Occurrence State of Fe-Ti Oxides and Its Response to Uranium Mineralization Process in Interlayer Oxidation Zone of Qianjiadian Uranium Deposit
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摘要: 铁钛氧化物对氧化-还原环境的变化极为敏感，是砂岩型铀矿成矿作用研究极为重要的标型矿物.然而，国内外对铁钛氧化物在砂岩型铀矿层间氧化带不同分带中形貌、含量及组合特征的研究却缺少量化数据的约束.鉴于此，本文以松辽盆地钱家店铀矿床层间氧化带中铁钛氧化物为研究对象，通过偏光显微镜、扫描电镜、电子探针等手段，识别出6种铁钛氧化物：钛铁矿、钛赤铁矿、钛磁铁矿、白钛石、金红石和锐钛矿，其中完全氧化亚带和部分氧化亚带以钛赤铁矿、钛磁铁矿为主，微弱氧化亚带以金红石、锐钛矿、钛磁铁矿为主，过渡带以白钛石、锐钛矿为主，还原带以金红石、锐钛矿、钛铁矿与白钛石为主.从钛铁矿氧化物与铀矿物的产出关系来看，锐钛矿、白钛石与金红石与铀成矿关系最为密切.根据各个分带中铁钛氧化物之间的穿插包裹关系，识别出7种蚀变序列，其中，完全氧化亚带、部分氧化亚带与微弱氧化亚带中以钛铁矿→钛磁铁矿→磁铁矿、钛铁矿→钛赤铁矿、白钛石→钛磁铁矿→磁铁矿以及白钛石→钛赤铁矿4种蚀变序列为主，记录了铀矿床的大规模层间氧化事件；过渡带中主要表现为白钛石→锐钛矿和金红石→锐钛矿两种蚀变序列，体现了晚期成矿阶段该矿床受到低温热液流体改造事件；还原带中主要表现为钛铁矿→白钛石的蚀变序列，反映了成岩时期弱酸性-弱碱性的环境.研究成果为铁钛氧化物作为标型矿物研究砂岩型铀矿床层间氧化带精细分带及铀成矿作用过程奠定了基础.Abstract: Fe-Ti oxides are extremely sensitive to changes in the redox environment and are extremely important indicator minerals for studying the mineralization of sandstone-type uranium deposits. However, there are few quantitative data constraints on morphology, contents and compositions of Fe-Ti oxides in the interlayer oxidation zone of sandstone-type uranium deposits. Therefore, in this study it focuses on illustrating Fe-Ti oxides in the interlayer oxidation zone of Qianjiadian uranium deposit in Songliao basin. Six types of Fe-Ti oxides including ilmenite, titanohematite, titanomagnetite, leucoxene, rutile and anatase have been identified by polarizing microscope, SEM and electron probe microanalyzer. The titanohematite and titanomagnetite mainly occur in the strong oxidised subzone and weak oxidised subzone; the leucoxene, anatase and titanium magnetite are mainly distributed in the faint oxidised subzone; the leucoxene and anatase are primarily formed in the transition zone, and the rutile, ilmenite and leucoxene are frequently found in the reduction zone. Seven alteration sequences are identified according to the interspersed wrapping relationship between Fe-Ti oxides in each zone. Four alteration sequences composed of ilmenite →titanomagnetite→magnetite, ilmenite→titanohematite, leucoxene→ titanomagnetite → magnetite and leucoxene → titanohematite are mainly found in the strong oxidised subzone, weak oxidised subzone and faint oxidised subzone, and these sequences record a large-scale interlayer oxidation event. Two alteration sequences including leucoxene → anatase and rutile → anatase primarily occur in the transition zone, these sequences reveal that the deposit was transformed by low-temperature hydrothermal fluids. The last alteration sequence is ilmenite→anatase which mainly occur in the reduction zone, and this sequence reflects a weakly acidic-weakly alkaline environment during diagenesis. The research provides a foundation for the studying Fe-Ti oxides as indicator minerals to study fine zoning of interlayer oxidation zones and mineralization process of sandstone-type uranium deposits.
