Cassiterite U-Pb Age, Geochemistry and Their Geological Significances of Rare Metal Pegmatites in Guanpo Area, North Qinling, China
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摘要: 北秦岭官坡-丹凤地区是我国重要的伟晶岩型铀和稀有金属成矿区，目前官坡地区稀有金属伟晶岩的形成时代和成因机制尚不清楚.通过对该地区花岗伟晶岩开展锡石U-Pb年代学、锆石Hf同位素地球化学及全岩主微量元素地球化学研究，分析了伟晶岩成因并探讨秦岭造山带古生代造山作用的时限.锡石LA-MC-ICP-MS U-Pb测年首次确定官坡地区南阳山稀有金属伟晶岩的成岩成矿时代为420±2 Ma，形成于末志留世，表明此时北秦岭造山带处于造山作用晚期或造山后相对稳定的构造背景. 花岗伟晶岩锆石εHf（420 Ma）值为-7.0~-7.8，二阶段Hf模式年龄为2.45~2.52 Ga，表明其源区为古老的地壳物质. 花岗伟晶岩铝饱和指数大于1.10，具有极低的稀土总量（ΣREE=0.43×10-6~23.14×10-6），变化范围较大的LaN/YbN值（0.7~22.3）和δEu值（0.09~1.84）. 岩石富集大离子亲石元素Rb、K和高场强元素Nb、Ta、P、Hf，亏损Ba、Nd、Zr、Ti，具有低的Nb/Ta比值（平均值2.66），稀土元素四分组效应明显，这些特征指示岩浆经历了高度结晶分异作用.同位素和岩石地球化学研究表明，官坡地区花岗金属伟晶岩与其南侧灰池子岩体和大毛沟岩体不具岩浆演化关系，稀有金属伟晶岩为过铝质花岗岩浆高程度结晶分异演化的产物.Abstract: The Guanpo-Danfeng area in the North Qinling Belt is the most important pegmatite-type uranium metallogenic and an important pegmatite-type rare metal metallogenic region in China. However, the formation age and the genetic mechanism of the rare metal pegmatites in this area still remain unclear. This paper presents LA-MC-ICP-MS cassiterite U-Pb age, Hf isotopic and geochemical data of granitic pegmatites in the Guanpo area to determine the formation age, the petrogenesis and tectonic setting of the rare metal pegmatites. Cassiterite LA-MC-ICP-MS dating of Nanyangshan rare metal pegmatites yields concordant age of420±2 Ma, representing the the formation age of the end of the Silurian, which indicated North Qinling was in late or postorogenic tectonic setting.The pegmaties exhibit a restricted range of negative zircon εHf(t) values of -7.0 to -7.8, with TDM2 age of 2.45 to 2.52 Ga, suggesting that the magma dominantly derived from ancient crust. The pegmatites are characterized by high A/CNK (A/CNK > 1.1), with extremely low rare earth content (ΣREE=0.43×10-6~23.14×10-6) and widely variable LaN/YbN ratios(0.7~22.3) and δEu(0.09~1.84). The enrichment in large ion lithophile elements(Rb and K) and high field strength elements (Nb, Ta, P and Hf), depletion in Ba, Nd, Zr, and Ti, low Nb/Ta ratios (average 2.66) and tetrad effects of rare earth elements comprehensively indicated that the magma has experienced high degree crystallization differentiation. The isotopic and geochemical data confirm that the rare metal pegmatite in the Guanpo area formed from high degree crystallization differentiation of peraluminous granitic magma and the genetic connection between the pegmatites and Huichizi and Damaogou granites is absent.
