Li Isotopic Composition and Its Constrains on Rare Metal Mineralization of Jiajika Two-Mica Granite, Sichuan Province
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摘要: 四川康定甲基卡超大型锂矿是我国最大的硬岩型锂矿床之一,矿区中南部呈岩株状出露的二云母花岗岩常被认为是成矿伟晶岩的"矿源岩",对其开展Li同位素地球化学研究,对探讨矿区稀有金属的来源与演化具有重要意义.研究工作基于详细的野外地质调查,采用MC-ICP-MS方法对岩体锂同位素组成开展了研究.研究结果显示,岩体Li含量介于192×10-6~470×10-6,均值为309×10-6,δ7Li值介于-1.56‰~+0.90‰,均值为-0.24‰,与平均上地壳值基本一致,具有高Li低δ7Li的特征.δ7Li与Li、Rb、Ga、SiO2及εNd(t)不存在明显的相关性,岩体锂同位素组成反映了其形成时的源区特征,未受岩浆结晶分异作用和蚀变作用的影响.岩体岩石地球化学、同位素地球化学资料表明,岩浆来源以三叠系西康群砂泥岩的部分熔融为主,可能有部分深源物质的加入.此外,岩体Li同位素的变化规律表明伟晶岩的成矿流体来源于二云母花岗岩.岩体Li含量与Li同位素组合不仅可用来划分锂矿床类型,而且对稀有金属找矿具有一定的指导意义.Abstract: Jiajika superlarge hard rock type lithium deposit is one of the most abundant lithium mineral resouces in China. The two-mica granite outcropped in the southern Jiajika orefield is generally regarded as source rocks of the ore-bearing pegmatites. Li isotopic composition is a useful tool to explore the origin and evolution of rare metal. Based on the detailed field work, the lithium isotopic composition of granite was tested by MC-ICP-MS in this study. The results show that the lithium content of the granite is from 192×10-6 to 470×10-6, and the mean value is 309×10-6; the value of δ7Li ranges from -1.56‰ to 0.90‰, and the mean value is -0.24‰, which is closed to the average value of upper crust. Jiajika two-mica granite apparently has higher content of lithium and lower value of δ7Li, and the δ7Li and Li, Rb, Ga, SiO2 and εNd(t) have no obvious correlation. Lithium isotopic composition of granite reflects its characteristics of source rock, and it has not been influenced by crystallization differentiation of magma and alteration. The geochemical and isotope geochemistry data indicate that the source of magma is mainly composed of partial melting of Triassic Xikang sand-mudstone, which may have been mixed with materials from deep source. In addition, variations of lithium content and Li isotopic composition show that the fluid of magma migrated from center to the north and south, and the metallogenic fluid of pegmatite is derived from Jiajika two-mica granite. The content of lithium and Li isotopic composition can not only be used to classify the types of lithium deposits, but also can facilitate the prospecting of rare metals.
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Key words:
- two-mica granite /
- pegmatite /
- lithium isotope /
- Jiajika /
- deposit /
- petrology
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图 1 甲基卡矿区地质简图
