Geochemical Characteristics and Sedimentary Environment of Li-rich Clay Rocks at the Southern Margin of the Central Yunnan Basin
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摘要: 沉积岩中的微量元素对沉积环境变化有较高的敏感度,是研究古沉积环境的有效手段。滇中盆地倒石头组是一套富锂的黏土岩地层,其古环境的研究对恢复该时期盆地沉积格局和锂元素富集具有重要意义。基于滇中盆地倒石头组两个典型钻孔样品详细的地球化学研究,探讨了倒石头组富锂黏土岩形成时的沉积环境及其对锂元素富集的影响。研究结果表明：所有样品Sr、Ga元素含量及Sr/Ba值指示研究区古水体介质为淡水陆相沉积环境；其δU值介于0.51~1.63,U/Th值介于0.11~1.49,V/（V+Ni）值介于0.48~0.86,V/Cr值介于0.45~1.24,同时在U（EF）-Mo（EF）协变模式图中,样品数据均未落在缺氧和硫化区域,表明研究区富锂黏土岩的沉积环境为氧化—弱还原环境；且样品Sr/Cu比值介于0.69~4.87,CIA值介于86.3~99.66,XRD全岩黏土矿物分析显示高岭石为主要的黏土矿物,表明富锂黏土岩在形成过程中处于温暖潮湿的沉积环境并伴随较为强烈的化学风化作用。Abstract: Trace elements in sedimentary rocks are highly sensitive to changes of sedimentary environment, and are an effective indicator of the paleosedimentary environment. The inverted rock formation in the Central Yunnan Basin is a set of claystone strata rich in lithium. The study of its paleoenvironment is of great significance for reconstructing the basin sedimentary pattern and lithium enrichment in this period. In this study a detailed geochemical investigation was carried out on two typical borehole samples from the formation, aiming to explore the sedimentary environment and influences on the lithium enrichment and provide a reference for future studies of lithium resources in the region. The Sr, Ga and Sr/Ba values indicate that the paleo-water medium in the study area was a freshwater continental sedimentary environment. The δU values in all samples were in the range 0.51-1.63； U/Th values were 0.11-1.49； V/（V+Ni） values were 0.48-0.86； and V/Cr values were 0.45-1.24. Sample data in the U（EF）-Mo（EF） covariant model lay outside the anoxic and sulfurized areas, indicating an oxygen-weak reducing sedimentary environment for the lithium-rich claystone. The Sr/Cu ratios of all samples were 0.69-4.87, with CIA values 86.3-99.66. Whole-rock XRD analysis showed kaolinite as the main clay mineral, indicating that the lithium-enriched claystone formed in a warm, humid sedimentary environment accompanied by strong chemical weathering.
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Key words:
- redox conditions /
- paleosalinity /
- paleoclimate /
- claystone /
- Central Yunnan Basin
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图 1 滇中盆地南缘地质简图（底图据云南省地质局第二区域地质测量大队七分队,1969 1 ）和ZK05、ZK06钻孔剖面图
Figure 1. Geological sketch of southern margin of Central Yunnan (modified by Yunnan Geological Brigade,1969) and profiles of boreholes ZK05, ZK06
Fig.1 
图 2 样品Li含量与Sr含量、Ga含量、Sr/Ba值的关系图解
Figure 2. Sample content of Li, Sr and Ga, and Sr/Ba relationship
Fig.2 