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Key words:
- Cassiterite U-Pb dating /
- geochemistry /
- granitic pegmatite /
- rare metal /
- Guanpo /
- North Qinling
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图 2 官坡地区南阳山矿区花岗伟晶岩分布图
Fig. 2. Distribution map of pegmatites in Nanyangshan deposit Guanpo area
图 3 官坡地区南阳山矿区Ⅵ-Ⅵ’剖面图
Fig. 3. Section map of line Ⅵ-Ⅵ' in Nanyangshan deposit Guanpo area
图 4 南阳山矿区稀有金属伟晶岩手标本和镜下照片
a. 锂辉石钠长石微斜长石伟晶岩中锂辉石和黑色电气石；b. 锂辉石钠长石伟晶岩中锂辉石和深灰色石英；c. 锂辉石微斜长石伟晶岩中锂辉石和黑色电气石；d. 锂电气石钠长石伟晶岩中粉色电气石和锂云母；e. 钠长石微斜长石伟晶岩中黑色电气石和白云母；f. 铌锰矿和黄铁矿反射光照片；g. 锂辉石、锡石和锂云母正交镜下照片；h. 钠长石、角闪石、锡石正交镜下照片；i. 钠长石、电气石正交镜下照片；j. 微斜长石、钠长石、白云母、电气石正交镜下照片；k. 锂辉石、锂云母单偏光下照片；l. 锂辉石、钠长石、石英、锡石单偏光下照片；Tur. 电气石；Spd. 锂辉石；Qz. 石英；Lpd. 锂云母；Mus.白云母；Mcol. 铌锰矿；Py. 黄铁矿；Cst. 锡石；Ab. 钠长石；Hb. 角闪石；Alf. 微斜长石
Fig. 4. Hand speciments and microscope images of rare metal pegmatites in Nanyangshan deposit
图 5 南阳山矿区伟晶岩锡石背散射图像
Fig. 5. Back-scattered electron(BSE) images of cassiterites from Nanyangshan deposit
图 6 锡石成因判别图解（底图据Tindle and Breaks，1998）
Fig. 6. Genesis covariation of cassiterite(base map after Tindle and Breaks, 1998)
图 7 南阳山矿区伟晶岩锡石U-Pb测年谐和图（a）和加权平均年龄（b）
Fig. 7. U-Pb Tera-Wasserburg concordia plot(a) and average age(b) of cassiterite from Nanyangshan raremetal pegmatites
图 8 花岗伟晶岩锆石U-Pb谐和图（a和b）、背散射图像（c）和阴极发光图像（d）
Fig. 8. U-Pb concordia diagrams(a and b), BSE images (c)and cathodoluminescence images(d)of zircons from Nanyangshan pegmatites
图 9 官坡地区花岗伟晶岩主量元素地球化学图解
TAS图解，底图据Middlemost（1994），5区为花岗闪长岩，6区为花岗岩，7区为硅英岩，11区为二长花岗岩；b. 底图据Yang（2007），A区代表非造山带的熔浆，B区代表造山带和岛弧的熔浆，C区代表A和B的衍生物；c. 为A/NK-A/CNK图解，底图据Maniar and Piccoli（1989）；d. 为硅钾图，底图据Peccerillo et al.，（1976）
Fig. 9. Major element diagram of granitic pegmatites in Guanpo area
图 10 花岗伟晶岩微量元素蛛网图
a. 含矿伟晶岩；b. 为不含矿伟晶岩；原始地幔数据据McDonough and Sun（1995）
Fig. 10. Primitive mantle-normalized spidergrams of granitic pegmatites
图 11 花岗伟晶岩、含榴二长花岗岩和秦岭岩群副片麻岩稀土元素球粒陨石标准化图
球粒陨石数据据Sun and McDonough（1989），含榴二长花岗岩数据黄龙庙岩体据赵如意等（2012），骡子坪岩体据张良等（2021），秦岭岩群副片麻岩数据据河南省地质调查院，2002.内乡县幅区域地质调查报告
Fig. 11. Chondrite-normalized REE distribution patterns of granitic pegmatites, garnet bearing monzogranite and paragneiss of Qinling Group
图 12 花岗伟晶岩Rb-Ba-Sr图解（a）和Rb-SiO2散点图（b）
a. 底图据Blouseily and Sokkary（1975）；AGG. 钠长石化和云英岩化花岗岩；DG. 分异的花岗岩；NG. 正常花岗岩；AG. 异常花岗岩；GD. 花岗闪长岩；QD. 石英闪长岩；D. 闪长岩；GAD. 与W、Mo、Sn有关矿化花岗岩
Fig. 12. Rb-Ba-Sr diagram (a), and Rb-SiO2scatter diagram (b) of granitic pegmatite
图 13 官坡地区伟晶岩主量元素哈克图解
