, the petrographic characteristics
Miaoya prospect are typical fertile carbonatites, with potential for REE suggest a low degree of alteration and REE mineralization.
mineralization during magmatic–hydrothermal events. However, REE Syenite and carbonatite at the Miaoya prospect occur together and
concentrations at the Miaoya prospect are lower than those at the have overlapping chemical compositions (Fig. 2). Syenite constitutes a
Lizhuang, Maoniuping, and Dalucao deposits in the Mianning–Dechang high proportion of the carbonatite–syenite complex, to the extent that
REE belt (Figs. 9 and 10) (Hou et al., 2009, 2015). the host rocks are composed primarily of syenite, with minor carbo-
The carbonatites at the Miaoya prospect are composed mainly of natite. More importantly, syenite was altered by hydrothermal fluids
calcite, with minor mica, K-feldspar, and albite. The syenites are com- directly as indicated by hydrothermal calcite, monazite and bastnäsite
posed mainly of K-feldspar, albite, and mica with minor quartz and overgrowths on altered syenite. These textural and chemical relation-
plagioclase. Calcite, apatite, biotite, augite, columbite, ilmenite, and ships indicate that the syenite played a role in REE mineralization.
plagioclase were analyzed by in situ LA–ICP–MS. Of these minerals, Schists are spatially associated with the carbonatite–syenite com-
only calcite and apatite hosted by carbonatite contain elevated con- plex at the Miaoya prospect. Whole-rock analyses reveal that the REE
centrations of REE, with total REE concentrations up to 35,000 and content of the schists is lower than that of the syenites and carbonatites
14,000 ppm, respectively (Table 4). Columbite and ilmenite contain (Table 1; Fig. 3). Furthermore, the results of in situ LA–ICP–MS analyses
lower REE concentrations than apatite and cannot account for the REE (Table 4; Fig. 6) indicate that calcite and biotite, the main rock-forming
mineralization (Table 4; Fig. 6). minerals in the schist, have very low REE contents, and that calcite from
Monazite is one of the important REE minerals in carbonatite-re- the schist contains low REE concentrations relative to those in carbo-
lated REE deposits (Chen et al., 2018) and is the most important pri- natite-hosted calcite. These data, combined with Sr–Nd isotope ratios
mary REE mineral at the Miaoya prospect (Xu et al., 2010b; Xu et al., for samples from the mineralized and barren carbonatites, suggest that
2015; Ying et al., 2017). Most of the monazite and bastnäsite grains are the schist is not a potential source of REE. Geological and geochemical
euhedral and closely spatially related to calcite and apatite (Figs. 3 and relationships suggest that the syenite, on the other hand, might have
4). contributed to the REE mineralization, even though elevated REE
Monazite contains higher REE concentrations than apatite (Table 3), concentrations are observed only in carbonatite-hosted minerals.
and petrographic relationships are consistent with the formation of
monazite by overgrowth on calcite and apatite (Figs. 4 and 5). This 5.2. Evolution of ore-forming fluids
observation implies that most of the monazite at the Miaoya prospect
formed after the magmatic stage. Bastnäsite crystals are relatively small Low-temperature isotope exchange between carbonates, meteoric
11
Table 4
Representative LA ICP-MS analyses (ppm) of apatite, augite, biotite, calcite, columbite, ilmenite, plagioclase and quartz crystal from carbonatite and syenite.
Sample No. minerals Rb Sr Y Th U Nb Ta Zr La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf ΣREE LaN/YbN δEu
D. Zhang, et al.
my10-1-1 apatite 0.15 7446 929 263 23.5 2.12 0.05 22.5 2455 4847 536 2116 359 110 308 41.1 210 35.2 74.2 7.70 37.1 4.02 0.18 11,140 62.4 1.09
my10-1-2 apatite 0.15 8257 656 241 29.5 2.92 0.05 24.6 1970 4237 494 2024 346 100 280 33.5 163 26.8 57.3 6.06 30.5 3.29 0.11 9771 60.8 1.07
my10-2-1 apatite 0.15 5625 480 65.7 9.15 5.67 0.10 3.15 824 1875 210 893 181 61.9 174 23.2 118 18.9 36.7 3.18 15.6 1.66 0.06 4437 49.9 1.15
my10-2-2 apatite 0.07 8360 639 223 30.3 1.54 0.03 9.20 2559 5522 635 2467 398 114 315 36.1 169 26.4 54.8 5.69 28.9 3.18 0.08 12,335 83.5 1.06
my10-2-3 apatite 0.12 8261 646 226 29.3 3.20 0.08 22.8 2025 4426 509 2087 348 101 278 34.0 162 26.4 55.2 5.93 29.3 3.26 0.11 10,090 65.1 1.07
my10-2-4 apatite 0.20 8302 967 312 19.3 1.31 0.03 6.25 3054 6502 746 2965 486 143 395 48.4 236 37.8 80.5 8.29 38.5 4.46 0.17 14,745 74.8 1.08
my11-1-1 apatite 0.03 13,186 342 8.85 0.00 0.68 0.01 0.75 1749 3633 384 1493 216 61.1 153 17.4 78.9 12.4 26.0 2.86 15.5 1.73 0.06 7844 107 1.11
my11-1-2 apatite 0.08 13,575 375 5.74 0.14 0.43 0.01 0.78 1942 4014 432 1684 235 66.8 164 18.5 84.6 12.9 28.2 2.96 15.8 1.94 0.06 8702 116 1.12
my11-1-3 apatite 0.06 12,468 279 8.83 0.43 0.46 0.01 0.76 1267 2661 290 1122 170 49.9 127 14.7 66.0 10.7 22.4 2.44 12.2 1.49 0.04 5817 97.7 1.12
my11-1-4 apatite 0.04 11,352 364 41.3 3.37 0.69 0.02 1.82 1542 3256 353 1366 208 62.4 159 18.7 86.0 13.9 29.1 3.24 16.4 1.95 0.03 7116 88.8 1.13
my11-2-1 apatite 0.06 14,616 500 14.5 0.50 0.58 0.00 0.47 1830 3841 409 1620 249 75.3 189 23.5 110 17.4 35.7 3.98 20.7 2.38 0.09 8427 83.3 1.14
my11-2-2 apatite 0.07 13,813 432 51.3 0.48 0.37 0.01 0.61 2685 5347 570 2100 288 82.8 193 21.5 94.2 14.8 31.1 3.54 17.9 2.00 0.05 11,451 141 1.16
my11-2-3 apatite 0.04 14,659 306 4.30 0.05 0.35 0.01 0.49 2116 4282 457 1682 229 63.2 154 16.1 72.8 11.7 23.8 2.63 13.7 1.64 0.01 9125 145 1.11
my11-2-4 apatite 0.08 11,142 263 18.3 0.00 1.81 0.01 1.36 1174 2530 279 1104 177 51.7 130 14.8 68.4 10.9 22.4 2.31 12.2 1.32 0.04 5576 90.5 1.13
