Petrology and geochemistry of Li-bearing pegmatites and related granitic rocks in southern Thailand: implications for petrogenesis and lithium potential in Thailand

Lithium (Li) can be found in many minerals, including lepidolite. Lepidolite is found in pegmatite-related tin deposits in the Phang Nga area in southern Thailand. According to their field occurrence, petrography, mineral chemistry, and whole-rock geochemistry, the Li-bearing pegmatites and the granitic rocks in the study area can be linked to tin deposits in southern Thailand as part of the SE Asian tin belt. The Li-bearing pegmatites are characterized by an abundance of lepidolite, K-feldspar, plagioclase, and quartz with some accessory minerals of fluorite, cassiterite, apatite, monazite, and beryl. The granitic rocks show various compositions, including porphyritic biotite–muscovite granite, biotite granite, and muscovite—tourmaline granite with different proportions of K-feldspar, plagioclase, quartz, biotite, muscovite, and tourmaline. Whole-rock geochemistry indicates that both the Li-bearing pegmatites and granitic rocks have a close relationship rooted in their peraluminous S-type granite affinity. The Li-bearing pegmatites evolved from highly fractionated S-type granitic rocks comparable with the Western Belt Granite of Thailand. The enrichment of large-ion lithophile elements (e.g., Rb and K) and the depletion of Ba, Nb, and Ti together with similar rare Earth element patterns reflect the collisional setting indicating the Sibumasu–West Burma and West Burma—Indo-Burma collisions during the Cretaceous to the Eocene. The crystallization pressure—temperature conditions of these rocks were 3.49–4.25 kbar and 622°C–675°C, respectively, with an emplacement depth of 13–15 km. The Li-bearing pegmatites had a relatively high average Li grade compared with those of other Li-bearing pegmatites in the world.

1 Introduction

Nowadays, lithium (Li) has become an important element in many industries (e.g., energy storage), especially in the energy industry. Li can be found in many minerals, such as spodumene, lepidolite, amblygonite, petalite in granitic rocks, and pegmatites (Averill and Olson, 1978; Gao et al., 2020; Zhang et al., 2020; Groves et al., 2022). These Li-bearing rocks evolved from highly fractionated granites (Cerny, 1991a; Cerny, 1991b; Muller et al., 2022; Shen et al., 2022) that migrated from parental granite to rare-metal-rich pegmatites, including Li-bearing pegmatites. Lepidolite pegmatites are well-defined Li sources in several deposits in the world, such as the Alakha deposits in Russia (Annikova et al., 2016), the Zavitinskoye deposits in Russia (Seltmann et al., 2010; Melentiev et al., 2022), and the La Vi, Quang Ngai deposits in Vietnam (Hien-Dinh et al., 2017).

Lepidolite pegmatite and related granitic rocks (Cobbing et al., 1992; Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993) have been discovered in the tin deposits in the Phang Nga area, southern Thailand (Figure 1) (Suthakorn, 1992; Nakapadungrat and Maneenai, 1993). These rocks comprise the SE Asia tin belt (Cobbing et al., 1992; Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993), which is associated with various types of tin deposits (DMR, 2009), such as argillic dissemination, quartz–cassiterite–wolframite vein swarm, and pegmatite types (Gocht and Pluhar, 1982; Nakapadungrat and Maneenai, 1993; DMR, 2009). Moreover, granitic rocks related to tin deposits are distributed in many areas along the Western Belt Granite (WBG) of Thailand, such as Chiang Mai, the Thai–Burma border in Kanchanaburi, Ratchaburi together with the Phang Nga–Phuket area, and other areas in SE Asia (e.g., Dhawai, Burma; Nakapadungrat and Putthapiban, 1992; Cobbing et al., 1992; Li et al., 2019).

FIGURE 1

FIGURE 1. (A) Index map of Thailand showing the distribution of three main granitic belts (Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993) and main tectonic terranes (Charusiri et al., 2002; Sone and Metcalfe, 2008; Sone et al., 2012; Zaw et al., 2014). (B) Geological map of the Phang Nga area, southern Thailand, together with the sample locations (DMR, 1985).

Although there are some reports about tin deposits related to lepidolite pegmatite in Thailand (Suthakorn, 1992; Nakapadungrat and Maneenai, 1993), detailed studies on the petrology and geochemistry of lepidolite pegmatite and related granitic rocks associated with tin deposits in Phang Nga area, southern Thailand, have never made. Therefore, this research aims to provide the petrology, mineral chemistry, and geochemistry of lepidolite pegmatite and related granitic rocks in the Phang Nga tin field, southern Thailand, to understand the petrogenesis, tectonic setting, and Li potential in Thailand and the SE Asia tin belt.

