Occurrence State of Lithium of a Greisen-Type Lithium Deposit in the Porphyry Sn-Ore Field, Southern Jiangxi Province
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摘要:
云英岩型锂矿作为近年来新的锂矿类型，具有重要的理论研究和经济价值。然而，在中国南岭及其周缘世界级的钨锡成矿省中，伴生云英岩型锂矿化的综合评价却稍显不足。本课题组在赣南岩背斑岩锡矿田新发现了云英岩型的锂矿，矿体产于密坑山岩体与上覆鸡笼嶂组火山岩的接触带附近的云英岩带内，发育三种矿化类型：云英岩带型和花岗岩、火山岩内的含锂云母-石英脉型。矿体中Li2O的含量最高可达1.04%，主要集中于0.2%～0.3%，具有显著的综合利用价值。为了确定云英岩型锂矿中Li的赋存状态及Li、Sn之间的关系等特征，本文开展了详细的镜下观察，扫描电镜、电子探针和LA-ICP-MS分析，确定了岩背矿田不同于国内外其他典型云英岩型锂矿床大量发育锂云母-铁锂云母系列，其Li载体矿物主要为黑鳞云母，具有高Si、Al、K、Fe、Li的特征，且未经历极端的流体分异演化过程。Li的成矿主要与矿区含斑细粒花岗岩有关，在岩浆晚期高温热液阶段与Sn共同富集，并以Si4++Li+↔AlⅣ+FeT耦合类质同象形式进入云母。
Abstract:Greisen-type Li ore, a new type of lithium ore in recent years, is of great theoretical research and economic value. However, there is slightly insufficient in comprehensive evaluation of greisen-type Li ore in such a world-class Nanling W-Sn metallogenic province and its surroundings. In this work, we found greisen-type Li mineralization firstly in the Yanbei Sn-ore field, Huichang district, Jiangxi Province. The lithium mineralization occurred at the greisen belt near the contact zone between the Minkengshan granitic batholith and overlying volcanic rock of the Jilongzhang Formation. Three types of mineralization were identified: the greisen type, the quartz vein type in granite, and the quartz vein type in volcanic rock. The content of Li2O reaches 1.04% and mainly ranges from 0.2%−0.3%, which is of significant comprehensive utilization value. The occurrence state of lithium and the metallogenic characteristics based on the detailed microscopic observation, scanning electron microscope (SEM) images, electron probe microanalysis (EPMA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is determined here. There is a potential difference between the Yanbei ore field and other domestic and international typical greisen-type lithium deposits, which develop lepidolite-ferrolepidolite series. The main Li-bearing mineral is protolithionite in the Yanbei ore field, and it is identified as high Si, Al, K, Fe and Li with no significant extreme fluid differentiation process. The Li, co-accumulated with Sn in the post-magmatic high-temperature gas-liquid stage, can be linked to the porphyritic fine-grained granite and enter mica via coupling substitution of Si4++Li+↔AlⅣ+FeT.
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表 1 云母中微量元素测定LA-ICP-MS仪器设定参数
Table 1. Measurement conditions for LA-ICP-MS analysis of trace elements in mica
激光参数 实验条件 ICP-MS参数 实验条件 激光源 ASI J-200飞秒激光 ICP-MS系统 X-Series电感耦合等离子体质谱仪 波长 343nm 功率 1400W 脉冲宽度 20ns 冷却气（Ar）流速 13.5L/min 激光束 均值化平顶光束 辅助气（He）流速 0.85L/min 脉冲能量 0.01~0.1mJ/pulse 传输气（He）流速 0.25L/min 能量密度 8J/cm2 传输气（Ar）流速 0.9L/min 焦点 表面 扫描模式 峰跳跃模式 光栅扫描速度 6Hz 获取模式 时间分辨分析 束斑直径 25μm 持续分析时间 70s 
