Correlation between the distribution characteristics of gallium and sedimentary environment of sedimentary bauxite in Pingguo County, Guangxi, China
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摘要: 广西平果上二叠统合山组沉积型铝土矿储量大，并以伴生稀散元素Ga为特色。从主量成分和微量元素角度研究平果铝土矿的地球化学特征、形成环境及其与Ga的相互关联性，对综合回收利用和提升矿床经济价值有重要帮助。通过对整个研究区内均匀采集的18件不同类型的矿石及铝土岩样品进行金属Ga和常量、微量元素测试，经统计学方法计算和相关性图解分析，发现样品中Ga平均含量已达到工业品位（0.002×10-2）。但在不同类型矿石中的富集程度不同：豆鲕粒状铝土矿>致密块状铝土矿>铝土岩。而且Ga含量与Al2O3含量呈显著正低相关性；与SiO2含量呈显著负相关关系；与V含量呈显著正低相关关系；与稀土元素相关性不强，无明显规律性。通过对那豆沉积型铝土矿床古地理环境和不同类型样品Sr/Ba比值、Ga的富集、LREE/HREE比值分析发现：区内沉积型铝土矿主成矿期为较稳定、酸性、潮湿的滨海至浅海相环境；而且从二叠纪合山组早期的滨海相氧化环境逐步过渡到二叠纪合山组后期的浅海相还原环境。矿石类型则由早期的紫红色致密块状矿化变化为青灰色至灰黑色鲕粒状矿化。Abstract: The Pingguo area in Guangxi Province has considerable reserves of sedimentary bauxite of the Upper Permian Heshan Formation which are characterized by the occurrence of associated dispersed element Ga (gallium). It is of great significance to study the geochemical characteristics and depositional environment of the sedimentary bauxite and their correlation with Ga in the deposit on the basis of major and trace element analyses. This research helps to improve the comprehensive recovery and utilization of bauxite, and also to increase the economic values of the deposit. The contents of major and trace elements, including the Ga concentrations, were measured in 18 different types of ores and bauxite samples which were collected in the study area. The results calculated by statistical method and analyzed by correlation diagram show that the average content of Ga in the samples reaches the industrial grade (0.002×10-2), but the enrichment degree of Ga in different ore types accords with the regular rule of oolitic bauxite>dense massive bauxite>aluminous rock. Ga shows a significantly positive lower correlation with Al2O3, but a significantly negative correlation with SiO2, In addition, the Ga concentrations show a slightly positive lower correlation with V and Zr, and no significant correlation with rare earth elements. Based on the analyses of the paleo-geographic environment, Sr/Ba ratios, Ga enrichment and LREE/HREE ratios of different types of samples, this study suggests a costal to shallow marine facies with a relatively stable, acidic and humid climatic condition during the main metallogenic period of the sedimentary bauxite in the Pingguo area. Moreover, an oxidation environment of the coastal facies during the early deposition of the Upper Permian Heshan Formation was gradually transformed into a reducing, shallow marine facies during the late deposition of the Upper Permian Heshan Formation. Correspondingly, the ore type changed from the purplish red, dense massive mineralization to lime gray to grayish dark, oolitic mineralization.
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图 1 桂西大地构造位置示意图(据张起钻，2011修改)
Figure 1. Tectonic map of western Guangxi (modified from Zhang, 2011)
