Discovery of Lithium-Rich Sedimentary Rocks in Mesoproterozoic Wumishan Formation in Eastern Hebei Province and Implications for Mechanism of Lithium Enrichment and Mineralization
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摘要: 2021年项目组在冀东地区发现中元古代富锂沉积岩系，是我国首次在前寒武纪地层中发现的富锂沉积记录.勘查区内共发现33层锂矿体，厚度为1.09~5.59 m，平均厚度2.32 m，Li2O品位为0.1%~0.42%，平均品位0.16%.富锂层位在冀东地区分布广泛、厚度大、层位稳定，因此，可预测的锂资源潜力巨大，具有重要的经济和理论研究价值.该富锂岩系发育于中元古代雾迷山组，XRD矿物分析、地球化学数据显示其主要矿物组成为白云石，其次为石英和伊蒙混层、伊利石等黏土矿物；富锂岩系具有高CaO、MgO含量和低Al2O3含量的特征；浸出实验结果表明，常温常压下富锂泥质白云岩与稀盐酸在封闭容器中反应可发生 > 77%的锂元素浸出.与华南地区晚古生代的富锂沉积岩系相比，该富锂岩系在成矿时代、赋矿层位、岩石类型、矿物组成、地化特征和赋存状态上存在显著差异，同时也不同于后者需要在加热条件下才发生锂的有效浸出.上述差异可能与以下原因有关：（1）研究区富锂岩系的成矿物质可能来源于山海关古陆的风化；（2）富锂岩系形成于干旱的碳酸盐岩潮坪-泻湖环境.因此，冀东雾迷山组富锂岩系的形成不同于前人提出的碳酸盐黏土型锂矿，指示了一种新的锂富集机制和成矿过程，但对该套岩系的锂富集成矿机制还需要进一步研究.Abstract: In 2021, the research group discovered the Mesoproterozoic lithium-rich sedimentary series in eastern Hebei Province. This is the first lithium-rich sedimentary record found in the Precambrian strata in China. A total of 33 lithium-rich layers were found in the exploration area, with a thickness of 1.09-5.59 m, an average thickness of 2.32 m, Li2O grade of 0.1%-0.42%, and an average grade of 0.16%. The target layer has wide distribution, huge thickness, stable horizon, and huge lithium resource potential, so it has a huge potential for lithium resources. Lithium-rich sedimentary rocks are developed in the Mesoproterozoic Wumishan Formation. Mineralogical and geochemical analyses show that dolomite is the dominant mineral with subordinate quartz, illite/smectite mixed layer, and illite. The lithium-rich rocks are characterized by high CaO, MgO and low Al2O3 contents. At room temperature and pressure, the reaction of argillaceous dolomite with dilute hydrochloric acid in a closed container can produce > 77% lithium leaching. Compared with the Late Paleozoic lithium-rich sedimentary rocks in South China, this type of lithium-rich rocks in North China has significant differences in metallogenic age, ore-bearing succession, lithology, mineral composition, major and trace elements and occurrence state. And it is also different from the former, which requires effective leaching of lithium under heating conditions. These differences are likely related to the likely derivation of the ore-forming materials of lithium-rich rocks in the study area from the weathering of Shanhaiguan ancient land and the deposition in a dry carbonate tidal flat-lagoon environment. Therefore, the formation of the lithium-rich rocks in the Wumishan Formation is different from the previously proposed carbonate clay-type lithium deposits, indicating a new lithium enrichment mechanism. The exact mechanism of lithium enrichment in this rock series still needs to be further studied.