图 4 样品Li含量与U/Th值、V/Cr值、V/（V+Ni）值、δU的关系图解
Figure 4. Sample Li content, U/Th value, V/Cr value, V/（V+Ni）value, δU relationship diagram
Fig.4 
图 5 样品Li含量与U/Th值、CIA值、Sr/Cu的关系图解
Figure 5. Sample content of Li, U/Th, CIA, and Sr/Cu relationship diagram
Fig.5 
图 7 样品的X射线衍射峰图谱
M.白云母；K.高岭石；B.勃姆石；Mo.蒙脱石；D.白云石；Py.黄铁矿；A.锐钛矿
Figure 7. XRD diffraction peak patterns for samples
Fig.7 表 1 滇中盆地南缘倒石头组黏土岩微量元素（μg/g）分析及比值计算结果
样号 岩性 Li Mo Sc Co Zr U Th V Cr Ni Sr Ga Ba Cu Sr/Cu Sr/Ba δU U/Th V/Cr V/(V+Ni) ZK05-H2 炭质泥岩 2 280 7.78 36.7 6.4 257 14.8 25.8 169 160 56.8 14 35.7 350 9.6 1.46 0.04 1.26 0.57 1.06 0.75 ZK05-H3 炭质泥岩 1 700 12.2 35.3 11.4 213 10.9 24.7 195 166 69.7 18.7 36.2 380 17.5 1.07 0.05 1.14 0.44 1.17 0.74 ZK05-H4 深灰色煤岩 3 220 15.45 26.6 6.7 332 5.4 40.9 169 352 28.3 35.4 32.3 280 11.2 3.16 0.13 0.57 0.13 0.48 0.86 ZK05-H5 浅灰色铝土质黏土岩 3 130 12.8 25.5 9.2 350 4.9 23.7 268 390 89.6 36.1 52.3 270 14.7 2.46 0.13 0.77 0.21 0.69 0.75 ZK05-H6 浅灰白色铝土质黏土岩 1 600 6.6 30.8 11.9 323 4.5 27 223 305 79.8 23.1 49.3 300 13.4 1.72 0.08 0.67 0.17 0.73 0.74 ZK05-H7 浅灰白色铝土质黏土岩 830 5 32.1 24.8 320 4.8 28.9 229 267 87.8 16.4 52.4 610 8 2.05 0.03 0.67 0.17 0.86 0.72 ZK05-H8 浅灰白色铝土质黏土岩 1 100 4.84 30.4 12.7 311 4.6 24.4 225 246 72.1 15.8 51.3 420 17.8 0.89 0.04 0.72 0.19 0.91 0.76 ZK05-H9 浅灰白色铝土质黏土岩 330 1.57 31.2 24.9 291 4.1 25.5 195 184 63.7 12.4 48.8 870 18.1 0.69 0.01 0.65 0.16 1.06 0.75 ZK06-H2 浅灰色铝土质黏土岩 364 4.94 24.2 5 279 4.5 31.8 164 316 29.7 3.9 43.5 80 1.7 2.29 0.05 0.60 0.14 0.52 0.85 ZK06-H3 深灰色薄—中层状炭质铝土黏土岩 373 16.2 23 19.1 216 5 23.1 153 260 97.2 8 35.9 80 5.9 1.36 0.10 0.79 0.22 0.59 0.61 ZK06-H4 深灰色薄—中层状炭质铝土黏土岩 1 070 5.96 28.7 10.4 313 4.7 20.5 143 298 109 6.2 39.9 30 3.1 2.00 0.21 0.82 0.23 0.48 0.57 ZK06-H5 深灰色铝土质黏土岩 970 5.89 25.6 12.1 261 3.6 11.4 151 244 108.5 6 35.8 30 2.1 2.86 0.20 0.97 0.32 0.62 0.58 ZK06-H6 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 1 360 6.76 29 8.2 279 4.7 14 131 253 127.5 5.3 37.4 20 2.8 1.89 0.27 1.00 0.34 0.52 0.51 ZK06-H7 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 1 290 6.56 31.5 9.8 334 4.7 13.9 132 256 130 5.6 38.3 20 2 2.80 0.28 1.01 0.34 0.52 0.50 ZK06-H8 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 1 300 7.17 31 10.5 320 4.7 11.25 134 243 131.5 5.6 38.4 30 2.6 2.15 0.19 1.11 0.42 0.55 0.50 ZK06-H9 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 1 290 9.21 28.2 9 300 4.6 10.5 121 266 129 4.9 38.2 30 2.8 1.75 0.16 1.14 0.44 0.45 0.48 ZK06-H10 浅灰色薄片状铝土质黏土岩 1 270 11.2 33 11.2 298 5.3 17.65 135 283 141 6.3 42.3 30 3.3 1.91 0.21 0.95 0.30 0.48 0.49 ZK06-H11 浅灰色薄片状铝土质黏土岩 1 410 9.45 29.4 10 299 4.8 12.4 142 296 135.5 5.6 39.6 30 