Geochemistry, zircon U−Pb and Hf isotopes of the high−purity pegmatite−quartz deposits in the Eastern Qinling and discussion on its prospecting direction
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摘要:
研究目的 高纯石英是战略性新兴产业的关键基础材料，是世界稀缺的战略性矿产资源。目前美国以Spruce−Pine花岗伟晶岩作为原料生产的4N8及以上高端石英砂产品几乎垄断国际市场。东秦岭4N级伟晶岩型高纯石英矿点的发现为研究高纯石英形成机制、实现找矿突破和建立成矿模型提供了难得的机遇。
研究方法 通过对东秦岭新发现的伟晶岩型高纯石英矿点开展野外调查，并与美国Spruce−Pine高纯石英矿床伟晶岩开展岩石地球化学、锆石U−Pb同位素年代学和Hf同位素等方面的对比研究。
研究结果 东秦岭10号高纯石英矿形成于早泥盆世，锆石U−Pb年龄为（406.8±0.8）Ma，稍早于美国Spruce−Pine的高纯石英花岗伟晶岩形成时代。东秦岭高纯石英矿点伟晶岩与美国Spruce−Pine高纯石英矿床伟晶岩形成温度均为600℃左右。东秦岭高纯石英矿点伟晶岩与美国Spruce−Pine高纯石英矿床伟晶岩具有相似的岩石地球化学特征，表现I型花岗岩和高分异演化特征，源区物质来源既有下地壳，也有幔源物质。仅通过对东秦岭高纯石英矿点伟晶岩和灰池子花岗岩体空间关系、形成时代和岩石地球化学特征，是不足以完全反演源区特征及成岩成矿过程，对于东秦岭高纯石英矿点伟晶岩和灰池子花岗岩体是否存在同源演化仍需要进一步研究。
结论 东秦岭与美国Spruce−Pine高纯石英矿床在花岗岩类型、岩浆特征和形成温度等方面具有相似性，为进一步揭示高纯石英成矿地质背景和实现找矿突破提供理论依据。
Abstract:This paper is the result of mineral exploration engineering.
Objective As the world's scarce strategic mineral resource, high−purity quartz is the key basic material of strategic emerging industries. Spruce−Pine granitic pegmatite was used as raw material by the United States to produce high−end quartz sand products, which were better than the quality of 4N8, and almost monopolized the international market. The discovery of 4N class high−purity pegmatite−quartz deposits in Eastern Qinling provides a rare opportunity to study the formation mechanism of high purity quartz, realize prospecting breakthrough and establish metallogenic model.
Methods Based on the field investigation of the newly discovered high−purity pegmatite-quartz deposits in the Eastern Qinling Mountains, the geochemistry, zircon U−Pb isotope chronology and Hf isotope of pegmatite deposits in Spruce−Pine high−purity quartz deposits in the United States were compared.
Results The Eastern Qinling 10 high purity quartz deposit was formed in the Early Devonian with a zircon U−Pb age of (406.8±0.8) Ma, which is earlier than that of high purity quartz granite−pegmatite in Spruce−Pine. The formation temperature of pegmatite from high purity quartz deposit in Eastern Qinling and Spruce−Pine is about 600℃. Pegmatite from the high purity quartz deposit in the Eastern Qinling has similar geochemical characteristics to pegmatite from the high purity quartz deposit in Spruce−Pine, showing features of I-type granite and high differentiation evolution. The materials in the source area come from both lower crust and mantle. It is not enough to completely invert the characteristics of the source area and the diagenesis and mineralization process by compared the spatial relationship with formation age and petrogeochemical characteristics. Whether the pegmatite of high purity quartz deposits and Huichizi granite pluton in the Eastern Qinling have the homologous evolution still needs further study.
Conclusions Compared with the granite type, magmatic characteristics and formation temperature of the high−purity quartz deposits (points) in the Eastern Qinling and Spruce−Pine are similar, which provides a theoretical basis for further revealing the geological background of high−purity quartz mineralization and achieving breakthroughs in high−purity quartz ore deposits prospecting.
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Key words:
- geochemistry /
- zircon U−Pb /
- Hf isotopes /
- high−purity quartz /
- pegmatite /
- mineral exploration engineering /
- Eastern Qinling
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图 4 东秦岭5号、10号伟晶岩脉和Spruce−Pine伟晶岩、灰池子花岗岩体TAS图解（a，底图据Middlemost, 1994）、A/CNK−A/NK图解（b，底图据Maniar and Piccoli, 1989）与SiO2−K2O图解（c，底图据Peccerillo and Taylor, 1976）（灰池子花岗岩数据据刘丙祥，2014； Spruce−Pine部分数据据张晔，2010）
Figure 4.
