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Article

A Combined EMPA and LA-ICP-MS Study of Muscovite from Pegmatites in the Chinese Altai, NW China: Implications for Tracing Rare-Element Mineralization Type and Ore-Forming Process

by
Qifeng Zhou
1,*,
Kezhang Qin
2,3,4,*,
Dongmei Tang
2,3 and
Chunlong Wang
5
1
Institute of Mineral Resources Research, China Metallurgical Geology Bureau, Beijing 101300, China
2
Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
3
Institutions of Earth Sciences, Chinese Academy of Sciences, Beijing 100029, China
4
College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
5
State Key Laboratory of Geological Process and Mineral Resources, Key Laboratory of Geological Survey and Evaluation of Ministry of Education, School of Earth Resources, China University of Geosciences, Wuhan 430074, China
*
Authors to whom correspondence should be addressed.
Minerals 2022, 12(3), 377; https://doi.org/10.3390/min12030377
Submission received: 16 February 2022 / Revised: 11 March 2022 / Accepted: 15 March 2022 / Published: 18 March 2022
(This article belongs to the Special Issue Rare Metal Ore Formations and Rare Metal Metallogeny)
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Abstract

:
The mineralogical studies of rare-element (REL) pegmatites are important for unraveling the ore-forming process and evaluating REL mineralization potential. The Chinese Altai orogenic belt hosting more than 100,000 pegmatite dykes is famous for rare-metal resources worldwide and diverse REL mineralization types. In this paper, we present the results of EMPA and LA-ICP-MS for muscovite from the typical REL pegmatite dykes of the Chinese Altai. The studied pegmatites are Li-Be-Nb-Ta, Li-Nb-Ta, Nb-Ta, Be-Nb-Ta, Be and barren pegmatites. The Li+ accompanied with Fe, Mg and Mn substitute for Al3+ at the octahedral site in muscovite from the REL pegmatites, and the substitution of Rb by Cs at the interlayer space is identified in muscovite from the Be pegmatites. The P and B contents increase with evolution degree and the lenses from the Nb-Ta pegmatite are produced at late fluid-rich stage with high fluxes (P and B). The enrichment of HFSE in muscovite indicates a Nb-Ta-Sn-W rich pegmatite magma for the Be-Nb-Ta pegmatite. From barren pegmatite, beryl-bearing zone, to spodumene-bearing zone, the evolution degrees of pegmatite-forming magmas progressively increase. In the Chinese Altai, the possible indicators of muscovite for REL mineralization types include Rb (ca. 400–600 ppm, barren pegmatite; ca. 1200–4000 ppm, Be pegmatite; >4500 ppm, Li pegmatite), Cs (ca. 5–50 ppm, barren pegmatite; ca. 100–500 ppm, Be pegmatite; >300 ppm, Li pegmatite) and Ge (<3 ppm, barren pegmatite; ca. 4–6 ppm, Be pegmatite; ca. 6–12 ppm, Li pegmatite) coupled with Ta, Be (both <10 ppm, barren pegmatite) and FeO (ca. 3–4 wt%, Be pegmatite; ca. 1–2.5 wt%, Li pegmatite). The plots of Nb/Ta vs. Cs and K/Rb vs. Ge are proposed to discriminate barren, Be- and Nb-Ta-(Li-Be-Rb-Cs) pegmatites. The Li, Be, Rb, Cs and F concentrations of forming liquid are evaluated based on the trace element compositions of muscovite. The high Rb and Cs contents of liquid and lower Be contents than beryl saturation value indicate that both highly evolved pegmatite magma and low temperature at emplacement contribute to beryl formation. The liquids saturated with spodumene have large variations of Li, possibly related to metastable state at Li unsaturation–supersaturation or heterogeneous distribution of lithium in the system.

1. Introduction

Granitic pegmatites hosting lots of rare elements (RELs) are the important targets for REL prospecting. The puzzles on genesis of granitic pegmatites and REL mineralization have always been explored. Most granitic pegmatites are interpreted as products of granitic fractionation and evolution [1,2], in which process rare elements and fluxes accumulate in residual melt [3,4,5]. Corresponding to various subtypes of granitic pegmatites and diverse REL mineralization types, the evolution degrees of pegmatite magma are different [6,7,8]. It is important to show the characteristics of pegmatite magma enriched in REL, clarify the evolution degrees to estimate the potential of REL enrichment and compare the differences of different REL mineralization types to look for potential indicators.
Mica is one of the most common rock-forming minerals for pegmatite. Micas occurring in pegmatites include biotite, muscovite, zinnwaldite, polylithionite, lepidolite, etc. The highly structural and chemical flexibility for micas make them become repositories for major, minor and trace elements that do not favorably enter into quartz and feldspars which are the major mineral phases [9,10]. The compositions of micas and changes among different mica types reflect the conditions of crystallization of magmas, including the evolution degree of melts [11,12,13,14] and the redox state [10], and further reveal the origins of magma [15,16,17]. Micas formed from higher evolved magma normally show enrichment in Li, Rb, Cs and F, with decrease in Mg, Ti and the K/Rb values, both from the external to internal zones in individual zoned bodies and from pegmatites with different degrees of evolution [7,12,13,14,18,19,20,21,22,23,24,25,26]. Muscovite as the most common mica during the whole pegmatite evolution and among diverse REL pegmatites is a good petrogenetic indicator of pegmatite evolution and REL mineralization. The incompatible trace element contents of the respective liquids (magma enriched in different REL) that are reconstructed from compositions of muscovite also show a correlation with REL mineralization types [27], supplying a way to survey REL-rich pegmatite magma.
The Chinese Altai orogenic belt, as the important part of the Central Asian Orogenic Belt, hosts more than 100,000 pegmatite dykes and a lot of REL resources. The REL mineralization types (Li-Be-Nb-Ta, Li-Nb-Ta, Nb-Ta, Be-Nb-Ta, Be and barren) of the REL pegmatites have been recognized [28]. These REL pegmatites with distinct features on internal zone patterns, mineralogy components, formation ages and country rocks are good examples to study the mineral indicators for REL mineralization and to reveal the REL enrichment. The previous studies mostly focus on formation ages and petrogenesis of the REL pegmatites [29,30,31,32,33,34,35,36,37,38], and concentrate on melt-fluid evolution and origin of the Koktokay No. 3 pegmatite, which is the largest Li-Be-Nb-Ta-Cs pegmatite deposit in the Chinese Altai [28,39,40,41,42,43,44,45,46]. This paper is concerned with muscovite from the typical pegmatites of diverse REL mineralization types in the Chinese Altai, since muscovite is the most common mica here. We present results of major and trace element compositions of muscovite. The chemical differences and compositional trends of muscovite would have been summarized to clarify the evolution degrees of the typical REL pegmatite dykes, and identify tracers that are proxies for various REL mineralization types. Moreover, some REL concentrations of pegmatite magmas are reconstructed to further reveal the Be and Li ore-forming process. This would shed light on REL mineralization mechanisms and be beneficial for rare-metal prospecting in this region to some extent.

