Genesis of garnet in pegmatite and its implication for Nb-Ta mineralization in the northwestern margin of the Mufushan granite (central Jiangnan Orogen): Comparison from mineralized and unmineralized pegmatites
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摘要:
江南造山带中段幕阜山地区已成为我国重要的稀有金属资源基地之一。断峰山地区伟晶岩型铌钽矿床是幕阜山复式花岗岩体西北缘唯一的大型矿床，其成因及物理化学条件不明确。新发现的微斜长石伟晶岩型铌钽矿化脉体中铌钽铁矿、石榴子石和电气石共生，其中石榴子石的成因研究可为该类型Nb-Ta成矿作用研究提供良好的制约。以断峰山地区成矿与未成矿2种微斜长石伟晶岩脉中石榴子石为研究对象，进行了背散射电子（BSE）和阴极发光（CL）微观结构观察、电子探针（EPMA）和激光电感耦合等离子质谱（LA-ICP-MS）原位微区主微量元素分析，探讨石榴子石成因及其对微斜长石伟晶岩成矿作用的指示。断峰山地区伟晶岩中的石榴子石均为岩浆成因，形成于中高温、中低压力环境，属于铁铝榴石−锰铝榴石（Alm48.61-Sps48.21）固溶体系列。成矿微斜长石伟晶岩脉中石榴子石以铁铝榴石为主（Sps42.56-Alm54.63），而未成矿微斜长石伟晶岩脉中石榴子石以锰铝榴石为主（Sps58.93-Alm37.18）。成矿微斜长石伟晶岩中石榴子石多与铌钽铁矿等共生，具有低的Mn、Nb和Ta元素含量，且由核部到边部Mn含量降低Fe含量增加，这可能是由于铌钽矿物的结晶导致，表明石榴子石中Nb、Ta、Fe、Mn等元素的演化关系可以指示幕阜山地区Nb-Ta成矿。
Abstract:Objective The Mufushan area, in the central Jiangnan Orogen, South China, has become one of the most significant rare metals resource bases in China. The Duanfengshan pegmatite-type Nb-Ta deposit is the only large-sized deposit in the northwestern margin of the Mufushan granitic batholith. However, its genesis and physicochemical conditions are still unclear. Niobium-tantalite, garnet and tourmaline coexist in the newly discovered Nb-Ta mineralized microcline pegmatite veins. Therefore, the study of garnet genesis can provide significant constraints for the Nb-Ta mineralization.
Methods This study focuses on garnets in the mineralized and unmineralized microcline pegmatite veins in the Duanfengshan area. Garnets were observed using cathodoluminescence (CL) and backscattered electron (BSE) imagery. The major and trace elements are determined by EPMA and LA-ICP-MS, and are used to discuss the genesis of garnet and the indication for Nb-Ta mineralization within microcline pegmatite veins.
Results These mineralogical and geochemical features suggest a magmatic origin for garnets within microcline pegmatite veins in the Duanfengshan area. Garnets from pegmatites in the Duanfengshan area formed in medium-high temperatures and medium-low pressures. Garnets in mineralized and unmineralized pegmatites both belong to the solid solution series of almandite-spssartite. Garnet in the mineralized pegmatites is dominated by almandite (Sps42.56 Alm54.63), whereas garnet in the unmineralized pegmatites is mainly characterized by spessartite (Sps58.93 Alm37.18).
Conclusion Garnets in mineralized pegmatites mostly coexist with columbite-tantalite, and have low Mn, Nb and Ta contents, as well as a decrease in Mn content and an increase in Fe content from the core to the rim. This mineralogical result is resulted by the crystallization of Nb-Ta minerals. It shows that the evolution relationship of Nb, Ta, Fe, Mn elements in garnet can indicate the pegmatite-type Nb-Ta mineralization in the Mufushan area.
