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. 2020 Sep 18;23(10):101575. doi: 10.1016/j.isci.2020.101575

In situ U-Pb Dating of Calcite from the South China Antimony Metallogenic Belt

Kai Luo 1,2, Jia-Xi Zhou 1,5,∗, Yue-Xing Feng 2, I Tonguc Uysal 3, Ai Nguyen 2, Jian-Xin Zhao 2, Jiawei Zhang 4
PMCID: PMC7530294  PMID: 33083741

Summary

Accurately determining the age of hydrothermal ore deposits is difficult, because of lack of suitable mineral chronometers and techniques. Here we present the first LA-MC-ICPMS U-Pb age of carbonates from hydrothermal Sb deposits. Three stages of hydrothermal carbonates from the giant South China Sb metallogenic belt were identified: (1) pre-ore dolomite (Dol-I), (2) syn-ore calcite (Cal-II), and (3) post-ore calcite (Cal-III). The U and Pb isotopic data show that Cal-II yielded a lower intercept age of 115.3 ± 1.5 Ma (MSWD = 2.0), suggesting a Sb mineralization that corresponds to an extension event occurred during the early Cretaceous in South China. Although Cal-III yielded an age of 60.0 ± 0.9 Ma (MSWD = 1.5), indicating a potential tectonothermal event occurred in this belt during the early Cenozoic. Hence, in situ U-Pb dating of calcite offers a new way to determine the age of hydrothermal ore deposits.

Subject Areas: Thermochronology, Isotope Geochemistry, Geochemistry Methods, Ore Geochemistry

Graphical Abstract

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Highlights

  • •

    The syn-ore calcite yielded an in situ U-Pb age of 115.3 ± 1.5 Ma

  • •

    The South China antimony mineralization occurred during the early Cretaceous

  • •

    Calcite in situ U-Pb dating can determine the timing of hydrothermal mineralization

Thermochronology; Isotope Geochemistry; Geochemistry Methods; Ore Geochemistry

Introduction

Dissolution-based carbonate U-Pb dating has been successfully applied to diagenesis of marine carbonate (Israelson et al., 1996; Cole, 2003), coral (Denniston, 2008), fossils (Walker et al., 2006) as well as speleothems (Richards et al., 1998; Woodhead et al., 2006; Victor et al., 2008; Pickering et al., 2010). However, previous bulk analysis using isotope dilution has limited application for most hydrothermal ore deposits. The limitations include: (1) the scarce of spike (e.g. 233U-205Pb) (Moorbath et al., 1987; Pickering et al., 2010; Engel et al., 2020); (2) low U and Pb contents (<1 ppm) within single hydrothermal carbonate minerals (Brannon et al., 1996; Grandia et al., 2000; Coveney et al., 2000; Meinhold et al., 2020); and (3) a small spread of 238U/206Pb due to the average of isotopic zonation within the analytical volume (Li et al., 2014; Guillong et al., 2020; Roberts et al., 2020).

Recently, in situ U-Pb isotopic analysis using laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) equipped with ion counters provides the potential to date these carbonates (Coogan et al., 2016; Methner et al., 2016; Roberts and Walker, 2016; Roberts et al., 2017). Such method can help to identify high U/Pb ratios regions in a sub-mm scale and enable high spatial resolution (less than ca. 100 μm) and low detection limits (ca. 1 ppb Pb) (Woodhead et al., 2006; Li et al., 2014; Roberts and Walker, 2016; Goodfellow et al., 2017; Nuriel et al., 2017; Salih et al., 2020). It potentially targets and utilizes endmember μ (238U/204Pb) domains, along with high-n datasets (Shen et al., 2019; Roberts et al., 2020), leading to an improvement in precision on the regressed age, and thus offers a new way to date hydrothermal ore deposits.

Antimony (Sb) is one of the critical metals and commonly found in epigenetic hydrothermal ore deposits (Seal et al., 2017). Precisely determining the age of Sb deposits can help to understand their origin and further prospecting (Scratch et al., 1984; Maheux, 1989; Lu, 1994; Wang, 2008; Tran et al., 2016; Xie et al., 2017). However, dating is a challenging work because of low radioisotope contents in their minerals (stibnite, carbonates, and quartz ± fluorite) (Gumiel and Arribas, 1987; Wu, 1993; Murao et al., 1999; Shen et al., 2011, 2013). Although there are some successful examples of calcite/fluorite Sm-Nd dating (e.g. Peng et al., 2003b), such method has certain limiting factors, such as high cost, low efficiency, unfavorable Sm/Nd ratios, and unavailability to differentiate multiple ore-forming generations (Uysal et al., 2007; Zhu et al., 2017).