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图 1 研究区大地构造位置略图(a)和冀东地区区域地质简图(b)
Fig. 1. Sketch of the tectonic location in the study area (a) and regional geological map of eastern Hebei Province (b)
图 2 雾迷山组富锂白云质泥岩野外照片(a、b)、镜下(c)及二次电子图像(d)
Fig. 2. Field (a, b), microphotographs (c) and SE (d) photographs of lithium-rich dolomitic mudstone of the Wumishan Formation
图 3 研究区样品上地壳标准化微量元素蛛网图(a)和上地壳标准化稀土元素配分曲线图(b)
标准化值据Taylor and McLennan，1985；红色为研究区富锂岩系，黑色为研究区非富锂的白云岩
Fig. 3. The upper crust normalized trace element spider diagram (a) and REE distribution curve (b) of the samples from study area
图 4 研究区泥质白云岩样品的锂离子浸出实验结果
Fig. 4. The result of lithium leaching from argillaceous dolomite samples in the study area
图 5 研究区泥质白云岩样品的锂离子吸附实验结果
Fig. 5. The result of lithium adsorption of argillaceous dolomite samples in the study area
图 6 研究区雾迷山组富锂岩系与豫西巩义地区上石炭统本溪组、桂西平果地区上二叠统合山组沉积序列对比
红色为富锂层位，豫西巩义地区柱状图引自张英利等（2023）；桂西平果地区柱状图引自姚双秋等（2021）
Fig. 6. Comparison of lithium-rich rock series of Wumishan Formation in the study area with sedimentary sequence of Upper Carboniferous Benxi Formation in Gongyi area of western Henan Province and Upper Permian Heshan Formation in Pingguo area of western Guangxi Province
表 1 研究区X射线衍射分析结果(%)
Table 1. The results of X-ray diffraction analysis (%) in the study area
层位 样品编号 岩石定名 白云石 石英 钾长石 方解石 黄铁矿 黏土矿物总量 伊蒙混层 伊利石 高岭石 绿泥石 海泡石 Jxw1 GBL1012-2 泥质白云岩 73.0 14.8 1.6 1.1 9.5 6.7 2.4 0.2 0.2 Jxw1 GBL1015-2 泥质白云岩 72.9 12.4 3.0 11.7 7.6 3.4 0.4 0.4 Jxw2 LBZ后-1 泥质白云岩 63.7 17.1 2.1 17.1 10.9 5.6 0.2 0.3 Jxw3 ZJG-2 泥质白云岩 71.4 19.6 2.1 6.4 0.4 5.9 Jxw3 ZK4001-4 泥质白云岩 70.7 14.1 1.8 0.9 12.5 5.4 4.0 3.1 Jxw3 ZK4001-11 泥质白云岩 80.5 11.9 1.7 5.2 0.9 4.2 0.1 Jxw3 ZK4001-33 泥质白云岩 66.8 16.7 4.6 11.9 1.2 1.2 9.5 
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表 2 研究区雾迷山组主量元素(%)分析结果
Table 2. The major element compositions (%) from the Wumishan Formation in the study area
样品编号 岩性 SiO2 TiO2 Al2O3 MgO CaO Na2O K2O P2O5 样品编号 岩性 SiO2 TiO2 Al2O3 MgO CaO Na2O K2O P2O5 ZK4001-1 泥晶白云岩 7.15 0.01 0.17 20.29 28.94 0.00 0.06 0.01 ZK4001-29 泥晶白云岩 1.29 0.00 0.07 21.44 29.65 0.00 0.05 0.03 ZK4001-2 白云质泥岩 27.48 0.12 2.84 16.17 18.80 0.02 2.00 0.09 ZK4001-30 粉晶白云岩 0.95 0.01 0.22 21.37 29.87 0.00 0.12 0.02 ZK4001-3 粉晶白云岩 8.92 0.03 0.76 18.52 29.06 0.01 0.32 0.02 ZK4001-31 白云质泥岩 22.14 0.03 0.83 17.18 23.24 0.00 0.49 0.20 ZK4001-4 泥质白云岩 27.69 0.16 3.75 16.57 18.01 