my11-2-5 apatite 0.05 10,006 423 22.4 0.11 1.26 0.01 1.11 963 2166 240 999 200 65.2 187 24.6 115 17.8 32.8 3.20 15.5 1.70 0.05 5031 58.7 1.11
my11-2-6 apatite 0.05 13,987 234 8.02 0.01 0.75 0.01 0.67 1516 3083 330 1244 176 49.8 123 13.4 58.9 9.30 19.6 2.19 10.1 1.21 0.02 6636 141 1.12
my11-2-7 apatite 0.08 12,489 325 22.1 4.31 0.83 0.01 2.54 1591 3242 350 1328 199 57.5 145 16.9 78.4 12.6 26.7 2.74 14.6 1.67 0.04 7066 103 1.12
my11-2-8 apatite 0.03 12,535 272 16.0 0.70 0.59 0.01 0.98 1485 3110 333 1263 190 54.3 135 15.0 69.6 10.8 22.4 2.46 11.9 1.45 0.02 6703 118 1.12
my11-3-1 apatite 0.07 11,150 355 19.2 1.91 1.29 0.01 2.16 1181 2533 283 1130 186 57.4 143 17.5 81.2 13.2 28.7 3.13 17.2 2.00 0.07 5677 64.7 1.16
my11-3-2 apatite 0.06 10,874 382 26.8 2.78 1.22 0.01 2.46 1014 2189 253 1011 175 57.6 144 17.7 85.0 14.2 30.0 3.25 17.8 2.01 0.07 5013 53.8 1.19
my11-3–3 apatite 0.05 10,376 381 51.1 6.55 1.14 0.02 3.94 1538 3255 356 1396 220 67.1 165 20.0 91.2 14.7 31.3 3.45 18.5 1.95 0.04 7178 78.4 1.16
my11-3-4 apatite 0.08 13,807 357 4.60 0.13 0.77 0.02 0.69 1871 3789 403 1525 220 65.2 154 17.5 82.2 13.0 27.1 3.12 16.2 1.85 0.05 8189 109 1.17
my11-3-5 apatite 0.06 12,298 382 8.62 0.72 1.75 0.01 1.43 1360 2947 325 1276 202 61.4 146 17.6 84.4 13.8 29.2 3.36 17.4 1.95 0.07 6484 73.6 1.18
my11-3-6 apatite 0.04 11,077 312 16.8 0.06 1.52 0.01 1.19 1203 2600 292 1155 187 56.3 141 16.2 74.5 12.0 25.2 2.70 13.8 1.57 0.06 5781 82.1 1.14
my11-4-5 apatite 0.10 10,058 416 11.8 0.21 1.51 0.01 0.70 905 2092 240 986 175 58.3 140 18.0 88.2 14.8 31.3 3.55 19.0 2.16 0.03 4773 44.8 1.23
12
my11-4-6 apatite 0.06 10,516 466 22.9 1.60 0.87 0.01 4.17 1196 2568 288 1172 199 65.4 165 20.5 99.3 16.5 34.4 3.83 21.7 2.55 0.07 5853 52.0 1.19
max 0.20 14,659 967 312 30.3 5.67 0.10 24.6 3054 6502 746 2965 486 143 395 48.4 236 37.8 80.5 8.29 38.5 4.46 0.18 14,745 145 1.23
min 0.03 5625 234 4.30 0.00 0.35 0.00 0.47 824 1875 210 893 170 49.8 123 13.4 58.9 9.30 19.6 2.19 10.1 1.21 0.01 4437 44.8 1.06
average 0.08 11,163 442 65.9 6.35 1.37 0.02 4.52 1654 3483 385 1508 239 71.5 185 22.2 105 16.9 35.2 3.76 19.1 2.17 0.07 7729 86.3 1.13
my11-4-1 Augite 50.7 2677 17.4 25.9 1.67 65.7 0.13 16.7 4.06 11.6 1.70 8.15 3.04 3.49 3.08 0.50 2.69 0.68 1.58 0.27 1.81 0.23 0.40 42.9 2.12 3.76
my11-4-7 Augite 0.19 1795 19.0 913 2.32 3.98 0.00 1.24 1.86 6.28 0.79 4.44 2.35 1.92 1.70 0.57 3.78 0.67 2.02 0.20 1.34 0.16 0.00 28.1 1.32 3.17
my11-4-8 Augite 167 826 12.1 644 1.02 117 0.10 1.22 0.67 2.50 0.56 1.97 0.84 0.67 1.33 0.28 2.01 0.46 0.88 0.22 0.85 0.15 0.05 13.4 0.74 2.10
max 167 2677 19.0 913 2.32 117 0.13 16.7 4.06 11.6 1.70 8.15 3.04 3.49 3.08 0.57 3.78 0.68 2.02 0.27 1.81 0.23 0.40 42.9 2.12 3.76
min 0.19 826 12.1 25.9 1.02 3.98 0.00 1.22 0.67 2.50 0.56 1.97 0.84 0.67 1.33 0.28 2.01 0.46 0.88 0.20 0.85 0.15 0.00 13.4 0.74 2.10
average 72.5 1766 16.2 528 1.67 62.1 0.08 6.40 2.20 6.81 1.02 4.85 2.07 2.03 2.04 0.45 2.83 0.60 1.49 0.23 1.33 0.18 0.15 28.1 1.39 3.01
my1-1-6 biotite 333 7.60 1.25 0.23 0.50 94.5 1.55 21.4 0.40 1.21 0.22 0.84 0.28 0.37 0.35 0.05 0.34 0.05 0.15 0.05 0.22 0.04 0.45 4.54 1.71 3.93
my1-1-7 biotite 278 52.4 4.35 0.58 0.91 99.3 1.31 161 0.26 0.67 0.11 0.44 0.18 0.40 0.26 0.05 0.37 0.16 0.67 0.11 0.85 0.17 2.41 4.71 0.29 6.11
my1-1-8 biotite 232 73.6 13.1 1.20 2.82 80.0 1.12 392 0.50 1.34 0.20 1.51 0.45 0.57 0.81 0.18 1.50 0.52 1.60 0.34 2.47 0.47 5.74 12.5 0.19 3.11
my1-2-5 biotite 188 97.5 12.4 1.83 4.16 63.3 0.73 517 2.20 4.77 0.58 2.73 0.47 0.63 1.20 0.22 1.32 0.43 1.65 0.29 2.99 0.46 13.9 19.9 0.69 2.75
my1-2-6 biotite 271 37.2 5.97 1.54 2.49 87.2 1.14 174 0.46 0.67 0.07 0.25 0.13 0.28 0.29 0.08 0.64 0.21 0.86 0.16 1.17 0.28 5.11 5.55 0.37 4.62
my1-2-7 biotite 230 58.0 0.95 0.21 3.98 72.8 1.01 8.74 0.82 1.77 0.20 0.85 0.38 0.32 0.31 0.04 0.24 0.03 0.18 0.02 0.11 0.04 0.28 5.32 7.11 3.12
my1-2–8 biotite 308 11.7 2.99 0.51 2.01 91.4 1.36 78.7 0.48 1.12 0.16 0.72 0.26 0.35 0.26 0.04 0.45 0.09 0.38 0.08 0.47 0.08 2.47 4.94 0.95 4.41
my1-4-6 biotite 180 59.4 3.87 7.44 1.11 160 3.58 147 0.29 0.60 0.05 0.19 0.19 0.28 0.34 0.04 0.39 0.24 0.53 0.09 1.04 0.13 3.64 4.41 0.26 3.64
my1-4-7 biotite 188 12.2 1.46 0.27 0.38 70.9 1.22 59.2 0.20 0.28 0.03 0.23 0.00 0.11 0.08 0.00 0.20 0.04 0.26 0.09 0.42 0.07 1.67 2.00 0.44 0.00
my6-3-4 biotite 497 1.33 0.86 0.03 0.42 33.7 0.05 35.5 0.01 0.02 0.01 0.00 0.00 0.06 0.03 0.00 0.13 0.04 0.16 0.06 0.49 0.06 1.24 1.08 0.01 0.00
my6-3–5 biotite 486 2.24 2.12 0.16 1.07 95.6 0.33 116 0.06 0.11 0.02 0.17 0.09 0.09 0.11 0.02 0.09 0.08 0.59 0.09 1.01 0.22 3.17 2.75 0.06 2.93
max 497 97.5 13.1 7.44 4.16 160 3.58 517 2.20 4.77 0.58 2.73 0.47 0.63 1.20 0.22 1.50 0.52 1.65 0.34 2.99 0.47 13.9 19.9 7.11 6.11
min 180 1.33 0.86 0.03 0.38 33.7 0.05 8.74 0.01 0.02 0.01 0.00 0.00 0.06 0.03 0.00 0.09 0.03 0.15 0.02 0.11 0.04 0.28 1.08 0.01 2.75
average 290 37.6 4.49 1.27 1.80 86.2 1.22 155 0.52 1.14 0.15 0.72 0.22 0.31 0.37 0.07 0.52 0.17 0.64 0.12 1.02 0.18 3.64 6.15 1.10 3.85
my1-3-1 calcite 0.18 10,906 137 0.00 0.01 0.02 0.01 0.01 0.93 2.93 0.60 4.63 2.66 1.43 6.49 1.82 17.5 4.85 15.3 2.20 15.8 2.36 0.03 79.5 0.06 1.14
my1-3-2 calcite 0.00 11,112 138 0.01 0.02 0.00 0.01 0.89 0.96 2.90 0.57 3.94 2.68 1.30 6.44 1.85 18.1 5.01 14.8 2.29 15.9 2.36 0.02 79.1 0.06 1.03
my1-3-3 calcite 19.9 10,109 127 0.04 0.00 3.81 0.05 0.07 1.35 3.67 0.76 5.08 3.16 1.48 6.78 1.72 15.6 4.47 13.6 1.96 14.0 2.13 0.02 75.9 0.09 1.06
my1-3-7 calcite 0.02 10,997 144 0.00 0.00 0.01 0.01 1.35 1.06 3.24 0.48 3.63 2.80 1.23 6.24 1.78 17.4 5.19 15.3 2.50 16.0 2.58 0.08 79.5 0.06 0.97