2 Geological background

Granitic rocks widely distributed throughout Thailand and SE Asia (Cobbing et al., 1992; Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993) are classified into three main belts: the Eastern Belt Granite, the Central Belt Granite, and WBG in a mainly N–S trend (Figure 1A). The WBG is the main exposed belt in western Thailand near the Thailand–Burma border and extending to western peninsular Thailand (Cobbing et al., 1992; Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993) (Figure 1A). It has been termed the Western Tin Belt or Tin Province (Cobbing et al., 1986), which includes the Phang Nga area, southern Thailand (Figure 1B) (Nakapadungrat and Maneenai, 1993). In the Phang Nga area (Figure 1B), granitic rocks are exposed in several locations, such as in the Khao Lak, Khao Khanim, Khao Lam Pi, Khao Kata Khwam, Khao Hang Hong, and Khao Po areas (DMR, 1985). These granitic are of various types, such as biotite granite, biotite–muscovite granite, muscovite–tourmaline granite, and pegmatite (Nakapadungrat and Maneenai, 1993). These granitic rocks are associated with tin deposits (Suwimonprecha, 1989; Nakapadungrat and Maneenai, 1993) distributed in several tin fields (Figure 1B).

The granites of the Phang Nga area are exposed along the western coast and central part of the Phang Nga were intruded into Permo-Carboniferous sedimentary rocks, Permian limestone, and Triassic–Jurassic sedimentary rocks and were covered by Quaternary sediment (DMR, 1985) (Figure 1B). The Permo-Carboniferous sedimentary rocks widely distributed in the Phang Nga area, especially the western part of the study area (Figure 1B), comprise mainly pebbly mudstone, laminated sandstone, siltstone, and shale (Tantiwanit et al., 1983; DMR, 1985). The Permian limestone, exposed in the central part of the area and extending to the southern part, is a gray bedded to massive fossiliferous limestone (DMR, 1985). Triassic–Jurassic sedimentary rocks, found only in the southern part of the area, include mainly sandstone, conglomerate, siltstone, and argillaceous limestone (DMR, 1985).

3 Analytical methods

Six representative Li-bearing pegmatites and five related granitic rocks exposed in the Phang Nga area, southern Thailand (Figure 1), were collected from the least weathered zone to study their petrography, mineral chemistry, and whole-rock geochemistry. Representative granitic rocks were collected from main granitic exposures, including Khao Po (PNG5), Khao Hang Hong (PNG15), Khao Khanim (PNG13), Khao Lak (PNG9), and Khao Kata Khwam (PNG8) (Figure 1B).

All rock samples were prepared as polished thin sections using grinding powder and diamond paste at the Department of Geology, Faculty of Science, Chulalongkorn University. A Nikon polarized light microscope was used to observe petrographic characteristics.

The mineral chemical study was conducted using an electron probe micro-analyzer (EPMA; model JEOL JXA-8100) installed at the Department of Geology, Faculty of Science, Chulalongkorn University. The conditions for the analysis were set at 15 kV and about 2 μA using a focused beam spot (1 μm). Mineral and pure oxide standards were used for calibration at the same conditions with automatic ZAF correction and the analyses are reported as oxide weight percentages. The Li₂O content of lepidolite was calculated after Tischendorf et al. (1997).

Representative samples were prepared using a disc mill and were fused to be fused beads for whole-rock geochemical analysis. The major and minor oxides of the samples were analyzed using an X-ray fluorescence spectrometer (Bruker model AXS S-4 Pioneer) based at the Department of Geology, Faculty of Science, Chulalongkorn University. The major and minor oxides, including SiO₂, TiO₂, Al₂O₃, FeO_total, MnO, MgO, CaO, Na₂O, K₂O, and P₂O₅, were analyzed along with international rock standards for calibration. Loss on ignition was also conducted by measuring weight loss after heating at 1,050°C for 3 h in a furnace. In addition, trace and rare Earth element (REE) compositions were analyzed through inductively coupled plasma-mass spectrometry (ICP-MS) at ALS, Vientiane, Laos PDR with detection limits from 0.0004 ppm to 0.01%.

4 Results

4.1 Field occurrence and petrographic description

In the Phang Nga area, one of the main tin fields of Thailand, Li-bearing pegmatites are found as lepidolite pegmatite dikes related to tin deposits near Khao Po in the Takua Thong tin field (Figure 1B). Li-bearing pegmatites with a width ranging from 1 to 10 m are oriented along the NE–SW trend and cut into Carboniferous–Permian mudstone (Figure 2A). These pegmatites appear to have a similar trend with that of the Khlong Marui Fault zone (Figure 1A).

FIGURE 2

FIGURE 2. (A) Outcrop exposure of the Li-bearing pegmatites cut into the host rock of mudstone; (B,C) lepidolite in the Li-bearing pegmatite; (D–F) granitic rocks associated with tin deposits exposed in the Phang Nga area, southern Thailand.

Representative samples from the pegmatites were collected from the least weathered Li-bearing pegmatites. The Li-bearing pegmatites show phaneritic with some porphyritic textures (Figures 2B, C) with coarse grains (1–2 cm). The main mineral assemblages (Figures 3A, B) include lepidolite, K-feldspar, plagioclase, and quartz with or without accessory minerals of fluorite, cassiterite, apatite, monazite, and beryl. The main minerals in the Li-bearing pegmatites comprised lepidolite at about 20%–30%, feldspar at 30%–40%, and quartz at 20%–40%, with 1%–5% other accessory minerals. The lepidolite was clearly subhedral micaceous with grain sizes that ranged from 0.2 mm to 1 cm. Meanwhile, subhedral and anhedral K-feldspars (0.5 mm–2 cm) were commonly presented as phenocrysts producing the seriate porphyritic texture of the pegmatite. Subhedral and anhedral plagioclase crystals with albite twinning were 0.5 mm–1 cm in size. Subhedral fluorite (0.3 mm–1 cm), anhedral beryl (0.2–0.5 mm), subhedral monazite (0.2–0.5 mm), and cassiterite (<0.1–0.2 mm) were present in some samples.