0.05 2.20 0.10 ZK4001-32 粉晶白云岩 9.82 0.00 0.06 19.82 27.63 0.00 0.02 0.02 ZK4001-5 大理岩化白云岩 1.12 0.01 0.18 21.87 29.70 0.00 0.08 0.01 ZK4001-33 泥质白云岩 23.61 0.11 2.50 17.44 20.72 0.01 1.30 0.09 ZK4001-6 砂屑白云岩 29.18 0.06 1.38 14.88 20.87 0.00 0.77 0.04 ZK4001-34 粉晶白云岩 0.27 0.00 0.01 21.70 30.08 0.00 0.01 0.00 ZK4001-7 粉晶白云岩 15.44 0.00 0.13 18.43 25.67 0.00 0.05 0.01 ZK4001-35 泥晶白云岩 1.56 0.01 0.20 21.05 29.94 0.01 0.07 0.01 ZK4001-8 细晶白云岩 2.72 0.00 0.07 21.40 29.22 0.00 0.03 0.01 ZK4001-36 白云质泥岩 3.76 0.01 0.18 21.10 29.03 0.00 0.05 0.01 ZK4001-9 粉晶白云岩 38.30 0.01 0.19 13.62 19.08 0.00 0.08 0.01 ZK4001-37 粉晶白云岩 0.32 0.01 0.07 21.86 30.34 0.00 0.07 0.00 ZK4001-10 泥晶白云岩 1.89 0.01 0.21 21.39 29.52 0.00 0.13 0.01 ZK4001-38 沥青质白云岩 7.12 0.01 0.05 20.21 28.30 0.00 0.04 0.01 ZK4001-11 泥质白云岩 25.83 0.13 3.26 16.63 18.71 0.07 2.22 0.08 GBL1012-1 粉晶白云岩 27.50 0.00 0.07 16.05 22.71 0.00 0.02 0.03 ZK4001-12 燧石白云岩 5.39 0.02 0.64 21.03 28.64 0.00 0.32 0.01 GBL1012-2 泥质白云岩 27.37 0.10 2.75 18.05 18.93 0.00 1.21 0.14 ZK4001-13 泥晶白云岩 1.74 0.01 0.29 21.26 30.14 0.00 0.17 0.01 GBL1012-3 白云质泥岩 28.27 0.11 2.95 18.14 17.87 0.00 1.24 0.17 ZK4001-14 粉晶白云岩 0.37 0.01 0.05 21.86 30.15 0.00 0.04 0.00 GBL1012-4 粉晶白云岩 0.69 0.00 0.14 21.29 30.41 0.00 0.05 0.04 ZK4001-15 泥晶白云岩 4.72 0.00 0.13 20.46 29.03 0.00 0.03 0.00 GBL1015-1 细晶白云岩 3.02 0.02 0.82 21.11 28.92 0.00 0.67 0.03 ZK4001-16 泥质白云岩 9.76 0.06 1.37 18.81 26.32 0.00 0.82 0.07 GBL1015-2 泥质白云岩 25.60 0.11 2.85 17.73 18.60 0.06 2.53 0.09 ZK4001-17 粉晶白云岩 1.01 0.01 0.10 21.42 30.10 0.01 0.07 0.01 GBL1015-3 粉晶白云岩 0.00 0.00 0.02 21.80 30.36 0.00 0.01 0.00 ZK4001-18 白云质泥岩 16.88 0.06 1.38 18.82 23.14 0.35 1.23 0.04 LBZ后-1 泥质白云岩 31.18 0.16 3.99 15.63 16.69 0.04 2.95 0.10 ZK4001-19 泥晶白云岩 2.00 0.00 0.07 21.61 29.48 0.00 0.04 0.00 LBZ后-2 粉晶白云岩 23.35 0.01 0.25 16.13 23.24 0.00 0.09 0.03 ZK4001-20 细晶白云岩 7.82 0.00 0.03 20.09 27.79 0.00 0.02 0.00 JJY-1 泥晶白云岩 9.81 0.05 1.11 19.12 27.35 0.02 0.38 0.04 ZK4001-21 白云质泥岩 20.97 0.10 2.15 17.18 22.11 0.03 1.43 0.06 JJY-2 白云质泥岩 18.97 0.10 2.27 17.48 23.13 0.02 0.98 0.07 ZK4001-22 细晶白云岩 0.55 0.00 0.02 21.69 29.97 0.00 0.02 0.01 JJY-3 泥质白云岩 19.35 0.09 1.78 17.53 23.02 0.02 0.87 0.06 ZK4001-23 白云质泥岩 25.64 0.12 3.11 15.47 20.61 0.04 1.85 0.10 JJY-4 白云质泥岩 25.05 0.12 2.82 16.42 19.29 0.04 1.79 0.08 ZK4001-24 粉晶白云岩 0.85 0.01 0.11 21.57 29.81 0.00 0.08 0.01 ZJG-1 粉晶白云岩 4.91 0.00 0.13 20.91 28.57 0.00 0.03 