Table 4 (continued)
Sample No. minerals Rb Sr Y Th U Nb Ta Zr La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf ΣREE LaN/YbN δEu

D. Zhang, et al.
my1-3-8 calcite 0.02 10,975 137 0.00 0.00 0.01 0.01 0.02 1.01 3.00 0.57 3.68 2.79 1.35 6.10 1.77 17.4 4.66 15.0 2.06 16.1 2.31 0.00 77.8 0.06 1.08
my1-1-1 calcite 0.04 10,506 83.4 0.00 0.01 0.00 0.00 1.29 0.56 1.73 0.37 2.51 1.49 1.03 3.81 0.99 9.57 2.76 9.93 1.63 14.8 3.32 0.01 54.5 0.04 1.42
my1-1-2 calcite 2.03 10,723 139 0.28 1.24 0.48 0.06 272 1.49 3.95 0.69 4.92 3.65 1.37 6.26 1.81 17.1 4.88 14.4 2.36 15.3 2.72 2.97 81.0 0.09 0.94
my1-1-3 calcite 0.15 10,746 135 0.19 0.02 0.03 0.01 0.56 3.16 7.60 1.12 6.23 3.83 1.69 6.50 1.93 16.9 4.86 14.9 2.20 15.4 2.43 0.04 88.8 0.19 1.12
my1-1-4 calcite 0.51 10,744 136 0.19 0.78 0.23 0.03 124 1.11 3.29 0.60 4.79 3.31 1.43 6.16 1.82 16.8 4.77 15.0 2.26 16.0 2.46 1.63 79.8 0.07 1.04
my1-1-5 calcite 0.40 9751 129 0.18 0.44 0.36 0.02 81.8 1.04 3.10 0.62 3.91 3.10 1.38 5.97 1.62 15.9 4.45 14.7 2.07 14.7 2.17 0.97 74.7 0.07 1.06
my1-2-1 calcite 1.47 9526 108 0.83 0.63 171 2.41 78.4 2.12 5.52 0.92 6.16 3.34 1.62 6.60 1.40 12.8 3.36 10.4 1.63 11.5 1.73 2.12 69.2 0.17 1.14
my1-2-2 calcite 13.4 8547 109 1.77 1.03 100 0.72 156 1.65 4.07 0.76 4.51 2.88 1.51 5.37 1.43 13.4 3.70 11.4 1.79 12.7 1.86 4.68 67.0 0.12 1.27
my1-2-3 calcite 3.21 9793 118 0.43 0.29 48.8 0.45 38.5 2.16 5.17 0.86 5.94 2.94 1.62 6.44 1.62 15.4 3.98 12.1 1.84 12.5 1.95 1.25 74.5 0.16 1.23
my1-2-4 calcite 1.00 10,044 115 0.09 0.09 0.12 0.00 6.37 2.08 5.06 0.84 4.89 3.18 1.43 6.17 1.49 14.2 3.89 11.8 1.69 13.3 1.97 0.31 72.0 0.15 1.07
my1-4-1 calcite 0.23 9840 75.8 0.15 0.09 49.2 1.07 8.52 1.26 3.63 0.65 3.71 2.39 1.09 4.08 0.94 8.43 2.27 7.33 1.30 10.2 1.88 0.26 49.1 0.12 1.15
my1-4-2 calcite 18.2 10,055 112 0.07 0.03 3.90 0.03 1.44 1.53 4.18 0.68 4.19 2.44 1.57 5.72 1.50 13.2 3.87 11.5 1.77 13.4 2.03 0.03 67.5 0.11 1.38
my1-4-3 calcite 3.07 10,317 126 0.17 0.15 1.40 0.03 29.9 1.21 3.43 0.54 4.22 2.95 1.32 5.48 1.61 15.8 4.34 13.3 2.12 13.7 2.19 0.96 72.2 0.08 1.09
my1-4-4 calcite 0.02 10,038 52.2 0.01 0.01 0.00 0.00 0.02 0.40 1.05 0.22 1.62 1.14 0.81 2.36 0.48 5.12 1.58 6.21 1.31 12.7 2.90 0.01 38.0 0.03 1.64
my1-4-5 calcite 0.04 10,066 54.3 0.09 0.03 0.03 0.00 0.14 0.64 1.70 0.28 1.83 1.02 0.66 2.78 0.54 5.60 1.64 6.49 1.32 11.9 2.58 0.02 39.0 0.05 1.30
my1-4–8 calcite 29.8 5858 61.8 2.02 2.11 377 7.10 16.3 4.55 10.3 1.26 7.56 3.13 1.33 4.67 1.04 7.53 1.95 6.40 0.95 7.31 1.11 0.37 59.1 0.59 1.14
max 29.8 11,112 144 2.02 2.11 377 7.10 272 4.55 10.3 1.26 7.56 3.83 1.69 6.78 1.93 18.1 5.19 15.3 2.50 16.1 3.32 4.68 88.8 0.59 1.64
min 0.00 5858 52.2 0.00 0.00 0.00 0.00 0.01 0.40 1.05 0.22 1.62 1.02 0.66 2.36 0.48 5.12 1.58 6.21 0.95 7.31 1.11 0.00 38.0 0.03 0.94
average 4.69 10,033 112 0.33 0.35 37.8 0.60 40.9 1.51 3.98 0.67 4.40 2.74 1.33 5.52 1.46 13.7 3.82 12.0 1.86 13.7 2.25 0.79 68.9 0.12 1.16
my6-1-3 calcite 0.07 7020 126 0.04 1.69 3.67 0.01 17.0 10.6 25.6 3.79 18.0 6.10 2.97 8.46 1.84 14.6 4.43 17.2 3.11 25.9 4.28 0.37 147 0.38 1.36
my6-1-4 calcite 0.11 7463 190 0.03 0.46 0.06 0.02 0.59 21.6 52.0 7.40 37.9 13.0 5.68 14.7 3.05 24.1 6.98 26.0 4.60 37.2 5.86 0.02 260 0.55 1.36
my6-1-5 calcite 0.02 8457 176 0.01 0.11 0.02 0.01 0.28 24.1 62.2 8.96 43.8 14.6 6.45 16.4 2.98 24.2 6.49 24.7 4.74 40.4 6.92 0.03 287 0.56 1.38
my10-1-3 calcite 0.06 27,393 219 0.54 0.04 0.01 0.00 0.72 973 1530 146 536 72.6 21.9 58.3 7.46 42.2 7.87 18.6 2.29 12.8 1.80 0.03 3431 71.4 1.11
my10-1-4 calcite 0.03 27,787 222 0.10 0.00 0.00 0.00 0.02 317 536 54.6 224 44.6 16.4 44.3 6.99 40.0 7.92 19.1 2.29 13.8 1.75 0.03 1329 21.7 1.21
my10-1-5 calcite 0.03 27,832 222 0.27 0.00 0.00 0.00 0.03 638 1038 99.8 377 59.9 20.3 55.7 7.61 42.0 7.82 18.8 2.34 12.1 1.77 0.07 2381 49.5 1.16
13