FIGURE 3

FIGURE 3. Photomicrograph under cross-polarization (XPL) of the (A,B) Li-bearing pegmatites and (C,D) related granitic rocks in the Phang Nga area, southern Thailand. Abbreviations: Lep (lepidolite); Q (quartz); Kfs (K-feldspar); Pl (plagioclase); Bi (biotite); Mu (muscovite); Ap (apatite).

In the study area, the Li-bearing pegmatites were associated with granitic rocks (Figures 2D–F) in the Phang Nga area (Figure 1B) in the WBG (Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993), SE Asia tin belt (Cobbling et al., 1992).

The above granitic rocks were characterized by porphyritic biotite–muscovite granite (with some biotite granite) and muscovite–tourmaline granite (Figure 2). The porphyritic biotite–muscovite granites were distributed in all granitic exposures in the study area (Figure 1B). Porphyritic textures with feldspar phenocrysts were very common (Figure 2F). Some equigranular texture with medium grains was also found in the muscovite-rich granite (Figure 2E). These granitic rocks were composed mainly of K-feldspar, plagioclase, quartz, biotite, muscovite with accessory minerals of opaque minerals, apatite, zircon, titanite, monazite, and tourmaline.

In terms of microscopic characters (Figures 3C, D), subhedral to anhedral K-feldspars were found as phenocrysts (5 mm–5 cm) and groundmass (0.5–3 mm). A gride twin was clearly observed in microcline. Perthitic textures of alkali feldspar were also found. Subhedral to anhedral plagioclase that ranged in size from 0.3 to 3 mm were clearly observed with significant albite twins and sometimes Carlsbad–albite twins. Anhedral quartz with a size of 0.5–1 mm was a typical composition. Myrmekitic texture was commonly found in quartz. Biotite was very common in the granitic rocks with typical subhedral to anhedral crystals (0.5–4 mm). The biotite showed a flaky texture with different proportions from 5% to 20% in the different granitic exposures. Subhedral to anhedral muscovite (0.5–3 mm) with a flaky texture was also common in the granitic rocks. For the other accessory minerals, suhedral to subhedral titanite (0.5–1 mm), subhedral to anhedral apatite (0.2–0.5 mm), subhedral zircon (0.1–0.3 mm), subhedral to subhedral monazite (0.2–0.5 mm), and subhedral tourmaline (0.4–1 mm) were commonly found in the granitic rocks. In addition, anhedral opaque minerals (0.1–0.3 mm) were also present as accessory minerals.

4.2 Mineral chemistry

The chemistry of selected minerals in the Li-bearing pegmatites and host granites was analyzed. These minerals include lepidolite, biotite, feldspar, cassiterite, ilmenite, and titanite. The analytical results are summarized in Tables 1–5.

TABLE 1

TABLE 1. Representative EPMA analyses of lepidolite in the Li-bearing pegmatites in the Phang Nga area, Southern Thailand.

4.2.1 Lepidolite

The compositions of lepidolite, an essential mineral in the Li-bearing pegmatite, are summarized in Table 1. These compositions showed high SiO₂ (50.25–51.88 wt%), Al₂O₃ (25.51–28.16 wt%), and K₂O (10.08–10.99 wt%) contents with low MnO (0.01–2.24 wt%) and MgO (0.00–0.08 wt%) contents. The Li₂O contents ranged from 4.86 to 5.34 wt%, as calculated after Tischendorf et al. (1997). The lepidolite compositions clearly plot in the lepidolite field (Figure 4A) of Tischendorf et al. (2001).

FIGURE 4

FIGURE 4. Mineral chemistry plots of (A) lepidolite compositions (after Tischendorf et al., 1997); (B) biotite compositions (after Morimoto et al., 1988); (C) feldspar compositions (after Smith and Brown, 1974); (D) ilmenite (after Deer et al., 2013).

4.2.2 Biotite

Biotite, commonly found in the granitic rocks in this study, showed an aluminum content that ranged from 3.31 to 3.56 pfu (17.05–18.38 wt% Al₂O₃) with the TiO₂ and FeO_total contents of 2.28–3.16 wt% and 24.46–25.71 wt%, respectively. Biotite was not present in the Li-bearing pegmatite. This biotite in the granitic rocks was classified into the annite–siderophyllite end-member following the classification of Deer et al. (1966) (Figure 4B). The mineral chemistry of the biotite is summarized in Table 2.

TABLE 2

TABLE 2. Representative EPMA analyses of biotite in the granitic rocks in the Phang Nga area, southern Thailand.

4.2.3 Feldspar

The mineral chemistry of feldspar, including K-feldspar and plagioclase, is presented in Table 3. The composition plots in the feldspar ternary diagram are shown in Figure 4C. The K-feldspar in the Li-bearing pegmatites showed higher orthoclase contents (Or_97–98) than those of the granitic rocks (Or_91–93) (Figure 4C). For the plagioclase compositions, the plagioclases in the granitic rocks were albite to oligoclase (An_0–22), whereas those in the Li-bearing pegmatites were in the albite range (An_0–5) (Figure 4C).