SPGZ.松潘-甘孜褶皱带;EKL.东昆仑构造带;STM.柴达木地块;YZ.扬子地块;JT.羌塘地块;GDS.冈底斯地块;QL.祁连构造带;①柴北缘蛇绿杂岩带;②昆中蛇绿杂岩带;③昆南-阿尼玛卿蛇绿杂岩带;④可可西里-金沙江缝合线;⑤班公湖-怒江蛇绿杂岩带;⑥龙门山断裂;⑦理塘蛇绿杂岩带;⑧若尔盖地块;T.上三叠统西康群地层;1.二云母花岗岩;2.微斜长石型伟晶岩;3.微斜长石钠长石型伟晶岩;4.钠长石型伟晶岩;5.钠长石锂辉石型伟晶岩;6.钠长石锂云母型伟晶岩;7.伟晶岩脉编号;8.新发现矿脉;9.类型分带线及编号;10.采样位置;Ⅰ.微斜长石伟晶岩带;Ⅱ.微斜长石-钠长石带;Ⅲ.钠长石带;Ⅳ.锂辉石带;Ⅴ.锂(白)云母带;据Li et al.(2013)
Fig. 1. Geological sketch of the Jiajika ore deposit
图 3 花岗岩和伟晶岩中锂同位素分布
花岗岩未分中花岗岩数据转苏嫒娜等(2010a);安徽荆山淡色花岗岩(S型)数据来自Sun et al.(2016);拉克兰河褶皱带S型花岗岩和I型花岗岩数据来自Teng et al.(2004);大陆下地壳数据来自Teng et al.(2008);中国东北A型花岗岩和和世界花岗岩δ7Li来自Teng et al.(2009);澳大利亚东部新英格兰岩基花岗岩、S型花岗岩、I型花岗岩数据引自Tomascak(2004);加拿大地盾花岗岩数据引自Tomascak(2004);苏格兰斯凯岛花岗岩数据来自Pistiner and Henderson(2003);加利福尼亚金斯山花岗岩-伟晶岩和南达科他州哈尼峰花岗-伟晶岩数据引自Tomascak(2004);四川甲基卡钠长锂辉石伟晶岩数据来自项目组未发表数据;四川甲基卡新三号脉含矿伟晶岩和不含矿伟晶岩数据来自刘丽君等(2017a);南达科他州布拉克山哈尼峰花岗岩和伟晶岩数据来自Teng et al.(2006);加拿大小纳汉尼伟晶岩群数据来自Barnes et al.(2012)
Fig. 3. Li isotopic compositions of different granites and pegmatites
图 7 岩体t-(87Sr/86Sr)i(a)和εNd(t)-(87Sr/86Sr)i(b)图解
华北上地壳和下地壳范围引自Jahnetal.(1999);扬子上地壳和下地壳范围引自 Chenetal.(2001);图例同上图
Fig. 7. Diagram of t-(87Sr/86Sr)i (a) and εNd(t)-(87Sr/86Sr)i (b) for two-mica granites
图 8 花岗岩和伟晶岩δ7Li-Li和δ7Li-lgLi的关系
1.甲基卡二云母花岗岩(S型);2.甲基卡钠长锂辉石伟晶岩;3.甲基卡伟晶岩脉围岩;4.中国东北A型花岗岩;5.荆山淡色花岗岩(S型);6.甲基卡ZK1101含矿伟晶岩;7.布拉克山哈尼峰花岗岩;8.厄尔士山花岗岩;9.加拿大小纳汉尼伟晶岩群;Ⅰ.甲基卡钠长锂辉石伟晶岩(项目组未发表数据);Ⅱ.加拿大小纳汉尼伟晶岩群(Barnes et al., 2012);Ⅲ.甲基卡伟晶岩脉围岩(刘丽君等,2017a);Ⅳ.甲基卡二云母花岗岩(本文自测数据);Ⅴ.厄尔士山花岗岩(Romer et al., 2014);Ⅵ.荆山淡色花岗岩(Sun et al., 2016);Ⅶ.布拉克山哈尼峰花岗岩(Teng et al., 2006);Ⅷ.中国东北A型花岗岩(Teng et al., 2009);a和b图例一致
Fig. 8. Plots of δ7Li versus Li and δ7Li versus lgLi diagram for granite and pegmatite
表 1 甲基卡二云母花岗岩主量、微量、稀土元素和Li同位素测试结果
Table 1. Major, trace, rare earth elements and Li isotope compositions of Jiajika two-mica granite
样号 J6 J7 J8 J9 J10 J11 J12 J13 J14 主量元素(%) SiO2 74.55 73.92 73.66 74.47 74.02 73.65 73.03 74.16 74.64 TiO2 0.06 0.06 0.05 0.06 0.06 0.05 0.06 0.07 0.05 Al2O3 14.90 15.10 14.89 14.82 14.7 14.76 14.78 14.70 14.95 Fe2O3 0.18 0.07 0.10 0.03 0.07 0.13 0.12 0.11 0.20 FeO 0.62 0.64 0.79 0.75 0.82 0.69 0.74 0.67 0.54 MnO 0.02 0.02 0.04 0.03 0.04 0.02 0.03 0.03 0.04 MgO 0.19 0.20 0.17 0.21 0.18 0.23 0.20 0.24 0.16 CaO 0.60 0.80 0.60 0.71 0.59 0.63 0.66 0.71 0.54 Na2O 3.41 3.46 3.63 3.19 3.30 3.22 3.21 3.31 3.45 K2O 5.00 5.07 4.65 5.05 4.83 4.88 4.90 4.76 4.84 P2O5 0.16 0.24 0.13 0.17 0.20 0.20 0.23 0.22 0.19 H2O+ 0.79 0.67 0.87 1.00 1.11 0.74 1.08 0.96 0.90 CO2 0.13 0.28 0.19 0.19 0.27 0.26 0.26 0.19 0.30 Total 100.61 100.53 99.77 100.68 100.19 99.46 99.3 100.13 100.8 微量元素(10-6) Li 264.00 