my10-1-6 calcite 0.10 17,042 221 0.02 0.01 0.01 0.01 0.03 20.4 57.6 8.89 48.2 16.8 8.26 25.1 4.66 34.6 7.50 20.7 2.93 18.6 2.48 0.04 277 1.03 1.33
my10-1-7 calcite 0.04 24,032 231 9.17 0.11 0.00 0.01 0.01 2784 3724 337 1126 112 26.0 81.5 7.76 41.0 7.98 19.9 2.45 15.4 2.15 0.00 8287 170 0.90
my10-2-5 calcite 0.36 26,747 221 3.08 0.05 0.00 0.01 0.06 3425 4623 400 1286 134 30.9 81.8 8.52 42.9 8.09 17.7 2.28 13.0 1.96 0.06 10,076 248 0.97
my10-2-6 calcite 0.09 27,801 202 0.00 0.00 0.00 0.00 0.01 30.4 109 17.4 92.6 35.0 15.7 45.5 7.08 38.3 7.43 17.0 2.16 12.1 1.71 0.00 432 2.37 1.30
my10-2-7 calcite 0.07 27,760 212 0.15 0.00 0.00 0.02 0.01 893 1356 126 446 60.6 18.8 52.9 7.13 40.1 7.38 18.1 2.10 13.0 1.73 0.03 3043 64.8 1.09
my6-2-1 calcite 0.10 8849 148 0.02 0.48 1.01 0.01 6.21 8.03 22.6 3.37 17.9 6.42 2.95 7.70 1.89 16.3 5.20 21.1 3.86 31.5 4.93 0.22 154 0.24 1.38
my6-2-2 calcite 0.43 6516 118 0.11 3.36 8.02 0.03 75.7 7.48 19.0 2.76 14.2 5.19 2.63 6.73 1.61 12.6 4.11 16.0 3.15 26.0 4.22 2.03 126 0.27 1.47
my6-2-3 calcite 0.07 8015 131 0.03 0.43 41.3 0.15 25.0 7.16 19.7 2.86 15.2 6.29 2.61 8.02 1.69 14.9 4.63 17.8 3.56 28.6 4.27 0.75 137 0.24 1.21
my6-4-1 calcite 0.24 7718 218 15.5 1.61 5.57 0.03 0.72 3041 4248 369 1169 122 27.5 55.0 5.82 35.2 8.54 29.1 5.35 40.0 6.20 0.08 9162 71.6 1.11
my6-4-2 calcite 0.03 9911 193 0.00 0.49 0.42 0.01 3.16 20.7 43.9 6.84 33.5 11.3 5.43 13.9 2.92 25.6 6.67 24.7 4.79 36.9 5.86 0.05 243 0.53 1.43
my6-4-3 calcite 0.06 10,687 239 0.01 0.14 0.04 0.01 0.44 32.9 63.2 10.7 54.3 19.2 7.65 21.4 3.94 33.2 8.68 31.5 5.64 43.5 6.73 0.05 343 0.71 1.25
my6-4-4 calcite 0.10 7475 261 63.9 2.83 0.07 0.00 0.73 12,644 16,128 1383 4333 402 77.0 164 11.8 51.7 10.1 30.8 5.05 37.0 5.60 0.04 35,283 322 0.99
max 0.43 27,832 261 63.9 3.36 41.3 0.15 75.7 12,644 16,128 1383 4333 402 77.0 164 11.8 51.7 10.1 31.5 5.64 43.5 6.92 2.03 35,283 322 1.47
min 0.02 6516 118 0.00 0.00 0.00 0.00 0.01 7.16 19.0 2.76 14.2 5.19 2.61 6.73 1.61 12.6 4.11 16.0 2.10 12.1 1.71 0.00 126 0.24 0.90
average 0.11 16,028 197 5.16 0.66 3.35 0.02 7.26 1383 1870 166 548 63.4 16.6 42.3 5.26 31.9 7.10 21.6 3.48 25.4 3.90 0.22 4189 57.1 1.22
my11-4-2 Columbite 2.25 235 4240 2263 1078 487,588 1686 1583 189 505 67.7 401 336 226 599 149 1014 199 499 64.3 141 141 141 35,283 322 1.64
my11-4-3 Columbite 0.66 85.0 2439 2180 482 504,501 1151 1871 142 446 58.4 322 208 150 319 76.3 507 98.4 234 31.3 230 230 230 126 0.24 0.90
my11-4-4 Columbite 0.37 148 1065 1620 353 498,224 1596 1559 263 613 63.2 266 95.8 67.5 128 28.9 203 40.1 105 13.7 82.1 82.1 82.1 4189 57.1 1.22
max 2.25 235 4240 2263 1078 504,501 1686 1871 263 613 67.7 401 336 226 599 149 1014 199 499 64.3 230 230 230 35,283 322 1.64
min 0.37 85.0 1065 1620 353 487,588 1151 1559 142 446 58.4 266 95.8 67.5 128 28.9 203 40.1 105 13.7 82.1 82.1 82.1 126 0.24 0.90
average 1.09 156 2581 2021 638 496,771 1478 1671 198 521 63.1 330 213 148 349 84.7 575 113 279 36.4 151 151 151 13,199 127 1.25
my6-1-1 ilmenite 0.23 151 265 0.01 67.1 24.1 0.03 263 22.8 49.8 6.22 28.5 10.4 4.78 15.0 3.47 31.1 9.83 39.4 7.68 131 131 131 88.8 0.59 1.64
my6-1-2 ilmenite 0.40 154 302 0.01 69.0 23.4 0.03 290 23.8 51.0 6.50 31.5 12.0 5.56 18.0 3.99 34.6 11.1 44.9 8.82 164 164 164 38.0 0.03 0.94
my6-3-1 ilmenite 1.79 410 72.4 0.24 39.0 147 0.42 279 5.36 10.1 1.19 5.74 2.44 1.10 3.62 0.84 7.89 2.52 9.74 1.72 180 180 180 68.9 0.12 1.16
my6-3-2 ilmenite 0.39 402 67.0 0.09 38.0 276 1.03 358 4.78 9.54 1.15 5.13 2.13 0.91 3.24 0.79 7.77 2.27 8.89 1.74 365 39.1 36.3 4653 0.49 1.66
max 1.79 410 302 0.24 69.0 276 1.03 358 23.8 51.0 6.50 31.5 12.0 5.56 18.0 3.99 34.6 11.1 44.9 8.82 365 180 180 4653 0.59 1.66
min 0.23 151 67.0 0.01 38.0 23.4 0.03 263 4.78 9.54 1.15 5.13 2.13 0.91 3.24 0.79 7.77 2.27 8.89 1.72 131 39.1 36.3 38.0 0.03 0.94
average 0.70 279 176 0.09 53.3 117 0.37 298 14.2 30.1 3.77 17.7 6.74 3.09 9.97 2.27 20.3 6.43 25.7 4.99 210 128 128 1212 0.31 1.35

