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Article

Titanite Spectroscopy and In Situ LA-ICP-MS U–Pb Geochronology of Mogok, Myanmar

by
Jialu Gu
1,
Bo Xu
2,*,
Shu Li
2 and
Yi Zhao
1
1
School of Earth Sciences and Resources, China University of Geosciences Beijing, 29 Xueyuan Road, Haidian District, Beijing 100083, China
2
School of Gemmology, China University of Geosciences Beijing, 29 Xueyuan Road, Haidian District, Beijing 100083, China
*
Author to whom correspondence should be addressed.
Crystals 2022, 12(8), 1050; https://doi.org/10.3390/cryst12081050
Submission received: 7 June 2022 / Revised: 12 July 2022 / Accepted: 18 July 2022 / Published: 28 July 2022
(This article belongs to the Special Issue Women in Mineralogical Crystallography and Biomineralization)
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Abstract

:
With the development of mineral testing technology and ore deposit geochemistry, titanite has become a hot topic in the study of accessory minerals. Two large-grained titanite crystals from Mogok, Myanmar, were used for a detailed study. In this study, the standard gemmological properties and spectral characteristics of titanite crystals were obtained by Fourier transform in-frared, micro ultraviolet-visible-near-infrared and Raman spectroscopy, respectively, which pro-vide a full set of data. Mineral major and trace elements were analysed using Electron-Probe Mi-croAnalysis (EPMA) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The purpose of this study is to report spectral characteristics and major and trace elements of Mogok, Myanmar, in order to find new potential titanite standard samples. The two titanite crystals have similar major element compositions, and both grains have relatively low Al content (0.011–0.014 apfu) and Al/Fe ratios (0.157–0.222), but high Fe content (0.063–0.079 apfu). The two titanite crystals have similar chondrite-normalised rare earth element (REE) patterns with significantly Light Rare Earth Element (LREE) (La–Gd) enrichment and deletion of Heavy Rare Earth Element (HREE) (Tb–Lu). The 238U/206Pb ages of the two titanite samples are 43.5 ± 5.8 Ma and 34.0 ± 4.2 Ma, respectively. Generally, magmatic titanite has a low Al/Fe ratio, metamorphic and hydrothermal titanite crystals have extremely low Th/U ratios close to zero, with flat chondrite-normalised REE patterns or depletions in light REEs relative to heavy REEs. Different genetic types of titanite can be distinguished by the characteristics of major and trace elements. Combined chemical features such as REE differentiation, Al/Fe and Th/U ratios with formation temperature, the analysed titanite samples are considered magmatic-hydrothermal titanites. Their 238U/206Pb ages may indicate a potential stage of magmatic hydrothermal conversion.

1. Introduction

Titanite (CaTiSiO5) is a common accessory mineral in various geological environments, including calc-alkalic plutonic rocks [1] (particularly I-type granites), metamorphic rocks [2] and hydrothermal products such as skarns [3]. The crystal structure of titanite is connected by SiO4 tetrahedron and TiO6 octahedron, and Ca2+ cations exist in the lattice with 7 coordination number [4]. The Ca2+ site can accommodate all large cations, including Y, rare earth elements (REEs), U, Th, Mn and Pb. These elements can indicate magmatic or hydrothermal evolution, which makes titanite a useful indicator of magma and/or fluid characteristics [5,6,7,8,9]. In addition, titanite is a good U–Th–Pb radiometric chronometer [10,11,12,13,14,15].
Recently, laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) instrumentation has been widely used to determine the in situ major trace element and isotopic compositions of titanites [1,14,16,17,18,19,20,21,22,23,24,25,26,27,28]. However, the lack of matrix matching standard materials is a significant barrier to the widespread adoption of this technology [29].
In this study, in situ major trace element compositions of two titanite single crystals in Mogok, Myanmar, have been studied through electron probe microanalysis (EPMA) and LA-MC-ICP-MS. Spectral features are obtained and compared with the calibration spectra in the RRUFF database [30]. Our aims were to establish potential young titanite standard samples and reveal the genesis of titanite.

2. Geological Setting

The Mogok area in Myanmar is a world-famous gem-producing area (Figure 1a) [31,32,33], which, extending in the north–south direction, is primarily composed of metamorphic rocks, mixed rocks and late Mesozoic granitic intrusive rocks (Figure 1b) [34,35,36]. The Mogok metamorphic zone was formed by the northward subduction of the Indian plate in 71 Ma and the collision between the Eurasian and Indian plate at approximately 50 Ma [37]. Previous studies show that deep crustal melting occurred with ages ranging from 20–15 Ma in this region, and this process was accompanied by granite intrusion. Precious age determinations indicate that metamorphism along the MMB occurred during 68–21 Ma with peak between the Middle Eocene and the early Oligocene [38,39,40,41]. The Mogok titanite samples can meet the requirement of younger standard samples.