TABLE 3

TABLE 3. Representative EPMA analyses of feldspars in the Li-bearing pegmatites and granitic rocks in the Phang Nga area, Southern Thailand.

4.2.4 Cassiterite

Cassiterite was found in the Li-bearing pegmatites as one of the traditional tin deposits in southern Thailand (Figure 1B). The mineral chemistry of cassiterite in the Li-bearing pegmatites is summarized in Table 4. The cassiterite consists predominantly of SnO₂ (97.04–98.57 wt%), with some SiO₂ (0.22–0.50 wt%), ZrO₂ (0.04–0.54 wt%), Sc₂O₃ (0.00–0.09 wt%), CaO (0.75–0.82 wt%), MgO (0.00–0.09 wt%), MnO (0.00–1.14 wt%), and Ta₂O₅ (0.00–0.92 wt%). The representative compositions of cassiterite are shown in Figure 5.

TABLE 4

TABLE 4. Representative EPMA analyses of cassiterite in the Li-bearing pegmatites in the Phang Nga area, Southern Thailand.

FIGURE 5

FIGURE 5. Composition mapping of cassiterite in the Li-bearing pegmatites in the Phang Nga area, Southern Thailand.

4.2.5 Ilmenite

Ilmenite was a dominant opaque mineral in the studied granitic rocks. Representative ilmenites were analyzed for their mineral chemistry (as summarized in Table 5). They comprised mainly TiO₂ that ranged from 51.57 to 52.88 wt% and FeO_total that ranged from 45.99 to 47.36 wt%, with low contents of Al₂O₃ (0.00–0.02 wt%), MnO (0.63–1.10 wt%), and MgO (0.01–0.03 wt%). Solid-solution end-member plots of these ilmenites are clearly defined in Figure 4D.

TABLE 5

TABLE 5. Representative EPMA analyses of ilmenite and titanite in the granitic rocks in the Phang Nga area, Southern Thailand.

4.2.6 Titanite

Titanite or sphene, an accessory mineral in the studied granitic rocks, showed high SiO₂ (30.22–30.85 wt%), Al₂O₃ (33.43–36.91 wt%), and CaO (27.75–28.36 wt%) contents, with less TiO₂ (1.77–5.77 wt%), FeO (0.71–1.86 wt%), and MnO (0.12–0.20 wt%). The analytical data for titanite are presented in Table 5.

4.3 Whole-rock geochemistry

Whole-rock major and trace compositions of the Li-bearing pegmatites and granitic rocks are summarized in Table 6. The Li-bearing pegmatites and granitic rocks had varying SiO₂ contents from 66.01 to 74.93 wt%, where the Li-bearing pegmatites had a slightly lower SiO₂ content (66.01–70.00 wt%) than that of the granitic rocks (70.31–74.93 wt%). Generally, the Li-bearing pegmatites showed lower FeO_total (0.12–0.48 wt%), MgO (0.12–0.48 wt%), and CaO (0.21–0.94 wt%) contents than those of the granitic rocks (1.15–3.07 wt% FeO_total, 0.17–0.95 wt% MgO, and 0.98–2.18 wt% CaO). Meanwhile, the Li-bearing pegmatites exhibited higher Al₂O₃ (19.28–22.59 wt%), MnO (0.24–0.80 wt%), and Na₂O (2.60–5.63 wt%) contents than those of the granitic rocks (12.64–13.59 wt% Al₂O₃, 0.03–0.05 wt% MnO, and 2.16–2.84 wt% Na₂O). Moreover, both the Li-bearing pegmatites and the granitic rocks showed high contents of Na₂O+ K₂O, which ranged from 7.66 to 8.29 wt% and 7.55 to 8.46 wt%, respectively. The total alkali–silica (TAS) plot of SiO₂ and total alkali (Cox et al., 1979) revealed that all samples of the Li-bearing pegmatites and the granitic rocks were in the granite field (Figure 6).

TABLE 6

TABLE 6. Representative whole-rock geochemistry of Li-bearing pegmatites and granitic rocks in the Phang Nga area, Southern Thailand.

FIGURE 6

FIGURE 6. TAS discrimination diagram (Cox et al., 1979) of the Li-bearing pegmatites and related granitic rocks in the Phang Nga area, Southern Thailand, together with the granitic rocks in WGB.

Chondrite-normalized spider diagrams (Figure 7A) of both Li-bearing pegmatites and granites show the marked enrichment of large-ion lithophile elements (LILEs), such as Rb and K, with the depletion of Ba, Nb, and Ti. Chondrite-normalized REE patterns (Figure 7B) of both groups show similar patterns that are slightly high in light REEs (LREEs). Moreover, the chondrite-normalized spider diagrams and REE patterns of both groups are clearly comparable with those of typical S-type granitic rocks in WBG reported by Li et al. (2019). In addition, the chondrite-normalized La/Yb of the Li-bearing pegmatites ranges from 1.14 to 6.15, whereas that of the granitic rocks ranges from 12.80 to 27.88. Meanwhile, the (La/Sm)_N ratio of the Li-bearing pegmatites and granitic rocks are 0.50–1.13 and 3.45–4.83, respectively. For the total REEs (∑REE), the granitic rocks (124–282 ppm) also feature values higher than those of the Li-bearing pegmatites (37–80 ppm).

