Geochemical Characteristics of Calcite and Bastnäsite U–Th–Pb Age of the Huangshui’an Carbonatite–hosted Mo–REE Deposit, Eastern Qinling
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摘要:
黄水庵矿床位于华北克拉通南缘熊耳山矿集区，是东秦岭钼矿带典型的碳酸岩型Mo–REE矿床之一。黄水庵矿床的Mo–REE矿体主要产于碳酸岩中，碳酸岩呈脉状和隐爆角砾岩体侵入太华群。笔者通过碳酸岩方解石微量元素、C–O同位素以及氟碳铈矿U–Th–Pb年龄的研究，探讨了碳酸岩岩浆的来源、成岩成矿年龄和构造地质背景，对东秦岭地区的构造演化和成矿作用提供约束。方解石的微量元素具有富集大离子亲石元素、亏损高场强元素的特征，稀土配分模式为轻稀土元素富集的右倾型（LREE/HREE=3.08～10.33）。方解石δ13 CV-PDB值为−4.11‰～−5.62‰、δ18OV-SMOW值为6.40‰～7.62‰，指示初始火成碳酸岩特征。氟碳铈矿U–Th–Pb定年的加权平均年龄为（213.5±2.9）Ma，代表了黄水庵REE矿化的时限。综合已有成岩成矿年龄和同位素研究结果，认为黄水庵矿床的成矿时代为晚三叠世，形成于秦岭造山带碰撞后的伸展背景。富Mo下地壳与富集地幔的部分熔融形成碳酸岩岩浆，其中地壳物质的再循环是形成碳酸岩型Mo–REE矿化的关键因素之一。
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关键词:
- 碳酸岩 /
- 方解石微量元素 /
- 碳氧同位素 /
- 氟碳铈矿U–Th–Pb定年 /
- 黄水庵矿床
Abstract:The Huangshui’an deposit, located in Xiong’ershan ore concentration area in the southern margin of the North China Craton, is one of the typical carbonatite–hosted Mo–REE deposit in the East Qinling Mo metallogenic belts. The Mo–REE ore bodies of the Huangshui’an deposit mainly are hosted in carbonatite which occur as veins and cryptoexplosive breccia intrusions in the Taihua Group. Based on the study of trace elements and C–O isotopic compostion of calcite, and bastnäsite U–Th–Pb dating, we discuss the origin of carbonatite, metallogenic age and tectonic setting, which provide constraints for tectonic evolution and mineralization in the East Qinling belt. The trace elements of calcite are characterized by enrichment of large ion lithophile elements and depletion of high field strength elements, and are enriched in LREE (LREE/HREE=3.08～10.33). The δ13 CV-PDB values of calcite ranging from −4.11‰ to −5.62‰ and δ18 OV-SMOW values ranging from 6.40‰ to 7.62‰ indicate the characteristics of primary mantle–derived carbonatite. The weighted average age of U–Th–Pb dating of bastnäsite is 213.5±2.9 Ma, representing the age of REE mineralization in the Huangshui'an deposit. Based on diagenetic and metallogenic age and available isotopic ages, we propose that the metallogenic age of the Huangshui’an deposit is Late Triassic. The Huangshui’an carbonatite–hosted deposit was formed in the post–collisional setting of the Qinling orogenic belt. The partial melting of Mo–fertile lower crust and enriched mantle formed the carbonatite magma, and the recycling of crustal material is one of the key factors for the formation of carbonatite–hosted Mo–REE mineralization.