0.02 ZK4001-25 白云质泥岩 1.75 0.01 0.08 21.71 30.06 0.00 0.03 0.00 ZJG-2 泥质白云岩 37.28 0.11 3.33 16.37 14.52 0.08 2.85 0.08 ZK4001-26 粉晶白云岩 1.35 0.01 0.06 21.41 29.56 0.00 0.04 0.01 ZJG-3 燧石白云岩 18.18 0.04 1.45 17.76 23.53 0.01 1.15 0.04 ZK4001-27 白云质泥岩 20.69 0.05 1.41 17.26 23.05 0.00 0.83 0.04 ZJG-4 泥晶白云岩 18.31 0.01 0.05 17.92 25.09 0.00 0.03 0.00 ZK4001-28 粉晶白云岩 12.86 0.00 0.05 18.93 26.30 0.01 0.02 0.00
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表 3 研究区雾迷山组微量元素(ppm)分析结果
Table 3. The trace element compositions (ppm) from the Wumishan Formation in the study area
样品编号 岩性 Li Cu Rb Sr Y Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Th U LREE/HREE Eu/Eu* Ce/Ce* ZK4001-1 泥晶白云岩 21 4.87 0.32 46.50 0.82 0.01 0.00 6.60 1.27 2.30 0.29 0.99 0.18 0.03 0.17 0.02 0.12 0.03 0.06 0.01 0.05 0.01 0.00 0.13 0.09 10.75 0.86 0.86 ZK4001-2 白云质泥岩 865 3.23 67.40 67.38 6.01 48.42 2.89 5 000.06 8.93 18.95 2.29 7.86 1.46 1.22 1.34 0.18 1.01 0.22 0.57 0.09 0.58 0.09 1.24 3.13 1.42 9.99 4.08 0.95 ZK4001-3 粉晶白云岩 32 2.00 1.29 47.51 1.79 0.05 0.00 46.55 2.83 5.39 0.68 2.35 0.41 0.09 0.39 0.05 0.27 0.06 0.15 0.02 0.14 0.02 0.00 0.52 0.23 10.63 1.01 0.89 ZK4001-4 泥质白云岩 494 2.69 71.71 59.07 6.65 39.55 3.55 2 450.21 10.10 20.32 2.58 8.87 1.61 0.78 1.47 0.19 1.12 0.24 0.63 0.10 0.63 0.10 1.04 3.44 1.80 9.86 2.37 0.91 ZK4001-5 大理岩化白云岩 1 0.50 0.19 23.08 0.67 0.10 0.00 4.61 0.98 1.96 0.25 0.83 0.14 0.02 0.13 0.02 0.10 0.02 0.05 0.01 0.04 0.01 0.00 0.12 0.08 10.85 0.83 0.90 ZK4001-6 砂屑白云岩 4 0.51 1.74 47.50 3.43 0.16 0.00 22.55 3.82 8.61 1.30 4.72 0.94 0.17 0.83 0.11 0.63 0.13 0.29 0.04 0.25 0.04 0.01 1.25 0.55 8.43 0.89 0.88 ZK4001-7 粉晶白云岩 2 0.66 0.17 36.96 0.75 0.04 0.00 110.08 1.18 2.39 0.27 0.89 0.14 0.04 0.14 0.02 0.09 0.02 0.05 0.01 0.04 0.01 0.00 0.09 0.47 13.52 1.41 0.97 ZK4001-8 细晶白云岩 1 1.08 0.07 28.36 0.75 0.06 0.00 5.59 1.08 1.79 0.24 0.82 0.12 0.02 0.13 0.02 0.09 0.02 0.04 0.01 0.03 0.01 0.00 0.04 0.17 12.01 0.85 0.80 ZK4001-9 粉晶白云岩 1 0.49 0.21 34.82 0.77 0.00 0.00 6.75 1.16 1.71 0.22 0.77 0.12 0.02 0.12 0.02 0.09 0.02 0.05 0.01 0.05 0.01 0.00 0.20 0.32 10.98 0.75 0.77 ZK4001-10 泥晶白云岩 11 0.26 0.48 49.82 1.17 0.05 0.00 791.09 1.67 3.45 0.44 1.49 0.28 0.21 0.25 0.04 0.20 0.04 0.09 0.01 0.08 0.01 0.00 0.16 0.14 10.47 3.71 0.92 ZK4001-11 泥质白云岩 971 1.93 75.28 48.58 5.58 47.98 2.93 1 423.10 7.79 16.49 2.02 6.97 1.30 0.50 1.18 0.16 0.92 0.20 0.53 0.08 0.54 0.08 1.19 