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Ore Geology Reviews 167 (2024) 105990
Available online 13 March 2024
0169-1368/© 2024 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
Mineralogy and
40
Ar-
39
Ar dating of the recently discovered tainiolite
occurrences in the Kaerqiaer uorite Belt, western Altyn Tagh Terrane
Yongbao Gao
a
,
b
,
*
, Long Zhang
a
,
c
, Leon Bagas
a
, Keiko Hattori
d
, Ming Liu
a
, Huanhuan Wu
a
,
Yuanwei Wang
a
, Zhenyu Chen
e
, Xinmin Zhao
b
, Yi Zhang
a
, Guangfeng Wu
f
a
Technology Innovation Center for Gold Ore Exploration, Xi’an Center of Mineral Resources Survey, China Geological Survey, Xi’an 710100, China
b
Key Laboratory for the Study of Focused Magmatism and Giant Ore Deposits, MNR, Xi’an Center of China Geological Survey, Xi’an 710054, China
c
School of Earth Science and Resources, Chang’an University, Xi’an 710054, China
d
Department of Earth Sciences, University of Ottawa, Ottawa K1N 6N5, Canada
e
Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China
f
Geology Institute of China Chemical Geology and Mine Bureau, Beijing 100101, China
ARTICLE INFO
Keywords:
Fluorite veins
Tainiolite
Alkali feldspar granite
Kaerqiaer western Altyn Tagh
ABSTRACT
The Kaerqiaer Fluorite Belt (KFB) contains the Kaerqiaer, Xiaobaihegou, Kumutashi, Northern Layidan, and
Gaijike uorite deposits in the western Altyn Tagh Terrane of NW China. An occurrence of Li-bearing mica
tainiolite (KLiMg
2
(Si
4
O
10
) F
2
) has been recently discovered, associated with uorite-bearing alkali feldspar
granite. The tainiolite is hosted by uorite-calcite veins that contain assemblages of tainiolite-uorite-calcite and
apatite-bastnaesite-tainiolite-uorite-calcite along the contact zone with alkali feldspar granite. The tainiolite
occurs as euhedral crystals and has high concentrations in the veins.
40
Ar-
39
Ar dating of the tainiolite from
Xiaobaihegou yields an age of 421 ±2 Ma, and single-crystal X-ray diffraction conrms the tainiolite has a
monoclinic 1 M−type with a C2/m (#12) space group. Minor structural variations in the mica are attributed to
the substitution of Li for Mg. EPMA and LA-ICP-MS analyses show that the tainiolite has high Li, Rb, Cs, Sn and
Nb concentrations, and low Ta, total REE concentrations. The average Li
2
O content of the uorite-tainiolite veins
reaches 0.36 %, surpassing the economic cut-off grade. We suggest that the uorite deposits formed from highly
fractionated Li-F-P-rich residual melt evolved from the parental magmas of alkali feldspar granite. The tainiolite
mineralisation may result from subsequent hydrothermal activities caused by the reactivation of regional faults
under the extensional regime between the Middle Altyn and Eastern Kunlun terranes. The discovery of tainiolite
occurrences made KFB a potential area for not only F but also Li resources.
1. Introduction
Fluorite as the source of uorine, is an important resource for in-
formation technology, medicine, and aerospace industries, and is
considered a strategic material (Wang et al., 2019). Fluorite deposits are
widely distributed globally, with the Pacic metallogenic belt ac-
counting for over 50 % of the world’s total reserves (USGS, 2022).
Fluorite deposits have recently been discovered in the area between
Kaerqiaer and Kumutashi (KFB) in western Altyn Tagh Terrane of the
Xinjiang Uygur Autonomous Region, including Kaerqiaer super-large
deposit (>22 Mt CaF
2
) and several large deposits (1–5 Mt CaF
2
) (Gao
et al., 2023; Wu et al., 2021, 2022a,b). The U-Pb age of apatite coeval
with uorite at Kumutashi uorite deposit is 448 ±27 Ma (Gao et al., in
prep.), which indicates that uorite mineralisation is related to Late
Ordovician magmatism (Gao et al., 2023).
Recent studies of uorite deposits at Xiaobaihegou and Kumutashi
(Fig. 2) found Li-bearing mica and uorite deposits formed during
magmatic-hydrothermal activity (Gao et al., 2023). In this study, we
have identied the mica as tainiolite (KLiMg
2
Si
4
O
10
F
2
), which has a
trioctahedral structure and is rich in Mg and Li. It is the rst reported
occurrence in the Altyn-Tagh Terrane after the discovery in southern
Greenland during the late 1800 s (Flink, 1899).
* Corresponding author.
E-mail addresses: gaoyongbao2006@126.com (Y. Gao), zhanglong242016@163.com (L. Zhang), Leon.Bagas@me.com (L. Bagas), khattori@uottawa.ca
(K. Hattori), mingl2005@163.com (M. Liu), whhcugb@163.com (H. Wu), 1036944931@qq.com (Y. Wang), czy7803@126.com (Z. Chen), 835177076@qq.com
(X. Zhao), 15501175101@163.com (Y. Zhang), 909691320@qq.com (G. Wu).
Contents lists available at ScienceDirect
Ore Geology Reviews
journal homepage: www.elsevier.com/locate/oregeorev
https://doi.org/10.1016/j.oregeorev.2024.105990
Received 1 February 2024; Received in revised form 6 March 2024; Accepted 11 March 2024
Ore Geology Reviews 167 (2024) 105990
2
The origin and physio-chemical characteristics and the occurrences
of the tainiolite have not been fully documented. This paper reports eld
occurrences of the Xiaobaihegou and Kumutashi uorite deposits and in-
situ analyses of tainiolite using EPMA and LA-ICP-MS. Combined with
40
Ar-
39
Ar geochronological data, this manuscript discusses the miner-
alisation characteristics, composition, crystal structure, and the genesis
of tainiolite. The information will be helpful in the exploration of tai-
niolite deposits in the region.