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图 1 秦岭造山带构造构架图（A）与熊耳山矿集区地质简图（B）（修改自Tang et al.，2021）
Figure 1. (A) Tectonic framework of the Qinling Orogen and (B) geological map of the Xiong’ershan area showing important ore deposits
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图 2 黄水庵矿床地质图（A）与a–b勘探线地质剖面图（B）（修改自曹晶等，2014）
Figure 2. (A) Geological map of the Huangshui’an Mo deposit and (B) the geological profile of exploration line a–b in this deposit
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图 3 黄水庵Mo–REE矿床的碳酸岩（A～C）与镜下矿物组成（D～F）
Figure 3. (A～C) Phorographs of carbonatite and (D～F) Photomicrographs of mineral composition in the Huangshui’an Mo–REE deposit
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图 4 黄水庵Mo–REE矿床方解石的稀土元素（A）与微量元素标准化分布模式（B）
Figure 4. (A) Normalized REE and (B) trace element patterns of calcites from the Huangshui’an Mo–REE deposit
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图 5 黄水庵碳酸岩中方解石C–O同位素图解（底图据Keller et al.，1995）
Figure 5. C–O isotopic diagram of carbonatites from the Huangshui’an carbonatite
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图 6 黄水庵Mo–REE矿床氟碳铈矿背散射图像、测点位置和208Pb/232Th年龄
Figure 6. Backscattered-electron (BSE) images of bastnäsite that show location of analyzed spots and corresponding 208Pb/232Th ages in the Huangshui’an Mo–REE deposit
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图 7 黄水庵Mo–REE矿床的氟碳铈矿U–Th–Pb年龄
Figure 7. LA–ICP–MS U–Th–Pb ages of the bastnäsite from the Huangshui’an Mo–REE deposit
表 1 黄水庵Mo–REE矿床方解石微量元素及稀土元素组成（10−6）
Table 1 Trace element and REE content (10−6) from the Huangshui’an Mo–REE deposit
样品号 HAS-9 HAS-10 HAS-11 HAS-12 HAS-13 HAS-14 18HAS-20 19HAS-13 Li 0.150 0.210 0.238 0.130 0.097 0.103 0.009 0.039 Be 0.648 0.646 0.021 1.490 0.155 0.274 0.100 0.124 Sc 3.230 3.340 0.315 3.050 0.970 2.030 1.310 2.710 V 1.390 1.060 0.369 1.250 0.307 0.376 0.576 0.350 Cr 1.65 1.47 1.32 1.63 1.38 1.70 1.28 1.58 Co 1.13 1.05 1.12 1.14 1.02 1.10 1.12 1.15 Ni 22.5 20.1 21.7 18.3 21.6 19.8 21.4 23.7 Cu 0.977 0.696 0.318 0.322 0.331 0.190 0.373 0.114 Zn 19.20 4.30 1.84 3.48 2.26 2.65 3.08 2.55 Ga 2.04 2.01 3.25 2.25 1.58 1.63 2.77 1.13 Rb 0.319 0.201 0.062 0.189 0.053 0.035 0.035 0.028 Sr 5997 5960 7546 5913 6040 5787 7890 5297 Y 193 193 167 193 137 169 171 148 Mo 14.3 18.90 22.00 1.89 0.64 1.36 0.17 0.09 Cd 0.643 0.488 0.303 0.533 0.366 0.259 0.660 0.421 Sb 0.067 0.024 0.066 0.036 0.023 0.016 0.014 0.111 Cs 0.031 0.014 0.022 0.023 0.027 0.022 0.021 0.016 Ba 923 772 236 806 789 788 1587 691 La 91.3 87.6 253 108 84.8 82.4 183 43.6 Ce 218 206 484 246 184 185 375 99.9 Pr 31.1 29.0 53.5 35.2 25.0 23.8 47.5 14.1 Nd 126 119 200 145 96.3 99.5 177 60.8 Sm 25.9 24.7 28.6 28.6 18.4 19.1 29.5 14.1 Eu 7.61 7.49 7.78 8.05 5.88 5.88 7.88 4.71 Gd 23.3 22.1 28.1 25.1 17.4 17.8 26.7 12.5 Tb 4.08 4.1 4.04 4.40 2.99 3.35 4.23 2.55 Dy 24.3 22.5 22.2 25.1 17.4 19.6 21.6 16.5 Ho 5.94 5.51 5.02 5.95 4.11 5.05 4.95 4.28 Er 19.5 19.3 17.0 20.9 14.7 17.2 17.3 15.6 Tm 3.69 3.49 2.84 3.81 2.61 3.26 2.97 2.88 Yb 25.6 25.0 18.1 24.6 16.8 21.4 19.4 20.0 Lu 3.51 3.46 2.12 3.49 2.45 2.95 2.59 2.66 W 4.770 0.836 0.514 0.590 0.426 0.346 0.548 0.247 Pb 86.0 85.7 43.0 45.5 46.0 41.8 53.0 43.1 Bi 0.164 0.203 0.029 0.038 0.012 0.011 0.033 0.016 Th 0.381 0.367 0.057 0.475 0.156 0.096 0.739 0.071 U 1.340 2.340 0.137 1.320 0.883 0.222 0.449 0.822 Nb 3.690 5.80 0.049 2.840 0.758 0.042 0.094 0.478 Ta 0.055 0.056 0.053 0.050 0.035 0.053 0.046 0.040 Zr 0.339 0.097 0.123 0.076 0.037 0.085 0.033 0.065 Hf 0.222 0.245 0.239 0.247 0.161 0.180 0.213 0.168 