2.80 2.20 9.51 1.89 0.95 ZK4001-12 燧石白云岩 19 2.86 1.07 45.79 1.72 0.03 0.00 20.97 2.22 4.28 0.58 2.12 0.37 0.07 0.37 0.05 0.25 0.05 0.12 0.02 0.09 0.01 0.00 0.43 0.26 10.06 0.91 0.86 ZK4001-13 泥晶白云岩 3 0.44 0.50 37.08 1.18 0.10 0.00 5.73 1.47 2.91 0.39 1.34 0.24 0.04 0.23 0.03 0.18 0.04 0.09 0.01 0.08 0.01 0.01 0.24 0.11 9.41 0.87 0.88 ZK4001-14 粉晶白云岩 1 0.17 0.09 21.22 0.25 0.03 0.00 1.18 0.36 0.44 0.05 0.18 0.03 0.01 0.03 0.00 0.03 0.01 0.02 0.00 0.02 0.00 0.00 0.04 0.06 10.52 0.81 0.72 ZK4001-15 泥晶白云岩 4 0.24 0.11 45.30 0.30 0.08 0.00 5.19 0.36 0.49 0.06 0.22 0.04 0.01 0.04 0.01 0.04 0.01 0.02 0.00 0.02 0.00 0.00 0.05 0.23 8.95 1.01 0.75 ZK4001-16 泥质白云岩 15 0.70 1.45 61.45 6.44 0.25 0.00 21.44 4.36 10.59 1.43 5.42 1.26 0.20 1.19 0.18 1.03 0.21 0.52 0.08 0.48 0.07 0.02 1.70 0.77 6.20 0.77 0.97 ZK4001-17 粉晶白云岩 5 0.23 0.22 61.90 0.51 0.19 0.00 7.06 0.59 1.15 0.14 0.50 0.10 0.02 0.09 0.01 0.07 0.02 0.04 0.01 0.03 0.01 0.00 0.11 0.21 9.28 0.97 0.90 ZK4001-18 白云质泥岩 1 262 1.17 41.49 44.02 2.77 19.93 1.28 76.09 3.36 7.02 0.91 3.16 0.60 0.12 0.53 0.07 0.44 0.10 0.26 0.04 0.27 0.04 0.50 1.19 0.72 8.67 1.02 0.91 ZK4001-19 泥晶白云岩 1 0.10 0.11 43.55 0.40 0.05 0.00 2.45 0.71 1.03 0.13 0.44 0.07 0.01 0.07 0.01 0.05 0.01 0.03 0.00 0.02 0.00 0.00 0.07 0.09 11.87 0.87 0.77 ZK4001-20 细晶白云岩 1 0.23 0.05 27.30 0.22 0.00 0.00 8.01 0.36 0.45 0.06 0.19 0.03 0.01 0.03 0.00 0.02 0.01 0.01 0.00 0.01 0.00 0.00 0.02 0.10 11.50 0.94 0.72 ZK4001-21 白云质泥岩 761 1.74 44.22 38.98 4.20 28.93 2.04 98.65 5.80 12.43 1.52 5.26 0.99 0.20 0.90 0.12 0.72 0.16 0.39 0.06 0.42 0.06 0.73 2.10 0.73 9.23 0.98 0.96 ZK4001-22 细晶白云岩 2 0.12 0.05 34.61 0.53 0.00 0.00 8.05 0.74 0.99 0.13 0.43 0.07 0.01 0.07 0.01 0.05 0.01 0.03 0.01 0.03 0.01 0.00 0.04 0.06 10.89 0.89 0.74 ZK4001-23 白云质泥岩 650 9.55 57.26 43.01 6.67 53.18 2.92 141.13 8.15 16.80 2.14 7.42 1.37 0.27 1.27 0.18 1.06 0.23 0.60 0.10 0.64 0.10 1.36 2.98 2.50 8.67 0.95 0.92 ZK4001-24 粉晶白云岩 2 0.09 0.14 29.65 1.17 0.06 0.00 2.59 0.55 0.83 0.13 0.46 0.09 0.02 0.09 0.01 0.10 0.03 0.07 0.01 0.07 0.01 0.03 0.08 0.07 5.31 0.89 0.72 ZK4001-25 白云质泥岩 4 0.21 0.78 32.86 0.37 1.15 0.07 5.54 0.63 0.86 0.12 0.41 0.06 0.01 0.07 0.01 0.05 0.01 0.03 0.00 0.02 0.00 0.03 0.07 0.21 11.28 0.89 0.71 ZK4001-26 粉晶白云岩 2 0.09 0.11 34.28 0.81 0.01 0.00 3.41 0.50 0.86 0.13 0.45 0.08 0.01 0.09 0.01 0.08 0.02 0.05 0.01 0.05 0.01 0.00 0.07 0.07 6.57 0.80 0.78 ZK4001-27 白云质泥岩 