2. Regional Geological Setting

The Altai orogenic belt is situated between the Sayan and Gorny Altai of southern Siberia to the north and the Junggar block to the south [47]. It comprises the Mongolian Altai, Chinese Altai and Russian Altai from east to west. The Chinese Altai, divided into six fault-bounded integral parts (the Altaishan terrane, the NW Altaishan terrane, the Central Altaishan terrane, the Qiongkuer-Abagong terrane, the Erqis terrane and the Perkin-Ertai terrane [48]), is composed of various deformed and metamorphosed Vendian to Paleozoic sedimentary, volcanic and granitic rocks [49,50,51,52,53,54,55,56]. The Chinese Altai is described as a middle Cambrian to early Permian magmatic arc [48,51,52,53,54,55,56,57]. It underwent a complex evolution of subduction and accretion events in the Paleozoic period [47,57,58,59,60], shown by ocean ridge subduction, massive granitic magma activities and Devonian high-temperature metamorphism [54,55,61], and completed the basic tectonic framework no later than the middle the Carboniferous period [48,57,59,62,63]. Then, the Chinese Altai progressed into the development of a relatively stable continent with alternating moderate tension and compression events. During the convergence between the Chinese Altai and the East and West Junggar arcs in the Permian [64,65] and the amalgamation of the Siberia and Tarim cratons in the Triassic [66], the major REL pegmatites formed accompanied with relatively small granitic magma activities [33,52,67,68,69,70].

3. Geology of Pegmatites

The pegmatite dykes in the Chinese Altai mostly occur within the Central Altaishan terrane and the Qiongkuer-Abagong terrane (Figure 1). The pegmatite dykes in the Chinese Altai are divided into nine pegmatite fields (Qinghe, Keketuohai, Kuwei-Jiebiete, Kelumute-Jideke, Kalaeerqisi, Dakalasu-Kekexier, Xiaokalasu-Qiebielin, Hailiutan-Yeliuman and Jiamanhaba, Figure 1) [28] and grouped into three mineralization types, which are muscovite, muscovite rare element (muscovite-REL) and rare element (REL). The formation times of these three-type pegmatites are 476–426 Ma [31,34], 369 Ma [32] and 403–154 Ma [29,35,36,37,38,68,70,71,72], respectively. The REL pegmatites formed in 403–386 Ma, 333–253 Ma and 250–154 Ma [29,35,36,37,38,68,70,71,72], corresponding to the orogenic stages of the Chinese Altai, including syn-orogenic (420–360 Ma), late-orogenic (350–250 Ma) and post-orogenic (250–180 Ma) settings [38,50,53,54,73,74]. The REL pegmatites formed in syn-orogenic settings are scarce, and those formed in late to post-orogenic settings are the major REL prospecting targets in the Chinese Altai [37]. Some of the REL pegmatite dykes are Be, Be-Nb-Ta, Li-Nb-Ta, Li-Be-Nb-Ta and Li-Be-Nb-Ta-Rb-Cs deposits [28].
In this study, seven typical REL pegmatite deposits and two barren pegmatite dykes from four pegmatite fields in the Chinese Altai are investigated (Figure 1). The Talate (Li-Be-Nb-Ta), Baicheng (Nb-Ta) and Kangmunagong (barren) pegmatite dykes are located in the Qinghe pegmatite field. The Qunkuer (Be) and Husite (Be) pegmatites belong to Kelumute-Jideke pegmatite field. The Dakalasu (Be-Nb-Ta) pegmatite is typical in the Dakalasu-Kekexier pegmatite field. The Xiaokalasu (Li-Nb-Ta), Weizigou (Be) and Taerlang (Barren) belong to the Xiaokalasu-Qiebielin pegmatite fields. The types, internal zonation patterns, mineralogy components, formation ages and country rocks of these pegmatites are listed in Table 1. Compared with the barren pegmatites, the REL pegmatites show complex internal zones. There is no obvious correlation between REL-minerlaization types and formation times [72]. The studied pegmatites mostly formed in the Permian to early Jurassic period [38,72]. The country rocks of the Dakalasu and Weizigou pegmatites are granites with large age discrepancies [75,76], and the rest of the studied pegmatites are mainly hosted in the middle Ordovician and middle Devonian mica schists (Figure 1) [53,77].

4. Samples and Analytical Methods

4.1. Samples

The following samples of muscovite from the Talate, Baicheng, Kangmunagong, Husite, Qunkuer, Dakalasu, Xiaokanasu, Weizigou and Taerlang pegmatite dykes were collected and studied. These samples are representative rocks from the barren pegmatites, Nb-Ta, Be, Be-Nb-Ta, Li-Nb-Ta and Li-Be-Nb-Ta pegmatites. The muscovites are assembled with columbite-group minerals in Nb-Ta pegmatite, with beryl in Be or Be-Nb-Ta pegmatites, and with spodumene in Li-Nb-Ta or Li-Be-Nb-Ta pegmatites. Descriptions of the samples are summarized in Table 2 and photographs are shown in Figure 2.

4.2. Analytical Methods

4.2.1. EMPA

Major-element compositions of the minerals were determined using a JEOL JXA-8100 electron microprobe at the State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences. An acceleration voltage of 15 kV and a beam current of 20 nA with beam diameters of 5 μm were used for quantitative analysis. The following standards were used for the quantitative analyses: Jadeite (Na-Kα; Al-Kα), fluorite (F-Kα), garnet (Fe-Kα), pyrope (Mg-Kα), diopside (Si-Kα; Ca-Kα), bustamite (Mn-Kα), rutile (Ti-Kα), K-feldspar (K-Kα), crocoite (Cr-Kα) and ZnO (Zn-Kα). Peaks and backgrounds were measured with counting times of 20 s or 40 s per element. The ZAF routine was used for data reduction [78]. The structural formula for muscovite was calculated on the basis of 24 anions, assuming stoichiometric amounts of H2O as (OH), i.e., OH + F = 4 apfu (atoms per formula unit).

4.2.2. LA-ICP-MS

In situ trace element analyses of individual muscovite grains were determined using an Agilent 7500a ICPMS coupled to a 193 nm excimer ArF laser ablation system at the State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences. The description of detailed analytical technique can be found in [79]. During analysis, spot size of 60 μm was applied with a repetition rate of 6 Hz, and the energy density employed was ~10 J/cm2. All measurements were performed in time-resolved analysis mode utilizing peak jumping with 1 point per mass peak. Each spot analysis consisted of approximately 30 s of background acquisition and 60 s of sample data acquisition. NIST 612 was used as external standards, and mean Si values on individual grain determined by EPMA were used for internal calibration. Raw counts were processed offline and data-reduction and concentration calculations were then performed by Glitter [80].

5. Results

5.1. Major Elements

The mica of the pegmatites in the Chinese Altai analyzed here belongs to muscovite and phengite occasionally (Figure 3). The muscovite crystals analyzed are homogeneous in BSE images. The EMPA results of mica from the Talate, Baicheng, Kangmunagong, Qunkuer, Husite, Dakalasu, Xiaokalasu, Taerlang and Weizigou pegmatite dykes are given in Supplementary Materials Table S1 and the representative data are shown in Table 3. The FeO contents vary from 0.54 wt% to 4.41 wt%. The MnO and MgO concentrations are in ranges below detection limit (bdl) –0.93 wt% and 0.01–1.12 wt%, respectively. The TiO2 and F contents are bdl–1.42 wt% and bdl–1.16 wt%, respectively. The Na2O contents are low (0.05–0.92 wt%), coupled with lower contents of ZnO (≤0.11 wt%), CaO (≤0.05 wt%) and Cr2O3 (≤0.04 wt%). The Li2O contents based on the LA-ICP-MS data reach up to 0.36 wt%, whilst the calculated H2O contents range between 3.89 wt% and 4.54 wt%, respectively.