water, and magmatic fluids produces positive shifts in δ18O values in
1.43
1.18
2.56
1.15
0.87
1.92
2.01
1.26
1.25
1.22
1.15
2.01
1.15
1.47
δEu
carbonates during the evolution of hydrothermal fluids (Zheng, 1993).
Such changes in C–O isotopic compositions are observed between bulk
LaN/YbN
primary carbonatite and hydrothermal calcite at the Miaoya prospect
12.3
2.56
1.15
0.87
0.76
2.84
0.32
0.30
0.41
0.37
2.84
0.30
0.83
196
(δ18OV-SMOW = 11.1‰ to 13.8‰ and δ13CV-PDB = −4.9‰ to −3.5‰)
(Fig. 8; Table 6). Carbon–oxygen isotopes, together with field ob-
ΣREE
servations of lithology, suggest that at least three possible fluid sources

2791
1986
2791
66.7
62.5
62.5
40.2
2.56
1.15
0.87
307
339
925
810
should be considered at the Miaoya prospect: meteoric water, magmatic
water, and CO2 derived from the decarbonation of carbonatite. In the
1.97
3.51
2.56
1.15
0.87
37.5
44.2
4.53
4.40
8.99
14.0
44.2
4.40
18.9
Hf
absence of interaction with meteoric water, the syenite–carbonatite