566 3.60 27.32 34.09 3.32 27.44 1.14 49.83 3.92 8.25 1.09 3.77 0.72 0.13 0.66 0.09 0.52 0.12 0.29 0.04 0.29 0.04 0.68 1.24 0.59 8.71 0.88 0.91 ZK4001-28 粉晶白云岩 2 0.26 0.10 35.53 0.38 0.00 0.00 3.97 0.27 0.33 0.05 0.19 0.04 0.01 0.04 0.01 0.04 0.01 0.02 0.00 0.02 0.00 0.00 0.02 0.07 6.07 0.86 0.63 ZK4001-29 泥晶白云岩 2 0.15 0.30 35.22 2.54 0.04 0.01 3.15 0.92 1.38 0.24 0.84 0.19 0.02 0.23 0.04 0.27 0.06 0.17 0.03 0.17 0.03 0.00 0.25 0.11 3.64 0.49 0.67 ZK4001-30 粉晶白云岩 4 0.19 0.39 54.81 1.09 0.41 0.01 6.51 0.83 1.59 0.22 0.78 0.16 0.03 0.15 0.02 0.13 0.03 0.08 0.01 0.09 0.02 0.01 0.19 0.18 6.67 0.76 0.86 ZK4001-31 白云质泥岩 44 0.77 1.58 51.43 11.52 0.24 0.00 244.07 6.07 17.14 2.29 8.33 2.08 0.29 1.93 0.31 1.97 0.44 1.17 0.19 1.29 0.20 0.01 1.15 0.44 4.82 0.68 1.05 ZK4001-32 粉晶白云岩 4 0.34 0.36 34.50 1.68 0.00 0.01 6.00 1.17 1.83 0.26 0.88 0.18 0.02 0.20 0.03 0.20 0.05 0.11 0.02 0.10 0.02 0.00 0.19 0.12 5.98 0.44 0.76 ZK4001-33 泥质白云岩 583 2.71 47.57 30.55 6.06 34.97 2.55 1 941.76 8.35 17.71 2.12 7.24 1.35 0.59 1.23 0.17 0.99 0.22 0.56 0.09 0.60 0.09 0.88 2.84 0.81 9.49 2.17 0.96 ZK4001-34 粉晶白云岩 4 0.27 0.10 41.52 0.38 0.00 0.00 3.85 0.74 0.91 0.10 0.35 0.06 0.01 0.06 0.01 0.04 0.01 0.02 0.00 0.02 0.00 0.00 0.03 0.13 13.04 0.72 0.75 ZK4001-35 泥晶白云岩 14 0.70 0.64 48.40 0.85 0.01 0.00 9.35 1.31 2.25 0.30 1.02 0.18 0.04 0.18 0.02 0.13 0.03 0.06 0.01 0.05 0.01 0.00 0.13 0.12 10.40 0.93 0.82 ZK4001-36 白云质泥岩 37 0.62 1.96 35.44 0.70 1.44 0.15 7.48 1.16 2.00 0.27 0.91 0.15 0.03 0.15 0.02 0.10 0.02 0.05 0.01 0.05 0.01 0.04 0.14 0.12 11.29 1.04 0.81 ZK4001-37 粉晶白云岩 3 0.14 0.14 54.15 0.35 0.11 0.01 3.20 0.40 0.67 0.09 0.31 0.05 0.01 0.05 0.01 0.04 0.01 0.02 0.00 0.02 0.00 0.00 0.17 0.26 9.16 0.89 0.80 ZK4001-38 沥青质白云岩 8 0.10 0.21 55.86 0.43 0.03 0.00 9.27 0.48 0.76 0.10 0.35 0.06 0.01 0.07 0.01 0.05 0.01 0.03 0.01 0.03 0.01 0.00 0.06 0.12 8.40 0.95 0.79 GBL1012-1 粉晶白云岩 2 0.20 0.70 56.63 3.11 0.00 0.03 58.28 1.80 3.21 0.47 1.66 0.36 0.04 0.37 0.07 0.42 0.09 0.23 0.03 0.20 0.03 0.00 0.37 0.21 5.25 0.52 0.80 GBL1012-2 泥质白云岩 491 2.43 35.98 32.75 10.19 63.39 3.20 663.28 11.76 25.55 3.10 10.82 2.05 0.44 1.94 0.27 1.65 0.36 0.95 0.15 0.95 0.14 1.65 5.53 1.54 8.40 1.04 0.96 GBL1012-3 白云质泥岩 538 2.31 40.56 36.27 11.95 68.60 3.69 1 158.99 13.01 27.14 3.36 11.70 2.27 0.56 2.17 0.31 1.89 0.42 1.08 0.17 1.08 0.17 1.79 6.37 1.63 7.96 1.18 0.94 GBL1012-4 粉晶白云岩 10 0.25 0.61 64.11 5.14 