Zircon U-Pb age, differentiation process, and its constraints on Rb mineralization of the ore-bearing granites of the Baitoushan rubidium deposit in the Beishan area
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摘要:
白头山铷矿位于北山造山带，为近年来新发现的超大型铷矿，含石榴子石白云母花岗岩是其重要的赋矿岩体，对于理解铷富集成矿机制具有重要意义。白头山含石榴子石白云母花岗岩具有高硅(SiO2为73.56%~75.60%)、富碱(Na2O+K2O为8.84%~10.39%)、富铝(Al2O3为14.41%~15.01%)，低Mg、Fe、Ca、P和Ti的特征，铝饱和指数较高(A/CNK=0.98~1.14)。微量元素方面，白头山含石榴子石白云母花岗岩富集Rb、Th、U、Ta，相对亏损Ba、Sr、P、Ti，具有明显的负Eu异常(Eu/Eu*为0.02~0.03)。岩石学、矿物学和地球化学特征指示，白头山含石榴子石白云母花岗岩属于高分异S型花岗岩，在岩浆演化过程中该花岗岩体系可能发生了云母、斜长石、锆石等矿物的结晶分异作用。稀土元素总量较低(32.06×10-6~45.33×10-6)，具有明显的四分组效应(TE1.3=1.28~1.31)，结合特征性元素对(Zr/Hf、Nb/Ta、Y/Ho、K/Rb)发育的non-CHARAC(不受离子电荷半径控制)行为，反映其经历了强烈的分异演化与熔流体作用。高分异花岗岩的强烈分异演化和熔流体作用是白头山铷矿富集成矿的关键控制因素。锆石U-Pb测年显示，白头山含石榴子石白云母花岗岩形成年龄为226±3.8 Ma，结合前人资料，表明印支期是东天山—北山地区高分异花岗岩和伴生稀有金属形成的重要阶段，为研究区稀有金属找矿提供了新的方向。
Abstract:The Baitoushan rubidium deposit is located in the Beishan orogenic belt, which is a newly discovered super-large rubidium deposit.The garnet-bearing leucogranite is the important ore-bearing rock and is crucial for understanding the mechanism of rubidium enrichment and mineralization of the deposit.The Baitoushan garnet-bearing leucogranite is enriched in silicon(SiO2=73.56%~75.60%), alkali(Na2O+K2O=8.84%~10.39%), and aluminum(Al2O3 14.41%~15.01%), lower in Mg, Fe, Ca, P, and Ti.The Al saturation index is high(A/CNK=0.98~1.14).In terms of trace elements, the Baitoushan garnet-bearing leucogranite is enriched in Rb, Th, U, and Ta, relatively depleted in Ba, Sr, P, and Ti, with strong Eu negative anomalies(Eu/Eu*=0.02~0.03).The petrological, mineralogical, and geochemical characteristics of the Baitoushan garnet-bearing leucogranite indicate that it is a highly fractionated S-type granite.Fractional crystallization of mica, plagioclase, and zircon may have occurred in this granitic system during magmatic evolution.The total amount of rare earth elements is low(REE=32.06×10-6~45.33×10-6), with an obvious tetrad effect(TE1.3=1.28~1.31).Combined with the non-CHARAC(no radius-controlled) behavior of the characteristic element pairs(Zr/Hf, Nb/Ta, Y/Ho, K/Rb), it reflects that they also underwent a strong differentiation evolution with melt fluid interaction.The extensive magmatic differentiation of highly fractionated granites and F-rich fluid interaction are the key controlling factors for the enrichment and mineralization of rubidium and other rare metals.Zircon U-Pb dating shows that the crystallization age of the garnet-bearing leucogranite is 226±3.8 Ma.Combined with previous studies, it is suggested that the Triassic is an important period for the formation of highly fractionated granites and associated rare metal mineralization in the Eastern Tianshan-Beishan region, which will provide a new direction for prospecting rare metals in the study area.
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图 1 中亚造山带简图(a，据Sengör et al., 1993修改)和北山地区区域地质简图(b，据He et al., 2018; Xiao et al., 2011修改)
Figure 1.
图 5 不同类型锆石球粒陨石标准化稀土元素配分模式(标准化值据Sun et al., 1989)
Figure 5.