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图 1 幕阜山地区大地构造 (a)及稀有金属矿床分布图 (b) [18]
Figure 1. Geotectonic map (a) and distribution map of rare metal deposits (b) in the Mufushan area
图 2 断峰山地区伟晶岩型Nb-Ta 矿床地质图[22]
Zr. 锆；Mz. 白云母
Figure 2. Geological map of the pegmatite type Nb-Ta deposit in Duanfengshan area
图 3 断峰山矿区124#成矿微斜长石伟晶岩脉相带剖面图
Figure 3. Geological section of the 124# mineralized microcline pegmatite in the Duanfengshan area
图 4 断峰山地区成矿微斜长石伟晶岩脉野外照片和镜下照片
a. 微斜长石伟晶岩与片岩的接触带；b. 锂云母−铌钽铁矿矿石；c. 铌钽铁矿矿石； d. 电气石−铌钽铁矿矿石；e. 电气石−绿柱石；f. 电气石和石榴子石共生；g. 扫面电镜下电气石包裹的铌钽铁矿；h，i. 微斜长石伟晶岩（正交偏光）；Ms. 白云母；Qtz. 石英；Mic. 微斜长石；下同
Figure 4. Field photos and micrographs of minerized microcline pegmatite veins in the Duanfengshan area
图 5 断峰山地区未成矿微斜长石伟晶岩野外照片和镜下照片
a，b. 岩体中未成矿微斜长石伟晶岩脉；c，d. 未成矿微斜长石伟晶岩（正交偏光）；Ab. 钠长石
Figure 5. Field photos and micrographs of the unmineralized microcline pegmatites in the Duanfengshan area
图 6 断峰山地区伟晶岩中石榴子石背散射和阴极发光照片
a，b. 成矿微斜长石伟晶岩中石榴子石（BSE图）；c. 未成矿微斜长石伟晶岩中石榴子石（BSE图）；d，e. 成矿微斜长石伟晶岩中石榴子石（CL图）；f. 未成矿微斜长石伟晶岩中石榴子石（CL图）
Figure 6. Backscattered electron (BSE) (a-c) and cathodoluminescence (CL) (d-f) images of garnets from pegmatites in the Duanfengshan area
图 7 断峰山地区伟晶岩石榴子石三角分类图解（a，据文献[9]修改）和CaO−MgO图解（b）
Sps. 锰铝榴石；Alm. 铁铝榴石；Adr. 钙铁榴石；Prp. 镁铝榴石；Grs. 钙铝榴石
Figure 7. Triangle classification (a) and CaO-MgO (b) diagrams of garnets from pegmatites in the Duanfengshan area
图 8 断峰山地区伟晶岩中石榴子石Fe-Mn含量变化特征图
Figure 8. Diagrams showing the variation of Fe-Mn contents in garnets from pegmatites in the Duanfengshan area
图 9 断峰山地区石榴子石稀土元素球粒陨石标准化图解(a，b)和原始地幔标准化微量元素蛛网图(c，d)（标准化值据文献[38]）
Figure 9. Chondrite-normalized REE patterns (a, b) and primitive mantle normalized spidergrams of trace elements (c, d) of garnets in the Duanfengshan area
图 10 断峰山地区石榴子石微量元素二元图
Figure 10. Trace elements binary plots for garnet samples in the Duanfengshan area
图 12 断峰山地区石榴子石w（MnO）−w（FeO）(a) 和Mg−Mn/（Mn+Fe）演化图解（b. 底图据文献[56]）
Figure 12. MnO content−FeO content (a) and Mg−Mn/(Mn+Fe) diagrams (b) of garnets in the Duangfengshan area
表 1 断峰山地区成矿与未成矿微斜长石伟晶岩差异对比
Table 1. Comparison of differences between mineralized and unmineralized microcline pegmatites in the Duanfengshan area
成矿微斜长石伟晶岩 未成矿微斜长石伟晶岩 围岩类型 新元古界冷家溪群片岩 黑云母二长花岗岩 与花岗岩的关系 岩体外的片岩内 岩体内部 展布方向 NE 向 NW向 规模及分带 数量较多，长度几百米至上千米，宽度几米至百余米，分带明显 数量较少，长度几米到几十米，宽度小于3 m，
分带不明显矿物组合 石英、斜长石、钾长石和白云母，副矿物石榴子石和电气石，
内带发育铌钽铁矿、锂云母、绿柱石石英、斜长石、钾长石和白云母，副矿物
石榴子石和电气石次级断裂构造 以NE向断裂为主，次为近NS向和近EW向断裂 以NW向断裂为主 