5.2. Trace Components

The trace element compositions of muscovites in the pegmatite dykes analyzed here are given in Supplementary Materials Table S1 and the representative results are shown in Table 3. The large concentration variations occur in Li (82.7–1659 ppm), B (42.3–495 ppm), Sc (bdl-143 ppm), Ga (57.8–403 ppm), Rb (420–8329 ppm), Nb (33.9–343 ppm), Sn (bdl-800 ppm), Cs (6.40–2600 ppm), Ba (bdl-579 ppm) and Ta (1.27–243 ppm). Muscovite samples show smaller variations for Be (0.26–36.4 ppm), V (bdl–66.7 ppm) and W (0.56–80.7 ppm). Low concentrations are obtained for Ge (1.86–19.5 ppm), Sr (0.13–44.0 ppm), Pb (2.68–12.9 ppm), Co (0.06–7.33 ppm) and Zr (bdl-1.95 ppm, except 1 point of 1523 ppm), respectively. Lower contents are observed for Hf (bdl-1.15 ppm), Mo (bdl-0.34 ppm) and U (bdl-1.53 ppm), whilst the concentrations of REE, Y and Th are extremely low (bdl). The K/Rb, K/Cs and Nb.Ta ratios are in broad ranges of 10.4–196, 33.4–12761 and 0.73–26.68, respectively (Supplementary Materials Table S1).

6. Discussion

6.1. Substitutions among Alkali Elements

Li, Rb and Cs are important alkali elements incorporated in muscovite since the contents of Li, Rb and Cs of muscovite generally increase during the progressive fractionation process of pegmatite dyke. In the Chinese Altai, from the barren to REL pegmatite dykes, Rb and Cs basically display a positive correlation with Li and these alkali elements are more incorporated in muscovites. It is believed that Li+ substitute for Al3+ at the octahedral site [82] and the incorporation of Li into Al-rich/dioctehedral micas appears to be controlled by the substitutions Si+2Li+1Al−3, Li+3Al−1□−2 [13], Li+1Fe+1□−1Al−1, Li+2Si+1AlVI−1AlIV−1, and Fe+1Mg+1Mn+1Li+1AlVI−1□−1 [83]. Here, a negative correlation between Li and VIAl and a positive correlation between Li and total Fe, Mg and Mn (Figure 4) suggest that Li+ accompanied with Fe, Mg and Mn substitute for Al3+ at the octahedral site. In general, Rb and Cs come into the interlayer site on account of large atomic radius [84]. In some of the Be pegmatites, Rb is negatively related to Cs and Li (Figure 4). The atomic radius of Li is obviously smaller than those of Rb and Cs, but Rb and Cs have similar atomic radius. Thus, there might be a substitution of Rb by Cs at interlayer space in muscovite from some of the Be pegmatites. In the Li-mineralized pegmatite dykes (Li-Nb-Ta and Li-Be-Nb-Ta pegmatites), Rb and Cs concentrations decrease and Li contents increase (Figure 4). Rb and Cs in muscovite might not be directly substituted by Li on account of difference concerning atomic radius. It is noted that muscovites in Li-mineralized pegmatite show trends of relatively high AlVI and low total Fe, Mn and Mg (Figure 4). Therefore, large amount of Li incorporation in muscovites from Li-mineralized pegmatite might be also related to other substitution mechanisms which involve the reduction of Rb and Cs in muscovite in some degree.

6.2. Implications of Fluxes and HFSE

Enrichment of fluxes (i.e., F, B and P) is an important feature for pegmatite magma because they favor the pegmatitic textures (i.e., graphic pegmatite UST, or giant crystals) and REL mineralization [85,86]. The concentrations of F and P of muscovite show a positive correlation with the Li and Cs contents, which are indicators of evolution degree (Figure 5). Fluxes (i.e., F and P) were mostly collected in pegmatite magmas with a high degree of fractionation. A positive correlation between P and B could be identified in Figure 5. The contents of P and B are basically positively related to evolution degree, but the quartz-muscovite-columbite-tantalite lens of the Baicheng Nb-Ta pegmatite with a middle evolution degree are obviously enriched in P and B (Figure 5), suggesting that fluxes (i.e., B and P) accumulated at late fluid-rich stage during pegmatite evolution compared to other zones of pegmatite.
Muscovite is mainly considered as a repository of Sn, Nb, Ta and W in evolved granitic rocks [87,88]. From barren to REL pegmatites, muscovites generally show higher Nb and Ta contents. The enrichment of both Nb and Ta of muscovites is possibly affected by highly evolved pegmatite magma. Due to the differences of partition coefficients of Nb and Ta and the presence of large amounts of Nb-Ta bearing phases, the correlation between Nb and Ta in muscovite among the REL pegmatites becomes complicated. There is a positive correlation between Sn and W, reflecting their similar behaviors in the pegmatite systems, and a weakly negative correlation between concentrations of Sn and W and evolution degree of magma can be seen (Figure 5), indicating that Sn and W contents might be related to fractional crystallization, fluid activities or other factors such as magma source [26,89,90,91]. Here, muscovites in the Dakalasu Be-Nb-Ta pegmatite are extremely enriched in Nb, Ta, W and Sn, mainly controlled by chemical features of magma, which is a Nb-Ta-Sn-W-rich pegmatite-forming magma [92], supported by occurrences of cassiterite and W-columbite-tantalite in the Dakalasu (Be-Nb-Ta) pegmatite (WO3 up to 4.31 wt% [72]).

6.3. The Evolution Degree of Different REL Pegmatites

It is believed that different REL mineralization types are controlled by evolution degree of pegmatite magma [93,94,95]. The indicators of evolution degree in mica include the K/Rb and K/Cs values [21], and the contents of Li [20], Rb, Cs [13,14] and F [22,24]. With increase of degree of evolution of pegmatites, the K/Rb and K/Cs values decrease and the contents of Li, Rb, Cs and F increase. The K/Rb value and Cs content of muscovites are relatively reliable indicators of evolution degree of pegmatite magma [7,18,19,24,25,27]. Plot of K/Rb vs. Cs is used to discriminate REL mineralization types of pegmatites [84,93,96]. The muscovite samples come from barren pegmatite, lens saturated in columbite group minerals (CGM) from Nb-Ta pegmatite, zones saturated in beryl from Be pegmatite, zones assembled with beryl and CGM from Be-Nb-Ta pegmatite, and zones saturated in spodumene from Li-Nb-Ta pegmatite. According to the consistent ranges of K/Rb ratios and Cs contents, there is no evidently fractional crystallization from the wall zone to core of the Talate Li-Be-Nb-Ta pegmatite dyke. Thus, the muscovites from these zones could reflect the chemical features of magma that formed the inner intermediate zone, which is saturated in beryl and spodumene. Moreover, muscovites from the Koktokay No.3 Li-Be-Nb-Ta-Rb-Cs pegmatite deposit in the Chinese Altai, which consists of nine zones and experienced three stages accompanied with Be-Nb-Ta, Li-(Be-)Nb-Ta and (Li-Ta-)Rb-Cs deposition [46,97,98,99,100], are added to discuss the evolution degree of REL pegmatites in this region and the data are from [45]. The compositions of these muscovites reflect the chemical features of pegmatite-forming magma that are at equilibrium of different REL minerals (beryl, spodumene, CGM and lepidolite) for pegmatites with diverse REL mineralization, respectively.
Overall, from barren pegmatite, the beryl-bearing zone, to the spodumene-bearing zone, the pegmatite-forming magma basically display an increasing evolution degree due to decreasing K/Rb ratios and increasing Cs contents (Figure 6). This is in accordance with the previous studies of other pegmatite fields (e.g., Totoral pegmatite field, Argentina [93]). The muscovites from the beryl-bearing zones of the Li-Be-Nb-Ta-Rb-Cs pegmatite (zones I-IV) have close K/Rb ratios and Cs concentrations compared to those from the Be-mineralized pegmatite dykes (Be and Be-Nb-Ta pegmatites) (Figure 6). It is noted that the muscovites from the lens of Nb-Ta pegmatite dyke and beryl-bearing zones in Be-Nb-Ta pegmatite display a similar evolution degree of magma, but host higher Cs contents than beryl-bearing zones in single Be pegmatite (Figure 6). This might be related to more fluid at formation of these zones, accompanied with higher fluxes and elevated amounts of Ta [101,102]. Similarly, spodumene-bearing zones of the Li-Be-Nb-Ta-Rb-Cs pegmatite (zones V-VI) show close K/Rb ratios but higher Cs concentrations than those zones from Li-Nb-Ta and Li-Be-Nb-Ta pegmatites (Figure 6). Finally, the lepidolite-bearing zone of the Li-Be-Nb-Ta-Rb-Cs pegmatite (zone VIII) displays higher evolution degree than spodumene-bearing zones of the Li-mineralized pegmatites (Figure 6).