表 1 白头山含石榴子石白云母花岗岩(BTS-13)锆石LA-ICP-MS主量和微量元素测试结果
Table 1. LA-ICP-MS zircon major and trace elements of the Baitoushan garnet-bearing muscovite granites
样品 SiO2 Ti Y ZrO2 Nb La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta Pb Pb Th U 1 32.7 104 1697 61.9 19.4 33.6 362 106 382 237 26.5 224 43.3 270 54.8 171 38.8 371 60.6 11504 3.75 570 221 932 1854 2 32.7 33.7 998 62.4 4.14 59.9 111 125 353 119 17.9 83.8 15.0 115 32.6 129 32.5 329 55.5 12320 3.65 160 147 610 1888 3 32.7 818 2964 48.4 772 89.7 878 298 1175 678 64.1 594 118 573 72.3 142 21.3 136 15.6 32178 219 3529 658 4019 1969 4 32.7 4.77 284 56.6 5.86 20.6 81.5 23.9 76.1 26.6 2.67 30.1 7.91 48.5 5.20 9.05 1.61 10.6 1.05 39921 7.36 40.3 136.4 207 3089 5 32.7 0.16 40.8 58.1 0.89 0.014 0.021 0.013 0.075 0.062 0.022 2.85 1.05 6.14 0.65 1.89 0.34 2.74 0.75 60803 9.27 15.1 32.9 10.3 1235 6 32.7 52.0 1197 55.6 21.6 22.2 249 90.3 381 178 14.1 129 17.1 141 41.2 166 39.8 378 63.9 10487 8.49 921 608 3798 4727 7 32.7 102 3045 61.1 10.2 838 2621 600 1600 389 22.5 310 51.0 395 108 374 78.1 682 103 9266 3.35 996 752 5119 3221 8 32.7 11.4 808 67.2 5.27 0.65 11.3 1.63 7.98 5.89 0.33 17.9 5.61 73.0 27.1 122 30.2 295 50.4 13770 4.59 40.2 169 548 2835 9 32.7 9.99 1227 67.0 0.60 0.003 0.71 0.23 1.71 5.17 0.18 23.1 9.29 121 40.4 153 32.9 288 46.2 13337 0.40 40.2 58.5 46.0 219 10 32.7 127 381 54.7 4.77 7.79 38.6 9.27 21.9 5.90 0.44 8.13 2.66 32.2 13.0 57.3 13.6 136 22.5 8823 0.99 0.00 26.7 21.3 36.0 11 32.7 20.3 3057 66.6 1.20 1.22 11.5 3.57 11.0 13.6 1.10 43.1 18.6 281 104 450 107 983 155 13974 0.99 62.5 81.1 186 636 12 32.7 3.06 1355 63.1 6.79 15.2 148 71.2 257 137 17.0 118 23.0 176 44.3 159 36.1 332 54.4 12405 4.58 475 214 714 1978 13 32.7 13.9 1850 68.3 1.66 0.00 5.17 0.13 5.10 7.19 0.42 34.5 12.5 173 63.3 265 61.9 583 93.1 12490 0.96 48.9 35.3 188 306 14 32.7 128 2048 53.4 268 59.9 1254 204 770 406 42.0 366 75.0 390 44.2 80.7 12.3 89.1 8.61 50583 46.6 928 225 1017 1966 15 32.7 44.5 829 64.6 5.26 23.9 110 69.0 267 134 10.8 88.7 13.5 101 27.7 109 25.5 252 41.0 13314 3.87 584 238 476 2372 16 32.7 9.39 952 66.7 7.14 2.26 46.8 10.3 43.7 24.7 2.13 26.0 7.30 88.2 31.7 141 36.9 334 58.8 13544 5.02 157 203 649 2869 17 32.7 6.91 638 58.8 1.33 0.0098 11.7 0.073 0.20 0.73 0.30 10.0 3.10 46.9 20.8 102 27.2 272 51.7 9532 0.62 44.3 21.4 145 206 18 32.7 0.66 274 70.5 16.9 2.48 36.9 10.7 38.7 18.2 1.85 21.7 6.11 35.5 5.14 12.7 2.88 26.1 2.90 63704 83.7 73.6 42.4 79.7 1627 19 32.7 15.2 3260 69.1 1.88 0.011 11.3 0.48 