3. Materials and Methods

Two Mogok titanite crystals (MG-5 and MG-6) were examined using standard gemmological techniques. The specific gravity (SG) of the samples was obtained using a hydrostatic weighing method. Spectroscopy tests for the samples were conducted at the Gemmological Research Laboratory of China University of Geosciences (Beijing) to obtain their spectral properties.
Infrared reflection spectra were obtained using the Tensor 27 Fourier transform infrared spectrometer, with a test spectral range of 2000–400 cm−1. An ultraviolet–visible (UV–Vis) spectroscopy test was conducted using a UV-3600 UV–Vis spectrophotometer (Shimadzu Corporation, Kyoto, Japan) to measure the absorption value with the following setting: slit width: 2.0 nm; time constant: 0.1 s; wavelength range (nm): 200.00–900.00; scanning speed: high speed; sampling interval: 0.5 A Horiba HR Evolution-type micro-confocal laser Raman spectrometer (Horiba, Ltd., Kyoto, Japan), which was used to conduct a Raman spectroscopy test with the following setting: laser source: 532 nm; slit width: 100 µm; grating: 600 gr/mm; scan time: 4 s; integration times: 3; ICS correction range: 100–2000 cm−1.
The titanite grains were mounted in epoxy, polished and examined using BSE images to select suitable targets for in situ analysis. The TESCAN field emission scanning electron microscope (MIRA 3LMH) was used to capture BSE images with the following setting: acceleration voltage: 7 kV; absorption current: 1.2 Na; scan time: 80 s.
Electron-Probe MicroAnalysis (EPMA) was conducted in the Laboratory of EPMA, China University of Geosciences (Beijing) with the following setting: acceleration voltage: 15 kV; electic current: 10 Na; beam spot diameter: 1 μm.
An Agilent 7900 Q-ICP-MS instrument coupled to a 193-nm ArF excimer laser ablation system was used to determine trace element compositions and U–Pb ages in the Laboratory of Mineral Laser Microzone Analysis, China University of Geosciences (Beijing). The Ontario standard was used for calibration, and the MKED1 standard was used as a standard reference.

4. Results

4.1. Visual Appearance and Gemmological Properties

The titanite samples are dark brown and translucent with medium cleavage and greasy lustre (Figure 2a,b). The MG-6 sample has crystal plane steps. Triangular etching on the crystal surface can also be observed. Some weak areas of MG-5 sample are dissolved into small pits by corrosion, forming regular shaped pits on the crystal surface (Figure 3).
The SG values of MG-5 and MG-6 are 3.51 and 3.56, respectively. Since the refractive index of titanite varied between 1.89 and 2.02, the index of refraction exceeded the refractometer’s value and could not be measured. The titanite samples do not change colour under a Chelsea colour filter. The titanite samples have a rare earth spectrum, as seen through spectroscopes, with multiple fine absorption lines and 580 nm double lines.

4.2. Spectral Characteristics

4.2.1. Fourier Transform Infrared Spectrum

The MG-5 and MG-6 samples have 432.04, 565.12, 725.21 and 939.30 cm−1 characteristic absorption peaks in the fingerprint region (Figure 4). The position of 420–440 cm−1 is the vibration band of TiO6 octahedron. The position of 550–570 cm−1 is the in-plane bending vibration band of SiO44− and Si–O bond; the position of 730 cm−1 is the stretching vibration band of Si–Si bond; and 800–1000 cm−1 is the position of the asymmetric stretching vibration band of the Si–O bond and triple simplification of SiO44−.

4.2.2. UV–Vis Spectrum

The colour origin of the titanite samples was analysed by UV–Vis spectra. MG-5 and MG-6 are brown titanite samples. The UV–Vis spectrum of MG-6 has an obvious absorption peak centred at 565 nm in the range of 550–600 nm, weak absorption peaks at 700–800 nm and a wide and slow absorption band at 220–300 nm (Figure 5). The yellow–green absorption band with 565 nm as the centre in the range of 550–600 nm is caused by the electron transition between Ti4+ and Fe4+.

4.2.3. Raman Spectrum

The following characteristic peaks of the titanite samples are found within the range of 200–2000 cm−1: an absorption peak at 242 cm−1 caused by the translational vibration of [SiO4]4+, an absorption peak at 316 cm−1 caused by the rotational vibration of [SiO4]4+, an absorption peak at 467 cm−1 caused by the bending vibration of [SiO4]4+, a strong absorption peak at 605 cm−1 and an absorption peak at 854 cm−1 both caused by the stretching vibration of [SiO4]4+ (Figure 6).