The giant South China Sb metallogenic belt has supplied >50% of the world's Sb metal resource (e.g. Wu, 1993; Fu et al., 2019b). Despite of much attention received (e.g. Xiao, 2014; Fu et al., 2019a, 2019b), the timing of Sb mineralization is still not well constrained. In this contribution, we use the Weizhai Sb deposit in the giant South China Sb metallogenic belt as a case study for LA-MC-ICPMS in situ U-Pb dating. The syn-ore calcite was identified by field mapping, mineralogy, in-situ elements, and C-O-Sr isotopic compositions. The aim of this study is to (1) establish a new and precise dating technique of hydrothermal ore deposits and (2) solve the currently challenging problem of timing and geodynamic setting of the South China Sb metallogenic belt.

Geological Setting

The giant South China Sb metallogenic belt covers an area between the Yangtze Block and the Cathaysia Block and is a part of the South China low-temperature metallogenic domain (Figure 1A; Hu et al., 2017). This belt hosts more than 500 Sb deposits accounting for 87% of the proven reserves in China and 55% of the world (Figure 1B; Wu, 1993; Fu et al., 2019b) and constitutes an important part of the circum-Pacific Sb metallogenic domain (Wu, 1993; Jin and Dai, 2007; Xiao, 2014). Antimony deposits in this belt are hosted in Proterozoic to Permian sedimentary rocks and structurally controlled by NE-trending folds and faults. The formation of these deposits was generally considered to be genetically related to large-scale extensional tectonics (e.g. Peng et al., 2003b; Hu et al., 2017; Li et al., 2018; Yang and Sun, 2018).

Figure 1.

Figure 1

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Simplified Geological Map of the Study Area

(A) Tectonic map of South China showing the location of the South China antimony metallogenic belt. Abbreviations: NCC = North China Craton, QDOB = Qinling-Dabie Orogenic Belt, YB = Yangtze Block, JOB = Jiangnan Orogenic Belt, CB = Cathaysian Block, SGFB = Songpan Ganzê Fold Belt, SOB = Sanjiang Orogenic Belt, SCAMB = South China antimony (Sb) metallogenic Belt; (B) tectonic map of the South China antimony metallogenic belt, showing the distribution of important hydrothermal Sb deposits and adjacent Au, Hg, and Pb-Zn deposits; (C) regional geological map of the Dushan Sb ore district (Xiao, 2014).

In the southwestern part of the South China Sb metallogenic belt, the Dushan Sb ore district hosts >30 Sb deposits (∼287,000t Sb), including the Weizhai, Banpo, Banian, and Jiabai deposits (Figure 1C). These deposits are controlled by folds and faults, including (1) the NE-trending Dushan anticline formed in the Caledonian; (2) the NE-trending Dushan normal fault (29 km in length, 3–10m in width, and dipping SE with an angle of 50–80°); (3) the NNE-trending Lantu normal fault (35km in length, 1–5m in width, and dipping NW with an angle of >70°), and (4) numerous secondary folds and normal faults (Figures 1B and S1; e.g. Wang and Jin, 2010; Shen et al., 2013). These fractures underwent multiple transitions from compression to tension. Strong silicification, carbonatization, and pyritization occur in these faults, accompanying with large amounts of hydrothermal Sb, Hg, As, Pb, and Zn deposits.

The Sb ore bodies normally occur as veinlets defined by these faults (e.g. the Weizhai and Banpo deposits), or stratiform and lens-shaped ore bodies controlled by anticline and bedding fractures (e.g. the Banian and Jiabai deposits) (Figure S1). Among them, the Weizhai deposit (∼21,000t Sb @ 4.18 wt. %) is hosted in argillaceous limestone and siltstone of the Lower Silurian. Sb mineralization is almost entirely constituted of stibnite occurring mainly columnar in texture. Field observations identified two modes of occurrence of the Sb ores, including brecciated and veined. Gangue minerals are quartz and carbonate minerals associated with sulfides (Figure 2A). The wall rock alteration includes silicification and carbonatization. The mineral assemblage and wall rock alteration can be compared with those of many other Sb deposits in the South China Sb metallogenic belt (Figures 2B and 2C).

Figure 2.

Figure 2

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Photographs of Representative Ores from the South China Sb Metallogenic Belt

Photographs of hand specimens from the South China Sb metallogenic belt (A–C), and CL-BSE images showing the structural relationship between stibnite and carbonates from the Weizhai Sb deposit (D–F). (A) Stibnite (Stb) cemented by late white calcite (Cal) crosscutting early dolomite (Dol) (the Weizhai Sb deposit); (B) quartz (Q) coexisting with stibnite hosted in the silicified wall rock (the Banpo Sb deposit); (C) calcite coexisting with stibnite (the Muli Sb deposit); (D) CL image identified carbonate wall rock and three generations of hydrothermal carbonates—Dol-I, Cal-II, and Cal-III; (E) enlargement BSE image of white rectangle area of (D), showing laser ablation pits; (F) Cal-III enclosing stibnite occurring as veins filling into minerals of early stages.