6.4. Possible Indicators of Different REL Mineralization

The chemical compositions of minerals are mainly controlled by characteristics of forming liquid, elements partition for mineral/melt and mineral/mineral and crystal structures. The trace element incorporations into muscovite on accounts of flexibility of crystal structure supply an opportunity to look for possible indicators of different REL mineralization and further be good for REL prospecting to some extent.
(1)
Barren, Be-mineralized and Li-mineralized pegmatites
Compared to the zones saturated in REL minerals from different pegmatite dykes with diverse REL mineralization types, muscovites from barren pegmatites are strongly poor in Rb (ca. 400–600 ppm), Cs (ca. 5–50 ppm), Ge (<3 ppm), Ta (<10 ppm), Be (<10 ppm) and F (negligible in EMPA), and relatively rich in MgO (~1 wt%) (Figure 7). In comparison with barren pegmatite and zones saturated with Li-silicate minerals from Li-mineralized pegmatites, muscovites intergrown with beryls from Be-mineralized pegmatite dykes host middle concentration levels of Rb (ca. 1200–4000 ppm), Cs (ca. 100–500 ppm) and Ge (ca. 4–6 ppm) and a high content level of FeO (ca. 3–4 wt%) (Figure 7). The muscovites from the Li-mineralized pegmatites have contents of Rb (>4500 ppm), FeO (ca. 1–2.5 wt%) and large variations of Cs (>300 ppm), and Ge (ca. 6–12 ppm) (Figure 7). While Li concentration of muscovite exceeding 600 ppm [103] or 500 ppm [82] was suggested as an indicator for the identification of spodumene-rich pegmatites, the muscovites from the Xiaokalasu Li-Nb-Ta pegmatite are relatively poor in Li and those from the Be pegmatites are rich in Li. Moreover, no consistent correlation can be seen between the Li content of muscovite and the presence of spodumene in spodumene-rich Moblan pegmatite [9,82]. Thus, Li content of muscovite might not be a reliable indicator of spodumene-bearing pegmatite in the Chinese Altai.
(2)
Nb-Ta-, beryl- and spodumene-(lepidolite)-bearing pegmatites
The lens of Nb-Ta pegmatite reveals the specific features of muscovite crystallizing from late fluid during Nb-Ta-bearing pegmatite evolution, including high B (334–495 ppm) and Ge (13.1–17.7 ppm) and low FeO (<1 wt%) contents (Figure 7). Compared to those of Be pegmatite, muscovite saturated with beryls from the Be-Nb-Ta pegmatite display extremely high contents of Ta, Cs and low contents of Li, Nb and FeO (Figure 7), reflecting the chemistry characteristics of Ta-rich pegmatite-forming magma and effected by large amounts of CGM crystallization. The muscovites assembled with spodumene from the Li-mineralized pegmatites are in consistent concentrations of Rb and Be, but those from the Li-Be-Nb-Ta pegmatite are rich in Cs, Ge, Nb, Ta, Li, F, MgO and FeO and poor in MnO (Figure 7). Both evolution degree of magma and features of magma for a single pegmatite dyke have effects on muscovite chemistry. The muscovites from zones I–IV and zones V–VIII of the Li-Be-Nb-Ta-Rb-Cs pegmatite have obviously higher contents of Li, Be and MnO than those from beryl-bearing and spodumene-bearing zones of other Be- and Li-mineralized pegmatites, respectively (Figure 7) [45], indicating a highly evolved pegmatite magma at emplacement.
On the basis of comparisons summarized above, some trace elements show evidential differences among diverse REL mineralization types, such as Rb, Cs, Ge, Ta, etc. The Nb/Ta ratios of muscovite are also different among the pegmatites with distinct REL mineralization types (Figure 8). The Nb/Ta values of muscovite normally decrease with an increasing evolution trend due to preferential incorporation of Nb in muscovite and columbite [27,104], lower solubility of columbite-(Mn) than tantalite-(Mn) in peraluminous granitic melts [104,105] and an enrichment of Ta relative to Nb in residual liquids [106]. The tantalite crystallization caused by supersaturation at strong undercooling [107] would make an effect on the Nb/Ta ratios. The muscovites from zone II of the Koktokay No.3 pegmatite display various Nb/Ta ratios, some of which overlap those of the Li pegmatites (Figure 8). The Nb and Ta contents of pegmatite magma also play roles in Nb/Ta ratios. The Dakalasu Be-Nb-Ta pegmatite has a middle evolution degree, but the muscovites show lower Nb/Ta ratios (Figure 8). The Nb/Ta ratios of muscovite generally change with evolution degree of magma and are scattered in some degree. Thus, combined with the K/Rb ratio and Cs content that are accepted indicators of fractionation [27], we propose potential plots of Nb/Ta vs. Cs and K/Rb vs. Ge to discriminate barren, Be- and Nb-Ta-(Li-Be-Rb-Cs)-bearing pegmatites (Figure 8).

6.5. Evaluation of the REL Concentrations of Liquids

The use of mineral composition and melt/mineral partition provides a semi-quantitative estimate of melt trace element contents during crystallization [27]. Micas offer better perspectives than feldspars that are easily re-equilibrated at low temperatures [108] and quartz that are generally very pure except for only a few trace elements [109]. Considering temperatures of pegmatite formation (620–700 °C) and saturation/trace level of rare elements (Li, Be, F, Rb and Cs), the partition coefficients Dims/melt (i = incompatible trace element) [10,110,111] are preferred as values in Supplementary Materials Table S2. The muscovite crystals analyzed here are from barren pegmatite or intergrown with Be- or Li- aluminate crystals in REL pegmatite. The calculated trace element contents of liquids (referring to forming medium for minerals) at equilibrium with these muscovites reflect the characteristics of trace elements of barren pegmatite-forming magma or REL-enriched magma with different REL mineralization types.
Overall, the calculated trace element concentrations for liquid (pegmatite melt) are close or similar to the reported data of those inferred for pegmatite melts (Table S3) (Li, 0.5–1.0 wt% 3000–10000 ppm, [85,112,113]; Be, 25–70 ppm, [111]; F, ca. 1–2 wt%, [85,113]; Rb, 0.05–0.15 wt%; Cs, 0.01–0.02 wt%, [27]). Rb(liq) and Li(liq) define correlation, respectively, positive with Cs(liq) as expected for pegmatite differentiation [114,115] and no clear correlation between Be(liq), F(liq) and Cs(liq) could be seen (Figure 9). The liquids of the barren and REL pegmatite dykes in the Chinese Altai calculated by muscovite (Supplementary Materials Table S3) display Be contents of <5 ppm and ca. 15–50 ppm. The liquids of the barren and spodumene-absent REL pegmatites show Li contents of ca. 400–2300 ppm and >1800–6000 ppm (Supplementary Materials Table S3). The magmas that produce beryl and CGM host more Be and Li contents than barren pegmatites. Fractional crystallization contributes to Be and Li accumulation in pegmatite magma.