4.3. Major and Trace Elements

Major element compositions of the titanite samples are presented in Table A1. The two titanite crystals have similar major element compositions (CaO 25.93–27.61 wt%, TiO2 36.67–38.25 wt% and SiO2 29.50–30.47 wt%). Both grains show relatively low Al contents (0.15–0.18 apfu) and low Al/Fe ratios (0.07–0.08), but high Fe content (1.77–2.22 apfu).
Forty analyses were conducted on the two titanite grains by LA-MC-ICP-MS. The trace element compositions are listed in Table A2 and Table A3 Titanite is an essential sink of the entire rock [43], Nb, Ta, Th and U (Nb: 203.6–846.8 ppm; Ta: 2.181–19.23 ppm; Th: 0.892–3.412 ppm; U: 0.6871–3 ppm), and is commonly enriched with LREEs. The two titanite crystals have similar chondrite-normalised REE patterns with moderate REE concentrations (REE: 1896–2857 ppm). They have significantly LREE enrichment and deletion of HREE (LREE/HREE: 6.55–10.39) (Figure 7a,b).
Previous studies have demonstrated that REEs replace Ca and Zr in titanite and high field strength elements such as Nd will displace Ti (Al, Fe) in the titanite lattice. The positive correlation of Nd–Zr in the samples shows that the two elements exhibit the same substitution characteristics (Figure 8).

4.4. Titanite U–Pb Ages

The titanite ages with common Pb [45] were calculated using the weighted mean of the 207Pb-corrected ages and the Tera–Wasserberg (TW) Concordia intercept age anchored through common Pb. Titanite U–Pb isotope results and ages are listed in Table A4 and Table A5. Overall 20 LA-ICP-MS analyses of each titanite sample were performed in different sections (Figure 9a,b). On the TW diagram, the common Pb-uncorrected data of MG-5 define a linear array, yielding a lower-intercept age of 44 ± 17 Ma (n = 20, 2σ, MSWD = 0.63) and a y-intercept of initial 207Pb/206Pb of 0.848 (Figure 10a,b). The common Pb-uncorrected data of MG-6 define a linear array, yielding a lower-intercept age of 34 ± 14 Ma (n = 20, 2σ, MSWD = 0.75) and a y-intercept of initial 207Pb/206Pb of 0.843 (Figure 10c,d). On the basis of this common Pb composition, a common Pb correction was performed using the method of fitting 207Pb/206Pbc. All analyses of MG-5 yielded a weighted average 206Pb/238U age of 43.5 ± 5.8 Ma (n = 20, 2σ, MSWD = 0.57), and those of MG-6 yielded a weighted average 206Pb/238U age of 34.0 ± 4.2 Ma (n = 20, 2σ, MSWD = 0.65).

5. Discussion

5.1. Comparision with RRUFF Database

The RRUFF database contains eight titanite standard samples from Brazil, the USA, Pakistan, Canada and Mexico. R050114 with yellowish-brown fragments from Pakistan was chosen for comparison. Fourier transform infrared spectra of titanite R050114 have 416.5, 559.3 and 848.5 cm−1 characteristic absorption peaks in the fingerprint region (Figure 11), indicating that these characteristic peaks occur in the range of peaks caused by different bonds; however, the positions of these characteristic peaks are different. Raman spectra of titanite R050114 have 252, 316, 423, 605, 873, 880 and 1177cm−1 characteristic peaks (Figure 12). The characteristic peak at 605 cm−1 is consistent with that of the analysed samples MG-5 and MG-6.
Raman spectra of common titanite reference samples are shown in Figure 13 [46]. All samples exhibited characteristic peaks near 255, 316, 342 and 850 cm−1, similar to analysed samples MG-5 and MG-6. The Raman spectra of the YQ82, BMB108 and MKED1 samples are similar, with characteristic peaks at 162, 231, 250, 540, 606 and 911 cm−1. The Raman spectra of the BLR-1, Ontario and OLT1 titanite samples are similar, with characteristic peaks at 573 and 650 cm−1. Bands occurred near 575 and 611 cm−1 in the Khan titanite, rendering this an intermediate sample between the above two groups.

5.2. Formation Temperature of Titanite

The Al2O3 content of titanite was used to estimate the formation pressure of titanite [47], and a pressure-dependent Zr in titanite geothermometer [48] was used to estimate the formation temperature of titanite. High temperatures enable more Zr to enter the structure of titanite. The Al2O3 content of titanite increases with pressure (P) according to the following: P (in MPa) = 101.66 × Al2O3 in titanite (in wt%) + 59.013 (R2 = 0.83). The pressures of MG-5 were estimated to be 88.39–92.15 Mpa (average = 90.14 Mpa, n = 10), and those of MG-6 were estimated to be 86.56–94.80 Mpa (average = 92.04 Mpa, n = 10). According to the studies by Hayden et al. (2008), αTiO2 = αSiO2 = 1. The Zr in titanite temperatures of MG-5 were estimated to be 466.5–467.1 °C (average = 466.79 °C, n = 20), and those of MG-6 were estimated to be 466.6–467.2 °C (average = 466.98 °C, n = 20).
Along with the weighted average 206Pb/238U ages of these two samples, the calculated temperature range is consistent with the geological background of their ages (Figure 14). However, there is a significant difference in the calculation results of temperature, which may be caused by the inaccuracy of cogenetic minerals in the calculation formula.