Hydrothermal carbonate minerals in the Weizhai deposit are formed by three stages: pre-ore dolomite (Dol-I), syn-ore calcite (Cal-II), and post-ore calcite (Cal-III). Dol-I enclosing breccia of organic-rich carbonate wall rocks is featured by fine-grained, light yellow Fe-Mn-dolomite with local recrystallization and several to tens of centimeters in width (Figures 2A, 2D, and 2E). Cal-II is characterized by gray thick veins with coarse-grained stibnite, organic matters (Figure 7), and minor pyrite (Figures 2A and 2F). This stage of calcite occurs irregularly in several to tens of meters in length. Cal-III occurs as relatively thinner veins crosscutting all of the early stage carbonate minerals (Figures 2D–2F).

Figure 7.

Figure 7

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Tera-Wasserburg Concordia Diagrams (238U/206Pb versus 207Pb/206Pb) of LA-MC-ICPMS U-Pb Data of Syn-ore and Post-ore Calcites from the Weizhai Sb Deposit Error ellipses are at 2σ.

Results

In Situ Trace Elements

Trace element contents of carbonates from the Weizhai deposit are listed in Table 1. Cal-II has an average 842 ppm Mg, 64.1 ppm Sr, 532 ppm Mn, 1927 ppm Fe, 0.07 ppm Pb, and 0.35 (0.04–0.88 ppm) ppm U (n = 44), whereas fifty-seven spot analyses of Cal-III have average 1241 ppm Mg, 146 ppm Sr, 970 ppm Mn, 2931 ppm Fe, 0.24 ppm Pb, and 0.27 (0.03–0.99) ppm U (n = 57), respectively. This is consistent with elemental mapping results, which shows that images of Ca are almost uniform, but Mg, Fe, and Mn are highly varied with a marked contrast between Cal-II and -III. Furthermore, U and Pb are heterogeneously distributed on the micrometer scale (Figures 3C and 4F).

Table 1.

LA-ICP-MS In Situ Element Composition (ppm) of Carbonates from the Weizhai Sb Deposit

Stage Mg Ca Sr Mn Fe La Ce Pr Nd Sm Eu Tb Gd Dy Ho Er Tm Yb Lu Pb Th U LREE/HREE LaN/YbN
Wall rock (n = 26) Max 145500 404500 2780 7010 182000 270 499 50.9 169 20.5 2.65 1.94 10.1 11.6 2.05 5.27 0.83 5.91 0.87 316 41.2 9.10
Min 38200 380600 321 2714 34600 2.34 5.37 0.67 3.39 2.14 0.64 0.67 3.91 4.36 0.79 2.11 0.28 1.78 0.25 1.15 0.89 0.61
Mean 95836 397896 1036 4552 79128 39.8 80.1 8.90 33.8 6.88 1.32 1.09 6.83 6.54 1.20 3.22 0.46 3.03 0.43 56.2 11.1 2.01 7.49 9.42
Dol-I (n = 43) Max 165700 402800 869 3519 99500 23.3 59.0 6.98 27.6 6.05 1.17 1.56 7.77 9.64 1.66 4.16 0.55 3.49 0.48 7.11 0.75 0.50
Min 87500 396400 212 2481 71920 6.30 13.5 1.52 6.50 1.69 0.38 0.37 2.77 2.23 0.43 1.07 0.12 0.57 0.08 1.61 0.02 0.08
mean 137751 400142 505 2946 89831 14.4 34.2 3.92 15.5 3.46 0.70 0.71 4.18 4.64 0.91 2.48 0.33 1.97 0.27 3.90 0.22 0.18 4.66 5.24
Cal-II (n = 69) max 1139 404700 218 896 2680 0.51 1.81 0.32 1.96 1.18 0.38 1.20 4.26 10.8 2.57 7.72 1.03 5.67 0.72 0.58 0.44 0.88
min 424 396400 15.0 206 856 0.01 0.03 0.01 0.07 0.09 0.05 0.16 0.65 1.03 0.17 0.40 0.04 0.22 0.03 0.00 0.02 0.04
mean 842 400362 64.1 532 1927 0.11 0.41 0.08 0.58 0.47 0.18 0.46 1.93 3.35 0.65 1.69 0.21 1.17 0.15 0.07 0.19 0.35 0.19 0.07
Cal-III (n = 19) max 2650 407700 1060 1700 4170 2.52 7.26 1.10 6.43 3.86 1.27 2.35 10.5 17.6 3.57 9.49 1.20 6.37 0.78 1.84 1.51 0.99
min 466 395700 15.1 568 1244 0.0007 0.0013 0.0011 0.01 0.02 0.01 0.02 0.10 0.13 0.03 0.06 0.01 0.04 0.01 0.0002 0.0010 0.03
mean 1241 400488 146 970 2931 0.25 0.77 0.14 0.95 0.80 0.27 0.47 2.25 3.30 0.64 1.69 0.21 1.22 0.16 0.24 0.17 0.27 0.32 0.15
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Note: LREE/HREE = (La + Ce + Pr + Nd + Sm + Eu)N/(Gd + Dy + Ho + Er + Tm + Yb + Lu)N; δEu = 2Eu/(Sm + Gd).

Figure 3.