Fig. 13. Harker diagrams of the major elements of granitic pegmatites in Guanpo area
表 1 南阳山矿区部分锂矿化伟晶岩脉特征表
Table 1. Characteristics of some lithium mineralized pegmatites in Nanyangshan deposit
矿脉编号 规模（m） 产状 平均品位（%） 主要矿物 长度 平均厚度 延伸 倾向 倾角 Li2O 工业 脉石 ρ401 36 1.19 11° 54°~40° 1.24 锂辉石、绿柱石、铌钽铁矿等 微斜长石、钠长石、石英、白云母等 ρ363 75 4.55 40 290° 73° 1.55 锂云母、锂辉石、绿柱石、铌锰矿等 钠长石、石英、白云母高岭石、红电气石等 ρ312 243 5.30 210 22°~35° 14°~40° 1.31 锂辉石、锂云母、铌锰矿、钽锰矿等 钠长石、微斜长石、石英、白云母、电气石等 ρ501 27 5.10 38.6 287° 65° 1.35 锂辉石、锂云母、绿柱石、铌锰矿等 钠长石、石英、白云母高岭石、红电气石等 ρ366 123 2.54 115 170°~203° 32°~69° 1.23 锂辉石、锂白云母、锰钽矿等 钠长石、微斜长石、石英、白云母等 ρ506 262 3.84 172 35° 79° 1.24 锂辉石、锂白云母、锰钽矿等 钠长石、微斜长石、石英、白云母等 
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表 2 南阳山矿区伟晶岩中锡石电子探针成分数据
Table 2. Chemical composition data of the cassiterite from pegmatites in Nanyangshan deposi(analyzed by EPMA)
样品号 NYSSN1 NYSSN2 NYSSN4 NYSSN5 NYSSN8 NYSSN9 NYSSN11 NYSSN12 MgO 0.06 0.08 0.09 0.07 0.08 0.12 0.08 0.10 Al2O3 0.02 0.01 0.04 0.02 0.01 BDL 0.03 0.01 Ta2O5 1.64 1.79 1.69 0.36 0.13 0.20 0.31 0.27 WO3 0.11 0.03 0.09 BDL BDL 0.11 0.01 BDL ZrO2 0.06 0.08 0.08 0.05 BDL 0.01 0.07 0.05 Nb2O5 0.55 0.48 0.70 0.14 0.05 0.06 0.13 0.09 SnO2 96.81 95.86 96.11 99.28 99.38 98.26 97.37 98.16 Sc2O3 BDL 0.02 BDL BDL 0.00 BDL BDL 0.02 TiO2 0.07 0.21 0.02 0.01 BDL 0.01 BDL 0.05 Cr2O3 0.04 BDL 0.01 0.01 0.02 0.02 BDL BDL MnO BDL 0.02 0.04 BDL BDL 0.02 0.01 BDL FeO 0.41 0.45 0.63 0.16 0.07 0.07 0.10 0.08 TOTAL 99.77 99.03 99.51 100.09 99.74 98.88 98.12 98.83 Mg 0.004 0.006 0.007 0.005 0.006 0.009 0.006 0.007 Al 0.001 0.001 0.002 0.001 0.000 BDL 0.002 0.000 Ta 0.022 0.024 0.023 0.005 0.002 0.003 0.004 0.004 W 0.001 0.000 0.001 BDL BDL 0.001 0.000 BDL Zr 0.002 0.002 0.002 0.001 BDL 0.000 0.002 0.001 Nb 0.012 0.011 0.016 0.003 0.001 0.001 0.003 0.002 Sn 1.927 1.908 1.913 1.976 1.978 1.956 1.938 1.954 Ti 0.002 0.008 0.001 0.000 BDL 0.001 BDL 0.002 Cr 0.001 BDL 0.000 0.000 0.001 0.001 BDL BDL Mn BDL 0.001 0.002 BDL BDL 0.001 0.000 BDL Fe 0.017 0.019 0.026 0.007 0.003 0.003 0.004 0.003 Nb+Ta 0.035 0.035 0.039 0.008 0.003 0.004 0.007 0.006 Mn+Fe 0.017 0.019 0.028 0.007 0.003 0.004 0.005 0.003 样品号 NYSSN13 NYSSN14 NYSSN17 NYSSN16 NYSSN18 NYSSN19 NYSSN20 NYSSN23 MgO 0.10 0.09 0.10 0.13 0.07 0.10 0.08 0.39 Al2O3 0.01 BDL 0.01 BDL BDL BDL 0.02 0.02 Ta2O5 1.59 0.60 0.13 0.35 0.23 1.35 1.96 0.47 WO3 BDL BDL BDL 0.02 BDL 0.03 0.15 0.09 ZrO2 0.06 BDL 0.03 BDL 0.04 0.06 0.08 0.05 Nb2O5 0.16 0.20 BDL BDL 0.09 0.10 0.60 0.15 SnO2 97.08 