5.3. Genesis of Analysed Titanite

The classification of the genetic types of titanite requires comprehensive consideration of the major and trace elements. In general, magmatic titanite has a low Al/Fe ratio, whereas metamorphic titanite, including hydrothermal titanite, has a high Al/Fe ratio. Both grains have been plotted in the igneous field of Kowallis et al. (1997) (Figure 15).
Metamorphic and hydrothermal titanite crystals commonly have extremely low Th/U ratios close to zero, along with flat chondrite-normalised REE patterns or depletions in light REEs relative to heavy REEs. In contrast, two analysed titanite grains show heavy light REE (La–Gd) to weak heavy REEs (Tb–Lu) differentiation [49].
The Th/U ratio is also an indicator of the origin of titanite. In general, hydrothermal titanite has a lower ratio of Th/U (mostly < 1) than magmatic titanite. In this study, the two samples yielded a similar ratio of Th/U (MG-5: 1.30–1.92; average: 1.61; MG-6: 1.08–1.57; average: 1.37). Thus, titanite that crystallises under high-temperature hydrothermal conditions would also have the characteristics of magmatic titanite Th/U > 1. To discriminate the origin of titanite using a single ratio of Th/U indicator is inaccurate.
However, considering that the calculated formation temperatures were lower and consistent with that of the hydrothermally modified titanite, EMPA data have shown low concentrations of La in the analysed titanite samples (Table A5), which is commonly related to late hydrothermal activity [50], and our samples can be recognized as products of magmatic hydrothermal conversion [27,51,52].
Analysed titanite samples are interpreted as magmatic-hydrothermal.

5.4. Tectonic Evolutionary History

Themelis (2007) divides the geological evolution of Mogok into six important stages: deposit, continental drift, plate convergence, continental plate collision, post-collisional extension, lifting and erosion (Figure 14). The continental plate collision occurred between 50 Ma and 30 Ma, and the Northeastern Indian plate subducted obliquely into the Eastern Asian plate. Continental collisions and the drift and collision of other microland masses continue today. The weighted average 206Pb/238U ages of the two titanite crystals are determined as 43.5 ± 5.8 Ma and 34.0 ± 4.2 Ma, respectively, limiting the formation age of titanite in the period of continental plate collision.

6. Conclusions

We have investigated the chemical composition, structure and genesis of titanite crystals from Mogok, Myanmar, through Fourier infrared, UV–Vis and Raman spectroscopy, EPMA and LA-MC-ICP-MS. These results are used to assess the potential of titanite as reference material for micro-analytical dating. In this paper, the analysis and summary of mineralogical and spectral characteristics based on the samples provide characteristics of a new production area of titanite not found in the RURFF database. According to U–Pb dating analysis, age data have a high concordant degree with weighted average 206Pb/238U ages 43.5 ± 5.8 Ma and 34.0 ± 4.2 Ma, respectively, which indicates the potential stage of magmatic hydrothermal conversion. Thus, these two grains can be used as potential stand samples for U–Pb dating analysis. Major and trace element analyses of titanites can be used to discuss the genetic type and explore their geological background.

Author Contributions

Writing and experimental data processing, J.G.; writing—review and editing, B.X., S.L. and Y.Z.; methodology, B.X.; software, J.G. and S.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by National Key Technologies R&D Program (2020YFA0714800, 2019YFA0708602); National Natural Science Foundation of China (42073038, 41803045), Young Talent Support Project of CAST, the Fundamental Research Funds for the Central Universities (Grant no. 265QZ2021012), and IGCP-662.

Data Availability Statement

The data presented in this study are available within this article.