Figure 3

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Cross-plots Showing Elemental Compositions of Different Stages of Carbonates from the Weizhai Sb Deposit

(A) Sr/Ca versus Ba/Ca ratios, displaying similar liner relationship between carbonate wall rocks and Dol-I, and (B) Fe versus Mn, showing contrasting liner relationship between Cal-II and Cal-III. (C) U versus U/Pb ratios, showing U/Pb ratios in Cal-II and Cal-III are highly variable.

Figure 4.

Figure 4

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Element Mapping of Different Stages of Carbonates from the Weizhai Sb Deposit

Transmitted light image (A) and element mapping of Ca (B), Mg (C), Mn (D), Fe (E), and U (F) of hydrothermal carbonates, showing U concentration heterogeneity in Cal-II and Cal-III.

Figure 5 shows the chondrite-normalized rare earth elements (REE) patterns for these carbonates. Dol-I is characterized by a light rare earth elements (LREE) enrichment with a mean LREE/HREE ratio of 4.66 (Figure 5B), which is similar to those of carbonate wall rocks (avg. 7.49) (Figure 5A). In contrast, Cal-II and Cal-III are enriched in HREE with mean LaN/YbN ratios of 0.07 and 0.15, respectively (Figures 5C and 5D).

Figure 5.

Figure 5

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Chondrite-Normalized REE patterns of Different Stages of Carbonates from the Weizhai Sb Deposit

Carbonate wall rock (A), pre-ore Dol-I (B), syn-ore Cal-II (C), and post-ore Cal-III (D). The chondrite values are from Sun and Mcdonough (1989).

Carbon and Oxygen Isotopic Compositions

δ13C and δ18O values of hydrothermal carbonates from the Weizhai deposit are listed in Table 2. Pre-ore dolomite has δ13C and δ18O values ranging from −2.8 to −1.9‰ and +17.8 to +18.4‰, respectively, as compared with those of syn-ore calcite ranging from −0.6 to +0.4‰ and +14.4 to +17.4‰, respectively (Figure 6).

Table 2.

C, O, and Sr Isotopic Compositions of Carbonates and Strata Units from the South China Sb Metallogenic Belt

Deposit/Strata Sample No. Stage δ13CPDB (‰) δ18OSMOW (‰) 88Sr 87Sr/86Sr ±2σ Ref.
Weizhai WZ05-4 Dol-I −1.9 +17.8 14.9 0.718653 0.000007 This study
WZ05-5 −2.8 +18.4 15.3 0.718173 0.000007
WZ05-2 Cal-II −0.4 +17.2 16.8 0.714795 0.000006
WZ05-3 −0.6 +17.4 16.1 0.716632 0.000006
WZ05-1 Cal-III −0.3 +16.1 15.3 0.714688 0.000007
WZ02 +0.4 +14.4
Banpo −2.4∼−0.5 +10.9∼+14.7 Xiao, 2014
Xujiashan Syn-ore calcite −3.9∼−2.1 +11.5∼+15.3 0.7109–0.7154 Shen et al. (2007)
Pre-ore calcite −0.7∼+2.0 +18.6∼+19.6 0.7096–0.7097
Xikuangshan Syn-ore calcite −7.0∼+2.1 +11.0∼+17.9 0.710198–0.714435 Peng and Hu (2001)
Banxi Stibnite 0.711244–0.717591 Li et al. (2018)
Qinglong Fluorite 0.70766–0.70932 Peng et al. (2003a)
Phanerozoic marine carbonates 0.7068–0.7092 Veizer and Compston, 1974
Mesoproterozoic Banxi Group 0.7127–0.7261 Ma et al., 2003;
Peng et al. (2003b)
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Note: Ore-forming age of 120 Ma was used to calculate initial 87Sr/86Sr ratios of metamorphism rocks, the Mesoproterozoic Banxi Group, which has 87Sr/86Sr ranging from 0.7131 to 0.7287.

Figure 6.

Figure 6

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Diagram of C, O and Sr Isotopic Compositions of Hydrothermal Carbonates and Strata Units from the South China Sb Metallogenic Belt

(A) Diagram of C and O isotopic compositions of hydrothermal carbonates from the South China Sb metallogenic belt. Plot of δ13CPDB versus δ18OSMOW for the Weizhai (WZ) (this study), Banpo (BP), Xikuangshan (XKS), and Xujiashan (XJS) Sb deposits (the data are from Peng and Hu (2001), Shen et al. (2007) and Xiao (2014)).

(B and C) Plot of 87Sr/86Sr versus δ18OSMOW (B) and 87Sr/86Sr versus δ13CPDB (C) for hydrothermal carbonates from the Weizhai Sb deposit, showing 87Sr/86Sr values of the Mesoproterozoic strata in South China higher than 0.7127 (Dashed lines) (Peng et al., 2003b) and those of Phanerozoic marine carbonates lower than 0.7092 (dashed lines) (Veizer and Compston, 1974).