0.05 0.01 1 463.34 5.04 8.50 0.98 3.49 0.70 0.34 0.72 0.11 0.67 0.14 0.36 0.05 0.30 0.04 0.00 0.29 0.12 7.97 2.23 0.87 GBL1015-1 细晶白云岩 3 0.45 0.17 22.19 2.20 0.40 0.01 2.91 1.87 4.12 0.62 2.19 0.46 0.05 0.39 0.06 0.38 0.08 0.21 0.03 0.22 0.03 0.01 1.27 0.12 6.62 0.57 0.88 GBL1015-2 泥质白云岩 1 824 6.43 65.53 28.18 6.34 33.42 2.81 88.84 8.67 17.66 2.11 7.18 1.33 0.21 1.19 0.17 1.01 0.22 0.59 0.09 0.61 0.09 0.89 3.68 0.91 9.36 0.80 0.94 GBL1015-3 粉晶白云岩 1 0.39 0.01 21.95 1.00 0.00 0.00 0.50 0.41 0.78 0.10 0.42 0.09 0.02 0.13 0.02 0.09 0.02 0.04 0.01 0.03 0.00 0.00 0.00 0.03 5.45 0.73 0.86 LBZ后-1 泥质白云岩 1 707 8.62 87.55 53.06 6.86 45.96 3.48 499.00 9.52 19.40 2.43 8.37 1.49 0.36 1.35 0.19 1.12 0.25 0.64 0.10 0.67 0.10 1.18 3.63 1.38 9.42 1.18 0.92 LBZ后-2 粉晶白云岩 6 1.40 0.04 32.58 3.13 0.05 0.01 3.05 1.22 3.65 0.49 2.03 0.55 0.13 0.61 0.10 0.57 0.11 0.25 0.03 0.19 0.03 0.00 0.04 0.07 4.26 1.01 1.08 JJY-1 泥晶白云岩 6 16.32 0.10 47.58 5.16 0.10 0.01 2.67 2.27 7.01 0.94 4.07 1.05 0.23 1.14 0.17 1.00 0.20 0.43 0.06 0.32 0.04 0.01 0.19 0.07 4.64 0.97 1.09 JJY-2 白云质泥岩 183 8.81 32.82 49.82 5.22 37.50 2.30 125.03 7.03 14.92 1.81 6.30 1.15 0.23 1.06 0.14 0.84 0.18 0.46 0.07 0.46 0.07 0.93 2.26 1.10 9.63 1.00 0.95 JJY-3 泥质白云岩 174 2.95 27.53 42.29 4.72 41.47 1.99 240.73 6.26 15.93 1.69 6.01 1.14 0.26 1.03 0.14 0.77 0.16 0.43 0.06 0.42 0.06 0.97 1.90 0.92 10.18 1.11 1.12 JJY-4 白云质泥岩 802 1.77 59.82 89.09 6.21 40.57 2.83 5 337.12 8.75 18.58 2.22 7.74 1.44 1.27 1.32 0.17 1.00 0.22 0.56 0.09 0.57 0.08 0.97 2.77 1.40 10.00 4.35 0.96 ZJG-1 粉晶白云岩 1 0.86 0.04 16.74 2.51 0.06 0.01 0.35 0.41 1.04 0.20 0.89 0.27 0.04 0.31 0.06 0.35 0.07 0.17 0.02 0.13 0.02 0.00 0.03 0.07 2.51 0.71 0.82 ZJG-2 泥质白云岩 1 910 6.03 80.27 31.88 5.26 56.56 2.99 245.16 8.31 16.35 2.01 6.71 1.22 0.25 1.10 0.15 0.87 0.19 0.48 0.08 0.52 0.08 1.46 3.17 0.95 10.04 1.01 0.91 ZJG-3 燧石白云岩 36 0.69 0.23 36.38 3.85 0.13 0.01 6.31 1.63 4.79 0.72 3.08 0.80 0.16 0.82 0.13 0.75 0.15 0.33 0.05 0.26 0.04 0.01 0.21 0.09 4.42 0.94 1.01 ZJG-4 泥晶白云岩 1 0.13 0.01 15.86 0.58 0.04 0.00 0.53 0.32 0.71 0.11 0.44 0.10 0.02 0.12 0.02 0.09 0.02 0.03 0.00 0.02 0.00 0.00 0.01 0.04 5.80 0.93 0.88
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表 4 雾迷山组样品锂浸出实验结果
Table 4. The results of the lithium leaching from samples of the Wumishan Formation
样品编号 Li
(ppm)样品Li质量(mg) 实验A-1(加去离子水) 实验A-2(盐酸) 溶液Li+浓度
(mg/L)溶液Li质量(mg) 浸出百分比