Acknowledgments

We thank the editor and reviewers for constructive comments which helped in improving our paper. This is the 8th contribution of B.X. for the National Mineral Rock and Fossil Specimens Resource Center.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table
Table A1. Chemical compositions with the structural formulas of analysed titanite from Mogok analysed by EMPA (wt.%).
Table A1. Chemical compositions with the structural formulas of analysed titanite from Mogok analysed by EMPA (wt.%).
MG-5-1MG-5-2MG-5-3MG-5-4MG-5-5MG-5-6MG-5-7MG-5-8MG-5-9MG-5-10MG-6-1MG-6-2MG-6-3MG-6-4MG-6-5MG-6-6MG-6-7MG-6-8MG-6-9MG-6-10
SiO229.90430.07129.68629.50430.03330.12529.55529.95429.96230.06930.21930.09430.17729.88929.77930.4729.61929.73329.97930.032
TiO237.14736.92938.24638.01637.13338.15337.69538.01637.37137.32437.03736.66837.17637.66237.97737.41737.95137.22437.09937.497
Al2O30.3080.3030.3260.3120.3010.3080.310.3040.2890.3010.2770.3430.3310.3480.3420.3520.2710.3380.3340.313
FeO2.4882.3222.5332.5872.2992.5672.4562.3532.4852.3082.5542.8112.8252.7222.3642.2832.4052.8552.6692.547
MnO0.0440.0140.039000000.0040.0920.01200.0160.0140.0250.0450.143000.131
MgO0.0290.0080.0420.00900.010.0120.0080.0190.0290.0360.0170.0250.0210.0090.0240.0130.0370.0280.005
CaO26.83927.07526.36326.55926.74826.47727.11926.45926.51926.57826.99427.61226.70727.06526.55326.37626.58326.25925.92826.975
Na2O0.4310.440.5520.5180.4410.430.3880.4220.4250.440.3810.3430.4130.3690.5990.5110.3930.4560.5910.345
K2O0.01300.0070.0090.00800.0140.0050.0020.0180.0010.0070.0120.0200.0140.0060.0080.020.002
F0.1790.1310.1510.130.3770.0970.1930.1720.220.2130.2480.3150.0010.0010.140.210.0130.3960.0490.055
Cr2O30.0080000.0360000.0160.08100.0280.007000.05500.02500
NiO0.0350.00900.0670.0780.0570.0510.002000.0160000.0190.06600.0280.0790.073
V2O50.3850.4850.5220.4220.3580.3330.3830.4770.40.3630.5210.4470.4880.3770.3710.520.3320.5220.4150.458
La2O300.03300.06400000.104000.0070000.1410.0070.09700
Ce2O30.8160.91.1931.4140.9180.7050.9180.9970.8911.0920.7680.9480.8330.9851.1951.0970.9580.7361.0891.062
Total98.62798.71999.6699.61298.7399.2699.09599.16998.70998.90699.06699.64299.0199.47299.37399.5898.69698.71498.2899.495
Cations (apfu)
Si1.003 1.0080.9880.986 1.003 1.002 0.988 0.998 1.003 1.005 1.007 1.001 1.010 0.998 0.993 1.011 0.995 0.995 1.0111.002
Al0.012 0.0120.0130.012 0.012 0.012 0.012 0.012 0.011 0.012 0.011 0.013 0.013 0.014 0.013 0.014 0.011 0.013 0.0130.012
Ti0.937 0.9310.9570.955 0.933 0.955 0.948 0.953 0.941 0.938 0.929 0.917 0.936 0.946 0.953 0.934 0.959 0.937 0.9410.941
Fe0.070 0.0650.0700.072 0.064 0.071 0.069 0.066 0.070 0.065 0.071 0.078 0.079 0.076 0.066 0.063 0.068 0.080 0.0750.071
Mn0.001 0.0000.0010.000 0.000 0.000 0.000 0.000 0.000 0.003 0.000 0.000 0.000 0.000 0.001 0.0010.0040.000 0.0000.004
Mg0.001 0.0000.0020.000 0.000 0.000 0.001 0.000 0.001 0.001 0.002 0.001 0.001 0.001 0.0000.0010.0010.002 0.0010.000
Ca0.964 0.9720.9400.951 0.957 0.944 0.972 0.945 0.951 0.952 0.964 0.984 0.958 0.968 0.949 0.938 0.957 0.941 0.9360.964
Na0.028 0.0290.0360.034 0.029 0.028 0.025 0.027 0.028 0.029 0.025 0.022 0.027 0.024 0.039 0.033 0.026 0.030 0.0390.022
K0.001 0.0000.0000.000 0.000 0.000 0.001 0.000 0.000 0.001 0.000 0.000 0.001 0.001 0.000 0.001 0.000 0.000 0.0010.000
F0.019 0.0140.0160.014 0.040 0.010 0.020 0.018 0.023 0.0230.0260.0330.0000.000 0.0150.0220.0010.0420.0050.006
Cr0.000 0.0000.0000.000 0.001 0.000 0.000 0.000 0.000 0.0020.0000.0010.0000.0000.0000.0010.0000.0010.0000.000