Strontium Isotopic Ratios

Table 2 lists 87Sr/86Sr ratios of hydrothermal carbonates from the Weizhai deposit, ranging from 0.714688 to 0.718653 (2σ). The mean 87Sr/86Sr ratios decrease from Dol-I (0.718413), to Cal-II (0.715714) and Cal-III (0.714688).

Calcite In Situ U-Pb Age

Among the pre-screened hydrothermal carbonates of three stages from the Weizhai deposit, Cal-II and -III has datable U/Pb ratios (0.05–70; Figure S2; Table 3) with 133–1281 ppb U (mean 475 ppb) and 11–215 ppb Pb (mean 58 ppb), compared with Dol-I of U/Pb ratios (0.03–0.12) with 81–504 ppb U (mean 183 ppb) and 1614–7110 ppb Pb (mean 3895 ppb). As shown in Figure 7, Cal-II has 27 spots with U-Pb data falling on well-defined lines in the isochron plot (2σ analytical and propagated uncertainty) and yields an age of 115.3 ± 1.5 Ma (MSWD = 2.0) (Table 3). Cal-III has an isochron defined by 16 U-Pb data points with a highly radiogenic lower intercept and a significantly younger age of 60.0 ± 0.9 Ma (MSWD = 1.5).

Table 3.

LA-MC-ICP-MS U-Pb Dating of Hydrothermal Calcite from the Weizhai Sb Deposit

Stage 238U/206Pb Int2SE 207Pb/206Pb Int2SE Approx_
U_ppb		 Approx_
Pb_ppb		 U/Pb
Cal-II 43.44 1.795 0.2340 0.0160 448 11 41
46.78 1.017 0.1640 0.0140 807 12 70
45.18 0.6398 0.2029 0.0082 1281 25 52
33.29 0.6829 0.3871 0.0095 807 41 20
39.60 0.6271 0.2838 0.0088 693 22 32
43.68 1.176 0.2310 0.0140 781 18 13
36.95 0.4132 0.3412 0.0074 1079 43 25
38.29 1.379 0.3230 0.0160 676 26 26
45.44 0.6917 0.2020 0.0120 977 19 53
16.44 0.3799 0.6682 0.0089 210 38 5.5
19.63 2.457 0.5980 0.0220 434 60 7.3
21.14 0.9661 0.6060 0.0130 172 23 7.4
25.38 2.158 0.5120 0.0290 311 28 11
22.74 1.733 0.5550 0.0310 156 19 8.1
15.64 0.4495 0.6840 0.0110 133 27 4.9
19.91 1.114 0.6130 0.0170 171 25 6.8
16.56 0.5925 0.6570 0.0100 288 52 5.6
19.35 1.376 0.6280 0.0160 298 46 6.5
13.76 0.7777 0.6970 0.0100 475 111 4.3
10.12 1.008 0.7349 0.0080 359 119 3.0
12.56 0.7678 0.7070 0.0110 285 79 3.6
10.36 1.055 0.7310 0.0120 208 67 3.1
5.723 0.0970 0.8140 0.0056 245 153 1.6
9.599 0.5165 0.7499 0.0098 283 101 2.8
6.115 0.4351 0.8169 0.0044 348 215 1.6
8.240 1.365 0.7820 0.0120 279 121 2.3
7.203 0.2030 0.8032 0.0095 152 72 2.1
Cal-III 37.28 0.9314 0.5642 0.0091 855 56 15
61.42 1.305 0.3930 0.0110 703 19 37
71.73 1.557 0.3280 0.0110 1018 19 53
42.19 1.924 0.5260 0.0170 460 26 18
70.99 2.560 0.2890 0.0180 289 7 44
24.28 0.5099 0.6709 0.0072 396 50 8.0
8.800 0.5441 0.7990 0.0110 132 54 2.5
22.63 1.550 0.6940 0.0140 179 23 7.8
68.51 3.855 0.3440 0.0280 781 17 45
36.99 3.402 0.5660 0.0250 414 33 13
58.30 4.408 0.3880 0.0330 420 13 32
5.228 0.4047 0.8110 0.0100 145 109 1.3
0.1770 0.0030 0.8510 0.0017 88 1925 0.05
0.1964 0.0045 0.8519 0.0014 107 2150 0.05
9.724 0.3800 0.7771 0.0076 241 87 2.8
10.70 0.2905 0.7780 0.0110 126 40 3.2
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Discussion

Reliability of Calcite In Situ U-Pb Age

Sampling technique using the laser ablation system help to exploit the potential for micro-scale heterogeneity in carbonates and obtain high μ (238U/204Pb) values and a large spread of U-Pb ratios (U/Pb = 0.05–70; Table 3). However, concentrations of U and Pb in calcites from the Weizhai Sb deposit range down to tens of ppb, compared with traditional U-bearing accessory minerals often with >100ppm U in zircon and > 1ppm U in meteoric-water-sourced carbonates (e.g. speleothem and tufas) (Woodhead et al., 2006). Such extremely low U and Pb contents in calcites cannot be sufficiently measured by conventional Q-ICP-MS or MC-ICP-MS (Kylander-Clark, 2020).