图 5 东秦岭伟晶岩、Spruce−Pine伟晶岩和灰池子花岗岩体球粒陨石标准化稀土元素配分图（a）及微量元素原始地幔标准化蛛网图（b）（球粒陨石标准化值据Anders和Grevesse, 1989；原始地幔标准化值据Sun和McDonough, 1989；灰池子花岗岩数据据刘丙祥, 2014；Spruce−Pine部分数据据张晔, 2010）
Figure 5.
表 1 东秦岭10号、5号伟晶岩脉和Spruce−Pine伟晶岩主量元素（%）微量元素（10−6）分析测试结果
Table 1. Major (%) and trace (10−6) element analyzed result of No.10 and No.5 pegmatite dikes in the Eastern Qinling and Spruce−Pine pegmatites
样品号 LD05-T1 LD05-T2 LD05-T3 LD10-T1 LD10-T2 LD10-T3 20SP01 SP01* SP02* SiO2 78.13 78.89 76.56 79.37 76.18 77.55 74.39 74.50 77.60 TiO2 0.03 0.02 0.03 0.08 0.03 0.04 0.02 0.02 0.02 Al2O3 12.74 12.22 13.70 11.30 13.08 12.24 14.31 15.60 12.95 Fe2O3 0.25 0.14 0.31 0.41 0.02 0.05 1.28 0.27 0.15 FeO 0.11 0.07 0.14 0.18 0.01 0.04 0.10 0.10 0.19 MnO 0.03 0.02 0.04 0.01 0.00 0.00 0.10 0.02 0.02 MgO 0.09 0.05 0.08 0.11 0.02 0.05 1.28 0.21 0.19 CaO 0.49 0.48 0.64 0.39 0.36 0.30 5.53 1.54 1.15 Na2O 2.87 3.64 3.91 1.85 1.91 1.58 1.79 6.62 4.76 K2O 4.21 4.07 3.97 6.24 8.11 7.99 0.01 1.29 2.49 P2O5 0.11 0.14 0.14 0.04 0.04 0.04 0.78 0.06 0.05 总量 99.05 99.74 99.52 99.98 99.77 99.88 99.58 100.23 99.57 σ 1.4 1.7 1.8 1.8 3.0 2.7 0.1 2.0 1.5 DI 96.0 97.9 96.5 97.8 99.2 99.1 89.5 98.1 98.5 TZr/℃ 609 601 648 611 611 554 796 657 526 K2O+Na2O 7.08 7.71 7.88 8.09 10.02 9.57 1.80 7.91 7.25 A/CNK 1.25 1.08 1.15 1.08 1.04 1.04 1.10 1.03 1.03 A/NK 1.37 1.18 1.28 1.15 1.10 1.09 4.84 1.27 1.23 AR 2.53 3.69 3.40 1.93 1.79 1.67 1.44 7.79 5.16 FeOT/MgO 3.88 4.06 5.45 5.20 1.45 1.72 1.07 1.71 1.69 Mg# 59.81 55.36 49.81 52.19 71.27 71.27 95.83 78.92 64.06 Rb 255 223 223 270 213 279 32 26.3 60.7 Ba 4.54 4.85 8.01 403 370 355 320 181 981 Th 0.67 0.17 1.00 8.93 34.5 1.79 12.4 1.58 0.92 U 15.2 7.16 22.7 7.38 11.8 3.36 8.83 1.25 1.48 Nb 4.37 3.67 6.87 2.88 5.79 2.84 16.7 3.75 2.86 Ta 0.95 0.87 1.69 1.08 2.09 1.01 1.32 0.28 0.31 Sr 9.22 6.99 10.7 62.6 60.3 59.3 144 219 313 Zr 10.6 9.20 19.5 10.8 10.9 5.33 181 30.0 3.10 Hf 0.57 0.49 1.04 0.46 0.49 0.25 17.0 1.17 0.20 Y 1.40 0.66 3.00 1.16 3.59 1.84 35.1 5.68 2.80 La 0.89 0.23 1.27 0.91 3.41 0.47 5.54 3.00 1.66 Ce 1.92 0.67 3.14 2.17 6.97 1.34 15.8 6.00 5.77 Pr 0.19 0.05 0.31 0.19 0.76 0.06 1.85 0.68 0.33 Nd 0.58 0.15 0.99 0.69 2.85 0.21 9.00 2.83 1.29 Sm 0.18 0.06 0.36 0.19 0.71 0.07 5.77 0.93 0.43 Eu 0.03 0.01 0.03 0.09 0.26 0.07 0.39 0.42 0.47 Gd 0.16 0.07 0.36 0.17 0.62 0.13 8.20 1.26 0.55 Tb 0.04 0.02 0.09 0.03 0.11 0.03 1.53 0.22 0.09 Dy 0.25 0.11 0.55 0.17 0.59 0.23 7.47 1.25 0.55 Ho 0.04 0.02 