Ni0.001 0.0000.0000.002 0.002 0.002 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.002 0.000 0.001 0.0020.002
V0.010 0.0130.0140.011 0.010 0.009 0.010 0.013 0.011 0.010 0.014 0.012 0.013 0.010 0.010 0.014 0.009 0.014 0.0110.012
La0.000 0.0000.0000.001 0.000 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.000 0.001 0.0000.000
Ce0.010 0.0110.0150.017 0.011 0.009 0.011 0.012 0.011 0.013 0.009 0.012 0.010 0.012 0.015 0.013 0.012 0.009 0.0130.013
Table
Table A2. Rare earth element content (ppm) of MG-5.
Table A2. Rare earth element content (ppm) of MG-5.
LaCePrNdSmEuGdTbDyHoErTmYbLu
MG-5-166.78517.4129.8748.5232.654.66132.714.2658.067.21514.681.6488.940.784
MG-5-267.10522.8131.1758.9237.655.37135.714.4659.127.35914.941.6999.230.8233
MG-5-379.89607.7153.2889.1284.867.84166.318.6778.319.80620.552.38613.091.138
MG-5-492.81703.2171.296128765.01155.915.8361.897.63615.641.89911.991.252
MG-5-568.72531.4133.7773.9240.756.22135.814.5059.567.35514.831.6939.330.8161
MG-5-666.88515.4129.9753.2235.654.84134.114.2458.147.23614.741.6689.100.811
MG-5-765.41508.4127.9737.4229.553.79130.313.9157.47.08114.291.6158.740.760
MG-5-867.35519.0130.2758.4235.455.19135.214.3558.747.28914.821.679.130.803
MG-5-967.61519.7130.3757.1236.355.28134.614.3659.147.29414.791.6639.110.794
MG-5-1070.98544.2136.0791.1245.157.46140.314.8260.637.49515.271.7329.550.840
MG-5-1193.26674.7162.5909.4267.161.19145.515.1461.637.50615.041.7079.350.811
MG-5-1280.34609.1153.9896.5285.668.46167.718.5879.419.86520.672.38913.221.149
MG-5-1363.76487.2122.8715.7223.852.57127.813.6657.277.03314.041.5858.350.716
MG-5-1459.66502.9133.4790.6250.958.18140.914.6660.327.33414.901.7079.7250.858
MG-5-1590.41691.7174.71009.9315.274.28180.919.6382.8410.17121.082.40013.21.147
MG-5-1666.65514.6129.7754.0234.754.88134.014.1758.947.21014.701.6569.020.7811
MG-5-1769.77532.1133.5770.0237.255.29135.014.1358.257.10414.561.6589.190.824
MG-5-1867.59524.5131.8768.8238.955.65135.614.3059.277.29014.801.6879.280.819
MG-5-1999.32715.4171.3957.5282.465.35155.416.1866.197.97916.021.7829.560.817
MG-5-2067.54523.6132.1771.0240.055.87137.214.4059.437.31614.871.6899.2660.816
Table
Table A3. Rare earth element content (ppm) of MG-6.
Table A3. Rare earth element content (ppm) of MG-6.
LaCePrNdSmEuGdTbDyHoErTmYbLu
MG-6-164.07522.5134.4785.6247.756.53138.213.9555.576.88114.221.75311.381.210
MG-6-258.69484.0125.8748.5241.355.56137.014.0557.237.09314.851.84511.791.217
MG-6-364.10543.8144.7885.8300.471.00180.819.2379.709.98021.352.66617.21.819
MG-6-459.31486.6126.0743.1239.855.22136.013.9056.397.06514.761.81711.691.223
MG-6-5102.70761.7182.3997.2283.461.75144.413.9453.836.42012.961.5639.710.982
MG-6-699.27729.9174.0958.5273.759.93140.713.6953.406.37812.871.5349.430.922
MG-6-765.05531.1135.3798.2251.657.47140.814.3357.057.06614.631.78211.381.182
MG-6-864.43541.9143.1873.7297.069.64177.018.7377.459.67520.752.55716.611.749
MG-6-9101.66763.8185.21039.0307.569.15164.616.7267.208.23516.962.02212.181.167
MG-6-1061.39498.6128.6759.1241.255.76137.214.1357.807.27415.011.81111.071.112
MG-6-11101.31761.5185.21034.5307.769.18164.616.8467.668.28017.042.03112.131.184
MG-6-1259.55484.7124.2731.5230.252.96127.713.1153.246.63313.681.65410.060.988
MG-6-1360.03491.6125.8738.4233.853.56129.613.1452.686.51613.441.6510.521.080
MG-6-1465.50550.3145.4890.2303.771.89183.219.5580.8110.21521.872.71517.391.836
MG-6-15100.36769.8188.81067.0321.572.25171.417.368.598.30817.172.12413.811.43
MG-6-16101.48778.1191.11079.0326.073.59175.417.8771.098.62917.822.20814.061.454