Accordingly, at the highest mass end of collector array of the Nu Plasma II MC-ICPMS, we employ an ETP (electron multiplier) discrete dynode multiplier dedicated to static measurement of low signal 238U. Such discrete dynode multiplier is characterized by higher sensitivity (100 μm, 3 J/cm2, 10 Hz; 238U > 500000 cps/ppm, 207Pb blank = 10–100 cps) with ∼3–10 times higher than that of Q-ICP-MS (Liu et al., 2019; Shen et al., 2019; Cheng et al., 2020).

Taking the advantage of high sensitivity and static analysis, our employment of LA-MC-ICPMS could achieve superior internal error (i.e. <1% 2σ) for U and Pb isotopic compositions with good signal intensity for samples as those in this study. As shown in plot of 238U/206Pb-207Pb/206Pb (Figure 7), the scatters (mean standard weighted deviation (MSWD = 2.0 & 1.5)) of U and Pb isotopic compositions are sufficiently small and less than 2.5, suggesting a precise regression due to well-behaved closed system behavior (Brooks et al., 1972). Besides, through cross-calibration by AHX-1a (Figure S3; Table S1), the matrix-matched carbonate reference materials ASH-15D (3.001 ± 0.012Ma; Mason et al., 2013; Vaks et al., 2013; Nuriel et al., 2017) attained the expected age within uncertainty (ASH-15D: 2.957 ± 0.033 Ma, MSWD = 1.7; the data have been shown in Figure S4 and Table S1), confirming that the derived ages are accurate.

In this study, therefore, the ages of 115.3 ± 1.5 Ma (MSWD = 2.0) and 60.0 ± 0.9 Ma (MSWD = 1.5) obtained from two types of calcites from the Weizhai Sb deposit (Figure 7) are meaningful and can represent significant geological events.

Determination of Syn-Ore Calcite

Since calcite often has multi-stage generation in hydrothermal systems, its relationship with Sb mineralization cannot be easily established using conventional optical microscope (Morishita, 2012; Zhu et al., 2017). In this study, CL petrography, major, minor, and trace elements, C-O and Sr isotopes, further help to characterize the syn-ore calcite.

The high spatial resolution of CL can be an useful tool for identifying micrometer-scale calcite grain growth zonation and alteration and characterizing different generations formed from different fluids (e.g. Barnaby and Rimstidt, 1989; Tullborg et al., 2008; Milodowski et al., 2018). Figure 2D shows that pre-ore Dol-I with a dark-grey CL color is cemented by calcite of two late stages. Syn-ore Cal-II filling in fissures of Dol-I is typically high in the CL intensity and forms a bright orange luminescent. Post-ore Cal-III gray calcite veinlets crosscut both Dol-I and Cal-II crystals with an immediate contact, which rules out the alteration and reprecipitation during the latest hydrothermal event (Roberts et al., 2020). Because of Fe2+ serving as the dominant luminescence quencher (Peyrotty et al., 2020), Cal-II with lower Fe concentration exhibits bright CL responses in calcite as being different from that of Cal-III, which is supported by the in situ element data (Table 1).

Other elements, such as Mg, Sr, Ba, Mn, and Fe, can be used to distinguish between syn-ore and post-ore calcites (e.g. Alexandre, 2010; Wang et al., 2018). Data of carbonates from the Weizhai deposit, which were plotted, form two distinct clusters in the Sr/Ca versus Ba/Ca (Figure 3A) and Fe versus Mn (Figure 3B) diagrams, supplemented by different REE patterns (Figure 5), indicating that Cal-II and Cal-III may have different origin from Dol-I and carbonate wall rocks (Scholle and Ulmer-Scholle, 2003; Uysal et al., 2007). Lower Mg, Sr, Mn, and Fe contents of Cal-II are unlikely to be attributed to less fluid-rock interaction, demonstrated by the inconsistent liner relationship of Fe versus Mn between Cal-II and Cal-III (Figure 3B; Bau and Dulski, 1995; Hori et al., 2013). Instead, such elemental signature may reflect separate fluid source with contrasting elemental compositions (e.g. Sb).

δ13C and δ18O values of Cal-II and Cal-III from the Weizhai deposit well overlap with those of calcites from other regional Sb deposits in South China (Figure 6A). Such calcites have slightly lower δ18O values than those of Dol-I. The 87Sr/86Sr ratios of Cal-II and -III ranging from 0.7147 to 0.7166 are also similar to those of the Xujiashan (0.7109–0.7154) and Banxi (0.7112–0.7176) Sb deposits but higher than 87Sr/86Sr ratios of Phanerozoic marine carbonates (0.7068–0.7092; Figure 6B; Veizer and Compston, 1974). The Cal-II and –III Sr isotopic values can be compared with those of the Mesoproterozoic strata in South China (87Sr/86Sr120Ma ranges from 0.7127 to 0.7261; Figure 6C; Ma et al., 2003; Peng et al., 2003b). This probably indicates that the Sb-bearing fluid derived or flowed through radiogenically 87Sr-enriched rocks, e.g. the Mesoproterozoic Banxi Group (Peng et al., 2003b).