0.09 0.03 0.11 0.05 0.94 0.19 0.09 Er 0.13 0.05 0.26 0.10 0.32 0.17 1.78 0.48 0.22 Tm 0.03 0.01 0.05 0.02 0.05 0.03 0.21 0.06 0.03 Yb 0.22 0.08 0.39 0.11 0.31 0.19 1.08 0.33 0.15 Lu 0.03 0.01 0.06 0.02 0.04 0.03 0.13 0.05 0.02 ∑REE 4.68 1.55 7.96 4.88 17.1 3.07 59.7 17.7 11.6 ∑LREE/∑HREE 4.23 3.17 3.29 6.65 6.96 2.61 1.80 3.61 5.85 (La/Yb)N 2.78 1.88 2.20 5.67 7.37 1.69 3.46 6.13 7.46 (La/Sm)N 3.14 2.22 2.21 3.01 3.03 4.27 0.60 2.03 2.43 δEu 0.47 0.56 0.28 1.55 1.16 2.11 0.18 1.19 2.95 δCe 1.08 1.44 1.17 1.20 1.00 1.64 1.18 0.97 1.77 注：*数据来自张晔，2010；FeOT=FeO+0.8998×Fe2O3；分异指数(DI) = Qz + Or + Ab + Ne + Lc + Kp；碱度率(AR)=[Al2O3+CaO+(Na2O+K2O)]/[Al2O3+CaO−(Na2O+K2O)]，当SiO2>50，K2O/Na2O大于1而小于2.5时，Na2O+K2O=2Na2O；里特曼指数(σ) = (Na2O+K2O)2/(SiO2−43)；Mg# =100×Mg2+/(Mg2++TFe2+)。 
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表 2 东秦岭10号高纯石英矿点伟晶岩LA−ICP−MS锆石U−Th−Pb测试数据
Table 2. LA−ICP−MS zircon U−Th−Pb isotopic data of the pegmatite of No.10 high−purity pegmatite−quartz deposits in the Eastern Qinling
测点号 Th/10−6 U/10−6 Th/U 同位素比值 表面年龄/Ma 207Pb/206Pb 1σ 207Pb/235U 1σ 206Pb/238U 1σ 207Pb/206Pb 1σ 207Pb/235U 1σ 206Pb/238U 1σ 1 170.7 6168.0 0.03 0.0547 0.0010 0.4897 0.0042 0.0654 0.0015 397.0 43.0 404.6 2.8 408.4 2.8 2 176.5 6030.0 0.03 0.0555 0.0011 0.4950 0.0100 0.0651 0.0019 426.0 45.0 408.0 7.1 406.3 7.1 3 289.9 8420.0 0.03 0.0549 0.0011 0.4935 0.0054 0.0652 0.0016 404.0 45.0 407.2 3.7 407.3 3.5 4 152.7 5740.0 0.03 0.0550 0.0011 0.4936 0.0050 0.0648 0.0015 408.0 44.0 407.2 3.4 404.5 2.5 5 426.0 10830.0 0.04 0.0542 0.0011 0.4897 0.0050 0.0652 0.0016 376.0 45.0 404.6 3.4 407.0 3.3 6 138.4 4655.0 0.03 0.0552 0.0010 0.4990 0.0044 0.0654 0.0015 416.0 42.0 410.9 3.0 408.3 2.9 7 156.8 5709.0 0.03 0.0550 0.0011 0.4962 0.0055 0.0652 0.0016 407.0 44.0 408.9 3.7 406.9 3.7 8 89.1 3428.0 0.03 0.0543 0.0011 0.4877 0.0051 0.0650 0.0015 378.0 46.0 403.6 3.6 405.9 2.4 9 331.6 9680.0 0.03 0.0551 0.0010 0.4977 0.0033 0.0653 0.0015 413.0 42.0 410.1 2.2 407.9 2.4 10 339.4 9070.0 0.04 0.0548 0.0010 0.4939 0.0045 0.0652 0.0015 402.0 42.0 407.4 3.0 407.0 2.8 11 176.8 5898.0 0.03 0.0548 0.0010 0.4894 0.0040 0.0648 0.0015 398.0 43.0 404.4 2.7 405.0 2.3 12 244.0 7240.0 0.03 0.0547 0.0011 0.4929 0.0052 0.0652 0.0016 402.0 41.0 407.4 3.3 407.2 3.2 13 185.6 6150.0 0.03 0.0544 0.0010 0.4899 0.0059 0.0654 0.0016 387.0 43.0 404.7 4.0 408.6 3.1
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表 3 东秦岭10号高纯石英矿点伟晶岩主锆石Hf同位素分析结果