6.5.1. Be Content of Beryl-Forming Magma for Be-Mineralized Pegmatite

The average Be contents of crust and granitic rocks are ~2 ppm and ~5 ppm, respectively [111]. Be contents of pegmatites have been estimated ranging from ~35 to ~575 ppm Be [111,117,118,119]. Beryl-bearing pegmatites contain >100 ppm Be and beryl-rich pegmatites have an average Be content of 230 ppm [111]. Be contents of pegmatites increase from beryl- to spodumene- and lepidolite-bearing pegmatites [111], since the solubility of beryl in melt with speciation reactions involving Li, F, B and P is greater [120]. It is inferred that a beryl-bearing pegmatite initially contains 140 ppm Be [121]. Silicic melts become saturated in beryl with as little as ~70 ppm Be [120]. Extended fractionation beyond ~95% total solidification by at least a three-step process is required to achieve beryl saturation in granite magmas [111]. Therefore, a high evolution degree of magma is required to achieve enough Be content in magma for the presence of beryl.
It is noted that the Be contents of the liquids at equilibrium with beryl in the Chinese Altai are commonly lower than the ~70 ppm (Figure 9) required for beryl saturation in silicic melts [120]. The beryl-bearing pegmatites investigated in this study show a relatively high evolution degree that is similar to those of Be-mineralized pegmatites (Figure 6) [93]. Thus, besides a higher evolution degree, there is another factor that could control beryl saturation. The solubility of beryl falls with decreasing temperature [120] and Be content of melt decreases with a lower temperature [111]. Temperature is an important control on beryl deposition, because BeO content of melt projects to a narrow range of similar values at low T and metaluminous to peraluminous granitic magmas with/without volatile and fluxing components will have similarly low BeO requirements for beryl saturation, if cooled to subsolidus temperatures [120]. This is the major reason why the BeO content of pegmatite-forming liquid for the beryl-bearing pegmatite rocks in the Chinese Altai is relatively low. Both highly evolved pegmatite magma and low temperature at emplacement are important factors for beryl formation in the REL pegmatites in the Chinese Altai.

6.5.2. Li Content of Spodumene-Forming Magma for Li-Mineralized Pegmatite

The average Li content of crust ranges from 13 to 35 ppm [122,123]. The average content of Li for the spodumene-bearing pegmatites is ~2323 ppm [112]. The Li-rich pegmatite magma come from extremely high fractionation of evolved granitic magma [95,124,125], low-degree partial melting [126] or exsolution of supercritical fluid enriched in alkalis and fluxes [127]. Granitic melts become saturated in spodumene with as little as ~6968 ppm Li, but Li-aluminosilicate would not crystallize until the system experienced a delay to accumulate thousands of ppm Li in the melts above the saturation value and supersaturation in the melt was achieved [116]. The liquids saturated with spodumene of the Li-Nb-Ta, Li-Be-Nb-Ta and Li-Be-Nb-Ta-Rb-Cs pegmatites in the Chinese Altai contain >1600 ppm, >6600 ppm and >24,000 ppm Li (Supplementary Materials Table S3). Compared to the Li saturation value, the Li contents of liquid of the Xiaokalasu Li-Nb-Ta are very low and those of the Talate Li-Be-Nb-Ta are close but could not reach up to Li supersaturation (Figure 9). However, the spodumene assembled with these muscovites in the same zone of pegmatites occurred. There are some possibilities. (1) When the Li supersaturation is achieved or nearly achieved, further cooling or Li-poor phase crystallization are required for initial spodumene crystallization [116,128]. Muscovite as one of the ‘Li-poor’ phases (KdLi = 0.12–0.82) formed, reflecting the state of melts at Li saturation or unsaturation. Thus, muscovite with low Li content occurs with spodumene. (2) The low Li content of liquid with spodumene saturation might be related to heterogeneous distribution of lithium. The boundary layers concentrate incompatible and fluxing components (e.g., Li and F) and further form Li-aluminosilicate [4,85,129]. Muscovites do not form by boundary layers. This is in accordance with low F contents of liquid of Li-Nb-Ta pegmatite (Figure 9). On the other hand, from the spodumene-glass interface to >200 μm outside, the Li concentrations of liquid could decrease from ~6000 to ~1600 ppm in the dissolution experiments [116]. The liquids outside spodumene crystals are not so rich in Li, leading to muscovite with lower Li contents. Thus, taking Li content of muscovite as a tracer for REL mineralization is in need of more investigation.

7. Conclusions

The chemistry of muscovites from the pegmatites of the Chinese Altai reveals that the pegmatite magmas for barren, Nb-Ta, Be, Be-Nb-Ta, Li-Nb-Ta and Li-Be-Nb-Ta are complex and diverse. The chemical studies of muscovite contribute to looking for REL mineralization type tracers and reflecting the ore-forming process in some degree.
  • Li+ accompanied with Fe, Mg and Mn substitute for Al3+ at the octahedral site in muscovite from the REL pegmatite in the Chinese Altai. The muscovite from some of the Be pegmatites shows a substitution of Rb by Cs at interlayer space.
  • The lenses of the Baicheng Nb-Ta pegmatite are produced at late fluid-rich stage with high fluxes including P and B. The enrichment of HFSE in muscovite indicates a Nb-Ta-Sn-W rich pegmatite magma for the Dakalasu Be-Nb-Ta pegmatite.
  • From barren pegmatite, beryl-bearing zone, to spodumene-bearing zone, the pegmatite-forming magma basically display an increasing evolution degree.
  • The possible indicators of muscovite for barren, Be- and Li-mineralized pegmatites mainly controlled by evolution degree are summarized. In the Chinese Altai, the muscovites from barren pegmatites contain ca. 400–600 ppm Rb, ca. 5–50 ppm, and Cs <3 ppm Ge with <10 ppm Ta and <10 ppm Be; those intergrown with beryl have ca. 1200–4000 ppm Rb, ca. 100–500 ppm Cs, ca. 4–6 ppm Ge and ca. 3–4 wt% FeO; those assembled with spodumene host >4500 ppm Rb, ca. 6–12 ppm Ge and ca. 1–2.5 wt% FeO with large variations of Cs (>300 ppm). The plots of Nb/Ta vs. Cs and K/Rb vs. Ge are proposed to discriminate barren, Be- and Nb-Ta-(Li-Be-Rb-Cs) pegmatites.
  • The Li, Be, Rb, Cs and F concentrations of liquid were evaluated using the trace element compositions of muscovites from barren and REL pegmatites in the Chinese Altai. The high Rb and Cs contents of liquid and lower Be contents than beryl saturation value indicate that both highly evolved pegmatite magma and low temperature at emplacement contribute to beryl formation. The liquids saturated with spodumene have large variations of Li, possibly related to metastable state at Li unsaturation–supersaturation or heterogeneous distribution of lithium in the system.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/min12030377/s1, Table S1: The EMPA and LA-ICP-MS results of muscovites from the pegmatite dykes in the Chinese Altai. Table S2: Muscovite/melt partition coefficients (Kd) used in this study. Table S3: The calculated Li, Be, F, Rb and Cs contents of liquids at equilibrium with muscovites from the pegmatite dykes in the Chinese Altai.