FIGURE 7

FIGURE 7. (A) Chondrite-normalized spider diagrams (chondrite values from Sun and McDonough, 1989) and (B) chondrite-normalized REE patterns (chondrite values from Sun and McDonough, 1989) of the Li-bearing pegmatites and related granitic rocks in the Phang Nga area, southern Thailand.

5 Discussion

5.1 Petrogenesis

The studied Li-bearing pegmatites and granites have porphyritic textures and significant amounts of biotite and muscovite, which are typical characteristics of the S-type granite in WBG (Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993). In addition, the presence of ilmenite in the rocks potentially indicates an ilmenite series (Ishihara, 1977), which is also consistent with the typical classified granites in the WBG (Cobbling et al., 1992; Nakapadungrat and Putthapiban, 1992; Putthapiban, 2002). The enrichment of LILEs (e.g., Rb and K) and the depletion of Ba, Nb, and Ti in the chondrite-normalized spider diagrams (Figure 7A) suggest collisional granite (Yao et al., 2014). The positive Rb and Th anomalies and low Yb together with LREE enrichment indicate that the rocks were derived from crustal sources (Yao et al., 2014). The chondrite-normalized REE patterns of both groups showing slightly high LREE patterns with negative Eu anomalies indicate fractional crystallization with plagioclase fractionation (Rollinson, 1993). The slightly positive Sm anomaly in the Li-bearing pegmatites might be related to the monazite crystallization caused by increasing fractionation (Cerny, 1991b). Moreover, the decreasing (La/Yb)_N ratios and total REE concentrations (∑REE) from the granitic rocks to the Li-bearing pegmatites suggest the evolution of fractional-crystallization-related plagioclase (Yin et al., 2019). The depletion of Ti might have been caused by the fractional crystallization of Fe–Ti oxides (ilmenite) (Yin et al., 2019). The TAS plot (Figure 6) reflects that both the Li-bearing pegmatites and the granitic rocks have a subalkali composition, comparable with the composition plot of the WBG reported by Nakapadungrat and Putthapiban (1992) and Li et al. (2019).

The SiO₂ and Na₂O+ K₂O–CaO plot (Figure 8A) of Frost et al. (2001) indicated that the Li-bearing pegmatites were of the alkalic to alkalic-calcic series, whereas the granites were of the calc-alkaline to alkalic-calcic series. In comparison, the plot of Al/(Ca + Na + K) against Al/(Na + K) of Shand (1943) clearly reflected that both the Li-bearing pegmatites and the granitic rocks were from peraluminous magma with S-type granite affinity (Figure 8B). Moreover, a plot of the Ba–Rb–Sr ternary diagram for the differentiation trend of granitic magma (Bouseily and Sokkary, 1975) (Figure 8C) shows a crystallization trend from the granitic rocks to the Li-bearing pegmatites, which potentially reflect the evolution of peraluminous granitic magma (Shen et al., 2022). Plots of Nb/Ta versus K/Rb (Yin et al., 2019) (Figure 9A) indicate the differentiation trend of granitic magma that links the granitic rocks to the Li-bearing pegmatites. Similarly, the plots of Ta versus K/Rb of Yin et al. (2019) (Figure 9B) also reflected the differentiation trend of the granitic magma of the granitic rocks to the Li-bearing pegmatites, respectively. These trends of high fractional crystallization are consistent with the crystallization features of the relationship of those highly evolved biotite granites to Li-mica granites in the Dahutang deposit, Southern China (Yin et al., 2019). The chemistry of mineral compositions seem to elucidate a relationship between the granitic rocks and the Li-bearing pegmatites in both K-feldspar and plagioclase. Moreover, the mineral chemistry of biotite (Figure 10) can reflect magmatic characteristics (Abdel-Rahman, 1994; Tukpho and Fanka, 2021; Zhao et al., 2022). The plot of Mg and FeO/(FeO + MgO) (Figure 10A) clearly indicates that the rocks were generated from crustal sources. In addition, the plots of MgO and Al₂O₃ (Figure 10B) and FeO–MgO–Al₂O₃ ternary diagram (Figure 10C) of Abdel-Rahman (1994) indicate collisional peraluminous magma related to S-type granite.

FIGURE 8

FIGURE 8. Plots of (A) SiO₂ and Na₂O+ K₂O−CaO diagram (after Frost et al., 2001); (B) Al/(Na + K) and Al/(Ca + Na + K) diagram (after Shand, 1943); (C) Ba–Rb–Sr ternary diagram (after Bouseily and Sokkary, 1975) of the Li-bearing pegmatites and related granitic rocks in the Phang Nga area, southern Thailand.

FIGURE 9

FIGURE 9. Plots of (A) K/Rb and Nb/Ta and (B) K/Rb and Ta diagrams (after Yin et al., 2019) of the Li-bearing pegmatite and related granitic rocks in the Phang Nga area, southern Thailand.

