In-Situ U-Pb Age and Elemental Characteristics of Pitchblende in Shulouqiu Uranium Deposit and Its Geological Significance
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摘要: 为深入研究华南长江铀矿田内“交点型”铀矿化类型，对书楼丘矿床中位于基性岩脉与硅化碎裂岩交切部位的沥青铀矿开展原位微区U-Pb定年及元素成分研究.激光剥蚀电感耦合等离子体质谱分析结果显示，书楼丘沥青铀矿的U-Pb加权平均年龄为71.3±1.1 Ma；微量元素以富集W、Bi、Mo等亲硫元素，亏损Nb、Ta、Zr、Hf、Th等高场强元素为特征；稀土元素配分模式表现为轻稀土微富集，轻重稀土分异不明显，总量较低，Eu呈现明显的负异常，与富铀围岩长江岩体的稀土元素配分模式基本一致，暗示其铀源可能主要与长江岩体关系密切，与脉型铀矿床稀土元素配分模式的对比及ΣREE-（U/Th）、ΣREE-（LREE/HREE）N图解指示其为低温、中低盐度热液成因，δCe值指示沥青铀矿的成矿环境为还原环境.矿床内“交点型”铀成矿作用主要受南雄断裂80~60 Ma期间拉张活动、产铀长江花岗岩体和基性岩脉的共同控制，进而在交切的构造部位形成了铀矿化信息.
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关键词:
- “交点型”铀矿化 /
- LA-ICP-MS原位分析 /
- U-Pb定年 /
- 元素分析 /
- 书楼丘矿床
Abstract: In order to penetrate into discussion the "intersection type" uranium mineralization in the Changjiang uranium ore field, South China. Here, it collected representative samples from geological structure that formed during the process of mafic dick penetrating silicified surrounding rock and then carried out a study applying in-situ U-Pb dating and elementary analysis via LA-ICP-MS system. Results show that the weighting average age of pitchblende in this region is 71.3±1.1 Ma. Besides, trace elements are characterized by the enrichment of sulfophilic elements (such as W, Bi, and Mo) and by the depletion of high field strength elements (like Nb, Ta, Zr, Hf, and Th). The signature of rare earth element (REE) curve shows low total amount with negative Eu anomalies, slight enrichment in light REE, and indistinct fractionation between light and heavy REEs. The uranium source of pitchblende probably relates to the Changjiang granite, as indicated by a REE pattern comparison between them. In addition, the pitchblende was formed under low-temperature and low-middle salinity condition. This is validated through a combination of ΣREE-(U/Th) plot, ΣREE-(LREE/HREE)N plot, and comparison against REE distribution pattern in vein-type uranium deposits. Moreover, δCe value indicates reducing environment. In this region, the pitchblende was controlled by the interplay among Nanxiong fault (during 80-60 Ma), uranium-rich Changjiang granite, and mafic dyke, therefore forming the "intersection type" uranium mineralization in the active region. -