complex host rock and CO2 produced by decarbonation would result in
11.2
12.6
2.05
2.10
20.8
2.05
9.91
0.20
0.27
2.56
1.15
0.87
20.8
10.7
Lu
relatively high oxygen isotope ratios that are typical of hydrothermal

fluids. At the Miaoya prospect, C–O isotope ratios suggest that meteoric
87.3
66.6
74.7
12.4
12.1
12.1
71.6
1.03
1.22
2.56
1.15
0.87
177
177
Yb
water and CO2 from decarbonation made minor contributions to the

ore-forming fluids. Thus, magmatic water was the most likely primary
0.08
0.18
2.56
1.15
0.87
31.3
13.7
7.68
8.82
1.72
1.74
31.3
1.72
10.8
Tm
contributor of fluid during mineralization.

39.4
44.9
9.74
8.89
8.89
73.7
0.69
0.75
2.56
1.15
0.87
234
105
234
Er
5.3. Potential of carbonatite-syenite complexes for REE mineralization

0.14
0.26
2.56
1.15
0.87
98.4
40.1
9.83
11.1
2.52
2.27
98.4
2.27
27.4
Ho
Globally, carbonatite-related REE deposits with high REE grades are

favored targets for exploration (Haas et al., 1995; Yang and Woolley,
31.1
34.6
7.89
7.77
7.77
0.53
1.29
2.56
1.15
0.87
507
203
507
132
Dy
2006; Xu et al., 2010a; Kynicky et al., 2012; Williams-Jones et al., 2012;

Hou et al., 2015; Hoshino et al., 2016; Pirajno, 2016; Xie et al., 2016).
0.05
0.28
2.56
1.15
0.87
76.3
28.9
3.47
3.99
0.84
0.79
76.3
0.79
19.1
Tb
Two REE-enrichment processes are necessary to form such deposits:

production of fertile carbonatite and subsequent upgrade by magma-
15.0
18.0
3.62
3.24
3.24
81.1
0.16
3.79
2.56
1.15
0.87
319
128
319
Gd
tic–hydrothermal processes. Fertile carbonatites that host REE deposits

commonly have high REE, Ba, and Sr contents, but fertility is not re-
67.5
4.78
5.56
1.10
0.91
0.91
38.3
0.13
2.15
0.00
4.16
1.68
150
150
Eu
lated to CaO:MgO or FeO:MgO ratios (Figs. 9 and 10). Concentrations of

REE, Ba, and Sr at the Miaoya prospect are lower than those at giant or
1062
95.8
10.4
12.0
2.44
2.13
2.13
55.2
0.54
9.57
0.04
2.99
208
208
Sm
large REE deposits elsewhere in the world, with data for the Miaoya
prospect plotting in the barren field or near to the boundary between
28.5
31.5
5.74
5.13
5.13
4.45
0.21
6.77
101
102
322
266
322
110
Nd
the barren and fertile fields in (REEs vs. CaO/MgO, FeO/MgO, Ba and
Sr/Ba) diagrams (Figs. 9 and 10). The low REE contents suggest that the
4526
1.55
33.4
1.98
11.0
58.4
63.2
6.22
6.50
1.19
1.15
63.2
1.15
22.8
carbonatite–syenite complex at the Miaoya prospect does not have the

