Preliminary Study of the Occurrence of Lithium in the Ertanggou Deposit, East Tianshan
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摘要: 新疆是我国重要的锂矿集中区，已知矿床多以伟晶岩型和卤水型产出. 最近在东天山二塘沟地区新发现有黏土型锂矿. 为厘定二塘沟锂矿锂的赋存状态，开展了详细的矿床地质、全岩化学成分、X射线衍射、全自动矿物定量分析（TIMA）、电子探针分析（EPMA）、LA-ICPMS矿物原位微区元素分析以及锂的浸泡实验. 结果显示，二塘沟锂矿体主要赋存于上石炭统祁家沟组富含生物碎屑的碳酸盐岩中. 矿石主要组成矿物包括方解石、石英、海泡石，全岩的Li2O含量相对较高，变化于0.10%~0.27%. 锂主要赋存于海泡石中，其含量高达9 519×10-6，并且Li含量与F含量具有极好的正相关关系. 二塘沟锂矿是新疆地区发现的首个黏土型锂矿，锂的赋存方式显著不同于其他黏土型矿床，具有重要的科学研究价值和找矿实践意义.Abstract: Xinjiang is an important lithium province in China. The ever-known deposits are dominated by pegmatite and brine type. Recently, a clay-type lithium deposit has been discovered in the Ertanggou area, East Tianshan. In order to determine the occurrence of lithium in the Ertanggou deposit, we carried out detailed deposit geology, whole-rock chemical composition, X-ray diffraction, automatic mineral Quantitative analysis (TIMA), electron probe microanalysis (EPMA), LA-ICPMS trace element analysis as well as soaking immersion experiments. The results show that, the lithium orebodies are mainly hosted by bioclasts-rich carbonate rocks of the Upper Carboniferous Qijiagou Formation. The ore mainly consists of calcite, quartz and sepiolite, with Li2O content of 0.10% to 0.27%. Sepiolite is the main Li-bearing phase (with Li content up to 9 519×10-6), and there is a good positive relationship between Li and F. Collectively, we propose that the Ertanggou deposit is the first clay-type lithium deposit discovered in Xinjiang. The occurrence of lithium in Ertanggou is significantly different from other clay-type deposits.It has important value of scientific research and practical significance of prospecting.
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Key words:
- occurrence /
- sepiolite /
- clay-type lithium deposit /
- carbonate /
- East Tianshan /
- mineral deposit
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图 3 祁家沟组含锂灰岩特征
a，b. L1和L2号锂矿体所赋存的祁家沟组灰岩；c. 灰岩中夹有硅质岩；d. 主要富锂层位-生物碎屑灰岩；e、f. 生物碎屑灰岩镜下特征，主要由方解石（Cal）、石英（Qtz）组成，可见大量生物碎屑（Cly）
Fig. 3. Characteristics of Lithium-bearing limestone of Qijiagou Formation in the study area
图 4 两件矿石样品的全自动矿物定量分析(TIMA)
显示矿石中主要矿物包括方解石、石英和海泡石，其中海泡石常沿方解石边缘或裂隙交代，或呈浸染状分布
Fig. 4. Fully Automated Mineral Quantitative Analysis (TIMA) of Two Ore Samples
图 5 海泡石SEM图像（a）及Li与F之间的相关关系（b）
图a中红圈为LA-ICPMS原位元素测试点；图b中Li含量由LA-ICPMS分析获得，F含量由电子探针分析获得
Fig. 5. SEM imaging of sepiolite (a) and the positive relationship between Li and F (b)
表 1 二塘沟锂矿石化学成分分析结果（%）
Table 1. Chemical composition of ores from the Ertanggou lithium deposit (%)