MG-6-1763.18526.9138.6841.2280.565.76166.217.4772.079.01618.812.34515.031.573
MG-6-1859.89486.4125.1737.0232.853.51129.413.2353.716.65213.791.66010.150.999
MG-6-1959.54492.9127.2754.7239.455.06133.613.6554.926.77914.201.76511.381.191
MG-6-2098.19722.4173.6971.2280.662.69147.814.6658.186.99414.161.6629.850.935
Table
Table A4. U–Pb dating data of MG-5.
Table A4. U–Pb dating data of MG-5.
PointIsotopic Ratios207Pb Corrected Age
238U/206Pb1σ207Pb/206Pb1σ207Pb/235U1σ206Pb/238U1σ206Pb/238U±σ
Mg-5-014.2105261.4315790.8330.01427.180.380.23750.003428.5929132.64977
Mg-5-024.089981.3905930.8220.01427.670.460.24450.003450.9610833.38145
Mg-5-038.5034011.3605440.8100.01413.040.150.11760.001635.8530616.00427
Mg-5-045.5340341.3835090.8170.01220.280.250.18070.002544.9206122.32279
Mg-5-055.2742622.1624470.8040.01520.820.410.18960.004166.8209626.94427
Mg-5-064.2319091.7350830.8210.01626.670.370.23630.004151.1457735.41699
Mg-5-073.9968031.5187850.8290.01528.360.480.25020.003838.1349735.96065
Mg-5-084.1067761.3141680.8210.01327.530.340.24350.003252.6998231.64773
Mg-5-094.1528241.4950170.8240.01327.250.400.24080.003646.340531.3618
Mg-5-103.8051751.522070.8210.01329.620.400.26280.00456.8642934.14393
Mg-5-115.4229931.2472890.8200.01420.760.260.18440.002341.4119625.17982
Mg-5-128.5910651.374570.8040.01412.850.150.11640.001641.0790315.79509
Mg-5-133.5587191.4946620.8250.01531.840.470.2810.004251.8085140.26918
Mg-5-143.6403351.7109570.8350.01431.540.510.27470.004728.6618337.79578
Mg-5-158.8339221.5017670.7980.01412.440.160.11320.001745.38715.32068
Mg-5-164.2607581.5338730.8140.01326.290.370.23470.003663.9263830.37737
Mg-5-174.4503781.6911440.8260.01425.570.340.22470.003839.6527430.76729
Mg-5-184.3177891.5544040.8360.01526.620.410.23160.003622.3135633.43115
Mg-5-195.1046451.3272080.8240.01422.270.300.19590.002637.7170626.80495
Mg-5-204.2498941.5299620.8270.01526.890.360.23530.003639.6359333.78872
Table
Table A5. U–Pb dating data of MG-6.
Table A5. U–Pb dating data of MG-6.
PointIsotopic Ratios207Pb Corrected Age
238U/206Pb1σ207Pb/206Pb1σ207Pb/235U1σ206Pb/238U1σ206Pb/238U±σ
Mg-6-014.8923681.3209390.8170.01323.100.320.20440.002742.8890025.15391
Mg-6-025.6980061.5384620.8220.01419.860.240.17550.002729.7639722.87941
Mg-6-037.4460161.3402830.8180.01415.140.180.13430.001827.1188717.49094
Mg-6-044.9407111.3339920.8120.01222.710.290.20240.002750.6158123.47389
Mg-6-054.9019611.4705880.8260.01123.170.250.2040.00328.0100622.50032
Mg-6-062.845762.4758110.8230.00839.901.000.35140.008757.8070432.76922
Mg-6-074.8638131.2159530.8240.01323.330.330.20560.002531.5449625.39222
Mg-6-087.363771.2518410.8250.01415.460.230.13580.001719.7514217.73803
Mg-6-098.5910651.0309280.8020.00912.910.140.11640.001238.4300311.50474
Mg-6-104.3917441.4492750.8280.01325.920.320.22770.003327.5866628.17365
Mg-6-118.8261251.1473960.8050.01112.620.130.11330.001334.7610212.3742
Mg-6-124.4130631.5004410.8270.01425.830.340.22660.003429.2809729.58775
Mg-6-134.8638131.7996110.8320.01423.590.380.20560.003718.2757926.91974
Mg-6-147.6511091.4537110.8110.01414.600.180.13070.001933.7697216.97535
Mg-6-157.1022731.56250.8090.01215.730.300.14080.002238.6430216.33509
Mg-6-167.9428121.1914220.8090.00914.050.130.12590.001534.3582312.57437
Mg-6-176.724951.344990.8210.01216.830.210.14870.00226.4244117.34914
Mg-6-183.5260932.6798310.8240.01132.140.880.28360.007643.4848331.21685
Mg-6-195.133471.4887060.8190.01421.890.290.19480.002937.7407525.35068
Mg-6-205.4054051.1351350.8160.01320.760.230.18500.002140.3168422.76337