Pr
potential to host large or giant REE deposits. As the evidence from the
Miaoya prospect, not all fertile carbonatites host REE deposits. The
4526
49.8
51.0
10.1
9.54
9.54
17.2
1.98
11.0
403
446
613
613
197
Ce
results of petrographic studies, geological observations, and laboratory

Note: analyses No. expressed by (sample No.) − (analyses region) − (LA ICP-MS spot numbers).
analyses performed during this study reveal possible reasons for the
lack of mineralization.
22.8
23.8
5.36
4.78
4.78
77.1
13.4
1.76
1.05
0.11
253
142
263
263
La
First, during the early stages of mineralization, local tectonic ac-

tivity produces fractures or fissures in carbonatite–syenite complexes,
0.03
1.96
0.07
0.06
0.27
72.8
66.0
40.9
1.71
30.9
1.71
59.9
147
147
Zr
facilitating fluid cycling and modifying the fluid chemistry by flui-

d–rock interaction. Circulation of ore fluids in tectonic fractures drives
0.03
0.09
0.42
0.26
2.93
6.62
1.51
0.06
0.13
0.04
0.20
6.62
0.04
1.43
Ta
alteration within the carbonatite and leads to high concentrations of

REE, F−, Cl−, CO2, (SO4)2−, and volatiles in the fluids. Deposits within
the Mianning–Dechang REE belt show structural controls and exhibit a
12.5
27.6
0.61
31.5
0.61
0.00
2.19
0.08
0.09
1.45
906
192
906
195
Nb
range of ore types associated with fluid infiltration, such as brecciated

ores and ore veins. In contrast, in the Lizhuang deposits, where weaker
2.63
0.08
0.00
0.10
21.8
0.99
1.18
0.68
0.66
0.29
0.57
1.18
0.29
0.73
tectonic activity is recorded, only disseminated ores have been found.

U
Thus, weak tectonic activity inhibits hydrothermal alteration and re-

0.23
0.22
0.00
0.22
65.2
0.21
1.94
0.12
33.3
0.12
0.12
22.8
101
101
stricts large-scale REE mineralization. Tectonic activity also drives the

Th
infiltration of meteoric water, which reduces temperature, thereby fa-

2268
0.40
1.11
0.15
5.41
2.89
6.16
1.83
1.16
37.2
1.03
37.2
1.03
8.38
cilitating the precipitation of REE-bearing minerals (Williams-Jones,

Y
2000, 2012, 2018). There is little evidence of tectonic activity within

the deposit at the Miaoya prospect, and petrography reveals a relatively
1341
0.55
9.60
0.03
2.21
24.2
28.4
32.1
33.7
48.0
26.8
48.0
24.2
32.2
intact inner structure in altered syenites and carbonatites. Microprobe

Sr
and BSE imaging reveal that calcite grains show clear mineral bound-
0.19
4.30
4.30
0.19
2.24
30.5
3.05
2.49
6.71
28.6
19.0
30.5
2.49
15.1
Rb
aries and clear cleavages; these features are rare in the altered carbo-
natite complexes that host the Mianing–Dechang REE deposits (Liu and
plagioclase
plagioclase
plagioclase
plagioclase
plagioclase
plagioclase
Hou, 2017). These features are consistent with weak tectonic activity,
minerals
average
average
quartz
quartz
Table 4 (continued)
which would have hindered the cycling of hydrothermal fluids.

max
max
min
min
Second, certain ligands in solution are necessary for REE transport

or precipitation, and mechanisms of REE enrichment by transportation
Sample No.
and precipitation are a major focus of current research into REE de-
my1-3-5
my1-3-6
my6-1-6
my6-1-7
my6-2-4
my6-3-3
my6-4-5
my6-4-6
posits. Laboratory experiments, theoretical studies, and analyses of