2. Regional metallogenesis
The KFB contains super-large (>30 Mt CaF
2
) uorite deposits in the
Middle Altyn Terrane at the northern margin of the Qinghai-Tibet
Plateau (Fig. 1a, b; Gao et al., 2023). The region experienced multiple
phases of deformation and metamorphism, and produced high pressure
(HP) to ultra-high pressure (UHP) metamorphic zones (Fig. 1c). These
HP-UHP zones formed during the continental subduction at ca. 504 and
Fig. 1. Altyn-Tagh terrane showing: (a) location of the study area; (b) geological units; (c) geological map of the Middle Altyn Terrane and Eastern Kunlun Orogen.
The geochronological data for the granitic rocks and deposits in Fig. 1(c) are listed in Supplementary Table S1.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
3
486 Ma along the southwestern margin of the Middle Altyn Terrane
(Song et al., 2009; Wu et al., 2004; Yang et al., 2001, 2003). The oldest
rocks in the region are Neoproterozoic (ca. 1000–800 Ma) orthogneiss of
ca. 504 and 486 Ma (Liu et al., 2007; Zhang et al., 2010; Xu et al., 2011;
Song et al., 2014). The terrane is bounded by the Altyn Tagh Fault from
the Mangya Ophiolitic M´
elange to the south (Fig. 1c; Xiao et al., 2013).
The m´
elange is exposed at the base of tectonic slices, which consists of
ultramac rocks, cumulate gabbro, and low-grade metamorphosed
mac volcanic rocks. The overlying rocks comprise low-grade meta-
morphosed tuff, phyllite, ne-grained sandstone, quartzite, and car-
bonate (Xiao et al., 2013).
The Palaeozoic to Mesozoic deformation of the KFB included accre-
tion during subduction and closure of the Paleo-Tethys Ocean and was
overprinted by Cenozoic deformation and volcanism associated during
the convergence of India and Euroasia plates (Robinson, 2009; Cui,
2011; Zhang et al., 2017).
There are several signicant faults in the belt known as the
Kaerqiaer-Kuoshi Fault located in the north, followed southward by the
Gaijile, Yuemakeqi-Kulangele, and Altyn Tagh Fault. The Kaerqiaer-
Kuoshi Fault, which is believed to be closely associated with uorite
mineralisation, trends NE for approximately 70 km. It cuts Paleozoic
intermediate to felsic plutons and exhibits a wavy pattern on the surface,
reecting its multiple periods of activity (Fig. 1c, Fig. 2). Extensional
secondary faults are widely developed between these regional faults.
Many of the large uorite deposits in the KFB occur in or near the
granites and along these regional faults. For instance, the uorite de-
posits at Piyazidaban, Tuogailike and Northern Bulake are all located
near the Yuemakeqi-Kulangele Fault (Fig. 2).
The multiple tectonic events in the Altyn Tagh Terrane are accom-
panied by the emplacement of felsic to intermediate plutons during the
Neoproterozoic, Palaeozoic, and Mesozoic (Fig. 1c, 2, Supplementary
Table S1). Neoproterozoic granodioritic and monzogranitic orthogneiss
Fig. 2. Geological map of the giant Kaerqiaer Fluorite Belt.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
4
are present in the eastern part of the area. Palaeozoic plutons are present
along or near the regional faults and include alkali feldspar granite
dykes and pegmatite veins, the latter of which are commonly mineral-
ised in uorite.
3. Characteristics of uorite deposits
The uorite resource in the KFB is estimated to be over 30 Mt (CaF
2
)
at an average grade of about 33 %. The country rocks are biotite
plagioclase gneiss and marble in the Palaeoproterzoic Altyn Tagh Group.
Our eld mapping shows that tainiolite at Xiaobaihegou and Kumutashi
is associated with uorite veins, and along the contact zone with alkali
feldspar granite.
3.1. Xiaobaihegou uorite deposit
The Xiaobaihegou uorite deposit is on the southern side of the
Kaerqiaer-Kuoshi Fault (Fig. 1c, 2). Biotite plagioclase gneiss and marble
of the Altyn Tagh Group are exposed on the surface, which are intruded
by dykes of alkali feldspar granite and uorite-bearing pegmatite. The
major fault in the area, which is an extensional secondary fault of the
Kaerqiaer-Kuoshi Fault, trends NE. Due to the surface sediments’ cover,
the fault plane’s dip is difcult to determine. However, the positions of
the mineralised veins on both sides of the valley suggest that the fault
exhibits a dextral strike-slip. Six mineralised zones have been recognised
to date and individual zones extend from 130 to 1200 m in length, 20 to
185 m in width, 90◦to 130◦in strike, and 30◦to 40◦in dip (Fig. 3a).
Trenches and drill holes show that tainiolite is present in the margins of
uorite(–calcite) veins in contact with alkali feldspar granite, where
columnar tainiolite form bands (0.3 to 2.4 m wide, 70–90 % purity).
These tainiolite bands contain 0.11–0.92 % Li
2
O (Supplementary
Table S2).