FIGURE 10

FIGURE 10. Biotite mineral chemistry plots of (A) MgO and MgO/(FeO + MgO) diagram (after Zhou, 1986), (B) MgO and Al₂O₃ diagram (after Abdel-Rahman, 1994), and (C) FeO*–MgO–Al₂O₃ diagram (after Abdel-Rahman, 1994).

The crystallization pressure–temperature (P–T) conditions of the studied granitic rocks have been widely studied using mineral chemistry data of single minerals or coexisting minerals (e.g., Henry et al., 2005; Uchida et al., 2007; Fanka et al., 2018; Tukpho and Fanka, 2021). For instance, according to the biotite composition of the granitic rocks related to the Li-bearing pegmatites the mineral chemistry of biotite was used for calculating the crystallization P–T conditions of the rocks using the biotite geothermometer of Henry et al. (2005) and the biotite geobarometer of Uchida et al. (2007). Meanwhile, the Ti-in-biotite geothermometer of Henry et al. (2005) was used to calculate the crystallization temperature using the following equation: T = {[ln (Ti)-a-c (X_Mg)³]/b}^0.333, where T is the temperature in degree Celsius, Ti is the number of atoms per formula unit on the basis of O = 22 atoms, X_Mg is Mg/(Mg + Fe), a = −2.3594, b = 4.6482 × 10⁻⁹, and c = −1.7283. The calculated crystallization temperatures of the granitic rocks related to the Li-bearing pegmatites ranged from 622°C to 675°C (with an average of 652°C) (Table 2). The calculated temperature in this study is probably comparable with the crystallization temperature of highly evolved peraluminous granitic melts (<650°C; London, 2008; Wu et al., 2020; Shen et al., 2022) and slightly lower than the crystallization temperature of normal S-type granite (795°C; Chappell and White, 1992). The plots of the differentiation trend of granitic magma (Bouseily and Sokkary, 1975) presented in Figure 8C together with the Nb/Ta and K/Rb (Figure 9A) and Ta vs. K/Rb (Figure 9B) plots for the relationship trends (Yin et al., 2019) reflect a highly differentiated granitic magma (Shen et al., 2022) that started from granitic rocks as the parental granite to the Li-bearing pegmatite, respectively. Therefore, the granitic rocks and the Li-bearing pegmatites were probably produced from the same parental granitic magma crystallized at a low crystallization temperature of about 652°C for the granitic rocks and at a lower temperature for the Li-bearing pegmatites, consistent with the differentiation of the granitic rocks to the Li-bearing pegmatites in the Koktolay deposits, China (Shen et al., 2022).

In terms of crystallization pressures, the Al-in-biotite geobarometer of Uchida et al. (2007) was applied to calculate the crystallization pressure using the following equation: P (kbar) = 3.03 × ^TAl–6.53 (±0.33), where ^TAl is the total content in biotite based on O = 22. The calculation pressures of the granitic rocks related to the Li-bearing pegmatites were 3.49–4.25 kbar, with an average of 3.87 kbar (Table 2). In addition, the calculated pressures were widely used to estimate the equilibration depth of plutonic rocks (e.g., Stein and Dietl, 2001; Helmy et al., 2004; Hossain et al., 2009; Fanka et al., 2016; 2018) using the following equation: P = ρgh, where P represents pressure (Gpa), ρ is the continental crust density (2.73 km/m³), g is the specific gravity (10.0 m/s²), and h represents depth (km). The intrusion depths estimated from the crystallization pressures of this study are presented in Table 2. The emplacement depths ranged from 13 to 15 km (depth_av. = 14 km), corresponding to the middle–upper crust level (Petrini and Podladchikov, 2000; Ramo, 2005; Fanka et al., 2018). Moreover, the emplacement depths were consistent with the calculated crystallization temperatures (622°C–675°C), which also indicate a middle–upper crust level (Peacock, 1993; Winter, 2001; Kelemen et al., 2003; Richards, 2003) with a geothermal gradient of about 20°C–40°C (Rothstein and Manning, 2003; Annen et al., 2006).

5.2 Tectonic implications

The tectonic setting of the study area (Phang Nga, southern Thailand) in the WBG as part of the SE Asia tin belt is implied by the combination of mineral chemistry and whole-rock geochemistry together with the findings of previous studies on the WBG. The geochemical plot of R1 (4Si-11(Na + K)-2(Fe + Ti)) and R2 (6Ca + 2 Mg + Al) diagrams (Figure 11A) suggest that the granitic rocks and the Li-bearing pegmatites relate to a syn-collision setting comparable with that of the WBG in Thailand reported by Nakapadungrat and Putthapiban (1992) and the WBG in Myanmar (Li et al., 2019). Moreover, the plots of the Yb + Ta versus Rb diagram (Figure 11B) and the plot of the Y + Nb and Rb diagram (Figure 11C) clearly indicate that these rocks are emplaced in syncollision granite. These diagrams are clearly consistent with the reported WBG in Myanmar (Li et al., 2019). Moreover, the mineral chemistry of biotite plotted in the MgO versus Al₂O₃ (Figure 10B) and FeOt–MgO–Al₂O₃ ternary (Figure 10C) diagrams also indicate a peraluminous magma related to a collision setting.