98.66 99.56 98.18 98.48 97.61 95.60 97.49 Sc2O3 BDL BDL 0.03 BDL BDL BDL BDL 0.01 TiO2 BDL 0.03 BDL BDL 0.05 0.01 0.09 0.07 Cr2O3 BDL BDL BDL 0.02 BDL BDL 0.01 0.01 MnO 0.01 0.01 BDL 0.01 BDL 0.02 BDL BDL FeO 0.30 0.17 0.06 0.07 0.06 0.27 0.60 0.12 TOTAL 99.30 99.74 99.92 98.79 99.02 99.55 99.18 98.86 Mg 0.007 0.007 0.007 0.010 0.005 0.007 0.006 0.029 Al 0.001 BDL 0.000 BDL BDL BDL 0.001 0.001 Ta 0.022 0.008 0.002 0.005 0.003 0.018 0.027 0.006 W BDL BDL BDL 0.000 BDL 0.000 0.002 0.001 Zr 0.001 BDL 0.001 BDL 0.001 0.001 0.002 0.001 Nb 0.004 0.005 BDL BDL 0.002 0.002 0.014 0.003 Sn 1.933 1.964 1.982 1.954 1.960 1.943 1.903 1.941 Ti BDL 0.001 BDL BDL 0.002 0.000 0.003 0.002 Cr BDL BDL BDL 0.001 0.000 BDL 0.000 0.000 Mn 0.000 0.000 BDL 0.000 BDL 0.001 BDL BDL Fe 0.013 0.007 0.002 0.003 0.002 0.011 0.025 0.005 Nb+Ta 0.025 0.013 0.002 0.005 0.005 0.021 0.040 0.010 Mn+Fe 0.013 0.007 0.002 0.004 0.002 0.012 0.025 0.005 注：阳离子数按照氧原子数为4来计算.
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表 3 南阳山花岗伟晶岩锡石LA-MC-ICP-MS U-Pb分析结果
Table 3. LA-MC-ICP-MS U-Pb isotope data of cassiteritefrom Nanyangshan pegmatites
样品 测点号 同位素比值 238U/206Pb ERR% 207Pb/206Pb ERR% 207Pb/235U ERR% NYS18 1 14.68 1.01 0.049 7 6.44 0.401 4 6.47 2 14.92 1.16 0.051 2 12.34 0.421 4 11.91 3 15.27 1.03 0.071 2 5.58 0.559 9 5.62 4 14.70 0.99 0.063 4 4.12 0.515 0 4.20 5 14.99 1.55 0.054 0 22.19 0.466 6 19.46 6 14.77 1.01 0.043 5 7.65 0.354 0 7.60 7 14.18 1.18 0.059 7 11.46 0.508 6 11.23 8 14.59 1.05 0.058 4 7.52 0.475 9 7.51 9 14.10 1.21 0.076 1 8.44 0.646 5 8.26 10 15.00 1.21 0.040 0 18.21 0.329 6 16.99 11 14.68 1.22 0.060 0 11.58 0.483 3 11.53 12 14.68 1.76 0.087 0 15.24 0.774 5 12.37 13 14.78 1.19 0.031 4 20.56 0.264 0 19.29 14 14.85 1.01 0.055 2 6.49 0.444 6 6.51 15 15.69 1.61 0.063 8 2.37 0.483 2 2.89 16 14.66 0.97 0.049 5 4.55 0.403 1 4.63 17 14.72 1.38 0.083 8 9.39 0.703 5 9.03 18 13.40 1.00 0.090 1 3.30 0.803 5 3.41 19 14.49 1.41 0.079 6 11.92 0.677 5 11.20 20 14.82 1.00 0.069 5 4.93 0.560 1 5.02 21 15.06 1.12 0.060 2 8.48 0.488 3 8.32 22 14.94 1.00 0.066 1 4.31 0.528 0 4.36 23 14.09 1.12 0.058 0 1.65 0.488 2 1.83 24 13.72 1.10 0.061 3 2.79 0.532 3 2.92 25 14.80 0.99 0.060 1 5.10 0.485 9 5.17 26 14.84 0.96 0.049 5 5.13 0.397 3 5.17 27 14.86 0.95 0.052 2 3.20 0.418 1 3.26 28 14.73 1.08 0.060 8 8.22 0.497 7 8.17 29 14.75 0.99 0.060 1 5.07 0.486 3 5.14 30 15.06 1.26 0.032 8 21.11 0.271 3 19.94 31 14.95 1.08 0.057 7 8.39 0.467 8 8.39 32 13.92 1.03 0.075 5 