Four uorite veins associated with tainiolite in the area are 200–600
m long and 0.3–2.4 m wide (Fig. 3b, c, d). The uorite exhibits massive
and brecciated, comprising 50 to 90 % in each vein, with the remainder
composed of quartz, calcite and books of tainiolite. Hand specimens of
uorite show purple, dark purple, white, and green colours. Carbona-
tization and kaolinization are developed in the country rocks. The
uorite veins extend to depth, as observed in diamond-drill holes ZK21
and ZK7
′
1, where uorite veins with thicknesses of 0.7 to 3.3 m are
Fig. 3. Geology of the Xiaobaihegou uorite deposit showing: (a) geological map; (b) section of trench TC06; (c) section of trench TC20; and (d) section of
trench TC25.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
5
observed at depths of 10 to 210 m (Fig. 4a, b).
3.2. Kumutashi uorite deposit
The Kumutashi uorite deposit is along the Gaijile Fault and its
country rocks are biotite plagioclase gneiss, banded marble, agglom-
erate, and monzogranitic orthogneiss of the Altyn Tagh Group (Fig. 1c).
The fault dips steeply to the NW, is ductile to brittle, and also shows
dextral strike-slip. Fluorite-calcite veins occur within the dykes of alkali
feldspar granite. At least 14 NE-trending uorite-rich veins have been
delineated in the area, which dips 40◦to 70◦NNW. The veins are
60–980 m long, and 0.3–3.6 m wide on the surface, and are composed of
lenticular to brecciated uorite (averaging 25 %), tainiolite, calcite, the
green columnar uorapatite, and chartreuse granular bastnaesite. The
wall rocks of granite are intensely altered, containing carbonate, K-
feldspar, illite, and kaolinite (Gao et al., 2023; Wu et al., 2021, 2022a,b).
The tainiolite is deposited in the margins of uorite-calcite veins, similar
to other tainiolite occurrences in KFB (Figs. 5 and 6). In addition, tai-
niolite is observed along the contact zone with alkali feldspar granite
dykes, suggesting a close genetic relationship between the two (Fig. 6b,
c). The tainiolite also occurs as aggregates of 2–500 mm in uorite-
calcite veins.
4. Mineralogical characteristics
The Xiaobaihegou uorite deposit is characterised by the assem-
blages of (1) tainiolite-uorite-calcite; (2) tainiolite-uorite-quartz; and
(3) tainiolite-K-feldspar-uorite-calcite in decreasing order of the
abundance of mineral assemblages.
Tainiolite is present along the contact zone between uorite veins
and alkali feldspar granite in the footwall in the trench TC25. The
uorite veins are ~ 1 m wide and contain (a) ~ 30 % tainiolite, 35 %
uorite and 35 % calcite; and (b) 40 % tainiolite and 60 % quartz. Pods
of tainiolite aggregates, <1 m in size, are observed in the diamond-drill
core ZK7
′
1, and aggregates containing ~ 80 % tainiolite are present at
depths of 169.7–170, 182.3–182.4, and 183.1–183.2 m of the core
(Fig. 6d, e). The tainiolite is dark brown, and aky aggregates are
stacked in hexagonal columns. Tainiolite crystals show perfect cleavages
and form euhedral to subhedral sheets, each measuring approximately
1–100 mm.
The Kumutashi uorite deposit shows assemblages of (1) tainiolite-
K-feldspar; and (2) apatite-bastnaesite-tainiolite-uorite-calcite. The
tainiolite constitutes up to 40 % of the latter assemblage that is typically
present along the outer margins of alkali feldspar granite dykes. The
highest grade and largest tainiolite-uorite-calcite vein is present away
(<500 m) from the main fault zone in the area. The tainiolite is dark
brown, idiomorphic to semi-idiomorphic forming hexagonal columnar
aggregates of 10–40 mm thick, with a sheet diameter of 10–20 mm.
Although Xiaobaihegou and Kumutashi uorite deposits share the
same metallogenic background and deposit type, tainiolites from the
two deposits show different features. The mineralogy of the Xiaobai-
hegou deposit is relatively simple, containing calcite, tainiolite, uorite,
and minor orthoclase (Fig. 7a, c). The calcite is commonly idiomorphic
and up to 12 mm long, and is cataclastic in places (Fig. 7b). The uorite
Fig. 4. Geology of the Xiaobaihegou uorite deposit showing cross-sections of (a) diamond-drill hole ZK21; and (b) diamond-drill hole ZK7
′
1.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
6
is commonly purple, 0.1–2 mm wide, and has an allosteric granular
shape (Fig. 7c). The tainiolite is in pegmatite dykes, and dark brown
under plane-polarised light, 0.5–50 mm in diameter, and forms idio-
morphic, or xenomorphic sheets. Tainiolite, having a tabular crystal
habit, usually contains bent edges or is folded in a mosaic structure
(Fig. 7a, c).
The Kumutashi sample collected from an alkali feldspar granite dyke
shows a cleaved or brecciated assemblage of uorite-calcite-apatite-
tainiolite and orthoclase–bastnasite-quartz (Fig. 7a, d, e, f, h). The
uorite is purple, allotriomorphic to granular, 0.1–20 mm long, and has
a well-developed cleavage containing tainiolite and 0.5–20 mm wide
metasomatic calcite (Fig. 7g, h, i). The uorite, 10–50 mm in size, is
twinned and has patchy cracks developed. Tainiolite, which is brown,
forms mica books oriented randomly (Fig. 6c).
5. Samples and analytical methods
Samples of tainiolite from the Xiaobaihegou and Kumutashi deposits
were selected for EPMA and in-situ LA-ICP-MS analyses,
40
Ar-
39
Ar
dating, and single-crystal X-ray diffraction analysis.