4.92 12.1 1.71 56.1 22.0 299 113 493 116 1092 173 12358 1.06 31.3 21.1 131 212 20 32.7 415 4740 52.0 571 74.8 1213 289 1085 805 58.3 1150 302 1221 88.2 126 16.7 108 12.1 43221 439 1387 296 2610 2578 21 32.7 0.84 64.2 70.2 2.74 1.03 9.83 3.45 12.5 7.86 0.45 9.99 2.63 11.4 0.88 1.92 0.27 1.85 0.16 86959 20.2 129 46.2 22.2 2125 22 32.7 4.37 1043 67.6 1.37 0.17 11.2 1.35 11.6 12.7 0.78 32.8 9.62 110 36.2 148 33.5 310 49.3 11165 0.98 0.00 87.0 404 1125 23 32.7 583 1777 64.2 15.4 46.6 661 234 894 413 29.4 272 41.1 256 59.9 214 48.7 480 80.5 9793 6.21 918 334 1505 2769 24 32.7 23.5 3199 54.0 809 114 1144 477 1889 954 107 727 124 602 77.1 156 22.9 143 17.3 42864 162 1965 396 1236 2686 25 32.7 15.4 1847 60.3 3.97 0.014 8.10 1.09 9.52 18.4 0.32 51.0 17.3 200 66.5 258 53.0 454 67.3 10055 1.92 95.5 66.6 735 817 注：主量元素含量单位为%，微量元素含量单位为10-6 
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表 2 白头山含石榴子石白云母花岗岩LA-ICP-MS锆石U-Th-Pb定年结果
Table 2. LA-ICP-MS zircon U-Th-Pb dating results of the Baitoushan garnet-bearing muscovite granites
样号 类型 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 BTS-13 1 Ⅱ 932 1854 0.50 0.0917 0.0027 0.8544 0.0251 0.0674 0.0010 1461 57 627 14 420 6 2 Ⅱ 610 1888 0.32 0.0660 0.0018 0.6216 0.0178 0.0681 0.0011 806 56 491 11 425 7 3 Ⅱ 4019 1969 2.04 0.2821 0.0085 2.3886 0.1064 0.0601 0.0014 3376 47 1239 32 376 9 4 继承锆石 207 3089 0.07 0.0540 0.0023 0.4434 0.0622 0.0600 0.0087 372 96 373 44 375 53 5 / 10.3 1235 0.01 0.0577 0.0023 0.3444 0.0142 0.0431 0.0007 520 89 301 11 272 4 6 Ⅱ 3798 4727 0.80 0.0795 0.0027 0.7509 0.0287 0.0682 0.0014 1187 66 569 17 425 8 7 Ⅱ 5119 3221 1.59 0.0949 0.0027 0.8977 0.0279 0.0684 0.0012 1528 58 650 15 427 7 8 继承锆石 548 2835 0.19 0.0573 0.0018 0.5368 0.0179 0.0677 0.0010 506 69 436 12 422 6 9 Ⅰ 46.0 219 0.21 0.1158 0.0038 3.9628 0.1424 0.2475 0.0041 1894 59 1627 29 1426 21 10 Ⅰ 21.3 36.0 0.59 0.1367 0.0068 7.4552 0.3700 0.4001 0.0095 2187 86 2168 44 2170 44 11 Ⅰ 186 636 0.29 0.0770 0.0026 1.5506 0.0576 0.1459 0.0024 1120 69 951 23 878 13 12 Ⅱ 714 1978 0.36 0.0828 0.0034 0.7641 0.0275 0.0680 0.0011 1265 81 576 16 424 6 13 继承锆石 188 306 0.62 0.0580 0.0046 0.5368 0.0393 0.0679 0.0016 528 176 436 26 423 10 14 Ⅱ 1017 1966 0.52 0.1524 0.0053 0.9316 0.0358 0.0441 0.0007 2373 54 668 19 278 5 15 Ⅱ 476 2372 0.20 0.0872 0.0029 0.8333 0.0318 0.0687 0.0011 1365 64 615 18 428 7 16 继承锆石 649 2869 0.23 0.0621 0.0017 0.5859 0.0187 0.0680 0.0011 680 61 468 12 424 7 17 继承锆石 145 206 0.70 0.0549 0.0041 0.4334 0.0338 0.0571 0.0013 