Therefore, the above geochemical evidence, supported by field observations, establishes a set of complementary criteria for confirming the syn-ore calcite.

Implications for Sb Mineralization of the South China Sb Metallogenic Belt

Due to the lack of suitable minerals for reliable radiometric dating, the age of Sb mineralization in South China is still under debate. A few conventional methods such as Rb-Sr and Ar-Ar dating of fluid inclusion of quartz/calcite, quartz electron spin resonance (ESR), and fluorite/calcite Sm-Nd dating have been employed in an attempt to constrain the timing of Sb mineralization, but yielded a large range of ages (mostly ca. 435–402 Ma and 156–101 Ma; Table 4). These ages were often questionable because of the isochron precision or the multi-stage presence of dating minerals and abundant non-primary fluid inclusions. For example, the Qinglong Sb deposit in the western South China Sb metallogenic belt was dated at quite different ages (ca. 146 Ma, 125 Ma, and 104 Ma) by using different dating minerals/methods (Zhu, 1998; Peng et al., 2003b).

Table 4.

Age Summary of Major Hydrothermal Ore Deposits in the South China Low-T Metallogenic Domain

Ore Deposit Host Strata Host Rock Ore-Type Dating Method Results (Ma) Ref.
Weizhai Devonian-Silurian Limestone, siltstone Sb Calcite in situ U-Pb 115.3 ± 1.5 This study
Banpo Devonian Sandstones Sb Quartz Fls K-Ar 145 Wang, 1994
Calcite Sm-Nd 130.5 ± 3.0 Xiao, 2014
128.2 ± 3.2 J.S. Wang (2012)
126.4 ± 2.7
Maxiong Cambrian, Devonian Dolostones, sandstones Sb Quartz Fls Ar-Ar 141 Wei (1993)
Quartz Fls Rb-Sr 156
Muli Devonian Carbonates Sb Quartz Fls Ar-Ar 165 Hu et al. (2007)
Qinglong Permian Marine volcanic rocks Sb (Au) Quartz Fls Rb-Sr 101.0 ± 2.9 Xiao, 2014
Fluorite ESR 104 Zhu (1998)
Quartz ESR 125.2
Fluorite Sm-Nd 148 ± 8 Peng et al., 2003b
142 ± 16
141 ± 20 Wang (2013)
Calcite Sm-Nd 148 ± 13 J.S. Wang (2012)
Fluorite Sm-Nd 142.3 ± 7.9
Xujiashan Upper Ediacaran Carbonates, clastic rocks Sb Calcite Sm-Nd 402 Shen, 2008
Pingcha Lower Ediacaran Carbonates, clastic rocks Sb Quartz Fls Rb-Sr 435 ± 9 Peng and Dai, 1998
Woxi Neoproterozoic Banxi Group Low-grade metamorphic rocks Sb-Au Scheelite Sm-Nd 402 ± 6 Peng et al., 2002
Quartz Fls Ar-Ar 423.2 ± 1.2
416.2 ± 0.8
Zhazixi Neoproterozoic Banxi Group Low-grade metamorphic rocks W-Sb Scheelite Sm-Nd 227.3 ± 6.2 Y.L. Wang (2012)
Banxi Neoproterozoic Banxi Group Low-grade metamorphic rocks Sb Stibnite Rb-Sr 129.4 ± 2.4 Li et al. (2018)
Stibnite Sm-Nd 130.4 ± 1.9
Zircon (U-Th)/He 130–120 Fu et al. (2019a)
123.8 ± 3.8 Li et al. (2020)
Xikuangshan Devonian Carbonates, clastic rocks Sb Calcite Sm-Nd 155.5 ± 1.1 Peng et al., 2003b
124.1 ± 3.7
156.3 ± 12 Hu et al. (1996)
Zircon (U-Th)/He 156–117 Fu et al. (2019b)
Lannigou Triassic Clastic rocks, carbonates Au Quartz Fls Rb-Sr 105.6 ± 4.5 Su et al. (1998)
142 ± 2 Liu et al. (2006)
Shuiyindong Permian Clastic rocks, carbonates Au Calcite Sm-Nd 134 ± 3 Su et al., 2009a
Zimudang Permian, Triassic Clastic rocks Au Calcite Sm-Nd 148.4 ± 4.8 Wang (2013)
Jiaoli-La'e Ordovician Carbonates Hg Calcite Sm-Nd 129 ± 20 Wang and Wen (2015)
Open in a new tab

Abbreviations: Fls, fluid inclusions; ESR, electron spin resonance.