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表 2 断峰山地区伟晶岩中石榴子石电子探针分析主量元素成分
Table 2. EPMA major element compositions of garnets from pegmatites in the Duanfengshan area
样品号 成矿伟晶岩 未成矿伟晶岩 124-1 124-2 165-1 165-2 Lj-1 Lj-2 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 5 6 7 1 2 3 4 5 1 2 3 4 5 SiO2 wB/% 34.13 35.90 35.43 35.79 35.69 35.95 35.89 35.53 35.93 35.22 35.71 35.29 35.85 35.60 35.79 35.71 35.87 35.73 35.81 35.87 35.51 35.44 35.50 35.43 35.52 35.43 35.40 35.58 35.44 TiO2 0.04 0.02 0.01 bdl 0.09 0.11 0.03 0.07 bdl 0.06 0.07 0.08 0.03 0.07 0.04 0.06 0.01 0.03 0.00 0.04 0.05 0.06 0.01 0.05 0.03 0.08 0.10 0.05 0.05 Al2O3 19.83 19.99 19.90 19.62 19.54 19.87 19.58 19.75 20.12 20.55 19.45 20.33 20.68 20.52 20.58 20.76 20.71 20.88 20.74 20.43 19.93 19.93 20.35 20.03 20.01 19.82 19.76 20.06 20.04 FeO 26.88 27.13 26.32 27.55 25.26 25.25 24.75 24.47 22.99 25.35 24.55 23.14 30.07 25.91 24.63 23.86 24.32 25.64 28.48 19.89 20.09 17.55 20.01 19.22 17.49 17.43 17.17 17.23 17.62 MnO 17.34 17.56 17.65 16.96 18.94 18.80 19.00 18.92 18.77 18.36 18.85 18.82 12.07 16.55 17.81 18.49 17.95 16.79 13.82 22.71 22.20 25.22 22.35 23.30 25.13 25.27 25.50 25.49 25.14 MgO 0.17 0.21 0.17 0.28 0.33 0.33 0.33 0.28 0.35 0.32 0.29 0.31 0.56 0.37 0.23 0.26 0.24 0.30 0.45 0.69 0.74 0.65 0.78 0.57 0.57 0.56 0.56 0.61 0.51 CaO 0.51 0.49 0.49 0.52 0.64 0.65 0.61 0.61 0.66 0.63 0.69 0.64 0.31 0.53 0.45 0.48 0.44 0.46 0.42 0.41 0.39 0.52 0.39 0.39 0.48 0.59 0.46 0.45 0.48 Na2O 0.01 bdl 0.02 0.01 bdl bdl 0.02 bdl bdl bdl bdl 0.08 0.01 0.03 0.00 0.02 0.02 0.01 bdl bdl bdl 0.00 0.03 bdl 0.01 0.01 0.03 0.01 0.01 K2O 0.02 bdl 0.01 bdl bdl 0.01 bdl 0.01 bdl 0.01 0.01 0.02 bdl bdl 0.00 bdl bdl bdl bdl bdl bdl 0.00 bdl 0.00 bdl bdl bdl 0.01 0.00 总计 98.92 101.29 100.00 100.73 100.48 100.95 100.20 99.65 98.82 100.50 99.62 98.70 99.58 99.58 99.53 99.64 99.54 99.84 99.72 100.03 98.93 99.38 99.42 98.99 99.23 99.17 98.98 99.49 99.29 Si 原
子
数2.86 2.93 2.93 2.94 2.94 2.94 2.96 2.95 2.99 2.89 2.97 2.94 2.96 2.95 2.96 2.95 2.97 2.95 2.96 2.95 2.95 2.94 2.93 2.95 2.95 2.94 2.95 2.94 2.94 Ti 0.00 0.00 0.00 bdl 0.01 0.01 0.00 0.00 bdl 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 0.00 Al 1.82 1.86 1.87 1.84 1.84 1.86 1.87 1.88 1.97 1.88 1.87 1.94 1.98 1.95 1.97 1.97 1.99 1.98 1.97 1.93 1.91 1.88 1.92 1.91 1.90 1.88 1.89 1.90 1.90 Fe 1.88 1.85 1.82 1.89 1.74 1.73 1.71 1.70 1.60 1.74 1.70 1.61 2.08 1.79 1.71 1.65 1.68 1.77 1.97 1.37 1.40 1.22 1.38 1.34 1.21 1.21 1.20 1.19 1.22 Mn 1.23 1.22 