Author Contributions

Conceptualization, Q.Z. and K.Q.; methodology, Q.Z. and D.T.; software, Q.Z.; validation, D.T.; formal analysis, Q.Z.; investigation, Q.Z., D.T. and C.W.; data curation, Q.Z.; writing—original draft preparation, Q.Z.; writing—review and editing, K.Q.; supervision, K.Q. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by Natural Science Foundation of China (grant number 41602095), the Key projects in National Science and Technology Pillar Program (grant number 2011BAB06B03), the Second Tibetan Plateau Scientific Expedition and Research Program (STEP) (grant number 2019QZKK0802, 2019QZKK0806), Key Research Program of the Institute of Geology and Geophysics, Chinese Academy of Sciences (grant number IGGCAS-201902), and National Geological Survey Project of Altay and Junggar (grant number DD20160006).

Acknowledgments

The authors are grateful to Qian Mao and Yueheng Yang for their help with the EMPA and LA-ICP-MS, respectively. Jinxiang Li, Junxing Zhao, Mingjian Cao, and Huaying Wu are thanked for their fruitful discussion and great suggestions that improved the quality of this manuscript. We also thank the reviewers for their valuable suggestions.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Geological sketch map of the Chinese Altai, modified from [47,49,57,72]. I, Altaishan terrane; II, NW Altaishan terrane; III, Central Altaishan terrane; IV, Qiongkuer-Abagong terrane; V, Erqis terrane; VI, Perkin-Ertai terrane. 1, Qinghe pegmatite field; 2, Keketuohai pegmatite field; 3, Kuwei-Jiebiete pegmatite field; 4, Kelumute-Jideke pegmatite field; 5, Kalaeerqisi pegmatite field; 6, Dakalasu-Kekexier pegmatite field; 7, Xiaokalasu-Qiebielin pegmatite field; 8, Hailiutan-Yeliuman pegmatite field; 9, Jiamanhaba pegmatite field.
Figure 1. Geological sketch map of the Chinese Altai, modified from [47,49,57,72]. I, Altaishan terrane; II, NW Altaishan terrane; III, Central Altaishan terrane; IV, Qiongkuer-Abagong terrane; V, Erqis terrane; VI, Perkin-Ertai terrane. 1, Qinghe pegmatite field; 2, Keketuohai pegmatite field; 3, Kuwei-Jiebiete pegmatite field; 4, Kelumute-Jideke pegmatite field; 5, Kalaeerqisi pegmatite field; 6, Dakalasu-Kekexier pegmatite field; 7, Xiaokalasu-Qiebielin pegmatite field; 8, Hailiutan-Yeliuman pegmatite field; 9, Jiamanhaba pegmatite field.
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Figure 2. Photographs of samples (a) 12TLT-4, (b) 12TLT-7, (c) BC-2, (d) KMNG-1, (e) HST-5, (f) HST-7, (g) QKE-2-1, (h) DKLS-3, (i) XKLS-2(2), (j) TEL-1(1), (k) WZG-4. Ab, albite; Kf, K-feldspar; Qz, quartz; Ms, muscovite; Spd, spodumene; Brl, beryl; CGM, columbite-group minerals; Tur, tourmaline; Grt, garnet. Photos g and k are from [72].
Figure 2. Photographs of samples (a) 12TLT-4, (b) 12TLT-7, (c) BC-2, (d) KMNG-1, (e) HST-5, (f) HST-7, (g) QKE-2-1, (h) DKLS-3, (i) XKLS-2(2), (j) TEL-1(1), (k) WZG-4. Ab, albite; Kf, K-feldspar; Qz, quartz; Ms, muscovite; Spd, spodumene; Brl, beryl; CGM, columbite-group minerals; Tur, tourmaline; Grt, garnet. Photos g and k are from [72].
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Figure 3. Mg-Li vs. Fetot + Mn + Ti-AlVI diagram according to [81].
Figure 3. Mg-Li vs. Fetot + Mn + Ti-AlVI diagram according to [81].
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Figure 4. Plots of Fe + Mg + Mn, AlVI vs. Li apfu, Rb, Cs vs. Li and Rb vs. Cs contents showing substitutions among alkali elements.
Figure 4. Plots of Fe + Mg + Mn, AlVI vs. Li apfu, Rb, Cs vs. Li and Rb vs. Cs contents showing substitutions among alkali elements.
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Figure 5. Plots of P vs. Cs and B, F vs. Li, Ta vs. Nb and Sn vs. W contents.
Figure 5. Plots of P vs. Cs and B, F vs. Li, Ta vs. Nb and Sn vs. W contents.
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Figure 6. Plot of K/Rb vs. Cs content for muscovites from the pegmatites studied and the Koktokay No.3 pegmatite in the Chinese Altai. The regions of zones I–IV and zones V–VIII of the Koktokay No.3 pegmatite are based on the data from [45,100].
Figure 6. Plot of K/Rb vs. Cs content for muscovites from the pegmatites studied and the Koktokay No.3 pegmatite in the Chinese Altai. The regions of zones I–IV and zones V–VIII of the Koktokay No.3 pegmatite are based on the data from [45,100].
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Figure 7. Whisker-box diagrams of variations of Rb, Cs, Ge, Ta, Nb, Li, Be, B, F, FeO, MnO and MgO contents, showing compositional trends of muscovites from pegmatites with diverse REL mineralization types. The Koktokay No.3 pegmatite represent the Li-Be-Nb-Ta-Rb-Cs mineralization type and zones I–IV and V–VIII are related to those assembled with beryl and spodumene/lepidolite, respectively. The data of muscovites of the Koktokay No.3 pegmatite are from [45,100]. The black and grey arrows represent trends of changes from barren to Li-Be-Nb-Ta-Rb-Cs pegmatite and among beryl-bearing or spodumene-bearing pegmatites, respectively.
Figure 7. Whisker-box diagrams of variations of Rb, Cs, Ge, Ta, Nb, Li, Be, B, F, FeO, MnO and MgO contents, showing compositional trends of muscovites from pegmatites with diverse REL mineralization types. The Koktokay No.3 pegmatite represent the Li-Be-Nb-Ta-Rb-Cs mineralization type and zones I–IV and V–VIII are related to those assembled with beryl and spodumene/lepidolite, respectively. The data of muscovites of the Koktokay No.3 pegmatite are from [45,100]. The black and grey arrows represent trends of changes from barren to Li-Be-Nb-Ta-Rb-Cs pegmatite and among beryl-bearing or spodumene-bearing pegmatites, respectively.