(%)溶液Li+浓度(mg/L) 溶液Li质量(mg) 浸出百分比
(%)UN-7 75.01 0.23 0.14 4.06×10-3 1.80 5.71 0.17 76.12 UN-4 188.31 0.57 0.19 5.81×10-3 1.02 18.03 0.54 95.40 GBL-HC-6 199.74 0.60 0.63 1.90×10-2 3.17 17.96 0.54 89.92 GBL-HC-4 505.97 1.52 1.04 3.13×10-2 2.06 46.20 1.39 91.31 GBL-HC-2 564.98 1.69 1.17 3.51×10-2 2.08 54.75 1.64 96.91 GBL-HC-3 606.18 1.82 1.47 4.42×10-2 2.42 55.72 1.67 92.22 GBL1012-3 538.05 1.61 0.65 1.96×10-2 1.22 42.29 1.27 79.56 GBL1015-2 1 824.11 5.49 1.89 5.66×10-2 1.03 140.13 4.20 77.36
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表 5 雾迷山组样品镁、钙浸出实验结果
Table 5. The results of the magnesium, calcium leaching from samples of the Wumishan Formation
样品编号 实验A-1 (加去离子水) 实验A-2 (加盐酸) Mg2+浓度(mg/L) Ca2+浓度(mg/L) Mg2+浓度(mg/L) Ca2+浓度(mg/L) UN-7 25 47 14 689 23 630 UN-4 18 23 13 029 16 971 GBL-HC-6 23 12 14 500 24 405 GBL-HC-4 14 16 15 589 24 484 GBL-HC-2 23 23 12 344 19 389 GBL-HC-3 20 19 14 709 22 731
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表 6 雾迷山组样品锂吸附实验结果
Table 6. The results of the lithium adsorption from samples of the Wumishan Formation
样品编号 Li标液浓度(mg/L) Li标液质量(mg) 实验B-1 实验B-2 溶液Li+浓度(mg/L) 溶液Li质量(mg) Li减少百分比
(%)溶液Li+浓度(mg/L) 溶液Li质量(mg) Li减少百分比
(%)GBL1015-2 103.99 3.12 99.17 2.98 4.64 100.80 3.02 3.07 GBL1012-3 100.43 3.01 3.43 97.06 2.91 6.67
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表 7 国内黏土型锂矿成矿特征(据张英利等, 2022; 张七道等, 2024)
Table 7. Geological characteristics of clay-type lithium deposits in China
分布地区 岩石类型 成矿时代 赋矿地层 沉积环境 物质来源 豫西、山西 黏土岩 晚石炭世 本溪组 滨岸‒泻湖 岩浆岩为主 滇中、黔中 黏土岩
铝土质泥岩早石炭世 九架炉组、倒石头组 陆相洪积作用及湖泊 碳酸盐岩 黔北‒渝南和黔东南 黏土岩
铝土质泥岩晚石炭世‒早二叠世 大竹园组 冲积扇、湖泊和潮坪 页岩、灰岩、白云岩 滇东南‒桂西 黏土岩
铝土质泥岩晚二叠世 合山组、吴家坪组和龙潭组 潮坪‒泻湖 玄武岩、碳酸盐岩 扬子周缘 凝灰岩 中三叠世 雷口坡组 长英质火山岩 黔西 黏土岩 早二叠世 梁山组 淡水陆相为主 白云岩或火山岩
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表 8 研究区雾迷山组与晚古生代的富锂岩系沉积特征对比
Table 8. The comparison of sedimentary characteristics between the Wumishan lithium-rich rock series and the Late Paleozoic lithium-rich rock series in the study area
晚古生代富锂岩系 研究区富锂岩系 分布区域 华南、西南、华北西部 华北东部 大地构造属性 被动大陆边缘 大陆裂谷 成矿时代 晚古生代 中元古代 赋矿层位 碳酸盐岩不整合面之上的泥质岩 碳酸盐岩沉积韵律层富泥质层 矿石类型 黏土岩、铝质黏土岩、铝土矿 泥质白云岩、白云质泥岩 矿物组成 主要由黏土矿物组成，不含白云石 主要由白云石组成，黏土矿物相对较少 富锂矿物 蒙脱石、伊利石、高岭石，勃姆石、一水硬铝石、三水铝石等 伊蒙混层、伊利石组成，含少量高岭石、绿泥石 主要化学成分 高Al2O3、SiO2 高CaO、MgO Li2O品位 0.10%~1.02%之间, 平均0.30% 0.10%~0.32%，平均0.16% 浸出实验 加热酸解 常温酸解 成矿物质来源 碳酸盐岩、岩浆岩 岩浆岩、变质岩 沉积环境 陆源碎屑岩潮坪‒泻湖亚相 碳酸盐潮坪‒泻湖亚相
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