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表 2 岩背矿田淘锡坝锡矿云母化学成分
Table 2. The chemical compositions of mica from Taoxiba deposit in Yanbei ore field
组分 Mica-1(云英岩中云母)中各成分测定值(n=8，%) Mica-2(石英-云母脉中云母)中各成分测定值(n=47，%) 极小值 上四分位 中位值 下四分位 极大值 平均值 极小值 上四分位 中位值 下四分位 极大值 平均值 SiO2 37.19 37.75 38.38 39.19 41.84 38.62 39.03 39.47 39.99 40.49 42.09 40.20 TiO2 0.00 0.13 0.26 0.44 0.63 0.28 0.00 0.05 0.13 0.17 0.34 0.13 Al2O3 18.02 18.46 18.86 19.80 20.94 19.10 19.53 20.06 20.29 20.60 20.89 20.31 FeO 19.74 22.83 25.38 25.74 28.34 24.35 18.08 21.34 21.60 22.86 23.64 21.77 MnO 0.49 0.53 0.57 0.59 0.63 0.56 0.44 0.51 0.55 0.59 0.79 0.56 MgO 0.21 0.37 0.48 0.53 0.61 0.44 0.03 0.08 0.09 0.09 0.14 0.09 CaO 0.00 0.00 0.00 0.01 0.06 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Na2O 0.06 0.08 0.15 0.17 0.48 0.15 0.16 0.20 0.22 0.25 0.31 0.22 K2O 9.65 9.80 9.88 9.91 10.31 9.89 9.54 9.80 9.86 9.92 10.15 9.86 Rb2O 0.01 0.16 0.18 0.20 0.28 0.17 0.09 0.18 0.22 0.24 0.34 0.21 F 1.28 1.80 2.23 2.88 3.09 2.30 1.93 2.72 2.94 3.30 3.69 2.99 Cl 0.02 0.08 0.11 0.13 0.32 0.11 0.11 0.15 0.15 0.19 0.22 0.16 Li2O* 1.12 1.28 1.46 1.70 2.46 1.53 1.65 1.78 1.93 2.07 2.53 1.99 Li2O# 0.87 1.08 1.31 1.59 1.80 1.32 1.07 1.49 1.66 1.85 2.08 1.63 H2O* 2.39 2.53 2.79 2.98 3.17 2.76 2.21 2.36 2.48 2.64 2.99 2.52 以22个O原子为基准计算（%） Si 5.82 5.90 5.95 6.02 6.13 5.96 5.97 6.02 6.06 6.09 6.23 6.06 AlIV 1.87 1.98 2.05 2.10 2.18 2.04 1.77 1.92 1.94 1.99 2.03 1.94 AlⅥ 1.23 1.29 1.37 1.57 1.74 1.43 1.56 1.62 1.67 1.70 1.87 1.67 Ti 0.00 0.02 0.03 0.05 0.07 0.03 0.00 0.01 0.02 0.02 0.04 0.01 Fe 2.42 2.93 3.30 3.39 3.67 3.15 2.24 2.66 2.72 2.92 3.03 2.75 Mn 0.07 0.07 0.07 0.08 0.08 0.07 0.06 0.07 0.07 0.08 0.10 0.07 Mg 0.05 0.08 0.11 0.12 0.14 0.10 0.01 0.02 0.02 0.02 0.03 0.02 Li* 0.71 0.81 0.91 1.04 1.45 0.95 1.02 1.08 1.17 1.25 1.50 1.20 Ca 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Na 0.02 0.02 0.04 0.05 0.15 0.05 0.05 0.06 0.06 0.07 0.09 0.06 K 1.90 1.92 1.94 1.98 2.01 1.95 1.80 1.89 1.91 1.92 1.94 1.90 Rb 0.00 0.02 0.02 0.02 0.03 0.02 0.01 0.02 0.02 0.02 0.03 0.02 OH* 2.49 2.59 2.87 3.08 3.33 2.85 2.21 2.39 2.54 2.67 3.03 2.53 F 0.64 0.88 1.09 1.39 1.49 1.12 0.93 1.29 1.42 1.58 1.75 1.42 Cl 0.00 0.02 0.03 0.03 0.09 0.03 0.03 0.04 0.04 0.05 0.05 0.04 总量 19.67 19.73 19.75 19.77 19.86 19.75 19.67 19.70 19.71 19.73 19.75 19.71 Y位置总量 5.63 5.71 5.74 5.76 5.86 5.74 5.67 5.69 5.72 5.74 5.88 5.73 X位置总量 1.96 1.98 2.00 2.03 2.12 2.01 1.86 1.96 1.99 2.01 2.03 1.98 注：Li2O*和H2O*测定值是通过电子探针分析结果计算得到，其中Li2O*测定值计算方法见Tischendorf等［35］；OH*和Li*测定值是电子探针分析结果以22个O原子为基准计算得到；Li2O#测定值来自LA-ICP-MS分析结果换算。
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