FIGURE 11

FIGURE 11. Plots of (A) R1 (4Si-11(Na + K)-2(Fe + Ti)) and R2 (6 Ca + 2 Mg + Al) tectonic discrimination diagrams (after Batchelor and Bowden, 1985); (B) Yb + Ta and Rb diagram (after Pearce et al., 1984); (C) Y + Nb and Rb diagram (after Pearce et al., 1984).

The LILE enrichment (including Rb, Ta, and K) in the chondrite-normalized spider diagram (Figure 7A) and the depletion of Ba, Nb, Ti, and Yb indicate an S-type-granite–related collision (Grosse et al., 2011). This collision is strongly supported by the magmatic event related to granitic rocks during the collision of the West Burma and Sibumasu terranes during the Cretaceous to Eocene (Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993; Watkinson et al., 2011; Li et al., 2019). The geochronology of granitic rocks reported in the Phang Nga area (e.g., Garson et al., 1975; Nakapadungrat et al., 1985; Chrusiri, 1989) includes Khao Lak (78 Ma; Nakapadungrat et al., 1985), Khao Khanim (65 Ma; Garson et al., 1975), Khao Kata Khwam (72 Ma; Charusiri, 1989), and Khao Po (52 Ma; Garson et al., 1975) and other areas along the WBG (Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993; Li et al., 2019).

Geochronological reports indicate collisional events during the Late Cretaceous and Paleocene to the Eocene (Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993; Li et al., 2019) related to S-type granite and related mineralization (Nakapadungrat and Maneenai, 1993; Li et al., 2019). The Late Cretaceous (88–65 Ma) (Nakapadungrat and Putthapiban, 1992; Charusiri et al., 1993; Li et al., 2019) probably reflect peraluminous S-type granites in the Khao Lak, Khao Kata Khwam, and Khao Khanim areas (Figure 1B) and related Sn–W mineralization (e.g., Nok Hook Sn mine in Khao Kata Khwam area; Figure 1B) (Nakapadungrat and Maneenai, 1993) of the WBG. Moreover, Paleocene to Eocene (60–50 Ma) magmatism (Garson et al., 1975; Charusiri et al., 1993) is also reported for the emplacement of granitic rocks in the WBG and the study area (e.g., the Khao Po area; Figure 1B) and related Sn–W mineralized pegmatites (Nakapadungrat and Maneenai, 1993), including the Li-bearing pegmatites of this study reflected by a cassiterite assemblage (Figure 5).

5.3 Lithium deposit and potential

The combined field occurrence, petrography, mineral chemistry, and geochemistry data indicate that the granitic rocks and related Li-bearing pegmatites in the Phang Nga, southern Thailand, have a close relationship, as reflected by the highly fractional crystallization trend in the plots of Ba–Rb–Sr (Figure 8C), Nb/Ta vs. K/Rb (Figure 9A), and Ta vs. K/Rb (Figure 9B). This probably indicates that the Li-bearing pegmatites are part of the late stages of the highly fractionated granitic magma in the study area (Yin et al., 2019). The close relationship of the Li-bearing pegmatites and highly fractionated granitic rocks, such as tourmaline–muscovite granite, was also mentioned in a study on the Nok Hook mine, Khao Kata Khwam area (Figure 1B) (Suwimonprecha, 1989; Nakapadungrat and Maneenai, 1993). This relationship is strongly consistent with those of highly fractionated granites and Li-bearing pegmatites in several areas, such as the Dahutang deposit, South China (Yin et al., 2019), Separation Lake area, Ontario, Canada (Tindle and Breaks, 2000), Gonçalo, central Portugal (Neiva and Ramos, 2010), and Maine, United States (Marchal et al., 2014), which can be linked link to the cogenetic granite and Li-pegmatite formation model (Cerny, 1991) from Li-barren granite to REE-Be–bearing pegmatite, REE-Be-Nb-Ta–bearing pegmatite, and Li-Cs-Be-Nb-Ta–bearing pegmatite (Cerny, 1991; Muller et al., 2022). Moreover, pegmatite formation related to granite according to Cerny (1991a), Cerny (1991b) for pegmatite migration from the rare-metal-barren granitic rocks to rare-metal-bearing pegmatite (Li, Cs, Sn, Nb, Ta enrichment) is consistent with the reported pegmatites in the Phang Nga–Phuket area, southern Thailand, classified into Sn–Ta–Nb–mica free pegmatite and Sn–Li–F–W–Ta–Nb–REE–mica–rich pegmatite (Gocht and Pluhar, 1982). The Li-bearing pegmatites exposed in the study area (Figure 1B) are well-defined as Sn–W mineralized granites in the SE Asia tin belt (Cobbing et al., 1986; Nakapadungrat and Putthapiban, 1992; Nakapadungrat and Maneenai, 1993). The Sn–W deposits related to these granitic rocks are mainly discovered in endogenous quartz–cassiterite–wolframite vein swarms, argillic disseminations, and lepidolite pegmatite types (Nakapadungrat and Maneenai, 1993). In this study, lepidolite pegmatite, one of the Sn–W sources in Thailand, is defined as the Li-bearing pegmatites in the Khao Po area (Figure 1B), considered as one of the large unzoned lepidolite pegmatites in the world (Garson et al., 1975).