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表 2 黄水庵Mo–REE矿床的方解石C–O同位素组成
Table 2 C–O isotope contents of calcite from the Huangshui’an Mo–REE deposit
样号 δ13 CV-PDB(‰) δ18 OV-PDB(‰) δ18 OV-SMOW(‰) HSA02 −5.18 −22.49 7.72 HSA03 −5.62 −23.00 7.19 HSA04 −4.11 −23.76 6.40 HSA14 −5.31 −23.07 7.12 19HSA-13 −5.14 −22.58 7.62 19HSA-14 −5.39 −22.62 7.58
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表 3 东秦岭黄水庵Mo–REE矿床氟碳铈矿U–Th–Pb分析结果表
Table 3 Bastnäsite U–Th–Pb isotopic data from the Huangshui’an Mo–REE deposit, East Qinling
分析点 Th U Th/U 同位素比值 表面年龄(Ma) 207Pb/206Pb ±1σ 207Pb/235U ±1σ 206Pb/238U ±1σ 208Pb/232Th ±1σ 19HSA-16-01 12 908 82.9 155.7 0.630 7 0.016 5 11.640 7 0.391 6 0.134 2 0.0032 217 2.5 19HSA-16-02 9 144 61.3 149.3 0.563 5 0.016 5 9.655 7 0.640 6 0.114 5 0.0056 225 2.6 19HSA-16-03 9 136 68.4 133.6 0.075 2 0.004 8 0.436 4 0.025 5 0.044 7 0.0010 216 2.5 19HSA-16-04 14 191 92.2 154.0 0.215 2 0.010 9 1.503 7 0.091 7 0.046 7 0.0010 218 2.4 19HSA-16-05 7 391 47.3 156.4 0.154 2 0.009 8 0.994 8 0.0783 0.045 0 0.0012 218 2.8 19HSA-16-06 8 723 55.1 158.3 0.251 7 0.019 4 2.133 1 0.201 2 0.054 0 0.0021 211 2.4 19HSA-16-07 7 222 53.8 134.2 0.210 6 0.013 3 1.994 9 0.178 2 0.058 8 0.0021 219 2.5 19HSA-16-08 11 312 53.2 212.5 0.259 2 0.018 6 3.398 8 0.479 4 0.071 3 0.0069 206 2.7 19HSA-16-09 7 420 50.6 146.5 0.372 4 0.011 6 3.505 8 0.128 3 0.069 0 0.0014 217 2.2 19HSA-16-10 6 284 105 59.7 0.263 0 0.012 3 2.359 5 0.217 4 0.053 4 0.0022 206 2.6 19HSA-16-11 5 586 55.1 101.4 0.138 4 0.013 4 1.132 4 0.174 7 0.046 5 0.0019 207 2.4 19HSA-16-12 17 925 85.4 209.9 0.149 4 0.010 9 1.416 4 0.138 2 0.054 9 0.0016 213 2.3 19HSA-16-13 3 139 64.2 48.9 0.248 0 0.012 5 1.594 1 0.092 2 0.046 0 0.0011 205 2.3 19HSA-16-14 19 660 109 179.6 0.076 5 0.004 5 0.437 7 0.026 3 0.042 4 0.0008 213 2.2 19HSA-16-15 12 267 97.5 125.8 0.129 1 0.005 8 0.749 4 0.037 0 0.041 7 0.0009 201 2.3
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表 4 秦岭造山带碳酸岩型矿床的成矿时代
Table 4 Geochronological data for the carbonatite deposits in the Qinling orogenic belt
矿床 矿床类型 测试方法 年龄(Ma) 资料来源 黄水庵 碳酸岩型Mo–REE矿床 辉钼矿Re–Os 209.5±4.2 黄典豪等，2009 辉钼矿Re–Os 208.4±3.6 曹晶等，2014 氟碳铈矿U–Th–Pb 206.5±3.8 Zhang et al.，2019 氟碳铈矿U–Th–Pb 211.7±3.1 Feng et al.，2022 209.6±2.1 氟碳铈矿U–Th–Pb 213.5±2.9 本文 黄龙铺 碳酸岩型Mo–REE矿床 辉钼矿Re–Os 221.5±0.3 Stein，1997 辉钼矿Re–Os 222.0±7.0 Huang et al.，1995 辉钼矿Re–Os 225.0 ± 7.6 Song et al.，2015 独居石U–Th–Pb 208.9±4.6
213.6± 4.0Song et al.，2016 华阳川 碳酸岩型U–Nb–Pb–REE矿床 独居石U–Th–Pb 222.5±6.7 王佳营等，2020 晶质铀矿U–Th–Pb 221.9±5.1
137.1±2.0黄卉等，2020 榍石U–Pb 208.5±3.2 Zheng et al.，2020 辉钼矿Re–Os 196.8±2.4 Zheng et al.，2020 庙垭 碳酸岩型Nb-REE矿床 独居石U–Th–Pb 233.6±1.7 Xu et al.，2014 氟碳铈矿U–Th–Pb 205.8±3.6 Zhang et al.，2019 独居石U–Pb 231.0±2.3 Zhang et al.，2019 锆石U–Th–Pb 426.5±8.0 Ying et al.，2017 独居石U–Th–Pb 238.3±4.1 Ying et al.，2017 铌铁矿U–Pb 232.8±3.7 Ying et al.，2017
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