The EMPA analysis used a JOEL JXA-8230, manufactured in Japan,
in the EMPA laboratory at the Institute of Mineral Resources, Chinese
Academy of Geological Sciences. The acceleration voltage was set at 15
kV, with a beam current of 10nA, a beam diameter of 5 µm on the
sample, and a single element data acquisition time of 30 s. The cali-
bration used natural jadeite (Na Al; Si:), forsterite (Mg), phlogopite (F),
wollastonite (Ca), hematite (Fe:), apatite (P), UO
2
(U), PbCO
4
(Pb), and
ThO
2
(Th). The calibration standard for rare earth elements is synthetic
rare earth pentaphosphate. F, Cl, Na, and K were analysed under a low
beam current to minimize their loss during the analysis. A, LDE1 (JEOL)
was used for analysing F, and the TDI (time-dependent X-ray intensities)
corrections were also performed to ensure the accuracy of the analysis
(Yang et al., 2022).
In-situ LA-ICP-MS mineral composition analyses were completed at
the Key Laboratory of Magmatism Mineralisation and Prospecting,
Natural Resources Ministry. A coherent Geolas Pro laser ablation system
coupled with an Agilent 7700X ICP-MS determines trace element
abundance in tainiolite. The beam is focused to 24 µm in diameter on the
mineral surface. Each time-resolved analysis data included a blank
signal of approximately 10 s, a sample signal of 40 s, and a purge signal
Fig. 5. Geologic map of the Kumutashi uorite deposit.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
7
of 10 s. The ofine processing of analytical data, including selecting
samples and blank signals, instrument sensitivity drift correction, and
element content and isotope ratio calculations, was completed using the
Iolite 4 software (Paton et al., 2011). Refer to Li et al. (2023) for detailed
instrument parameters. The trace element content is quantitatively
calculated using the NIST SRM 610 and 612 as the external calibration
and monitor, and Si as the internal standard. The recommended values
for element content in NIST610 glass are quoted from the Geo ReM
database (https://georem.mpch-mainz.gwdg.de).
The
40
Ar-
39
Ar dating of the tainiolite samples was carried out in the
lab at the Beijing Createch Testing Technology Co., Ltd. Tainiolite grains
(~330
μ
m, 10 mg) were handpicked under a binocular microscope after
separation from the rock samples from Xiaobaihegou. The mineral
separates were cleaned with 5 % nitric acid and 2 % hydrouoric acid
followed by an ultrasonic water bath with deionised water and acetone,
and were irradiated in quartz tubes with fast neutrons in the Min Jiang
Testing Reactor (MJTR) in Sichuan Province. The neutron ux of the
reactor was about 2.65 ×10
13
cm
−2
s
−1
and the total irradiation time
was 24 hrs. The biotite reference GA1550 was used to monitor the
analysis. After the cooling process, the samples were extracted from the
reactor for the subsequent
40
Ar-
39
Ar stepwise heating analyses, during
which they were analysed in 14 laser intensity increments from 1.6 % to
10 %. Mass spectrometry was carried out using a Thermo-Fisher Scien-
tic Argus VI static vacuum noble gas mass spectrometer. The
interfering isotope correction factors were (
36
Ar/
37
Ar)
Ca
=0.000311,
(
39
Ar/
37
Ar)
Ca
=0.000777, (
40
Ar/
39
Ar)
K
=0.001926. They were ob-
tained by analysing the synchronously irradiated CaF
2
and K
2
SO
4
. The
plateau ages and isochrone ages were calculated using
40
Ar-
39
Ar CALC
(Koppers, 2002).
The crystal structure of tainiolite was examined using an Xta-LAB-
PRO-007-HF single-crystal X-ray diffractometer at the Experimental
Center of the Academy of Sciences, China University of Geosciences
(Beijing). The analyses used a Mo K
α
X-ray (0.71037 ×10
-1
nm), with 50
kV voltage, and 24 mA current.
6. Analytical results
6.1. Chemical compositions
The major element abundance of tainiolite is determined using an
EPMA except for Li
2
O, which was calculated after Tischendorf et al.
(1997, 1999). The average values of individual minerals were used to
calculate the crystal formula. Tainiolite grains (n =9) from various veins
in the Xiaobaihegou uorite deposit show a similar composition. An
average formula is K
0.93
Li
1.11
Mg
2.16
Fe
0.14
Ti
0.01
(Si
3.52
Al
0.34
)
O
10
(OH
0.08
F
1.92
). And the average chemical formula for tainiolite (n =
6) in Kumutashi uorite deposit is K
0.95
Na
0.02
Li
0.61
Mg
2.25
Fe
0.29
Ti
0.03
(-
Si
3.27
Al
0.71
) O
10
(OH
0.40
F
1.60
). It should be noted that the Cl content in all
Fig. 6. Photos of uorite and tainiolite occurrences: (a) bright red calcite and tainiolite at Kumutashi; (b) the contact boundary between alkali feldspar granite and
tainiolite at Kumutashi; (c) uorite, calcite and idiomorphic tainiolite at Kumutashi; (d) brecciated vein of tainiolite and uorite in the contact zone between alkali
feldspar granite and potassium biotite plagioclase gneiss in drilling core ZK 6
′
1 at Xiaobaihegou: (e) scaly tainiolite aggregation, uorite and calcite of drilling core ZK
7
′
1 at Xiaobaihegou; (f) tainiolite symbiosis with calcite and uorite in trench TC06 at Xiaobaihegou; (g) columnar tainiolite aggregation in calcite at Xiaobaihegou;
(h) tainiolite fragments in uorites on the edge of alkali feldspar granite at Xiaobaihegou; and (i) coarse-crystalline tainiolite from Xiaobaihegou. Abbreviations:
χρ
γ-alkali feldspar granite; Cal-calcite; Fl-uorite; Tai-tainiolite. (For interpretation of the references to colour in this gure legend, the reader is referred to the web
version of this article.)