3.7 1.51 0.19 1.07 0.39 0.48 0.51 ZK06-H12 浅灰色薄片状铝土质黏土岩 1 340 10.8 29.4 11.1 295 4.9 13.75 138 286 138.5 6.3 39.8 30 3.2 1.97 0.21 1.03 0.36 0.48 0.50 ZK06-H13 浅灰色薄片状铝土质黏土岩 970 5.24 21.6 12.8 283 3.9 14.1 167 247 107.5 5 37.1 40 2.2 2.27 0.13 0.91 0.28 0.68 0.61 ZK06-H14 浅灰色薄片状铝土质黏土岩 950 7.59 22 14.4 270 3.8 10.25 160 260 116.5 5.1 37.1 30 3.1 1.65 0.17 1.05 0.37 0.62 0.58 ZK06-H15 浅灰色薄片状铝土质黏土岩 730 4.01 26.3 10.7 262 4.7 28.1 163 228 92.1 6.8 38.8 50 1.6 4.25 0.14 0.67 0.17 0.71 0.64 ZK06-H16 深灰色中—厚层状铝土岩 570 5.72 23 13.1 220 5.9 23.7 146 195 75.9 11.4 34 50 5.1 2.24 0.23 0.86 0.25 0.75 0.66 ZK06-H17 深灰色中—厚层状铝土岩 1 220 12.45 28.5 13.4 313 5 13.65 141 280 128.5 6.5 41.6 30 3.1 2.10 0.22 1.05 0.37 0.50 0.52 ZK06-H18 深灰色中—厚层状铝土岩 449 3.7 22.9 12.9 211 4.6 21.7 198 175 59.2 11.6 40.1 160 3 3.87 0.07 0.78 0.21 1.13 0.77 ZK06-H19 深灰色中—厚层状铝土岩 750 7.73 21.2 15.5 246 4.4 12.85 165 235 88.8 6.8 35.6 60 4.1 1.66 0.11 1.01 0.34 0.70 0.65 ZK06-H20 深灰色层状铝土岩 1 260 5.05 26.7 9.1 262 4.4 9.04 133 239 117.5 4.8 38.6 10 2 2.40 0.48 1.19 0.49 0.56 0.53 
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表 2 滇中盆地南缘倒石头组黏土岩常量元素（%）分析及比值计算结果
样号 岩性 Al2O3 Na2O CaO K2O CIA ZK05-H2 炭质泥岩 29.57 0.51 0.22 1.99 91.57 ZK05-H3 炭质泥岩 26.36 0.39 0.28 1.60 92.06 ZK05-H4 深灰色煤岩 26.64 0.08 0.08 1.13 95.37 ZK05-H5 浅灰色铝土质黏土岩 33.82 0.05 0.05 0.37 98.60 ZK05-H6 浅灰白色铝土质黏土岩 32.50 0.09 0.09 1.31 95.58 ZK05-H7 浅灰白色铝土质黏土岩 31.56 0.12 0.12 2.72 91.41 ZK05-H8 浅灰白色铝土质黏土岩 31.93 0.13 0.13 2.47 92.10 ZK05-H9 浅灰白色铝土质黏土岩 29.67 0.18 0.18 4.36 86.30 ZK06-H2 浅灰色铝土质黏土岩 31.18 0.09 0.51 0.03 97.59 ZK06-H3 深灰色薄—中层状炭质铝土黏土岩 25.70 0.23 1.14 0.10 96.26 ZK06-H4 深灰色薄—中层状炭质铝土黏土岩 37.32 0.09 1.70 0.05 98.97 ZK06-H5 深灰色铝土质黏土岩 28.44 0.03 2.51 0.03 99.56 ZK06-H6 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 35.15 0.03 1.65 0.02 99.61 ZK06-H7 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 41.00 0.03 2.23 0.03 99.58 ZK06-H8 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 41.57 0.04 2.58 0.03 99.55 ZK06-H9 灰—深灰色夹黑色夹杂少量黄铁矿铝土质黏土岩 39.68 0.04 1.81 0.03 99.53 ZK06-H10 浅灰色薄片状铝土质黏土岩 34.77 0.04 1.70 0.02 99.50 ZK06-H11 浅灰色薄片状铝土质黏土岩 36.85 0.04 1.88 0.03 99.52 ZK06-H12 浅灰色薄片状铝土质黏土岩 36.94 0.04 2.12 0.05 99.49 ZK06-H13 浅灰色薄片状铝土质黏土岩 33.26 0.04 6.58 0.05 99.47 ZK06-H14 浅灰色薄片状铝土质黏土岩 29.57 0.03 4.79 0.03 99.66 ZK06-H15 浅灰色薄片状铝土质黏土岩 30.99 0.04 8.21 0.05 99.28 ZK06-H16 深灰色中—厚层状铝土岩 23.90 0.03 13.02 0.03 99.03 ZK06-H17 深灰色中—厚层状铝土岩 39.11 0.04 2.51 0.05 99.46 ZK06-H18 深灰色中—厚层状铝土岩 24.28 0.08 10.51 0.10 95.31 ZK06-H19 深灰色中—厚层状铝土岩 29.38 0.04 6.44 0.05 98.68 ZK06-H20 深灰色层状铝土岩 29.76 0.03 1.70 0.03 99.66
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