natural examples suggest that REE can be transported in a diverse range
14
Table 5
Whole rock Sr-Nd-Pb isotopic data of carbonatite from the Miaoya REE prospect.
87
Sample Rock type Sr/86Sr 87
Rb/86Sr (87Sr/86Sr)i 143
Nd/144Nd 147
Sm/144Nd (143Nd/144Nd)i εNd(t) TDM (Ma)
My1 schist 0.708874 0.95348 0.7069 0.512504 0.08824 0.512419 −0.6 788
My2 carbonatite 0.704212 0.01200 0.7042 0.512401 0.13661 0.512269 −3.5 1483
My3 carbonatite 0.703793 0.00430 0.7038 0.512479 0.00250 0.512477 0.5 486
My5 carbonatite 0.703956 0.02728 0.7039 0.512488 0.09159 0.512400 −1.0 829
My7 carbonatite 0.703768 0.00820 0.7038 0.512532 0.09765 0.512438 −0.2 814
My4 syenite 0.705278 0.34514 0.7046 0.512455 0.07796 0.512380 −1.3 783
My6 syenite 0.705180 0.14732 0.7049 0.512506 0.08470 0.512424 −0.5 764
My8 syenite 0.717462 3.80120 0.7095 0.512524 0.08764 0.512439 −0.2 760
My9 mixed rock 0.704769 0.09623 0.7046 0.512492 0.09048 0.512405 −0.8 816
My10 mixed rock 0.704430 0.15567 0.7041 0.512390 0.05511 0.512337 −2.2 732
My11 mixed rock 0.703860 0.03107 0.7038 0.512479 0.08961 0.512392 −1.1 827
Fig. 7. Whole rock Sr-Nd isotopic compositions of syenite and carbonates (Table 5) from the Miaoya REE prospect showing the distinct isotopic arrays in barren and
fertile carbonatite, dolomitic dikes with low REE concentrations have lower 87Sr/86Sr ratios than calcitic dikes at the Bayan Obo, suggesting that the former involved
lesser metasomatic refertilization and the addition of REEs and LILEs to the SCLM.DM.HIMU, EMI, and EMII are mantle end-members (i.e. depleted mantle (DM),
High-μ mantle (HIMU), Enriched mantle 1 (EM1),and enriched mantle II (EMII); Hart, 1984).
of high-temperature fluid systems that are rich in sulfate, carbonate, activity has been well established in hydrothermal carbonatite-related
fluoride, chloride, and hydroxyl ions (Williams-Jones et al., 2012; Song deposits such as Bayan Obo and Maoniuping in China, the Wicheeda
et al., 2016a; Song et al., 2016b; Liu and Hou, 2017). Sulfate and deposit in Canada, and the Sin Quyen deposit in Northwestern Vietnam
fluorite ions form stable complexes with the REE and could be im- (Smith, 2000; Trofanenko et al., 2016; Liu and Hou, 2017; Li and Zhou,
portant for REE transport and precipitation, respectively (Williams- 2018). Moreover, REE-sulfate and -carbonate complexes are particu-
Jones et al., 2012; Migdisov et al., 2018). Carbonate ions are also larly important at high-temperature and mildly acidic to near-neutral
known to form strong complexes with REE (Wood, 1990; Haas et al., pH conditions (Williams-Jones et al., 2012; Migdisov and Williams-
1995), and the positive correlation between REE enrichment and CO2 Jones, 2014; Williams-Jones and Vasyukova, 2018). Large and giant
15
Fig. 8. Correlation diagram of δ13CPDB‰−δ18OSMOW‰for carbonatite from the Miaoya REE prospect compared to other REE deposits in China. All the data plot
outside the fields of mantle-derived primary carbonatite (Taylor, 1967) and in the low temperature alteration field. Data from Dalucao and Maoniuping; Dalucao and
Maoniuping data are taken from Hou et al. (2015).
Fig. 9. (A) REEs Vs. CaO/MgO and (B) REEs Vs. total FeO/MgO diagrams of main global examples of carbonatites. These data indicate that REE enrichment is
unrelated to the type of carbonatite and its major element composition; data are taken from Hou et al. (2015) and Liu and Hu (2017).
REE deposits generally contain large amounts of fluorine- and sulfate- 6. Conclusions
bearing minerals, such as fluorite, fluorapatite, barite, and celestite, as
the main gangue minerals. The abundance of these minerals implies The whole-rock composition of schist and trace-element con-
high fluoride and sulfate contents in the ore-forming fluids (Oreskes centrations in schist-hosted minerals at the Miaoya prospect suggest
and Einaudi, 1990; Kynicky et al., 2012; Liu and Hou, 2017). However, that the schist adjacent to the carbonatite–syenite complex was not the
fluorite and barite are rare at the Miaoya prospect, suggesting that main source of REE in the prospect. Two lines of the evidence suggest
fluorine and sulfate contents were low in the ore-forming fluids, with a that REE at the Miaoya prospect were derived from the carbonatite–-
consequent reduction in transport and precipitation of REE. We con- syenite complex itself: the Sr–Nd isotope values of altered syenite and
clude that a low concentration of suitable ligands for REE is another carbonatite are similar to those of fresh carbonatite and syenite; and
factor that inhibited REE mineralization at the Miaoya prospect. trace-element contents of apatite and calcite in mineralized samples are
16
Fig. 10. (A) REEs Vs. Ba (ppm), (B) REEs Vs. Sr/Ba diagrams for the majority of global examples of fertile and barren carbonatite. Miaoya data fall into the fields of
barren region (Hou et al., 2015; Liu and Hu, 2017); Data are taken from Hou et al. (2015) and Liu and Hu. (2017).
Table 6 References
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Ore Geology Reviews

Mineralogical and geochemical characteristics of the Miaoya REE prospect, T

ARTICLE INFO ABSTRACT

Fig. 2. A) Outcrop of biotitic carbonatite; B) Hand

rock types schist carbonatite syenite mixed rock

Trace element (ppm)

Rare Earth Elements (ppm)

rock types schist carbonatite syenite mixed rock

My1 schist quartz:6.5%; calcite:2.9%; mica:89.1%; Chlorite:1.5%

(continued on next page)

Sample No. minerals Rb Sr Y Th U Nb Ta Zr La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf ΣREE LaN/YbN δEu

(continued on next page)

water, and magmatic fluids produces positive shifts in δ18O values in

primary carbonatite and hydrothermal calcite at the Miaoya prospect

servations of lithology, suggest that at least three possible fluid sources

absence of interaction with meteoric water, the syenite–carbonatite

relatively high oxygen isotope ratios that are typical of hydrothermal

water and CO2 from decarbonation made minor contributions to the

contributor of fluid during mineralization.

5.3. Potential of carbonatite-syenite complexes for REE mineralization

Globally, carbonatite-related REE deposits with high REE grades are

2006; Xu et al., 2010a; Kynicky et al., 2012; Williams-Jones et al., 2012;

Two REE-enrichment processes are necessary to form such deposits:

tic–hydrothermal processes. Fertile carbonatites that host REE deposits

lated to CaO:MgO or FeO:MgO ratios (Figs. 9 and 10). Concentrations of

carbonatite–syenite complex at the Miaoya prospect does not have the

results of petrographic studies, geological observations, and laboratory

First, during the early stages of mineralization, local tectonic ac-

facilitating fluid cycling and modifying the fluid chemistry by flui-

alteration within the carbonatite and leads to high concentrations of

range of ore types associated with fluid infiltration, such as brecciated

tectonic activity is recorded, only disseminated ores have been found.

Thus, weak tectonic activity inhibits hydrothermal alteration and re-

stricts large-scale REE mineralization. Tectonic activity also drives the

infiltration of meteoric water, which reduces temperature, thereby fa-

cilitating the precipitation of REE-bearing minerals (Williams-Jones,

2000, 2012, 2018). There is little evidence of tectonic activity within

intact inner structure in altered syenites and carbonatites. Microprobe

which would have hindered the cycling of hydrothermal fluids.

Second, certain ligands in solution are necessary for REE transport

posits. Laboratory experiments, theoretical studies, and analyses of

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