327.00 470.00 298.00 340.00 192.00 301.00 266.00 320.00 Be 14.00 10.00 10.00 8.00 30.00 6.00 12.00 8.00 8.00 Ga 17.80 17.20 19.10 15.50 17.50 15.95 15.70 17.70 17.70 Rb 313.00 354.00 475.00 308.00 388.00 299.00 334.00 320.00 315.00 Sr 33.50 31.50 21.40 29.30 28.90 33.75 25.80 33.80 32.10 Cs 47.10 51.70 136.00 44.80 70.15 32.65 61.30 56.00 35.40 Ba 57.70 53.40 37.30 63.40 48.30 62.80 44.60 56.00 58.40 Pb 43.80 41.40 37.20 43.20 40.30 45.15 40.90 44.30 40.50 Th 3.60 3.17 2.75 3.86 3.04 3.34 3.42 3.99 3.52 U 3.72 3.13 2.48 3.36 2.99 4.01 3.10 3.02 8.73 Nb 14.70 14.00 26.60 16.40 19.55 7.76 16.50 15.80 19.20 Ta 4.27 3.09 10.70 3.50 6.11 1.65 3.60 3.58 4.22 Zr 29.10 29.30 24.90 32.50 28.00 29.60 31.00 32.40 29.40 Hf 1.52 1.49 1.44 1.70 1.47 1.44 1.62 1.65 1.58 W 375.00 380.00 6.00 433.00 196.00 219.00 409.00 381.00 325.00 Sc 2.45 2.16 2.43 2.28 2.45 2.41 1.78 2.68 2.80 Sn 19.10 20.50 37.50 24.20 30.35 14.95 25.20 19.50 20.70 稀土元素(10-6) La 6.40 6.03 4.52 7.64 5.70 6.62 5.94 7.10 6.39 Ce 13.00 12.00 8.96 15.60 11.25 13.35 13.50 14.50 13.00 Pr 1.43 1.35 0.97 1.68 1.25 1.50 1.31 1.62 1.37 Nd 4.88 4.70 3.28 5.81 4.33 5.18 4.63 5.74 4.83 Sm 1.53 1.46 1.09 1.66 1.34 1.62 1.39 1.76 1.42 Eu 0.29 0.25 0.17 0.30 0.23 0.30 0.25 0.32 0.28 Gd 1.51 1.43 1.09 1.66 1.33 1.62 1.28 1.73 1.46 Tb 0.26 0.25 0.22 0.27 0.25 0.30 0.22 0.28 0.27 Dy 1.09 1.11 1.03 1.27 1.13 1.31 0.88 1.20 1.26 Ho 0.13 0.13 0.13 0.14 0.14 0.16 0.09 0.15 0.17 Er 0.21 0.25 0.29 0.25 0.28 0.30 0.16 0.27 0.33 Tm 0.03 0.03 0.04 0.03 0.03 0.04 0.02 0.03 0.04 Yb 0.17 0.18 0.18 0.19 0.20 0.21 0.12 0.18 0.25 Lu 0.03 0.03 0.02 0.02 0.03 0.03 0.02 0.03 0.04 Y 3.49 3.88 3.96 3.79 4.11 4.44 2.61 3.89 4.85 Li同位素(%) δ7Li±2 δ -1.21±0.03 +0.29±0.02 +0.52±0.03 -1.56±0.03 +0.90±0.02 +0.00±0.02 -0.07±0.02 -1.31±0.02 +0.07±0.02 表 2 甲基卡二云母花岗岩全岩Sr-Nd同位素测试结果
Table 2. Whole-rock Sr-Nd isotopic compositions of Jiajika two-mica granite
样号 年龄(Ma) Rb(10-6) Sr(10-6) Rb/Sr 87Rb/86Sr 87Sr/86Sr (87Sr/86Sr)i Sm(10-6) Nd(10-6) Sm/Nd 147Sm/144Nd 143Nd/144Nd (143Nd/144Nd)t εNd(t) J9 223 182.9 3.1 58.5 19.250 4 0.771 71 0.710 66 0.41 1.45 0.28 0.170 0 0.512 17 0.511 92 -8.41 J10 223 233.6 3.5 67.6 21.257 6 0.777 39 0.709 97 0.37 1.29 0.28 0.172 1 0.512 08 0.511 82 -10.29 J11 223 0.57 2.06 0.28 0.168 0 0.511 98 0.511 74 -11.94 J13 223 0.37 1.26 0.29 0.175 6 0.512 00 0.511 75 -11.83 J14 223 0.16 0.65 0.24 0.145 5 0.512 13 0.511 91 -8.52 注:223 Ma据郝雪峰等(2015);由于全岩Rb含量较高,Sr明显亏损,Rb/Sr比较高,放射性87Sr/86Sr不能准确扣除,导致送出的5件Sr同位素样品仅成功2件. -
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