Table 3. Zircon Hf isotopic data of the pegmatite of No.10 high−purity pegmatite−quartz deposits in the Eastern Qinling
锆石点号 年龄/Ma 174Yb/177Hf 176Hf/177Hf 2σ 176Lu/177Hf 2σ εHf(t) TDM/Ma TCDM/Ma 1 408.4 0.093161 0.282669 0.000014 0.003118 0.000010 4.1 875 1114 2 406.3 0.057485 0.282658 0.000011 0.001817 0.000016 4.1 859 1114 3 407.3 0.083697 0.282650 0.000015 0.002843 0.000007 3.5 897 1152 4 404.5 0.076034 0.282691 0.000014 0.002471 0.000002 5.1 827 1052 5 407.0 0.103616 0.282712 0.000013 0.003486 0.000007 5.5 819 1023 6 408.3 0.055215 0.282692 0.000014 0.001751 0.000009 5.3 810 1039 7 406.9 0.088308 0.282690 0.000013 0.002834 0.000022 4.9 837 1061 8 405.9 0.043717 0.282696 0.000013 0.001388 0.000014 5.6 795 1022 9 407.9 0.098038 0.282668 0.000017 0.003175 0.000009 4.1 877 1116 10 407.0 0.074028 0.282687 0.000014 0.002411 0.000003 5.0 831 1060 11 405.0 0.064612 0.282685 0.000014 0.002093 0.000021 5.0 827 1059 12 407.2 0.078494 0.282704 0.000016 0.002579 0.000006 5.5 811 1026 13 408.6 0.080175 0.282699 0.000016 0.002571 0.000006 5.3 818 1036
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表 4 东秦岭地区伟晶岩及灰池子花岗岩体年龄一览
Table 4. Age of the pegmatites and the Huizhi granitic pluton in the Eastern Qinling
采样位置 样品岩性 年代学方法 年龄/Ma 谐和年龄区间/Ma 数据来源 陕西光石沟 花岗伟晶岩 LA−ICP−MS独居石U−Th−Pb 399.6±0.8 武勇等，2022 陕西光石沟 花岗伟晶岩 LA−ICP−MS独居石U−Th−Pb 400.2±4.3 武勇等，2022 陕西光石沟 花岗伟晶岩 LA−ICP−MS独居石U−Th−Pb 400.8±2.4 武勇等，2022 陕西光石沟 花岗伟晶岩 LA−ICP−MS独居石U−Th−Pb 403.5±3.6 武勇等，2022 陈家庄屋沟村 含铀伟晶岩 LA−ICP−MS锆石U−Pb 404.3±1.4 395.1~409.4 王江波等，2020 南阳山 稀有金属伟晶岩 LA−ICP−MS锆石U−Pb 406.2±5.2 Yuan et al., 2022 龙泉坪 花岗伟晶岩 LA−ICP−MS锆石U−Pb 406.8±0.8 404.5~408.6 本文 南阳山 稀有金属伟晶岩 LA−ICP−MS铌铁矿物U−Pb 406.8±3.3 Yuan et al., 2022 南阳山 稀有金属伟晶岩 LA−MC−ICP−MS锡石U−Pb 410.6±7.9 Yuan et al., 2022 陕西光石沟 黑云母花岗伟晶岩 LA−ICP−MS锆石U−Pb 413.6±2.4 袁峰等，2017 陕西陈家庄 花岗伟晶岩 LA−ICP−MS锆石U−Pb 414±4 张帅等，2019 陕西光石沟 黑云母花岗伟晶岩 LA−ICP−MS锆石U−Pb 415.1±2.6 袁峰等，2017 陕西陈家庄 花岗伟晶岩 LA−ICP−MS锆石U−Pb 416±3 张帅等，2019 陕西陈家庄 花岗伟晶岩 LA−ICP−MS锆石U−Pb 417±3 张帅等，2019 龙泉坪 花岗伟晶岩 LA−ICP−MS独居石U−Pb 420.2±2.2 415~429 Zhang et al., 2022 南阳山 锂辉石钠长石伟晶岩 LA−MC−ICP−MS锡石U−Pb 420±2 曾威等，2021 灰池子 黑云母二长花岗岩 LA−ICP−MS锆石U−Pb 421±27 王涛等，2009 灰池子 黑云母二长花岗岩 SIMS锆石U−Pb 434±7 王涛等，2009 灰池子 花岗岩 LA−ICP−MS锆石U−Pb 454.9±7.7 431~480 刘丙祥，2014 灰池子 花岗岩 LA−ICP−MS锆石U−Pb 457±13 420~486 刘丙祥，2014 灰池子 花岗岩 LA−ICP−MS锆石U−Pb 460±3.9 440~473 刘丙祥，2014 灰池子 花岗岩 LA−ICP−MS锆石U−Pb 462.8±6.0 446~485 刘丙祥，2014
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