1.24 1.18 1.32 1.30 1.33 1.33 1.33 1.28 1.33 1.33 0.84 1.16 1.25 1.29 1.26 1.17 0.97 1.58 1.56 1.77 1.56 1.64 1.77 1.78 1.80 1.79 1.77 Mg 0.02 0.03 0.02 0.03 0.04 0.04 0.04 0.03 0.04 0.04 0.04 0.04 0.07 0.05 0.03 0.03 0.03 0.04 0.06 0.08 0.09 0.08 0.10 0.07 0.07 0.07 0.07 0.08 0.06 Ca 0.05 0.04 0.04 0.05 0.06 0.06 0.05 0.05 0.06 0.06 0.06 0.06 0.03 0.05 0.04 0.04 0.04 0.04 0.04 0.04 0.03 0.05 0.03 0.03 0.04 0.05 0.04 0.04 0.04 Na 0.00 bdl 0.00 0.00 bdl bdl 0.00 bdl bdl 0.00 bdl 0.01 0.00 0.00 0.00 0.00 0.00 0.00 bdl bdl bdl 0.00 0.01 bdl 0.00 0.00 0.00 0.00 0.00 Sps wB/% 44.49 42.94 43.35 42.00 47.16 45.92 46.61 46.38 44.25 44.43 46.38 45.62 28.54 39.51 42.16 43.97 42.46 39.83 32.70 54.06 54.09 61.77 53.80 56.64 60.97 61.98 62.89 61.90 61.19 Prp 0.78 0.89 0.73 1.22 1.42 1.42 1.43 1.21 1.46 1.37 1.24 1.34 2.34 1.55 0.97 1.10 0.98 1.25 1.88 2.88 3.17 2.80 3.29 2.42 2.44 2.40 2.43 2.62 2.18 Alm 53.23 54.70 54.42 55.16 49.69 51.01 50.18 50.75 52.32 52.45 50.47 51.34 68.27 57.56 55.64 53.69 55.26 57.62 64.17 41.96 41.70 34.02 41.76 39.92 35.21 34.08 33.59 34.27 35.32 Grs 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.66 0.00 0.00 1.65 0.85 0.86 1.14 1.24 1.30 1.30 1.26 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Adr 1.50 1.46 1.50 1.62 1.72 1.65 1.78 1.65 1.30 1.75 1.91 0.05 0.00 0.52 0.08 0.00 0.00 0.00 0.00 1.10 1.04 1.41 1.16 1.01 1.38 1.54 1.09 1.21 1.31 注：FeO为全铁含量；Sps. 锰铝榴石；Prp. 镁铝榴石；Alm. 铁铝榴石；Grs. 钙铝榴石；Adr. 钙铁榴石；bdl. 低于检测限；晶体化学式基于12个氧原子计算
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表 3 断峰山地区伟晶岩中石榴子石 LA-ICP-MS原位微区分析微量元素成分
Table 3. LA-ICP-MS trace element compositions of garnets from pegmatites in the Duanfengshan area
样品号 成矿伟晶岩 未成矿伟晶岩 124-1 124-2 165-1 165-2 Lj-1 Lj-2 1 2 3 4 1 2 3 4 5 1 2 3 4 1 2 3 4 5 6 7 1 2 3 4 5 1 2 3 4 5 wB/10−6 Li 147.61 156.83 183.94 150.58 116.74 154.17 129.47 134.93 147.38 63.00 147.09 121.48 125.35 106.89 116.55 151.46 121.12 98.78 106.02 111.07 119.17 113.64 119.74 132.20 125.73 84.14 105.03 84.82 67.85 118.60 Be 0.00 0.20 0.18 0.13 0.10 0.19 0.05 0.00 0.06 0.00 0.00 0.31 0.31 0.32 0.00 0.00 0.32 0.06 0.00 0.25 0.51 0.05 0.05 0.26 0.13 0.11 0.11 0.00 0.24 0.00 B 1.81 0.03 1.88 0.27 0.47 4.36 0.00 1.67 0.00 1.44 1.76 1.21 0.00 0.14 2.36 0.00 0.35 1.06 0.74 1.37 2.15 1.38 1.46 1.37 0.12 0.96 2.92 0.94 0.00 0.51 Sc 4.22 6.83 11.64 5.98 20.17 20.60 16.57 15.56 14.77 4.91 14.79 13.24 14.29 7.31 5.65 7.73 11.94 9.27 8.61 7.92 4.48 5.37 5.25 4.82 2.53 6.83 4.75 2.60 2.46 2.64 