图 2 那豆矿床地质简图及采样位置示意图(据龚玉爽和艾国梁，2017修改)
1—第四系沉积物；2—三叠系页岩、砂岩；3—二叠系灰岩；4—石炭系灰岩、白云岩；5—泥盆系灰岩；6—矿体；7—断层；8—背斜轴迹；9—向斜轴迹；10—采样点
Figure 2. Geological sketch and sampling position diagram of the Nadou deposit (modified from Gong and Ai, 2017)
1-Quaternary sediments; 2-Triassic shale and sandstone; 3-Permian limestone; 4-Carboniferous limestone and dolomite; 5-Devonian limestone; 6-Ore body; 7-Fault; 8-Anticline axis; 9-Syncline axis; 10-Sampling point
图 3 那豆矿床典型矿石照片
a、b—致密块状矿石；c、d—鲕粒状矿石
Figure 3. Pictures of typical ores from the Nadou deposit
(a, b) Dense bauxite; (c, d) Oolitic bauxite
图 4 那豆矿床Ga含量与主量成分含量相关性图解
a—Ga含量与Al2O3含量相关性图解；b—Ga含量与Fe2O3含量相关性图解；c—Ga含量与SiO2含量相关性图解；d—Ga含量与TiO2含量相关性图解；e—Ga含量与A/S相关性图解
Figure 4. Diagrams showing the correlation between Ga content and major element content in the Nadou deposit
(a) Diagram of correlation between Ga content and Al2O3 content; (b) Diagram of correlation between Ga content and Fe2O3 content; (c) Diagram of correlation between Ga content and SiO2 content; (d) Diagram of correlation between Ga content and TiO2 content; (e) Diagram of correlation between Ga content and A/S
图 5 那豆矿床Ga含量与微量元素含量相关性图解
a—Ga含量与V含量相关性图解；b—Ga含量与Cr含量相关性图解；c—Ga含量与Co含量相关性图解；d—Ga含量与Ni含量相关性图解；e—Ga含量与Rb含量相关性图解；f—Ga含量与Sr含量相关性图解；g—Ga含量与Zr含量相关性图解；h—Ga含量与Ba含量相关性图解
Figure 5. Diagrams showing the correlation between Ga content and trace element content in the Nadou deposit
(a) Diagram of correlation between Ga content and V content; (b) Diagram of correlation between Ga content and Cr content; (c) Diagram of correlation between Ga content and Co content; (d) Diagram of correlation between Ga content and Ni content; (e) Diagram of correlation between Ga content and Rb content; (f) Diagram of correlation between Ga content and Sr content; (g) Diagram of correlation between Ga content and Zr content; (h) Diagram of correlation between Ga content and Ba content
图 6 平果地区基底构造格架示意图
1—海水运移方向；2—矿床；3—断裂带
Figure 6. Tectonic frame of the Pingguo area
1-Seawater migration direction; 2-Deposit; 3-Fault zone
图 7 平果沉积型铝土矿含矿层位野外剖面图
Figure 7. Field profile of the ore-bearing horizon of the Pingguo sedimentary bauxite deposit
图 8 那豆矿床稀土元素球粒陨石标准化配分模式图
Figure 8. Chondrite-normalized REE distribution of the Nadou deposit
表 1 那豆矿床主量和微量元素测试结果(主量元素/%、微量元素/×10-6)
Table 1. Test results of major and trace elements in the Nadou deposit (major elements/%, trace elements/×10-6)
样品编号 样品名称 Al2O3 Fe2O3 SiO2 TiO2 A/S Ga V Cr Co Ni Sr Zr Ba U Th ND-01 致密块状铝土矿 63.99 17.07 4.27 3.44 14.98 57.67 306.59 36.01 8.19 21.90 9.80 1560.92 6.92 19.32 28.49 ND-02 致密块状铝土矿 57.97 16.14 11.78 3.62 4.92 47.43 169.08 20.95 3.20 2.35 17.04 1257.10 18.07 10.23 36.23 ND-03 致密块状铝土矿 49.98 30.61 7.20 3.94 6.95 44.16 293.14 30.80 10.57 6.06 28.97 1295.61 20.16 16.84 25.29 ND-04 致密块状铝土矿 51.51 24.39 10.37 2.88 4.97 61.32 407.38 43.36 0.65 2.21 26.37 1354.32 97.66 15.25 53.30 ND-05 致密块状铝土矿 