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
8
tainiolite samples is either extremely low or below the detection limit
(Supplementary Table S3), therefore Cl is not considered in the calcu-
lation of the average chemical formula, and the remaining anions are
assumed to be hydroxide. Due to the inability of EPMA to analyse hy-
droxide ions (OH
–
), the presence of hydroxide is inferred based on
charge balance after Tindle and Webb (1990). Tainiolite in both deposits
has a trioctahedral structure, and plots in the tainiolite eld on a mica
classication diagram by Tischendorf et al., 2004 (Supplementary
Table S3) (Fig. 8).
6.2. Trace elements
LA-ICP-MS analysis of tainiolite samples from Xiaobaihegou shows
high Li (9420–10220 ppm), Rb (1440–1780 ppm), Cs (32.6–49.9 ppm),
Nb (57.2–61.9 ppm), and Sn (3.15–3.75 ppm) (Supplementary
Table S4). The samples from Kumutashi also contain high Li
(4680–5540 ppm), Rb (1580–1710 ppm), Cs (61.6–85.3 ppm), Nb
(53.0–61.4 ppm) and Sn (5.48–8.40 ppm). All samples from both de-
posits have high Nb/Ta ratios: 799–2370 for the Xiaobaihegou samples
and 2130–14000 for the Kumutashi samples (Supplementary Table S4).
The chondrite-normalised multi-element diagrams show that all samples
exhibit similar patterns (Fig. 9a). Of the two groups of samples, the
samples from Kumutashi have higher concentrations of Cs, Ba, W, Sn, Ti
and lower concentrations of Th, Ta, La and Ce.
The abundance of REEs of samples of alkali feldspar granite, biotite-
plagioclase gneiss, calcite and uorite show a negatively sloped
chondrite-normalized pattern with enrichment in light REEs (LREE) and
negative Eu anomalies (Fig. 9b–d).
6.3.
40
Ar/
39
Ar dating
40
Ar-
39
Ar analytical results for tainiolite are presented in Table 1 and
illustrated in Supplementary Fig. 1. The tainiolite sample yields a well-
dened plateau age of 421 ±2 Ma (MSWD =1.04) at the 95 % con-
dence level (2
σ
). The plateaus comprise fourteen continuous steps, ac-
counting for 97.38 % of the total
39
Ar released, which suggests that the
minerals remained closed since their formation. In addition, the
40
Ar/
36
Ar-
39
Ar/
36
Ar normal isochron age was yielded at 420 ±3 Ma
(MSWD =0.97), which is consistent with the plateau age within the
margin of error. Thus, the results of
40
Ar-
39
Ar dating are interpreted to
be a reliable crystallisation age.
Fig. 7. Photomicrographs of alkali feldspar granite. showing: (a) euhedral apatite in tainiolite and uorite (plane-polarised light) at Kumutashi; (b) uorite lling
fractures in apatite (plane-polarised light) at Kumutashi; (c) semi-euhedral orthoclase at the contact zone between calcite and tainiolite (plane-polarised light) at
Kumutashi; (d) mosaic structure of tainiolite and calcite (crossed-polarised light) at Xiaobaihegou; (e) euhedral tainiolite crystal (plane-polarised light) at Xiao-
baihegou; (f) mosaic structure of tainiolite and uorite (crossed-polarised light) from Xiaobaihegou; (g) bastnaesite, uorite, and calcite(BSE) from Kumutashi; (h)
symbiosis of bastnaesite, uorite and calcite (BSE) from Kumutashi; (i) parisite and bastnaesite (BSE) from Kumutashi; Abbreviations: Kfs-K-feldspar; Cal-calcite; Tai-
tainiolite; Fl-uorite; Ap-apatite; Or-orthoclase; Bas-bastnaesite; Par-parasite.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
9
6.4. Crystal structure
Single-crystal X-ray diffraction measurements of the tainiolite (n =
3) show that the tainiolite crystals are monoclinic 1 M type, and belong
to C2/m (#12) space group. Their cell parameters are:
(1) Sample XBH-01: a =5.2440(5)Å, b =9.0846(9)Å, c =10.1252
(11)Å, β =99.974 (10)◦, V =475.07(8)Å
3
; Z =2.
(2) Sample KM2-1: a =5.2778(5)Å, b =9.1373(9)Å, c =10.1076
(10)Å, β =100.036(1)◦, V =479.99(8)Å
3
; Z =2.
(3) Sample KMT-01: a =5.2745(7)Å, b =9.1318(10)Å, c =10.1780
(16)Å, β =99.987(14)◦, V =482.80(11)Å
3
; Z =2.
These parameters are consistent with those of monoclinic 1 M type
tainiolite reported by Toraya et al. (1977) (where a =5.254(2) \AA, b =
9.110(4) \AA, c =10.187(2) \AA, β =99.85(4), and V =480.40 Å
3
; Z =
2). All samples from the two deposits show trioctahedral layered
structures. The cations at the octahedral position are Li
+
or Mg
2+
, and
K
+
is lled between the layers. The slight difference between the two
deposits is due to the amounts of Li substituting Mg (Fig. 10).
7. Discussion
7.1. The genesis of tainiolite
Several opinions have been proposed for the origin of tainiolite.