The newly obtained ca. 115 Ma may indicate the Sb mineralization event between the Yangtze Block and the Cathaysia Block, corresponding to the large-scale Early Cretaceous (ca. 125–100 Ma) extension after the Yanshanian orogenic period (ca. 180–125 Ma) (Mao et al., 2010; Wang, 2012; Wang, 2013; Hu, 2015). Despite the poor timing constraints, the Yanshannian movement (ca. 180–100 Ma) is generally considered to be the main driving force for the widespread low-T hydrothermal Hg, Sb, and Au mineralization in South China (Table 4; Wang and Wen, 2015; Su et al., 2009a; Hu et al., 2017). These hydrothermal mineralization are predominantly located in Jurassic NE trending folds and thrusts, and Early Cretaceous NE trending normal faults (Wan, 2010), which is in good agreement with NE-trending trap structures the Dushan Sb ore district featured in this study (Figure 1C).

The younger age (ca. 60 Ma) may reflect a tectonothermal event during the early Cenozoic in the region. This age is within previously published age range of 66.4–51.6 Ma through ESR dating of quartz from the giant Xikuangshan Sb deposit in the South China Sb metallogenic belt (Jin, 2002). At the same time, it is temporally consistent with the apatite fission track age (61.5 ± 5.9 Ma; Wang et al., 2018), indicating an uplift event in South China. This is probably attributed to a change in the direction and speed of the subduction (ca. 60–40 Ma) of the Pacific Plate beneath the Eurasian Plate (Li et al., 2005; Tang et al., 2014).

Furthermore, compared with enrichment of LREE signature of pre-ore stage (Figures 5A and 5B), enriched HREE signatures were observed in both stage-II and -III calcites (Figures 5C and 5D). The HREE enrichment may reflect a source of (bi) carbonate-rich ligands in an evolving and cooling hydrothermal fluid, which preferentially mobilize HREE in near neutral to basic waters in basinal environments (Wood, 1990; Bau and Dulski, 1995; Rolland et al., 2003; Middleton et al., 2015). This REE signature can also be found in many other hydrothermal Sb and Au deposits in South China (e.g. the Qinglong and Xikuangshan Sb deposits, the Paiting, Miaolong, and Shuiyindong Au deposits; Figure 1B; Peng et al., 2003a, Xie et al., 2013; Peng et al., 2014, Su et al., 2009b).

Therefore, our new calcite in situ U-Pb ages indicate that the Sb mineralization of the giant South China Sb metallogenic belt occurred during the early Cretaceous, followed by a significant tectonothermal event during the early Cenozoic.

Conclusion

  • (1)

    The calcite LA-MC-ICPMS in situ U-Pb dating is recommended for future use in age determination of hydrothermal ore deposits with extremely low U and Pb contents and a large spread of U/Pb ratios.

  • (2)

    The new U-Pb age of 115.3 ± 1.5 Ma represents the timing of main-stage Sb mineralization during the early Cretaceous; 60.0 ± 0.9 Ma probably indicates a tectonothermal event occurred during the early Cenozoic.

Limitations of the Study

More in situ U-Pb ages of calcites from the giant South China antimony metallogenic belt are required. Future systematic studies would shed light on this issue.

Resource Availability

Lead Contact

Further information and requests for resources should be directed to and will be fulfilled by the Lead Contact, Prof. Jia-Xi Zhou (email: zhoujiaxi@ynu.edu.cn).

Materials Availability

This study did not generate new unique reagents.

Data and Code Availability

This study did not generate code. The published article contains all datasets generated in this study.

Methods

All methods can be found in the accompanying Transparent Methods supplemental file.

Acknowledgments

This research was financially supported by the National Natural Science Foundation of China (41872095 and U1812402), Guizhou Scientific and Technology Fund (QKHJZ [2015] 2081), and the Talents Program Project of Yunnan Province (YNQR-QNRC-2018-104). We thank Mr. Xiu-Ting Shen, De-Lin Tang, Yong-Gao Lu, and Tian-Long Meng for the help in field work; Drs. Gang Xia and Faye Liu (The University of Queensland) for the help in laboratory; Dr. Guo-Tao Sun (Yunnan University), Prof. Mei-Fu Zhou (The University of Hongkong), and Dr. En-Tao Liu (China University of Geosciences, Wuhan) for fruitful discussions.

Author Contributions

Study design: K.L. and J.X.Zhou. Sampling: K.L., J.X.Zhou, and J.W.Z. Analytical methods design: Y.X.F and J.X.Zhao. Data analysis and interpretation: K.L., A.N., and Y.X.F. Drafting manuscript: K.L., J.X.Zhou, I.T.U, and Y.X.F. Revising manuscript: All authors.

Declaration of Interests

The authors declare no competing interests.

Published: October 23, 2020

Footnotes

Supplemental Information can be found online at https://doi.org/10.1016/j.isci.2020.101575.

Supplemental Information

Document S1. Transparent Methods, Figures S1–S4 and Table S1
mmc1.pdf (699.7KB, pdf)

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Document S1. Transparent Methods, Figures S1–S4 and Table S1
mmc1.pdf (699.7KB, pdf)

Data Availability Statement

This study did not generate code. The published article contains all datasets generated in this study.

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