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Figure 8. Variation diagrams of Nb/Ta vs. Cs content and K/Rb vs. Ge content, indicating the differences of muscovites from the barren, Be and Nb-Ta-bearing pegmatites in the Chinese Altai. The regions of zones I–IV and zones V–VIII of the Koktokay No.3 pegmatite are based on the data from [45,100].
Figure 8. Variation diagrams of Nb/Ta vs. Cs content and K/Rb vs. Ge content, indicating the differences of muscovites from the barren, Be and Nb-Ta-bearing pegmatites in the Chinese Altai. The regions of zones I–IV and zones V–VIII of the Koktokay No.3 pegmatite are based on the data from [45,100].
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Minerals 12 00377 g009 550
Figure 9. Calculated trace element contents (Li, Be, F and Rb) of liquids at equilibrium with muscovite from REL pegmatite dykes plotted as a function of the calculated Cs concentration of the liquid. The Koktokay No.3 pegmatite represents the Li-Be-Nb-Ta-Rb-Cs mineralization type and the compositions of muscovites from zones I–IV and V–VIII [45,100] are used for calculating the trace elements content of liquids that are saturated with beryl and spodumene/lepidolite, respectively. The green dashed and solid lines refer to Be contents of liquid saturated with beryl and beryl-bearing pegmatite [111]. The pink dashed and solid lines indicate Li contents of liquid saturated with Li-aluminosilicate and spodumene-bearing pegmatite [112,116].
Figure 9. Calculated trace element contents (Li, Be, F and Rb) of liquids at equilibrium with muscovite from REL pegmatite dykes plotted as a function of the calculated Cs concentration of the liquid. The Koktokay No.3 pegmatite represents the Li-Be-Nb-Ta-Rb-Cs mineralization type and the compositions of muscovites from zones I–IV and V–VIII [45,100] are used for calculating the trace elements content of liquids that are saturated with beryl and spodumene/lepidolite, respectively. The green dashed and solid lines refer to Be contents of liquid saturated with beryl and beryl-bearing pegmatite [111]. The pink dashed and solid lines indicate Li contents of liquid saturated with Li-aluminosilicate and spodumene-bearing pegmatite [112,116].
Minerals 12 00377 g009
Table
Table 1. Main characteristics of the pegmatite dykes studied in the Chinese Altai.
Table 1. Main characteristics of the pegmatite dykes studied in the Chinese Altai.
PegmatitePegmatite FieldPegmatite TypePegmatite SubtypeMineralization TypeInternal Zonation and Mineralogy ComponentsAgesCountry Rock
TalateQinghecomplexspodumeneLi-Be-Nb-TaWZ: fine Ab-Qz-Ms-Grt-Brl; OIZ: graphic intergrowth; IIZ: Spd-Qz-Ab; CZ: blocky Mc and Qz block.286 Ma * [72], 386 Ma [37]Mica schist
BaichengQingheberylberyl-columbiteNb-TaKf-Ab-Qz-Ms; lenses: Mc block and Qz-Ms-CGM-Tur block; MU: saccharoidal Ab-Qz-Ms.297 Ma * [72]Mica schist
KangmunagongQinghe BarrenHomogeneous body: Kf-Ab-Qz-Ms-Tur-Grt.265 Ma * [72]Mica schist
QunkuerKelumute-
Jideke		berylberyl-columbiteBesaccharoidal Ab-Qz-Ms; coarse Grt-Ab intergrowth; Mc block; smoky Qz-Brl-Ms194 Ma [72]Mica schist
HusiteKelumute-
Jideke		berylberyl-columbiteBeBZ: fine Ab-Qz-Ms; WZ: coarse Ms-Qz-Brl-Grt; IZ: blocky Mc and graphic intergrowth with Brl; MU: saccharoidal Ab.199 Ma [72]Mica schist
DakalsuDakalasu-
Kekexier		berylberyl-columbiteBe-Nb-TaBZ: fine Ab-Qz-Ms-Grt-Tur; WZ: graphic intergrowth-CGM; IZ: Mc block-Qz-Ms-Brl columns-CGM; MU: Ab; CZ: Qz.240 Ma [72]; 258 Ma [38]Biotite granite (270 Ma) [75]
XiaokalasuXiaokalasu-
Qiebielin		complexspodumeneLi-Nb-TaWZ: Mc block and fine Ab-Qz-Ms-Grt-CGM; OIZ: Qz-Ms-Kf-Grt; IIZ: Spd-Qz-Ms-CGM and blocky Mc.258–262 Ma [72]Mica schist
WeizigouXiaokalasu-
Qiebielin		berylberyl-columbiteBeBZ: Qz-Ms-Tur; WZ: fine Ab-Qz-Ms-Grt-Brl; IZ: blocky Mc-Brl and coarse Qz-Ms-Brl-Tur block.237 Ma [72]Two mica granite (398–412 Ma) [76]
TaerlangXiaokalasu-Qiebielin BarrenBZ: Kf-Qz-Ms-Bi-Grt-Tur;WZ: graphic intergrowth and Qz-Ms block248 Ma [72]Mica schist
Note: * represents muscovite Ar-Ar plateau ages and other ages of pegmatites are CGM or zircon U-Pb ages. BZ, border zone; WZ, wall zone; IZ, intermediate zone; OIZ, outer intermediate zone; IIZ, inner intermediate zone; CZ, core zone; MU, metasomatic unit; Ab, albite; Kf, K-feldspar; Mc, microcline; Qz, quartz; Ms, muscovite; Spd, spodumene; Brl, beryl; CGM, columbite-group minerals; Tur, tourmaline; Grt, garnet; Bi, biotite.
Table
Table 2. Descriptions of the studied samples in the Chinese Altai.
Table 2. Descriptions of the studied samples in the Chinese Altai.
Pegmatite FieldPegmatiteSampleZoneMineralogy Components
QingheTalate
(Li-Be-Nb-Ta)		12TLT-4WZAb (50)—Qz (25)—Ms (15)—Grt (2–5)—Brl (2–5)—CGM (2–5)
12TLT-7CZMc (45)—Ab (10)—Qz (30)—Ms (10)—CGM (5)
Baicheng
(Nb-Ta)		BC-2LensQz (70)—Ms (10)—Kf (10)—Ab (5)—Col-Tan (2–5)
Kangmunagong
(Barren)		KMNG-1 Kf (55–60)—Qz (25–30)—Ms (5–8)—Tur (5)—Grt (2)
Kelumute-
Jideke		Qunkuer
(Be)		QKE-2-1 Qz (70)—Ms (15)—Ab (10)—Brl (5)
Husite
(Be)		HST-5IZKf (45)—Qz (35)—Ms (10–15)—Brl (2–5)
HST-7IZKf (40)—Qz (45)—Ms (10)—Grt (2–5)
Dakalasu-
Kekexier		Dakalsu
(Be-Nb-Ta)		DKLS-3IZKf (50–55)—Qz (10–15)—Ms(20)—CGM(5)—Brl(2–5)
Xiaokalasu-
Qiebielin		Xiaokalasu
(Li-Nb-Ta)		XKLS-2(2)IZAb (50–55)—Qz (15–20)—Spd (25)—Ms (5–10)
Weizigou