Tainiolite in Kings Valley Li deposit in Nevada, USA, may have formed in
the complex volcanic-magmatic-hydrothermal system, which is
enriched in Li and F. Mg in the tainiolite is proposed to be provided by
the mac intrusions related to the mantle plume. (Glanzman et al., 1978;
Camp et al., 2015; Benson et al., 2017). Zhang et al. (1991) suggested
that tainiolite in the Bayan Obo deposit in northern China crystallised
from REE-F-CO
3
2
-rich hydrothermal uids. Armbruster et al. (2007)
proposed that the brous Na-rich tainiolite in marble xenoliths in the
Mont Saint-Hilaire, Canada, formed during metasomatic alteration
involving F-Na-Li-rich uids. Ohnenstetter et al. (2011), and Feneyrol
et al. (2012) considered tainiolite in lenticular anhydrite in the Neo-
proterozoic Mozambique metamorphic belt formed from metamorphic
uids. Sharygin (2017) reported tainiolite and bastnaesite in the
Chuktukon carbonatite intrusion in Russia formed from Li-F-rich silicate
melt. Tainiolite has also been recognised in REE deposits related to
alkaline intrusions in southern Greenland and the Kola Peninsula (Flink,
1899; Fersman, 1926; Bøggild, 1953; Bailey et al., 1993; Yakovenchuk
Fig. 8. Classication diagram for mica from the Kumutashi and Xiaobaihegou F-Li deposits, the diagram is from Tischendorf et al. (2004). “FeAl” and “MgLi” in the
axes represent the added or subtracted values of atoms per formula unit of cations. (FeAl =Fe
tot
+Mn +Ti –
VI
Al. MgLi =Mg – Li.).
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
10
et al., 2010). But Bailey et al. (1993) noted that tainiolite only forms at a
specic range of Li/Mg weight ratio (~0.1). The abnormally high Li/Mg
weight ratio of ~ 150 and low Mg content (100 to 1000 ppm), at the REE
mineralisation in the Ilímaussaq Complex of southern Greenland, hin-
dered the formation of tainiolite in the deposit.
Alkali feldspar granite in the study area is characterised by high F
contents, ranging from 0.24 to 0.28 wt%. The residual melt likely con-
tained high concentrations of incompatible elements such as F, Li, Nb,
Ta, and Be. The enrichment level of Li in tainiolite is signicantly higher
than that in the granite, and there is a certain positive correlation be-
tween the contents of F and Li according to Fig. 11a. Previous workers
used K/Rb ratios and K/Cs ratios in minerals, such as K-feldspar (ˇ
Cerný
Fig. 9. Plots of normalised geochemistry of the Kumutashi and Xiaobaihegou F-Li deposits and average for the Kaerqiaer Fluorite Belt showing: (a) mean upper crust-
normalised multi-element diagrams of tainiolite; (b) chondrite-normalised rare earth element diagram of alkali feldspar granite and biotite plagioclase gneiss; (c)
chondrite-normalised REE diagram of calcite; and (d) chondrite-normalised REE diagram of uorite. The data for calcite, uorite, alkali feldspar granite and biotite-
plagioclase gneiss are from Wu et al. (2021), Gao et al. (2023) and Zhao et al. (2023). The mean upper crust values are after Rudnick et al. (2003) and chondrite
normalisation values are from Sun and McDonough (1989).
Table 1
Tainiolite
40
Ar-
39
Ar geochronological data of the Xiaobaihegou uorite deposit.
Laser intensity
40
Ar/
39
Ar
36
Ar/
39
Ar
37
Ar/
39
Ar
38
Ar/
39
Ar
39
Ar(10
-14
mol)
40
Ar/
39
Ar ±2
σ
39
Ar (%) Age (Ma) ±2
σ
(Ma)
XBH-01 tainiolite
1.6 % 198.8945 0.0368 0.0019 0.0368 0.51 182.8814 ±1.8904 1.58 422.0 ±3.9
1.8 % 190.8449 0.0310 0.0032 0.0310 1.15 182.6690 ±1.5213 3.57 421.6 ±3.1
2.0 % 189.5301 0.0304 0.0030 0.0304 1.40 182.4451 ±1.2574 4.36 421.1 ±2.6
2.2 % 188.3492 0.0297 0.0024 0.0297 2.03 182.4021 ±1.2426 6.32 421.0 ±2.6
2.4 % 187.9279 0.0292 0.0013 0.0292 2.37 182.5284 ±1.1744 7.37 421.3 ±2.4
2.6 % 187.1563 0.0287 0.0015 0.0287 2.43 182.4543 ±1.1932 7.56 421.1 ±2.5
2.8 % 187.7887 0.0290 0.0020 0.0290 1.74 183.3605 ±1.4558 5.42 423.0 ±3.0
3.1 % 186.9608 0.0288 0.0019 0.0288 2.38 182.2243 ±1.1355 7.41 420.7 ±2.3
3.4 % 187.2258 0.0287 0.0013 0.0287 2.54 182.7274 ±1.1577 7.91 421.7 ±2.4
3.7 % 185.7157 0.0284 0.0014 0.0284 3.01 181.5781 ±1.1206 9.37 419.3 ±2.3
4.0 % 185.7867 0.0284 0.0012 0.0284 3.04 181.6865 ±1.1382 9.47 419.6 ±2.4
4.5 % 184.8827 0.0282 0.0012 0.0282 3.01 180.8125 ±1.1925 9.37 417.8 ±2.5
5.0 % 185.7483 0.0284 0.0012 0.0284 1.93 181.5379 ±1.3402 5.99 419.3 ±2.8
10.0 % 186.4637 0.0284 0.0015 0.0284 4.59 182.3327 ±1.1175 14.29 420.9 ±2.3
Weight =10 mg, J =0.00143730, sensitivity =3.3 ×10
-15
(mol/volt).