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Crystals 12 01050 g001a 550Crystals 12 01050 g001b 550
Figure 1. Geological maps of Mogok metamorphic belt and adjacent regions (modified from Win et al., 2018) (a) [42]. The main geological structures for the Mogok area (modified from Searle et al., 2020) (b) [39].
Figure 1. Geological maps of Mogok metamorphic belt and adjacent regions (modified from Win et al., 2018) (a) [42]. The main geological structures for the Mogok area (modified from Searle et al., 2020) (b) [39].
Crystals 12 01050 g001aCrystals 12 01050 g001b
Crystals 12 01050 g002 550
Figure 2. The titanite crystals of MG-5 (a) and MG-6 (b).
Figure 2. The titanite crystals of MG-5 (a) and MG-6 (b).
Crystals 12 01050 g002
Crystals 12 01050 g003 550
Figure 3. Triangular etching of MG-5.
Figure 3. Triangular etching of MG-5.
Crystals 12 01050 g003
Crystals 12 01050 g004 550
Figure 4. Fourier Transform Infrared Spectrum of MG-5 and MG-6.
Figure 4. Fourier Transform Infrared Spectrum of MG-5 and MG-6.
Crystals 12 01050 g004
Crystals 12 01050 g005 550
Figure 5. UV–Vis spectrum of MG-6.
Figure 5. UV–Vis spectrum of MG-6.
Crystals 12 01050 g005
Crystals 12 01050 g006 550
Figure 6. Raman spectra of MG-5 and MG-6.
Figure 6. Raman spectra of MG-5 and MG-6.
Crystals 12 01050 g006
Crystals 12 01050 g007 550
Figure 7. Chondrite-normalised REE patterns of titanite samples MG-5 (a) and MG-6 (b). Chondrite REE values from McDonough, W.F. and Sun, S.S. (1995) [44]. Lines with different colors represent data of different spots in measurement by LA-ICP-MS.
Figure 7. Chondrite-normalised REE patterns of titanite samples MG-5 (a) and MG-6 (b). Chondrite REE values from McDonough, W.F. and Sun, S.S. (1995) [44]. Lines with different colors represent data of different spots in measurement by LA-ICP-MS.
Crystals 12 01050 g007
Crystals 12 01050 g008 550
Figure 8. Correlations between Nd (ppm) and Zr (ppm) of titanites.
Figure 8. Correlations between Nd (ppm) and Zr (ppm) of titanites.
Crystals 12 01050 g008
Crystals 12 01050 g009a 550Crystals 12 01050 g009b 550
Figure 9. Backscattered electron images of the Mogok titanites MG-5 (a) and MG-6 (b). Red circles show positions for simultaneous LA-ICP-MS measurements of U–Pb ages. 206Pb/238U ages are in red.
Figure 9. Backscattered electron images of the Mogok titanites MG-5 (a) and MG-6 (b). Red circles show positions for simultaneous LA-ICP-MS measurements of U–Pb ages. 206Pb/238U ages are in red.
Crystals 12 01050 g009aCrystals 12 01050 g009b
Crystals 12 01050 g010 550
Figure 10. LA-ICP-MS titanite U–Pb TW diagram (a) and 206Pb/238U weighed age for MG-5 (b); LA-ICP-MS titanite U–Pb TW diagram (c) and 206Pb/238U weighed age for MG-6 (d).
Figure 10. LA-ICP-MS titanite U–Pb TW diagram (a) and 206Pb/238U weighed age for MG-5 (b); LA-ICP-MS titanite U–Pb TW diagram (c) and 206Pb/238U weighed age for MG-6 (d).
Crystals 12 01050 g010
Crystals 12 01050 g011 550
Figure 11. Fourier transform infrared spectrum of titanite R050114 from RRUFF database.
Figure 11. Fourier transform infrared spectrum of titanite R050114 from RRUFF database.
Crystals 12 01050 g011
Crystals 12 01050 g012 550
Figure 12. Raman spectrum of titanite R050114 from RRUFF database.
Figure 12. Raman spectrum of titanite R050114 from RRUFF database.
Crystals 12 01050 g012
Crystals 12 01050 g013 550
Figure 13. Raman spectra of common titanite reference samples (modified from a part of Figure 3 of Ling X-X et al., 2022) [46].
Figure 13. Raman spectra of common titanite reference samples (modified from a part of Figure 3 of Ling X-X et al., 2022) [46].
Crystals 12 01050 g013
Crystals 12 01050 g014 550
Figure 14. Tectonic evolution model of Mogok area (modified from Themelis et al., 2008) [37].
Figure 14. Tectonic evolution model of Mogok area (modified from Themelis et al., 2008) [37].
Crystals 12 01050 g014
Crystals 12 01050 g015 550
Figure 15. Fe vs. Al cations per formula unit.
Figure 15. Fe vs. Al cations per formula unit.
Crystals 12 01050 g015
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Gu, J.; Xu, B.; Li, S.; Zhao, Y. Titanite Spectroscopy and In Situ LA-ICP-MS U–Pb Geochronology of Mogok, Myanmar. Crystals 2022, 12, 1050. https://doi.org/10.3390/cryst12081050

AMA Style

Gu J, Xu B, Li S, Zhao Y. Titanite Spectroscopy and In Situ LA-ICP-MS U–Pb Geochronology of Mogok, Myanmar. Crystals. 2022; 12(8):1050. https://doi.org/10.3390/cryst12081050

Chicago/Turabian Style

Gu, Jialu, Bo Xu, Shu Li, and Yi Zhao. 2022. "Titanite Spectroscopy and In Situ LA-ICP-MS U–Pb Geochronology of Mogok, Myanmar" Crystals 12, no. 8: 1050. https://doi.org/10.3390/cryst12081050

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