矿体编号 样品编号 Li2O CaO MgO SiO2 L2 21Ⅱ-ET-BT2-H2 0.27 31.04 9.42 29.77 21Ⅱ-ET-BT4-H3 0.19 40.16 5.54 18.95 21Ⅱ-ET-BT3-H2 0.25 26.60 6.24 40.76 L3 21Ⅱ-ET-BT5-H12 0.16 37.72 5.91 22.71 21Ⅱ-ET-BT5-H13 0.10 32.77 7.07 27.33 L1 21Ⅱ-ET-BT0-H6 0.10 33.55 4.20 33.04 21Ⅱ-ET-L1BT3-H7 0.11 41.00 4.11 19.67 21Ⅱ-ET-L1BT5-H2 0.15 10.35 19.72 51.26 平均值 0.17 31.65 7.78 30.44 
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表 2 二塘沟锂矿石X射线衍射分析结果
Table 2. Results of X-ray diffraction analysis of ores from the Ertanggou lithium deposit
样品编号 矿物成份及含量（%） 方解石 云母 石英 海泡石 L2-1BT3H1 49.25 11.20 39.55 L2-1BT3H2 83.45 8.63 7.92 L1BT2H1 75.24 19.22 5.54 L1BT2H2 87.72 4.21 8.07 L2BT2H1 38.13 5.34 41.33 15.20 L2BT2H2 44.06 3.52 32.96 19.46 L2BT4-1H1 88.62 3.19 6.21 1.98 L2-1BT4-1H2 81.41 12.72 5.87 L3BT5H1 80.17 2.58 14.65 2.60 L3BT5H2 62.58 5.45 22.36 9.61 L2BT4H1 51.44 3.69 38.39 6.47 L2BT4H2 57.11 3.29 39.60 L3BT9H1 76.13 2.01 21.86 L3BT9H2 70.78 3.75 21.30 4.16 L3BT9H3 55.35 27.97 16.68 L3BT9H4 78.08 6.89 15.03 最大值 88.62 27.97 41.33 19.46 最小值 38.13 2.01 4.21 1.98 平均值 67.47 7.16 21.70 8.12
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表 3 二塘沟锂矿石全自动矿物定量分析结果（%）
Table 3. Automated mineral quantitative analysis of ores from the Ertanggou lithium deposit (%)
样品编号 方解石 石英 海泡石 白云石 磷灰石 菱铁矿 黄铁矿 钛铁矿 黑云母 正长石 L1BT2 71.63 7.52 20.46 0.39 0.00 0.00 0.00 L2-1BT3 34.75 41.80 23.31 0.12 0.00 0.00 0.00 0.00 L2BT2 40.02 46.41 13.42 0.11 0.01 0.00 0.00 L3BT5 86.40 0.71 12.70 0.18 0.01 0.00 0.00 0.00 0.00 L3BT9 66.40 29.59 3.02 0.92 0.01 0.02 0.00 0.00 最小值 34.75 0.71 3.02 0.11 0.00 0.00 0.00 0.00 0.00 0.00 最大值 86.40 46.41 23.31 0.92 0.01 0.02 0.00 0.00 0.00 0.00 平均值 59.84 25.20 14.58 0.34 0.00 0.01 0.00 0.00 0.00 0.00
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表 4 二塘沟锂矿海泡石电子探针分析结果（%）
Table 4. EMPA analytical data of sepiolite from the Ertanggou lithium deposit (.%)
样品编号 Na2O MgO Al2O3 SiO2 P2O5 K2O CaO TiO2 MnO FeO NiO Cl F L3-BT5-1 0.04 25.20 0.35 59.89 0.01 5.23 0.18 0 0.02 0.09 0.01 0.02 4.83 L3-BT9 0.27 23.36 1.81 57.82 0.01 3.03 0.60 0.03 0.02 1.67 0 0.05 2.03 L2-1BT3 0.06 25.46 1.06 59.08 0 5.70 0.16 0 0 0.31 0.01 0 4.69 L2-BT2 0.30 29.98 0.08 62.70 0.01 0.05 0.05 0 0.01 0.12 0.01 0 0.81 L1-BT2 0.27 30.02 0.29 62.59 0.01 0.29 0.05 0 0.02 0.27 0 0.01 0.94 最小值 0.04 23.36 0.08 57.82 0 0.05 0.05 0 0 0.09 0 0 0.81 最大值 0.30 30.02 1.81 62.69 0.01 5.69 0.60 0.03 0.02 1.67 0.01 0.05 4.83 平均值 0.19 26.80 0.72 60.41 0.01 2.86 0.21 0.01 0.02 0.49 0 0.01 2.66
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表 5 二塘沟锂矿石中方解石LA-ICPMS成分分析结果
Table 5. LA-ICPMS analytical result of calcite from the Ertanggou lithium deposit