图 1 长江铀矿田地质构造简图
1.第四系；2.寒武系；3.燕山早期第二阶段花岗岩；4.燕山早期第一阶段花岗岩；5.印支期第三阶段花岗岩；6.印支期第二阶段花岗岩；7.海西期第二阶段花岗闪长岩；8.燕山晚期基性岩脉；9.断裂；10.剖面位置；11.铀矿床
Fig. 1. Geological sketch map of Changjiang uranium ore field
图 2 书楼丘矿床87勘探线剖面示意
1.燕山早期中粒黑云母花岗岩；2.燕山晚期煌斑岩脉；3.构造带；4.铀矿体；5.钻孔；6.采样位置及编号
Fig. 2. The geological cross section section of 87 lines in Shulouqiu deposit
图 3 书楼丘铀矿床矿石样品照片
a.手标本照片可见明显的团块状沥青铀矿；b.矿石样品的光学显微照片，可见沥青铀矿与黄铁矿共生；c、d.沥青铀矿的背散射照片，沥青铀矿旁可见黄铁矿；红圈代表U-Pb定年测点；Q.石英；Py.黄铁矿；Ura.沥青铀矿；Chl.绿泥石化
Fig. 3. Photography of the ore from the Shulouqiu uranium deposit
图 4 沥青铀矿U-Pb年龄谐和图(a)与206Pb/238U年龄加权平均图(b)
Fig. 4. Concordina diagram of U-Pb age (a) and the weighted mean age of 207Pb/238U for uraninite (b)
图 5 书楼丘铀矿床沥青铀矿主量元素成分与UO2相关图
Fig. 5. The correlation diagram of pitchblende major elements and UO2 of Shulouqiu uranium ore
图 6 长江铀矿田沥青铀矿电子探针主量元素成分与UO2相关图
红色投影点为棉花坑矿床样品，蓝色投影点为书楼坵矿床样品，绿色投影点为长排矿床样品；数据来源据钟福军等（2019b）
Fig. 6. The correlation diagram of pitchblende major elements and UO2 of Changjiang uranium ore field by EPMA
图 7 书楼丘铀矿区沥青铀矿ΣREE-(U/Th)(a)和ΣREE-(LREE/HREE)N图解(b)
a.底图据Frimmel et al.（2014）；b.底图据Mercadier et al.（2011）
Fig. 7. The ΣREE vs. U/Th (a) and ΣREE vs. (LREE/HREE)N (b) discrimination diagrams of the pitchblende
图 8 沥青铀矿的球粒陨石标准化稀土元素配分图
稀土元素的数据来源：长江、油洞岩体和基性岩脉朱捌（2010），不同类型铀矿床引自Mercadier et al.（2011）；标准化值据Sun and McDonough（1989）
Fig. 8. Chondrite-normalized REE patterns diagrams for the picthblende
表 1 书楼丘地区矿石矿物类型和矿物组合
Table 1. Ore mineral types and mineral combinations in Shulouqiu area
热液矿物 矿物组合 铀矿物 金属矿物 脉石矿物 成矿前 成矿阶段 成矿后 主要 次要 主要 次要 主要 次要 Ⅰ Ⅱ Ⅲ 沥青铀矿 钛铀矿 黄铁矿 方铅矿 石英 萤石 红棕色、白色石英为主 紫黑色萤石-黄铁矿-沥青铀矿 粉红色方解石-黄铁矿-沥青铀矿 赤红色微晶石英-黄铁矿-沥青铀矿 灰白色方解石、梳妆石英、灰白色石英为主 氧化沥青铀矿 赤铁矿 黄铜矿 水云母 方解石 铀钍矿 闪锌矿 绿泥石 
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表 2 书楼丘铀矿床沥青铀矿LA-ICP-MS U-Pb同位素分析结果
Table 2. U-Pb isotope compositions of uraninite in the Shulouqiu uranium deposites by LA-ICP-MS.
测点编号 207Pb/206Pb 207Pb/235U 206Pb/238U 207Pb/206Pb 207Pb/235U 206Pb/238U 比值 1σ 比值 1σ 比值 1σ 年龄(Ma) 1σ 年龄(Ma) 1σ 年龄(Ma) 1σ ZGCJ-5 01 0.049 6 0.004 6 0.081 2 0.007 7 0.011 2 0.000 2 176.0 200.0 79.0 7.2 71.9 1.1 02 0.050 8 0.004 7 0.076 8 0.007 0 0.011 2 0.000 2 232.0 15.7 75.0 6.5 72.0 1.0 03 0.052 0 0.004 2 0.078 6 0.006 4 0.011 1 0.000 2 287.0 180.5 77.0 6.0 71.1 0.9 04 0.048 3 0.003 4 0.072 0 