V 0.03 0.00 0.12 0.04 0.04 0.11 0.13 0.00 0.07 0.06 0.09 0.06 0.09 0.00 0.10 0.01 0.04 1.41 0.86 1.19 0.14 0.07 0.12 0.79 0.06 0.15 0.09 1.48 0.74 0.99 Cr 2.64 0.81 2.06 0.99 0.00 0.00 0.58 0.00 0.00 0.70 2.23 0.19 1.52 0.00 0.00 0.97 0.06 0.97 0.00 0.88 0.00 0.00 0.20 0.46 0.05 0.00 0.00 0.88 0.00 0.21 Co 1.40 1.21 1.13 1.34 0.79 0.79 0.95 0.82 0.61 0.72 0.75 0.92 0.68 1.80 1.22 1.20 1.18 2.56 2.89 2.87 4.33 2.95 3.04 5.43 3.77 2.63 2.70 2.33 2.56 2.88 Ni 0.54 0.16 0.00 0.43 0.56 0.37 1.09 0.00 0.26 0.00 0.07 0.00 0.27 0.40 0.14 0.25 0.00 0.00 0.00 0.00 0.41 0.00 0.00 0.01 0.00 0.49 1.39 0.00 0.46 0.00 Cu 0.00 0.00 0.00 0.28 0.15 0.00 0.01 0.11 0.00 0.01 0.13 0.02 0.00 0.01 0.07 0.00 0.43 0.06 0.00 0.13 0.00 0.00 0.00 0.00 0.13 0.00 0.00 0.14 0.10 0.00 Zn 437.56 401.21 384.54 406.53 263.86 255.93 261.13 274.92 264.24 309.67 244.60 248.47 244.55 360.71 344.45 352.01 295.83 307.59 325.67 314.77 357.05 240.91 232.26 388.94 305.97 247.05 229.43 271.39 270.72 277.60 Ga 23.13 22.94 25.43 23.65 28.24 27.45 26.52 25.80 27.53 21.65 25.14 24.28 23.68 21.45 24.29 31.90 25.97 19.51 20.08 21.04 26.22 27.21 27.52 23.69 25.05 27.75 26.93 29.03 28.51 26.39 Rb 0.06 0.24 0.23 0.12 0.00 0.55 0.09 0.00 0.09 0.00 0.09 0.10 0.19 0.00 0.15 0.01 0.11 0.03 0.13 0.01 0.17 0.03 0.23 0.02 0.04 0.13 0.03 0.12 0.08 0.09 Sr 0.03 0.01 0.09 0.04 0.04 0.04 0.02 0.03 0.04 0.01 0.04 0.06 0.08 0.00 0.04 0.01 0.19 0.04 0.03 0.06 0.07 0.07 0.07 0.02 0.00 0.13 0.08 0.04 0.03 0.02 Y 412.70 491.11 719.37 399.24 613.71 551.78 514.67 457.63 549.46 41.67 532.36 527.06 549.03 321.23 379.42 454.46 208.79 254.55 568.45 742.88 712.33 775.60 849.18 585.37 462.66 831.41 679.86 606.30 497.87 517.41 Zr 12.82 13.11 13.36 12.34 17.74 19.41 17.95 18.90 19.33 8.91 19.34 17.76 17.85 8.96 8.80 8.67 10.93 6.93 7.17 7.52 21.13 18.18 18.33 9.55 14.29 20.84 20.26 23.40 21.48 17.26 Nb 0.30 0.38 0.74 0.31 1.00 1.00 0.96 0.84 0.98 0.26 1.07 0.71 0.68 0.12 0.69 1.97 0.63 0.02 0.02 0.05 5.14 2.88 3.81 1.52 0.70 2.32 4.86 5.70 3.77 0.93 Ag 0.02 0.00 0.01 0.01 0.05 0.00 0.00 0.00 0.01 0.00 0.00 0.02 0.03 0.00 0.00 0.01 0.07 0.05 0.06 0.00 0.00 0.01 0.05 0.01 0.04 0.00 0.03 0.03 0.00 0.00 Cd 11.24 10.41 12.40 10.70 7.62 10.55 9.05 8.47 6.06 6.94 6.79 6.91 6.97 8.31 7.89 10.14 6.55 7.93 10.09 7.23 6.90 6.14 5.43 8.10 6.81 7.97 6.19 8.64 9.66 10.15 Sn 6.61 6.79 7.38 5.64 6.29 6.22 6.98 6.57 7.03 1.68 7.69 7.12 6.67 3.89 4.31 6.49 6.35 1.63 1.18 0.91 11.41 12.10 11.42 6.11 7.88 12.94 12.87 9.85 