4.58 0.648 8 4.78 33 14.93 1.04 0.069 3 6.38 0.554 8 6.35 34 14.88 0.94 0.059 7 1.95 0.476 9 2.05 35 15.42 1.98 0.053 5 29.55 0.506 7 21.44 36 13.16 1.49 0.070 1 17.41 0.654 7 15.59 37 14.71 0.98 0.056 6 5.43 0.457 9 5.46 38 14.45 0.97 0.081 3 3.06 0.669 8 3.15 39 14.73 1.03 0.074 0 5.37 0.598 0 5.49 40 15.87 1.09 0.063 1 7.05 0.478 2 7.08 41 14.84 0.96 0.050 6 4.11 0.405 6 4.14 42 14.79 0.98 0.054 8 4.99 0.443 4 5.08 43 15.38 2.00 0.083 7 23.83 0.738 6 18.64 44 13.74 1.34 0.075 2 11.05 0.657 3 10.86 45 14.56 1.08 0.078 6 6.07 0.650 2 6.06 46 15.28 1.65 0.092 9 14.40 0.753 6 13.72 47 14.72 0.97 0.060 3 3.78 0.489 3 3.86 48 14.80 1.01 0.051 1 6.17 0.415 1 6.19
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表 4 花岗伟晶岩锆石LA-ICP-MS U-Pb分析结果
Table 4. LA-ICP-MS U-Pb isotopic data of zircons from Nanyangshan pegmatites
样品 测点号 含量（×10-6） Th/U 同位素比值 年龄（Ma） Th U 207Pb/206Pb 1σ 207Pb/235U 1σ 206Pb/238U 1σ 207Pb/206Pb 1σ 207Pb/235U 1σ 206Pb/238U 1σ NYS18 10 4 1 365 0.002 7 0.054 5 0.000 6 0.468 6 0.006 5 0.062 2 0.000 5 391 26 390 5 389 3 11 5 1 534 0.003 0 0.054 3 0.001 0 0.463 0 0.009 6 0.061 6 0.000 6 387 45 386 7 385 4 22 7 1 670 0.004 3 0.054 5 0.001 8 0.481 9 0.011 4 0.064 0 0.001 0 391 71 399 8 400 6 47 8 1 321 0.006 0 0.054 4 0.001 9 0.472 5 0.019 0 0.062 7 0.000 9 387 78 393 13 392 5 50 4 1 440 0.003 1 0.054 8 0.000 6 0.494 8 0.008 0 0.065 4 0.000 9 406 19 408 5 408 5 79 7 1 699 0.003 9 0.059 0 0.001 2 0.518 0 0.011 4 0.063 5 0.000 8 569 46 424 8 397 5
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表 5 花岗伟晶岩锆石Hf同位素组成
Table 5. Hf isotopic composition data of zirconsfrom Nanyangshan pegmatites
样品 测点 176Yb/177Hf 2σ 176Lu/177Hf 2σ 176Hf/177Hf 2σ 176Hf/177Hfi εHf（0） εHf（t） TDM（Ma） TDM2（Ma） NYS18 10 0.000 054 0.000 001 0.000 002 0 0.282 303 0.000 007 0.282 303 -16.6 -7.4 1 306 2 475 11 0.000 091 0.000 001 0.000 003 0 0.282 313 0.000 007 0.282 313 -16.2 -7.0 1 293 2 446 22 0.000 042 0.000 001 0.000 001 0 0.282 290 0.000 007 0.282 290 -17.0 -7.8 1 324 2 516 47 0.000 033 0.000 001 0.000 001 0 0.282 302 0.000 006 0.282 302 -16.6 -7.4 1 307 2 479 50 0.000 095 0.000 001 0.000 003 0 0.282 296 0.000 007 0.282 296 -16.8 -7.6 1 316 2 499 79 0.000 101 0.000 001 0.000 003 0 0.282 306 0.000 006 0.282 306 -16.5 -7.2 1 302 2 466 注：计算过程所用参数：176Lu衰变常数为1.865×10-11a-1; （176Lu/177Hf）CHUR=0.033 2, （176Hf/177Hf）CHUR, 0=0.282 772;（176Lu/177Hf）DM, 0=0.038 4，（176Hf/177Hf）DM=0.283 25
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