(Be)		WZG-4IZQz (60)—Mc (20)—Ms (10)—Brl (5)—Tur (2–5)
Taerlang
(Barren)		TEL-1(1)WZKf (40)—Qz (35–40)—Ms (15)—Bi (5)
Note: The numbers in brackets represent percent contents; BZ, border zone; WZ, wall zone; IZ, intermediate zone; CZ, core zone; Ab, albite; Kf, K-feldspar; Mc, microcline; Qz, quartz; Ms, muscovite; Spd, spodumene; Brl, beryl; CGM, columbite-group minerals; Tur, tourmaline; Grt, garnet; Bi, biotite. The samples KMNG-1, QKE-2-1 and WZG-4 are from [72].
Table
Table 3. The representative EMPA and LA-ICP-MS results of muscovites in the pegmatite dykes of the Chinese Altai.
Table 3. The representative EMPA and LA-ICP-MS results of muscovites in the pegmatite dykes of the Chinese Altai.
Pegmatite DykeKangmunagongTaerlangBaichengWeizigouQunkuerHusiteDakalasuXiaokalasuTalate
Mineralization TypeBarrenBarrenNb-TaBeBeBeBe-Nb-TaLi-Nb-TaLi-Be-Nb-Ta
Rock TypeMc-Qz-Ms-Tur-GrtWZLensIZQz-Ms-Ab-BrlIZIZIIZWZCZ
Sample No.KMNG-1TEL-1(1)BC-2WZG-4QKE-2-1HST-5HST-7DKLS-3XKLS-2(2)12TLT-412TLT-7
/wt%
SiO246.9546.7046.7046.3645.9846.7846.6046.4646.2646.1646.15
TiO20.120.510.031.290.07bdl0.090.230.030.340.41
Al2O334.6532.4136.9031.2233.4534.6433.9533.3836.8133.9032.45
Cr2O3bdlbdl0.030.02bdlbdl0.030.02bdl0.030.02
FeO1.863.480.833.944.122.403.503.791.022.302.55
MnO0.040.060.030.110.060.040.090.100.130.040.04
MgO0.811.060.211.020.170.240.240.100.040.921.11
ZnObdl0.020.070.040.04bdlbdl0.070.050.080.08
CaObdlbdl0.02bdlbdlbdl0.020.02bdl0.020.04
Li2O *0.080.020.100.280.150.160.150.080.100.340.28
Na2O0.430.600.570.500.910.360.430.650.750.390.45
K2O10.119.849.839.529.629.969.599.419.5210.1310.39
Fbdlbdl0.330.461.160.240.470.510.080.760.82
O = Fbdlbdl0.140.200.490.100.200.210.030.320.35
H2O *4.504.444.394.193.874.364.244.194.474.104.02
Total99.5499.1399.9098.7399.1299.0799.1998.7799.2399.1798.47
(O, OH, F) = 24
Si6.2536.3056.1576.2996.2326.2666.2666.2876.1416.2036.272
IVAl1.7471.6951.8431.7011.7681.7341.7341.7131.8591.7971.728
IVSum8.0008.0008.0008.0008.0008.0008.0008.0008.0008.0008.000
VIAl3.6943.4643.8923.2993.5773.7373.6483.6123.9023.5723.471
Ti0.0120.0520.0030.1320.0070.0000.0090.0230.0030.0340.042
Cr0.0000.0000.0030.0030.0000.0000.0030.0020.0000.0030.002
Fe0.2070.3930.0920.4470.4670.2690.3940.4290.1130.2580.290
Mn0.0040.0070.0040.0120.0070.0040.0100.0110.0150.0050.005
Mg0.1600.2140.0420.2060.0340.0470.0470.0200.0090.1840.224
Li0.0440.0110.0520.1510.0840.0860.0830.0440.0530.1850.151
Zn0.0000.0020.0070.0040.0040.0000.0000.0070.0050.0080.008
VISum4.1224.1434.0944.2534.1794.1444.1944.1484.0994.2494.195
Ca0.0000.0000.0030.0000.0000.0000.0030.0020.0000.0020.006
Na0.1110.1560.1450.1310.2390.0930.1110.1710.1930.1010.118
K1.7171.6951.6541.6501.6641.7021.6451.6251.6121.7361.802
XIISum1.8281.8521.8021.7811.9031.7941.7591.7991.8051.8391.927
F0.0000.0000.1380.1990.4980.1000.1980.2170.0340.3240.354
OH4.0004.0003.8623.8013.5023.9003.8023.7833.9663.6763.646
/ppm
Li38594.7453127971774571638046115911287
Be0.4015.5324.826.020.523.121.327.022.5925.523.7
B82.260.138278.971.313313114614186307
P13423.817528.112658.938.058.553.3139145
Sc22.999.51.766.71.862.111.364.482.198.793.94
V0.03336.128.343.00.1510.3343.184.051.4747.321.1
Mn172536264781320744812617908311246
Co0.3171.320.791.360.0700.1970.3240.2820.086.665.14
Ga60.014567.311212011412438812272.167.7
Ge2.822.2713.83.844.283.714.586.796.019.0819.5
Rb428455443412054015296329643843473347748329
Sr3.2116.36.549.341.123.530.5150.2663.073.754.2
Zr15231.61bdl1.180.3930.3081.081.121bdl0.730.237
Nb40.386.3170122301257305169159231300
Mo0.1120.324bdl0.087bdl0.1760.0960.092bdl0.093bdl
In0.1970.996bdl0.310.2560.1230.0454.860.0790.0690.021
Sn12.434.7bdl15.862.321.29.6077318.11.730.92
Cs7.696.447210093.51071015172803321514
Ba6.573155.08252bdl1.391.411.242.8582.528.3
Hf0.27bdlbdl0.14bdlbdl0.1950.826bdl0.510.133
Ta1.863.7758.126.724.516.124.722546.853.9109
W22.578.20.9417.031.617.616.857.35.815.991.62
Pb7.46.885.636.334.625.084.512.14.92.964.14
Thbdlbdlbdl0.032bdl0.016bdlbdlbdlbdlbdl
Ubdlbdl1.530.082bdlbdlbdlbdlbdlbdlbdl
K/Rb195.77179.6518.4065.5519.8927.8726.8420.3216.6817.6010.35
K/Cs10,90412,76117378685476978615128225356.95
Li/Cs50.0614.800.9612.747.676.937.070.731.644.800.85
Nb/Ta21.6922.902.924.5612.2815.9312.370.753.404.282.75
Note: bdl, below detection limit; *, calculated using LA-ICP-MS data; WZ, wall zone; IZ, intermediate zone; IIZ, inner intermediate zone; CZ, core zone; Ab, albite; Mc, microcline; Qz, quartz; Ms, muscovite; Brl, beryl; Tur, tourmaline; Grt, garnet.
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Zhou, Q.; Qin, K.; Tang, D.; Wang, C. A Combined EMPA and LA-ICP-MS Study of Muscovite from Pegmatites in the Chinese Altai, NW China: Implications for Tracing Rare-Element Mineralization Type and Ore-Forming Process. Minerals 2022, 12, 377. https://doi.org/10.3390/min12030377

AMA Style

Zhou Q, Qin K, Tang D, Wang C. A Combined EMPA and LA-ICP-MS Study of Muscovite from Pegmatites in the Chinese Altai, NW China: Implications for Tracing Rare-Element Mineralization Type and Ore-Forming Process. Minerals. 2022; 12(3):377. https://doi.org/10.3390/min12030377

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Zhou, Qifeng, Kezhang Qin, Dongmei Tang, and Chunlong Wang. 2022. "A Combined EMPA and LA-ICP-MS Study of Muscovite from Pegmatites in the Chinese Altai, NW China: Implications for Tracing Rare-Element Mineralization Type and Ore-Forming Process" Minerals 12, no. 3: 377. https://doi.org/10.3390/min12030377

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