75.37 0.80 5.90 4.76 12.79 54.80 276.99 13.33 2.86 7.56 382.33 1741.00 16.65 11.49 30.02 ND-06 致密块状铝土矿 75.90 0.97 3.38 4.69 22.43 28.19 243.86 136.17 15.79 87.89 15.71 1996.90 5.09 19.21 51.27 ND-07 致密块状铝土矿 56.06 21.38 4.94 2.87 11.36 50.89 302.32 27.30 2.27 2.55 6.20 1315.32 5.28 12.11 31.98 ND-08 致密块状铝土矿 46.18 22.82 14.78 3.17 3.12 18.39 154.84 77.59 11.86 45.45 13.85 1302.72 43.35 11.29 46.78 ND-09 豆鲕粒状铝土矿 70.82 6.74 4.60 3.87 15.40 30.07 285.66 114.20 9.78 56.15 12.01 1762.92 8.16 32.89 54.69 ND-10 豆鲕粒状铝土矿 76.58 1.45 3.49 5.41 21.93 43.54 262.70 33.38 11.40 31.00 4.81 1601.34 2.26 16.24 19.56 ND-11 豆鲕粒状铝土矿 78.27 2.24 3.39 3.62 23.07 55.48 323.71 27.30 16.33 15.17 15.10 2133.49 28.22 32.36 35.22 ND-12 豆鲕粒状铝土矿 52.52 22.85 11.57 2.40 4.54 56.59 330.72 21.08 0.32 4.01 9.71 1614.48 9.32 17.84 29.41 ND-13 豆鲕粒状铝土矿 73.04 1.51 4.09 5.64 17.85 50.14 292.06 8.70 1.98 10.89 24.48 2329.93 7.97 28.22 38.60 ND-14 豆鲕粒状铝土矿 74.66 0.77 3.45 4.55 21.67 47.83 243.33 5.56 0.50 10.83 4.23 1862.80 0.38 16.15 20.41 ND-15 豆鲕粒状铝土矿 56.12 16.05 8.69 5.12 6.45 50.55 23.80 12.71 2.23 4.81 2.98 1734.70 14.30 13.84 6.84 ND-16 豆鲕粒状铝土矿 47.85 26.01 10.35 2.82 4.62 62.10 235.46 2.72 2.08 12.65 193.31 1136.75 48.31 4.42 31.59 ND-17 铝土岩 6.70 1.34 88.10 0.26 0.08 6.15 85.60 1.10 5.78 4.25 63.10 85.74 91.21 6.54 9.53 ND-18 铝土岩 48.80 2.15 32.35 2.33 1.51 40.67 36.39 1.63 2.45 9.96 4.37 1021.24 267.07 2.53 13.27 测试单位：广西隐伏金属矿床勘查重点实验室；测试仪器：X射线荧光光谱仪(ZSX PrimusⅡ)、电感耦合等离子体质谱(Agilent 7500cx)；A/S为铝硅比；测试年份：2020年 
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表 2 那豆矿床Ga含量与主量成分含量的相关性及显著性
Table 2. Correlation and significance between Ga and major elements in the Nadou deposit
主量成分 Al2O3 Fe2O3 SiO2 TiO2 A/S 相关系数(r) 0.458 0.305 -0.636 0.323 0.169 显著性(双尾) 0.056 0.218 -0.005 0.191 0.502 注：样本数n=18；A/S为铝硅比
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表 3 那豆矿床Ga含量与微量元素含量相关性及显著性
Table 3. Correlation and significance between Ga and trace elements in Nadou deposit
微量元素 V Cr Co Ni Rb Zr Sr Ba 相关性系数(r) 0.497 -0.390 -0.410 -0.466 -0.175 0.447 0.204 -0.161 显著性(双尾) 0.036 0.110 0.091 0.051 0.488 0.063 0.416 0.522 注：样本数n=18
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表 4 那豆矿床不同类型铝土矿和铝土岩中指示性元素比值计算结果
Table 4. Calculation results of the ratio of indicative elements in different types of bauxite and aluminous rocks in the Nadou deposit
样品编号 样品名称 Mn/Sr S/A Sr/Ba V/Cr V/(V+Ni) Ga/Al ND-01 致密块状铝土矿 0.00 0.07 1.42 8.51 0.93 0.90 ND-02 致密块状铝土矿 0.00 0.20 0.94 8.07 0.99 0.82 ND-03 致密块状铝土矿 0.00 0.14 1.44 9.52 0.98 0.88 ND-04 致密块状铝土矿 0.00 0.20 0.27 9.40 0.99 1.19 ND-05 致密块状铝土矿 0.00 0.08 22.96 20.77 0.97 0.73 ND-06 致密块状铝土矿 0.02 0.04 3.09 1.79 0.74 0.37 ND-07 致密块状铝土矿 0.00 0.09 1.17 11.08 0.99 0.91 ND-08 致密块状铝土矿 0.00 0.32 0.32 2.00 0.77 0.40 ND-09 豆鲕粒状铝土矿 0.00 0.06 1.47 2.50 0.84 0.42 ND-10 豆鲕粒状铝土矿 0.00 0.05 2.13 7.87 0.89 0.57 ND-11 豆鲕粒状铝土矿 0.00 0.04 0.54 11.86 0.96 0.71 ND-12 豆鲕粒状铝土矿 0.00 0.22 1.04 15.69 0.99 1.08 ND-13 豆鲕粒状铝土矿 0.00 0.06 3.07 33.57 0.96 0.69 ND-14 豆鲕粒状铝土矿 0.00 0.05 11.05 43.80 0.96 0.64 ND-15 豆鲕粒状铝土矿 0.01 0.15 0.21 1.87 0.83 0.90 ND-16 豆鲕粒状铝土矿 0.00 0.22 4.00 86.63 0.95 1.30 ND-17 铝土岩 0.00 13.14 0.69 77.80 0.95 0.92 ND-18 铝土岩 0.00 0.66 0.02 22.33 0.79 0.83