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
11
et al., 1985), muscovite (Canosa et al., 2012) and biotite (Lentz, 1992),
to constrain the degree of magma evolution. In the plots of K/Rb vs Rb
and K/Cs vs Cs, our samples landed on the Rayleigh fractionation tra-
jectories after Hulsbosch et al. (2014) which show a high degree of
fractionation (degree of fractionation >0.9, Fig. 11c and d), indicating
they crystallised from highly fractionated magmatic melts. The
extremely low Cl content, <0.05 wt%, in tainiolite (Supplementary
Table S3) and in co-existing apatite (~0.02 wt%, Gao et al., in prep.) also
supports a magmatic origin of tainiolite.
In granitic systems. the fractional crystallisation of mac minerals (e.
g., amphibole and mica) can result in a decrease of Mg and Fe contents in
the residual melts, generally showing a compositional change of mica
Fig. 10. Comparison of tainiolite crystal structure at (a) Xiaobaihegou; (b) Kumutashi; and (c) from Toraya et al. (1977).
Fig. 11. Plots for the Xiaobaihegou and Kumutashi uorite deposits showing: (a) Li vs F; (b) MgO vs F for tainiolite, alkali feldspar granite and biotite-plagioclase
gneiss; (c) K/ Rb vs Rb of tainiolite; and (d) K/Cs vs Cs of tainiolite. F =degree of fractionation. The grey lines are modeled Rayleigh fractionation trajectories for
alkali metal trends in micas by Hulsbosch et al. (2014). The data for alkali feldspar granite and biotite-plagioclase gneiss are from Wu et al. (2021), Gao et al. (2023)
and Gao et al. in prep.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
12
from Fe-Mg-rich biotite to Li-rich lepidolite (Li et al., 2015; Wu et al.,
2020). Therefore, the presence of Mg-rich tainiolite suggests the intro-
duction of Mg from an external source. The country rocks for the uorite
deposits are biotite-plagioclase gneiss and marble, which contain high
Mg content (Fig. 11b). In the eld, tainiolite veins are not in contact with
marble. We consider the biotite-plagioclase gneiss, which is in contact
and contains relatively elevated Mg, could have supplied the Mg for the
formation of the tainiolite. This is further supported by the trend of Mg
content in biotite-plagioclase gneiss, which gradually decreases from ~
8 % to 1 % as it approaches the vein (Gao et al., in prep.). Thus, the Mg-
rich tainiolite in the KFB probably formed during the interaction be-
tween highly evolved melt and the country rocks.
7.2. The uorite-tainiolite mineralisation and its potential in western
Altyn Tagh
The southwestern margin of Altyn Tagh Terrane was subject to
multiple tectonic and magmatic events during the early Paleozoic. The
HP-UHP metamorphic belt in the terrane formed during the deep sub-
duction of the Paleo-Tethys lithosphere at ca. 500 Ma and exhumation at
ca. 450 Ma (Liu et al., 2007; Zhang et al., 2010; Xu et al., 2011; Liu et al.,
2012). Early Paleozoic magmatism in this region includes the ca. 462 Ma
Washixia diorite (Cao et al., 2010), a ca. 467 Ma ultramac intrusion at
Changshagou (Ma et al., 2011; Guo et al., 2014), a ca. 460 Ma gneissic
granite at Tatelekebulake (Zhang et al., 2016), ca. 460 Ma Paxialayidang
granite, 472 Ma Tugeman Li-Be bearing pegmatites (Gao et al., 2021).
These data suggest the post-collisional extension between the Middle
Altyn Terrane and the Southern Altyn Terrane (Supplementary Table S1,
Fig. 1, Fig. 12). A large W-Sn mineralisation occurred in the Baiganhu
area during the post-collisional extension. Various intrusions related to
the mineralisation also formed under post-collisional extensional regime
at ca. 432–412 Ma between the Middle Altyn and Eastern Kunlun ter-
ranes (Supplementary Table S1, Fig. 1, Fig. 12) (Dong et al., 2018; Gao
et al., 2010, 2014, Li et al., 2012, 2013a,b; Wang et al., 2014; Zhang
et al., 2014; Zhou et al., 2015).
Alkali feldspar granite in the KFB yields a zircon U-Pb date of 450 ±
3 Ma (Gao et al., 2023) and tainiolite yields a
40
Ar-
39
Ar plateau age of
421 ±2 Ma (this study). The evidence suggests that the uorite min-
eralisation occurred under this extensional regime between the Middle
Altyn and Southern Altyn terranes at ca. 412–432 Ma. As shown in
Fig. 12, it is believed that major faults, like the Kaerqiaer-Kuoshi Fault,
could provide the conduits for the magmas of the alkali feldspar granite,
and uids that supply Ca, Mg, P and other elements required for the
formation of uorite and tainiolite. Despite minor variations between
the Xiaobaihegou and Kumutashi uorite deposits, they have similar
features, such as the association with alkali feldspar granite, mineral
assemblages and their occurrences along the major faults. Although the
two deposits are apart more than 40 km, the evidence suggests that they
likely formed during the same geological event.