0.005 2 0.010 9 0.000 1 122.0 150.0 71.0 4.9 69.8 0.8 05 0.047 9 0.005 7 0.074 1 0.008 7 0.011 3 0.000 2 100.0 250.0 73.0 8.1 72.0 1.1 06 0.049 9 0.006 8 0.075 4 0.010 7 0.011 1 0.000 2 187.0 292.5 74.0 10.0 71.0 1.2 07 0.046 6 0.008 0 0.069 9 0.010 8 0.010 6 0.000 2 28.0 370.3 69.0 10.2 68.0 1.1 08 0.047 9 0.005 1 0.071 5 0.007 7 0.010 9 0.000 2 100.0 227.7 70.0 7.3 70.0 1.0 09 0.049 1 0.006 7 0.078 0 0.010 5 0.011 7 0.000 2 150.0 292.5 76.0 9.9 75.0 1.2 10 0.047 6 0.005 7 0.076 1 0.008 2 0.011 1 0.000 2 80.0 259.2 74.0 7.7 71.0 1.1 11 0.050 0 0.003 7 0.078 7 0.005 7 0.011 7 0.000 2 195.0 174.0 77.0 5.4 75.0 1.0 12 0.046 9 0.005 0 0.078 0 0.008 7 0.011 4 0.000 2 56.0 224.0 76.0 8.1 72.8 1.4 13 0.047 6 0.008 1 0.077 2 0.012 6 0.011 5 0.000 2 80.0 359.2 76.0 11.9 74.0 1.2 14 0.046 9 0.005 5 0.069 7 0.007 7 0.010 8 0.000 2 43.0 259.2 68.0 7.3 69.2 1.1 15 0.047 7 0.005 9 0.073 6 0.009 0 0.010 9 0.000 1 83.0 270.3 72.0 8.5 69.8 0.8
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表 3 书楼丘矿床沥青铀矿LA-ICP-MS主量元素(%)、微量元素(10-6)分析结果
Table 3. Major and Trace element composition of pitchblende from the Shulouqiu ore deposit by LA-ICP-MS
样品号 ZGCJ-5-16 ZGCJ-5-17 ZGCJ-5-18 ZGCJ-5-19 ZGCJ-5-20 ZGCJ-5-21 ZGCJ-5-22 ZGCJ-5-23 ZGCJ-5-24 ZGCJ-5-25 Na2O 0.20 0.12 0.17 0.22 0.17 0.13 0.13 0.17 0.13 0.18 SiO2 2.75 1.35 1.43 1.91 1.28 1.89 1.76 2.26 1.75 2.15 FeO 0.19 0.06 0.08 0.17 0.06 0.18 0.19 0.24 0.18 0.29 UO2 84.45 86.77 86.38 85.58 86.39 85.55 85.6 84.96 85.58 85.21 CaO 10.57 10.56 10.78 10.79 10.92 9.29 9.29 9.57 9.45 9.37 MgO 0.05 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 Al2O3 0.26 0.15 0.15 0.18 0.13 0.16 0.15 0.19 0.16 0.18 P2O5 0.03 0.03 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 K2O 0.03 - 0.01 0.02 0.01 - - 0.02 — 0.02 MnO 0.17 0.15 0.16 0.21 0.13 0.21 0.22 0.21 0.22 0.23 Total 98.70 99.20 99.21 99.12 99.15 97.47 97.40 97.67 97.50 97.69 Sr 168.57 118.12 131.05 170.84 114.66 118.58 117.78 150.35 118.29 160.03 Cs 8.66 1.59 2.97 3.5 1.62 2.04 1.89 4.76 1.93 4.49 Rb 5.32 0.86 1.78 2.64 1.22 0.93 0.77 2.81 0.84 2.61 Ba 27.38 18.17 19.34 26.46 16.70 16.07 16.19 21.23 16.37 23.75 Nb 0.02 0.02 0.02 0.03 0.03 - 0.01 0.01 0.01 0.01 Zr 0.02 0.06 0.04 0.02 0.03 0.06 0.06 0.04 0.05 0.05 Be 40.28 34.64 36.73 42.74 31.41 42.69 44.61 46.42 