9.67 9.44 Cs 0.04 0.01 0.02 0.03 0.03 1.36 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.04 0.06 0.03 0.01 0.00 0.00 0.00 0.00 0.06 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.05 Ba 0.08 0.00 0.02 0.04 0.04 0.00 0.02 0.00 0.04 0.00 0.04 0.00 0.01 0.06 0.00 0.04 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.04 0.04 0.00 0.00 0.00 0.04 La 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Ce 0.00 0.00 0.02 0.00 0.02 0.01 0.01 0.00 0.01 0.02 0.02 0.01 0.00 0.01 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.00 0.01 0.01 0.01 0.01 Pr 0.01 0.00 0.01 0.00 0.01 0.02 0.02 0.01 0.01 0.00 0.02 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.02 0.01 0.01 0.01 0.00 0.01 0.01 0.00 0.02 0.02 Nd 0.11 0.11 0.01 0.09 0.31 0.15 0.26 0.22 0.40 0.12 0.22 0.35 0.30 0.07 0.02 0.03 0.20 0.00 0.05 0.05 0.17 0.19 0.20 0.02 0.15 0.23 0.24 0.24 0.21 0.15 wB/10−6 Sm 0.89 1.07 1.69 0.81 2.17 2.32 2.35 2.15 2.29 1.26 2.39 1.91 2.08 1.35 0.94 0.77 0.99 0.71 1.08 1.35 1.76 1.39 1.57 0.63 1.41 1.24 1.71 1.85 1.37 1.27 Eu 0.00 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.00 0.01 0.00 0.03 0.02 0.03 0.03 0.02 0.05 0.03 0.02 0.01 0.09 0.10 0.11 0.07 0.06 0.12 0.13 0.04 0.05 0.04 Gd 6.23 8.69 9.68 6.43 11.79 11.03 12.04 10.69 11.51 4.47 12.01 11.84 10.99 10.21 8.68 5.71 6.05 5.42 9.33 15.51 11.05 9.82 10.47 6.28 7.45 7.52 9.94 10.50 8.03 8.56 Tb 3.96 5.05 5.98 3.86 6.60 6.29 6.30 5.82 6.19 1.22 6.08 6.19 5.88 5.45 4.90 4.21 3.13 3.57 5.85 9.02 6.92 6.65 7.23 4.50 4.92 5.44 6.27 6.42 5.14 5.15 Dy 46.64 55.92 73.70 44.38 72.36 66.12 65.10 57.73 63.80 5.57 62.86 60.25 63.57 47.17 49.21 49.00 27.50 34.05 68.48 96.68 81.93 84.28 93.57 59.15 54.19 79.66 75.11 70.20 57.45 55.21 Ho 9.90 12.19 19.92 9.42 17.02 15.36 13.32 11.80 14.55 0.74 13.88 13.54 14.05 8.09 9.90 11.68 4.73 5.79 15.74 20.96 19.10 20.61 22.96 16.44 11.17 23.68 17.84 14.38 11.92 12.72 Er 33.20 39.76 79.42 30.52 61.37 51.80 47.58 40.31 50.85 2.57 46.29 44.72 49.46 19.37 28.69 43.56 13.91 15.51 48.30 66.16 66.28 76.52 85.58 63.21 34.77 113.59 69.14 46.86 39.66 43.41 Tm 6.76 7.74 19.50 6.22 13.84 10.98 10.32 8.58 11.15 0.62 9.87 9.99 11.15 3.44 5.53 10.22 2.68 2.40 9.53 12.84 14.53 17.87 20.85 13.09 6.45 34.21 17.01 9.78 8.22 8.81 Yb 57.11 63.16 187.59 52.81 122.96 99.92 96.19 81.37 98.13 5.56 89.30 89.26 103.69 24.38 46.96 92.96 22.01 17.89 72.94 100.04 128.98 169.54 196.62 106.20 49.22 381.86 171.94 84.68 71.18 79.36 Lu 6.37 7.10 25.15 5.63 15.52 12.40 