409 169 366 24 358 8 18 Ⅱ 79.7 1627 0.05 0.0565 0.0030 0.2774 0.0148 0.0355 0.0007 472 119 249 12 225 4 19 继承锆石 131 212 0.62 0.0542 0.0038 0.4479 0.0293 0.0605 0.0012 376 157 376 21 378 7 20 Ⅱ 2610 2578 1.01 0.1694 0.0091 0.8460 0.0479 0.0360 0.0006 2552 90 622 26 228 4 21 Ⅱ 22.2 2125 0.01 0.0527 0.0022 0.2628 0.0111 0.0362 0.0008 317 94 237 9 229 5 22 继承锆石 404 1125 0.36 0.0552 0.0018 0.5144 0.0181 0.0675 0.0012 420 77 421 12 421 7 23 Ⅱ 1505 2769 0.54 0.0952 0.0038 0.7696 0.0203 0.0600 0.0017 1532 74 580 12 376 10 24 Ⅱ 1236 2686 0.46 0.2204 0.0073 1.0920 0.0486 0.0356 0.0008 2984 54 749 24 226 5 25 Ⅰ 735 817 0.90 0.0524 0.0029 0.2536 0.0130 0.0355 0.0007 306 128 229 11 225 4
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表 3 白头山含石榴子石白云母花岗岩主量、微量和稀土元素组成
Table 3. Major, trace and rare earth element compositions of the Baitoushan garnet-bearing muscovite granites
送样编号 20BTS-05 20BTS-09 20BTS-11 20BTS-12 送样编号 20BTS-05 20BTS-09 20BTS-11 20BTS-12 SiO2 74.07 74.30 73.71 75.43 Hf 2.9 2.9 2.9 2.3 TiO2 0.01 0.01 0.01 0.01 Ta 39.2 53.2 54.1 26.0 Al2O3 14.64 15.05 14.88 14.38 Th 4.16 3.45 3.71 3.90 TFe2O3 0.80 0.65 0.71 0.75 U 2.41 1.41 1.76 1.31 MnO 0.19 0.14 0.16 0.12 La 5.6 3.5 4.7 6.1 MgO 0.05 0.03 0.02 0.02 Ce 13.6 9.8 12.1 14.5 CaO 0.86 0.37 0.28 0.23 Pr 1.80 1.38 1.57 1.80 Na2O 6.11 5.85 4.88 4.73 Nd 7.6 5.8 6.6 7.8 P2O5 0.02 0.02 0.02 0.02 Sm 3.58 3.05 3.47 3.73 K2O 3.05 3.83 5.52 4.09 Eu 0.04 0.02 0.04 0.03 总计 99.80 100.25 100.20 99.78 Gd 3.60 3.80 3.82 3.83 K2O+Na2O 9.17 9.66 10.39 8.84 Tb 0.58 0.62 0.63 0.68 K2O/Na2O 0.50 0.65 1.13 0.86 Dy 2.88 2.65 2.96 3.35 A/NK 1.10 1.09 1.06 1.18 Ho 0.41 0.28 0.36 0.47 ASI 0.98 1.04 1.02 1.14 Er 0.95 0.53 0.80 1.18 刚玉 0.30 1.05 0.70 2.22 Tm 0.15 0.07 0.12 0.18 分异指数(DI) 95.10 96.88 97.43 96.24 Yb 1.09 0.48 0.75 1.44 固结指数(SI) 0.50 0.29 0.18 0.21 Lu 0.16 0.08 0.11 0.24 Li 2.1 1.5 1.5 2.9 K/Rb 27.65 24.92 35.40 25.11 Sc 2.1 1.5 1.5 2.9 Nb/Ta 2.02 1.69 1.55 3.21 Ga 40.3 40.9 40.8 39.7 Zr/Hf 7.93 6.90 7.24 9.57 Rb 933 1280 1305 1390 Y/Ho 37.80 46.43 40.28 39.57 Sr 19.7 11.0 13.4 12.2 TE1.3 1.28 1.31 1.30 1.29 Y 15.5 13.0 14.5 18.6 LREE/HREE 1.50 0.91 1.21 1.51 Zr 23 20 21 22 ΣREE 42.04 32.06 38.03 45.33 Nb 79.1 90.1 84.1 83.4 Eu/Eu* 0.03 0.02 0.03 0.02 Sn 58 47 28 76 (La/Lu)N 3.63 4.54 4.44 2.64 W 1.9 1.7 1.4 2.1 10000×Ga/Al 5.72 5.54 5.31 5.32 Cs 23.6 34.4 37.1 39.2 Zr+Nb+Ce+Y 131.2 132.9 131.7 138.5 Ba 20.7 22.6 22.5 16.5 注：主量元素含量单位为%，微量和稀土元素含量单位为10-6
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