43.7 45.97 Sc 0.30 0.27 0.32 0.62 0.73 0.09 0.09 0.11 0.08 0.19 V 64.89 60.70 61.43 68.83 54.26 229.76 259.79 221.37 242.89 226.63 Cr 4.92 6.67 3.06 2.99 4.50 3.50 2.14 3.83 2.00 10.85 W 1 285.55 1 089.78 1 157.28 1 547.82 1 143.94 2 591.28 2 730.1 2 583.02 2 657.55 2 658.69 Mo 79.62 81.34 79.25 71.85 71.24 148.77 142.96 146.14 141.94 139.87 Bi 197.22 276.44 277.19 476.65 848.35 423.10 442.13 386.17 475.45 494.55 Tl 0.83 0.15 0.19 0.55 0.21 0.11 0.14 0.34 0.12 0.30 Ag 0.61 0.37 0.27 0.77 0.48 0.03 0.04 0.08 0.03 0.21 Pb 8 804.02 4 854.02 4 668.46 4 574.95 4 471.41 17 416.70 17 748.97 15 730.92 16 968.03 15 236.69 Th 0.001 3 0.000 4 - - - 0.000 5 - 0.000 5 - - Zn 3.32 3.32 3.32 3.32 3.32 3.32 3.32 3.32 3.32 3.32 Cu 0.37 0.11 0.17 0.32 0.19 0.73 0.91 1.13 0.88 0.89 Co 0.04 0.04 0.04 0.02 0.05 0.09 0.10 0.09 0.12 0.11 Ni 0.08 0.08 0.03 0.05 0.07 - 0.09 0.03 - 0.06 La 23.86 18.74 19.99 30.74 28.43 42.00 53.10 37.44 48.34 49.86 Ce 19.07 19.05 20.67 49.57 68.50 22.27 29.06 21.58 27.55 32.32 Pr 2.15 1.91 2.15 5.54 6.90 2.15 2.88 2.23 2.72 3.63 Nd 8.60 8.42 9.25 23.1 29.3 8.37 11.65 8.71 10.64 14.28 Sm 2.37 2.65 2.61 6.95 9.84 1.90 2.63 1.84 2.46 3.14 Eu 0.41 0.46 0.50 1.29 1.71 0.36 0.48 0.33 0.43 0.64 Gd 2.98 3.48 3.49 7.84 10.6 5.30 7.16 4.54 6.54 6.56 Tb 0.56 0.71 0.69 1.66 2.26 0.82 1.14 0.71 1.01 1.10 Dy 4.01 4.97 4.96 11.40 15.90 6.10 8.65 5.41 7.66 8.24 Ho 0.90 1.08 1.11 2.46 3.34 1.51 2.20 1.33 2.03 2.06 Er 2.73 3.45 3.31 7.21 9.80 4.41 6.43 3.76 5.63 5.97 Tm 0.42 0.55 0.53 1.11 1.57 0.53 0.77 0.47 0.70 0.75 Yb 2.93 3.93 3.69 8.06 10.9 2.80 3.98 2.49 3.48 3.94 Lu 0.44 0.55 0.53 1.10 1.42 0.39 0.57 0.39 0.48 0.53 ΣREE 71.42 69.94 73.46 157.97 200.46 98.92 130.69 91.24 119.68 133.00 LREE 56.45 51.23 55.17 117.15 144.65 77.05 99.79 72.13 92.13 103.86 HREE 14.79 18.71 18.29 40.82 55.81 21.87 30.90 19.11 27.54 29.14 (LREE/HREE)N 1.52 1.07 1.18 1.11 0.97 1.53 1.39 1.61 1.43 1.52 (La/Yb)N 5.84 3.42 3.88 2.74 1.87 10.77 9.57 10.80 9.96 9.08 (La/Sm)N 6.49 4.56 4.94 2.86 1.87 14.29 13.04 13.16 12.71 10.25 (Gd/Yb)N 0.84 0.73 0.78 0.81 0.80 1.57 1.49 1.51 1.55 1.38 δEu 0.47 0.47 0.51 0.53 0.51 0.33 0.32 0.33 0.31 0.42 δCe 0.51 0.63 0.63 0.86 1.16 0.36 0.37 0.39 0.39 0.42 注：“-”表示元素含量低于仪器检测限.
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