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表 5 那豆矿床不同类型铝土矿和铝土岩稀土元素测试结果(×10-6)
Table 5. Test results of REE in different types of bauxite and aluminous rocks in the Nadou deposit(×10-6)
样品编号 样品类型 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ΣREE LREE HREE LREE/HREE δEu δCe ND-01 致密块状铝土矿 19.50 80.91 2.36 8.10 1.94 0.42 2.89 0.76 5.89 1.31 4.03 0.68 4.57 0.67 134.04 113.22 20.81 5.44 0.54 2.93 ND-02 致密块状铝土矿 62.70 100.15 7.01 23.89 5.18 1.04 6.40 1.46 11.94 3.05 10.50 1.82 12.10 1.88 249.12 199.97 49.16 4.07 0.55 1.17 ND-03 致密块状铝土矿 105.74 182.15 12.53 33.07 4.56 0.82 5.41 1.24 9.95 2.35 6.88 1.02 6.02 0.85 372.57 338.86 33.71 10.05 0.50 1.23 ND-04 致密块状铝土矿 53.53 125.68 8.76 28.42 5.01 1.03 6.30 1.50 13.01 3.39 10.80 1.64 9.79 1.44 270.31 222.43 47.87 4.65 0.56 1.42 ND-05 致密块状铝土矿 19.74 195.32 5.04 19.10 4.49 0.80 3.84 0.60 3.15 0.53 1.47 0.25 1.77 0.25 256.35 244.49 11.86 20.62 0.59 4.80 ND-06 致密块状铝土矿 9.11 67.05 2.15 9.65 4.25 0.93 4.72 1.28 9.07 1.78 4.77 0.90 6.51 0.93 123.10 93.14 29.96 3.11 0.63 3.72 ND-07 致密块状铝土矿 5.08 71.49 1.31 6.50 2.92 0.69 3.63 0.79 5.49 1.17 3.67 0.65 4.55 0.65 108.60 88.00 20.61 4.27 0.65 6.79 ND-08 致密块状铝土矿 16.03 257.06 3.02 11.95 4.07 0.85 5.82 1.20 8.50 1.89 5.50 1.06 7.60 1.12 325.69 292.99 32.70 8.96 0.54 9.06 ND-09 豆鲕粒状铝土矿 6.62 32.98 1.50 6.43 2.19 0.49 3.85 1.52 15.52 4.23 12.96 2.27 13.76 1.99 106.30 50.20 56.10 0.89 0.51 2.57 ND-10 豆鲕粒状铝土矿 3.63 52.87 0.55 2.11 0.78 0.17 1.02 0.19 1.22 0.25 0.73 0.12 0.81 0.12 64.57 60.11 4.46 13.47 0.59 9.17 ND-11 豆鲕粒状铝土矿 53.33 89.08 7.59 21.95 4.90 0.98 5.60 1.71 13.55 2.81 8.75 1.62 11.67 1.68 225.23 177.84 47.39 3.75 0.57 1.09 ND-12 豆鲕粒状铝土矿 21.43 84.70 2.49 8.56 1.81 0.39 2.86 0.79 7.38 1.94 6.14 0.96 5.86 0.85 146.16 119.38 26.78 4.46 0.53 2.84 ND-13 豆鲕粒状铝土矿 165.67 233.53 16.54 49.19 7.55 1.25 6.91 1.48 11.33 2.54 7.91 1.38 9.35 1.36 515.98 473.73 42.25 11.21 0.53 1.09 ND-14 豆鲕粒状铝土矿 2.74 62.71 0.55 2.17 0.91 0.22 1.20 0.26 1.86 0.40 1.25 0.23 1.61 0.23 76.35 69.30 7.05 9.83 0.64 12.51 ND-15 豆鲕粒状铝土矿 2.04 59.58 0.51 2.86 1.03 0.21 1.11 0.22 1.38 0.26 0.74 0.12 0.81 0.11 70.99 66.24 4.75 13.94 0.60 14.29 ND-16 豆鲕粒状铝土矿 162.66 330.68 34.90 136.86 19.45 2.03 13.50 1.99 12.36 2.66 7.75 1.15 6.92 1.01 733.92 686.58 47.35 14.50 0.38 1.08 ND-17 铝土岩 22.17 30.23 4.44 17.12 3.85 0.70 3.36 0.52 2.90 0.55 1.48 0.22 1.35 0.19 89.10 78.52 10.58 7.42 0.59 0.75 ND-18 铝土岩 15.28 8.09 3.74 15.06 2.75 0.44 2.26 0.48 3.95 1.05 3.54 0.60 3.91 0.60 61.75 45.36 16.39 2.77 0.54 0.26 测试单位：广西隐伏金属矿床勘查重点实验室；测试仪器：电感耦合等离子体质谱(Agilent 7500cx)；测试年份：2020年
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