样品编号 Na2O MgO Al2O3 SiO2 P2O5 K2O CaO TiO2 MnO FeO 总量 Li L1BT2-Cal@1 0.01 0.38 0.00 0.17 0.00 0.00 98.80 0.00 0.03 0.03 99.40 1.3 L1BT2-Cal@2 0.00 0.42 0.00 0.62 0.00 0.00 98.20 0.00 0.03 0.03 99.29 0.5 L2-1BT3-Cal@2 0.00 0.31 0.00 0.65 0.03 0.00 97.80 0.00 0.27 0.06 99.16 8.5 L2-BT2-Cal@1 0.05 1.62 0.00 2.46 0.12 0.03 94.80 0.02 0.01 0.02 99.14 92 L2-BT2-Cal@2 0.09 1.02 0.00 1.11 0.06 0.01 96.90 0.00 0.01 0.02 99.23 62 L3BT5-Cal@1 0.06 0.27 0.00 0.38 0.05 0.00 98.80 0.00 0.02 0.02 99.60 2.3 L3BT5-Cal@2 0.07 0.32 0.00 0.38 0.02 0.00 98.60 0.00 0.02 0.02 99.38 0.42 L3BT9-Cal@2 0.02 0.53 0.03 1.40 0.00 0.00 96.40 0.00 0.15 0.13 98.72 23 L3BT9-Cal@3 0.00 0.40 0.01 0.60 0.00 0.00 98.10 0.00 0.17 0.10 99.36 16 最小值 0.00 0.27 0.00 0.17 0.00 0.00 94.80 0.00 0.01 0.02 98.72 0.42 最大值 0.09 1.62 0.03 2.46 0.12 0.03 98.80 0.02 0.27 0.13 99.60 92 平均值 0.03 0.59 0.00 0.86 0.03 0.01 97.60 0.00 0.08 0.05 99.25 23 注：扣除CO2贡献，将氧化物归一化为100%；除Li单位为10-6外，其余单位为%
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表 6 二塘沟锂矿石中海泡石LA-ICPMS成分分析结果
Table 6. LA-ICPMS analytical result of sepiolite from the Ertanggou lithium deposit
样品编号 Na2O MgO Al2O3 SiO2 P2O5 K2O CaO TiO2 MnO FeO 总量 Li L1BT2-Sep@1 0.28 32.00 0.31 66.80 0.01 0.14 0.07 0.00 0.00 0.27 99.83 706 L1BT2-Sep@2 0.24 32.10 0.31 66.70 0.02 0.12 0.05 0.00 0.00 0.26 99.84 663 L2-1BT3-Sep@1 0.07 26.90 1.31 63.40 0.00 5.87 0.21 0.00 0.00 0.41 99.26 8 267 L2-1BT3-Sep@2 0.03 26.40 1.23 62.90 0.02 6.77 0.22 0.00 0.00 0.30 98.76 9 519 L2-BT2-Sep@1 0.31 32.00 0.09 66.60 0.17 0.08 0.11 0.00 0.00 0.17 99.51 855 L2-BT2-Sep@2 0.24 29.00 0.08 55.70 0.99 0.17 13.10 0.00 0.01 0.14 99.47 852 L3BT5-Sep@1 0.12 27.10 0.38 64.80 0.00 5.37 0.15 0.00 0.00 0.10 98.01 8 967 L3BT5-Sep@2 0.15 27.40 0.37 64.70 0.03 5.15 0.13 0.00 0.00 0.11 98.09 8 715 最小值 0.03 26.40 0.08 55.70 0.00 0.08 0.05 0.00 0.00 0.10 98.01 663 最大值 0.31 32.10 1.31 66.80 0.99 6.77 13.10 0.00 0.01 0.41 99.84 9 519 平均值 0.18 29.11 0.51 63.95 0.15 2.96 1.75 0.00 0.00 0.22 99.10 4 818 注：扣除各种形式水（或羟基）的贡献，将氧化物归一化为100%；除Li单位为10-6外，其余单位为%
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表 7 水溶矿与盐酸溶矿实验得到的溶液Li含量（mg/L）
Table 7. The Li content of solution obtained by dissolving experiment of water and hydrochloric acid (mg/L)
样品编号 L2-1-BT3 H2 L2-BT4 H1 L3-BT9 H2 水溶矿 0.18 0.38 0.35 盐酸溶矿 66.85 45.09 11.01 盐酸溶矿/水溶矿 382.00 118.60 31.50 注：每件样品用量为30 g，所用溶液为500 mL
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表 8 水溶矿与盐酸溶矿后矿渣中的Li含量（%）
Table 8. The content of Li in slag after dissolution by water and hydrochloric acid(%)
样品编号 L2-1-BT3 H2 L2-BT4 H1 L3-BT9 H2 水溶矿渣 0.18 0.30 0.12 盐酸溶矿渣 0.16 0.10 0.12 盐酸溶矿渣/水溶矿渣 0.90 0.30 1.00
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