7.2.1. Metallogenetic model
The geodynamic evolution of the KFB has been proposed by Fang
et al. (2014), Wu et al., (2021, 2022), and Gao et al. (2023). Under the
Late Ordovician extensional setting, mantle-derived magmas intruded
and upwelled, causing partial melting of the lower to middle crust. As A-
type magma ascends along deep-seated extensional faults, it undergoes
differentiation and evolution, which results in the formation of highly
fractionated melts and uids. The high degree of evolution of the magma
is reected in the analyses of K/Rb and K/Cs ratios in tainiolite. These
melts are enriched in incompatible elements and volatiles such as F and
Li. As the magma continues to rise, the melts interact with the rocks of
the Altyn Tagh Group. Fluorine becomes supersaturated at shallow crust
levels and combines with dissolved Ca, Mg, and Na to form uorite and
calcite. Around 30 Ma later, regional faults, such as the Kaerqiaer-
Kuoshi and Gaijike faults, were reactivated during the extensional
event. Fluids ascent the same conduit where alkali feldspar granite
Fig. 12. Mineralisation model and tectonic background of the Kaerqiaer Fluorite Belt.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
13
intruded and a large amount of coarse-grained tainiolite likely formed
through the metasomatic process (Munk et al., 2018; Ellis et al., 2022;
Troch et al., 2022; Zhou et al., 2022). The reactivation of the faults
resulted in the brecciation of earlier minerals and later cementation by
recrystallised uorite and calcite at a lower temperature (Supplemen-
tary Table S2, Fig. 6d).
7.2.2. Potential F and Li mineralisation in western Altyn Tagh Terrane
The uorite-tainiolite deposits within the KFB were initially
discovered through geological mapping and geochemical surveys of
stream sediments (Li et al., 2013a). This study shows the importance of
regional faults controlling the distribution of alkali feldspar granite
dykes and subsequent uorite-tainiolite deposits. These deposits can
lead to anomalies in stream sediments of F, Li, La, and Nb (Fig. 13).
Satellite-based remote sensing data may be used to locate these faults,
alkali feldspar granite dykes, and carbonate anomalies that are related to
uorite-calcite veins. Therefore, by overlaying these identied locations
combined with the range of stream sediment anomalies, several areas in
the KFB have high potential of hosting F-Li mineralisation (Fig. 13).
Although economic utilization of tainiolite still requires further
research, the discovery of tainiolite deposits documented in this paper
likely promotes the development of efcient extraction of Li and F.
8. Conclusions
Many tainiolite-bearing veins have been discovered in the
Xiaobaihegou and Kumutashi uorite deposits. The average chemical
formulas of tainiolite in the two deposits are K
0.93
Li
1.11
Mg
2.16
Fe
0.14
-
Ti
0.01
(Si
3.52
Al
0.34
) O
10
(OH
0.08
F
1.92
) and K
0.95
Na
0.02
Li
0.61
Mg
2.25
Fe
0.29
-
Ti
0.03
(Si
3.27
Al
0.71
) O
10
(OH
0.40
F
1.60
), respectively. X-ray single-crystal
diffraction analyses reveal that tainiolite belongs to 1 M type mono-
clinic with a C2/m (#12) spacing. Its unit cell parameters are consistent
with those reported by previous studies, and its crystal structure exhibits
isomorphism. Tainiolite contains high Li content (>0.36 wt%). The
average Li
2
O grade in the tainiolite-uorite mineralisation reaches 0.36
%, exceeding the economic cut-off grade.
Based on the spatial relationship in the eld, mineral assemblages,
geochemical characteristics and tectonic setting, the uorite-calcite
veins likely crystallised from highly fractionated Li-F-P-rich magmatic
melts, which interacted with Ca-Mg-rich country rocks. The renewed
activity of faults resulted in the formation of the tainiolite. The
40
Ar-
39
Ar
dating suggests the mineralisation at 421 ±2 Ma during the regional
extensional event.
The KFB has been known for uorite mineralisation, and the dis-
covery of tainiolite suggests that the area has signicant potential for Li
mineralisation.
CRediT authorship contribution statement
Yongbao Gao: Conceptualization, Funding acquisition, Data cura-
tion, Writing – original draft, Project administration. Long Zhang: Data
curation, Visualization, Formal analysis, Investigation. Leon Bagas:
Fig. 13. Tainiolite prospectivity in the Kaerqiaer-Kumutashi area of western Altyn-Tagh Terrane.
Y. Gao et al.
Ore Geology Reviews 167 (2024) 105990
14
Supervision, Writing – review & editing. Keiko Hattori: Supervision,
Writing – review & editing. Ming Liu: Investigation, Methodology.
Huanhuan Wu: Formal analysis, Data curation. Yuanwei Wang:
Validation, Investigation. Zhenyu Chen: Data curation, Methodology.
Xinmin Zhao: Investigation, Data curation. Yi Zhang: Investigation.
Guangfeng Wu: Investigation.
Declaration of competing interest
The authors declare that they have no known competing nancial
interests or personal relationships that could have appeared to inuence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The authors thank Professor Li Guowu of China University of Geo-
sciences (Beijing) and Dr. Li Jiankang of the Institute of Mineral Re-
sources, Chinese Academy of Geological Sciences for their guidance on
this study. Zhou Ningchao, Cheng Xiuhua, Li Yanguang and other col-
leagues from the Xi’an Center of China Geological Survey are thanked
for their assistance in sample analyses. This study is supported by the
Natural Science Basic Research Program of Shaanxi (grant No. 2023-JC-
YB-241), National Natural Science Foundation of China (NSFC grant No.
92262302), National Natural Science Foundation of China (NSFC grant
No. U2244204), Second Tibetan Plateau Scientic Expedition and
Research (STEP) (grant No. 2019QZKK0806), and China Geology Survey
projects (grant Nos. DD20190143, ZD20220304, ZD20220318,
DD20230060, DD20230378, and DD20243309).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.oregeorev.2024.105990.
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