12.36 10.10 12.38 0.67 11.22 11.49 13.68 2.40 5.21 11.81 2.41 1.77 8.34 11.82 16.01 22.40 25.85 14.69 5.32 57.98 22.96 10.11 8.90 9.59 Hf 0.32 0.37 0.53 0.46 0.58 0.62 0.66 0.49 0.70 0.24 0.64 0.68 0.63 0.31 0.36 0.34 0.47 0.23 0.13 0.25 1.05 0.90 1.00 0.53 0.48 0.80 1.18 1.16 1.00 0.70 Ta 0.46 0.34 0.89 0.37 1.13 1.07 1.01 0.90 1.15 0.40 0.90 0.69 0.79 0.15 0.39 1.66 1.44 0.07 0.06 0.05 3.24 2.30 2.90 1.92 1.17 3.03 2.83 4.54 3.58 1.68 Bi 0.01 0.00 0.00 0.02 0.01 0.00 0.00 0.02 0.02 0.00 0.02 0.02 0.03 0.01 0.01 0.00 0.14 0.00 0.00 0.00 0.05 0.04 0.01 0.09 0.08 0.03 0.05 0.05 0.06 0.07 Pb 0.04 0.00 0.00 0.03 0.02 0.09 0.00 0.00 0.02 0.02 0.01 0.00 0.02 0.00 0.03 0.00 0.36 0.03 0.02 0.00 0.04 0.04 0.01 0.03 0.02 0.04 0.03 0.11 0.00 0.16 Th 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.06 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.03 0.02 0.00 0.01 U 0.12 0.12 0.19 0.14 0.36 0.33 0.37 0.35 0.35 0.12 0.33 0.28 0.28 0.08 0.63 0.18 2.49 0.03 0.03 0.03 1.79 0.62 1.10 0.28 0.27 0.88 1.61 1.44 0.71 0.38 ∑REE 171.18 200.81 422.67 160.19 323.99 276.40 265.86 228.80 271.28 22.82 254.14 249.60 274.89 121.97 160.07 229.99 83.70 87.15 239.67 334.44 346.86 409.38 465.04 284.30 175.12 705.55 392.32 255.07 212.18 224.32 ∑LREE 1.02 1.20 1.74 0.92 2.52 2.50 2.65 2.40 2.71 1.41 2.65 2.30 2.41 1.46 0.99 0.83 1.27 0.75 1.17 1.42 2.07 1.70 1.90 0.74 1.63 1.62 2.10 2.14 1.67 1.50 ∑HREE 170.16 199.60 420.93 159.27 321.46 273.90 263.21 226.40 268.57 21.41 251.50 247.29 272.48 120.50 159.08 229.16 82.43 86.40 238.50 333.02 344.80 407.68 463.14 283.56 173.49 703.93 390.22 252.93 210.51 222.82 (La/Yb)N 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 (La/Sm)N 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 (Gd/Yb)N 0.09 0.11 0.04 0.10 0.08 0.09 0.10 0.11 0.10 0.66 0.11 0.11 0.09 0.35 0.15 0.05 0.23 0.25 0.11 0.13 0.07 0.05 0.04 0.05 0.13 0.02 0.05 0.10 0.09 0.09 Eu/Eu* 0.00 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.00 0.01 0.00 0.01 0.01 0.02 0.02 0.02 0.05 0.04 0.02 0.01 0.05 0.06 0.06 0.07 0.05 0.09 0.08 0.02 0.04 0.03 Y/Gd 66.27 56.54 74.35 62.10 52.05 50.01 42.73 42.82 47.75 9.33 44.33 44.51 49.94 31.46 43.72 79.56 34.50 46.93 60.93 47.91 64.48 78.96 81.08 93.27 62.14 110.62 68.37 57.76 61.96 60.45 Y/Dy 8.85 8.78 9.76 9.00 8.48 8.35 7.91 7.93 8.61 7.48 8.47 8.75 8.64 6.81 7.71 9.27 7.59 7.48 8.30 7.68 8.69 9.20 9.08 9.90 8.54 10.44 9.05 8.64 8.67 9.37
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