For the Li grade, the Li content of the Li-bearing pegmatites was 0.43% Li (0.17%–0.65% Li) in this study, comparable with those of other Li-bearing pegmatites in the world (Table 7; Figure 12). According to the overall Li deposits in the world (Table 7; Figure 12), high Li grades are found in spodumene pegmatite deposits, such as the Tastyq deposits in Russia (1.86% Li; Kuznetsova and Prokof’ev, 2009), the Greenbushes deposits in Australia (1.05% Li; Groves et al., 2022), the Kalba deposits in Kazakhstan (0.95% Li; Oitseva et al., 2017; Khromykh et al., 2020; D’yachkov et al., 2021; Zimanovskaya et al., 2022) and the South Fulugou deposits in China (0.88% Li; Gao et al., 2020). These are followed by spodumene, lepidolite, and petalite pegmatite deposits, such as the Rubicon and Helikon deposits in Namibia (1.40% Li; Kesler, 1978) and the Koktokay no. 3 deposits in China (1.25% Li; Wang et al., 2021). In addition, amblygonite pegmatite deposits are also high-Li-grade sources, as reported in the Jiangxi deposits in China (0.77% Li; Wang et al., 2020). For the Li-bearing pegmatites in this study, the Li grade is probably the same as those of the well-known lepidolite pegmatite deposits in the world, such as those in La Vi, Quang Ngai, Vietnam (0.51% Li; Hien-Dinh et al., 2017), Zavitinskoye, Russia (0.37% Li; Seltmann et al., 2010; Melentiev et al., 2022), and Alakha, Russia (0.46% Li; Annikova et al., 2016) (Table 7; Figure 12). Moreover, the Li grade in the lepidolite type of this study is also slightly higher than those of some well-known spodumene pegmatite deposits, such as the Kalaka deposit in China (0.43% Li; Teng and Gao, 2019), the Quebec Lithium in Canada (0.28% Li; Canada Lithium Corp., 2012), and the Kamativi belt in Zimbabwe (0.23% Li; Sinclair, 1996). For the Li grade in spodumene and petalite pegmatite deposits, some deposits have lower grades than that in this study, such as the Fregeneda–Almendra deposit in Portugal (0.3% Li; EDICOES, 1998) and the Goltzovoe deposit in Russia (0.37% Li; Seltmann et al., 2010; Vladimirov et al., 2012) (Table 7; Figure 12).

TABLE 7

TABLE 7. Overview of the Li grade from Li-pegmatites in the main lithium deposits in the world.

FIGURE 12

FIGURE 12. Overview of the Li grade of the Li-bearing pegmatites in the Phang Nga area, southern Thailand, and lithium deposits in the world. The details of the Li grades of the lithium deposits are presented in Table 7.

6 Conclusion

The Li-bearing pegmatites and related granitic rocks in the Phang Nga area, southern Thailand, can elucidate geological processes for petrogenesis, tectonic implications, and Li-mineralization together with the Li potential in Thailand as follows.

1. The Li-bearing pegmatites are characterized by lepidolite pegmatite and relate to the granitic rocks including porphyritic biotite–muscovite granite, biotite granite, and muscovite–tourmaline granite.

2. The geochemical characteristics of both the Li-bearing pegmatites and related granitic rocks indicate a peraluminous S-type granite affinity.

3. The enrichment of LILEs (e.g., Rb and K) and the depletion of Ba, Nb, and Ti together with the slightly high LREE contents indicate that the studied rocks were emplaced from a collisional setting.

4. The Li-bearing pegmatites that evolved from highly fractionated S-type granitic rocks are comparable with the WBG in Thailand, which took place during the West Burma and Sibumasu collision during the Cretaceous to Eocene.

5. The crystallization P–T conditions of the granitic rocks related to Li-bearing pegmatites were 3.49–4.25 kbar and 622°C–675°C, respectively, with an emplacement depth of 13–15 km.

6. The Li-bearing pegmatites, being among the Sn–W pegmatite deposits in southern Thailand, SE Asia tin belt, evolved from granitic rocks.

7. The Li-bearing pegmatites contained an average Li grade of 0.43% Li (0.17%–0.65% Li), which is similar to those of several well-known Li-bearing pegmatites in the world.

Data availability statement

The original contributions presented in the study are included in the article/supplementary material, further inquiries can be directed to the corresponding author.

Author contributions

AF contributed to the research initiation, field investigation, sample collection, laboratory studies, data collection, discussion, manuscript preparation, and revision. JT contributed to the laboratory studies and data collection. All authors contributed to the article and approved the submitted version.

Funding

This research was funded by the Thailand Science Research and Innovation Fund Chulalongkorn University [CU_FFB65_ind (3)_108_23_38].

Acknowledgments

The authors would like to acknowledge the Department of Geology, Faculty of Science, Chulalongkorn University, for the laboratory studies, the Pan Asia Metal (Thailand) Company Limited, and Mr. Sakda Thorraneethip for the support regarding the samples and accessible study site. The authors would like to thank the Department of Primary Industries and Mines and Miss Alissara Prasertying for the valuable discussions.

Conflict of interest

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Publisher’s note

All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.

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