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图 1 区域地质背景
a.钱家店铀矿床区域构造位置；b.钱家店地区地层综合柱状图；c.钱家店铀矿床层间氧化带位置展布；据 荣辉等（2016） 修改
Fig. 1. Regional geological background
图 3 铁钛氧化物含量统计示意图
a.样品4-56-08-1的一张统计图像；b.图a经过矿物分类处理后的图像；c.图a对应钛赤铁矿处原子数占比能谱元素；d.图a中对应的锐钛矿原子数占比能谱图像
Fig. 3. Statistical diagram of Fe-Ti oxides content
图 4 钱家店铀矿床中钛铁矿与钛赤铁矿的形貌特征
a.碎屑状钛铁矿蚀变为白钛石，QC17-22；b.碎屑状钛铁矿表面发生蚀变局部形成白钛石，发育大量裂纹，4-14911-2；c.钛铁矿由裂隙处蚀变为白钛石，QC17-22；d.碎屑状钛铁矿局部区域发生蚀变，4-11311-6；e.钛铁矿发生微弱蚀变表面发育大量裂纹，4-11311-6；f.碎屑状钛铁矿被赤铁矿交代，残留钛铁矿呈条状分布，QC90-20；g.钛赤铁矿交代铁钛氧化物，蚀变边缘可见锐钛矿，4-56-08-11；h.钛赤铁矿交代白钛石再氧化为赤铁矿，4-17-120；i.完全交代铁钛氧化物的钛赤铁矿，裂纹中填充锐钛矿，4-56-08-1
Fig. 4. Morphological characteristics of ilmenite and titanium hematite in Qianjiadian uranium deposit
图 5 钱家店铀矿床中钛磁铁矿与白钛石的形貌特征
a.布纹状钛磁铁矿解理缝中充填胶状锐钛矿，4-56-08-10；b.条状的钛铁矿从边缘被钛磁铁矿交代并呈现出不规则片层，4-17-120；c.钛磁铁矿内部残留少量白钛石，边缘逐渐蚀变为磁铁矿并以网格状生长，4-56-08-11；d.钛磁铁矿边缘氧化为磁铁矿，QC90-20；e.白钛石边缘蚀变为锐钛矿，外侧发育草莓状黄铁矿，4-WT3-U3；f.白钛石内部残留部分钛铁矿，表面发育裂隙呈叶片状，4-56-08-11；g.碎屑状白钛石边缘向锐钛矿蚀变，锐钛矿呈胶状、絮状，4-14911-3；h.白钛石被菱铁矿包裹，QC17-22；i.白钛石被菱铁矿包裹，QC17-22
Fig. 5. Morphological characteristics of titanomagnetite and leucoxene in Qianjiadian uranium deposit
图 6 钱家店铀矿床中金红石与锐钛矿的形貌特征
a.针状自形金红石被高岭石包裹充填，4-14911-3；b.针状金红石间隙中发育了粒状黄铁矿，4-WT3-U6；c.金红石与碎屑颗粒之间生长了大面积胶状黄铁矿，金红石间隙被少量黄铁矿充填，4-14911-3；d.金红石逐渐被菱铁矿包裹，QC17-26；e.针状金红石边缘溶蚀形成锐钛矿，QC17-22；f.黄铁矿在锐钛矿表面生长后期被高岭石包裹，QC17-26；g.锐钛矿在高岭石表面生长，IV29-02-1；h.白钛石边缘蚀变为锐钛矿，QC17-26；i.颗粒间自生的粒状锐钛矿吸附少量铀，其中锐钛矿表面存在少量亮斑为铀矿物，4-WT3-U2
Fig. 6. Morphological characteristics of rutile and anatase in Qianjiadian uranium deposit
图 7 钱家店铀矿床层间氧化带中铁钛氧化物平均含量分布
Fig. 7. The average content distribution of Fe-Ti oxides in interlayer oxidation zone of Qianjiadian uranium deposit
图 8 钱家店铀矿床铁钛氧化物蚀变类型及组合特征
铁钛氧化物数据源于本文，其他矿物数据源于 荣辉等（2016） 和 贾俊民等（2018）
Fig. 8. Alteration types and assemblage characteristics of Fe-Ti oxides in Qianjiadian uranium deposit
图 9 钱家店铀矿床中铁钛氧化物的蚀变演化模式
Fig. 9. Alteration evolution models of Fe-Ti oxides in the Qianjiadian uranium deposit
图 10 钱家店铀矿床中铁钛氧化物与铀矿物的关系
a.含铀锐钛矿被沥青铀矿包裹，4-WT3-U2；b.含铀锐钛矿部分被沥青铀矿包裹，IV29-02-1；c.含铀锐钛矿表面充填沥青铀矿，4-WT3-U2；d.含铀锐钛矿内部残留部分白钛石，边缘被沥青铀矿逐渐包裹，4-WT3-U2；e.碎屑状白钛石与邻近锆石吸附少量铀，4-WT3-U2；f.自形六边形白钛石裂隙中吸附少量铀，4-WT3-U2；g.含铀白钛石局部被铀交代形成铀石，IV29-02-1；h.网格状结构的钛铀矿，4-WT3-U2；i.网格状金红石吸附铀，铀矿物呈星点状分布在表面，IV29-02-1
Fig. 10. Relationship between Fe-Ti oxides and uranium minerals in Qianjiadian uranium deposit
图 11 钱家店铀矿床中典型矿物蚀变演化序列
铁钛氧化物资料源于本文，其他矿物数据源于 荣辉等（2016） 和 贾俊民等（2018）
Fig. 11. Alteration sequence of typical minerals in the Qianjiadian uranium deposit
表 1 钱家店铀矿床中铁钛氧化物电子探针分析结果
Table 1. Analysis results of Fe-Ti oxides electron probe in Qianjiadian uranium deposit
序号 CaO K2O UO2 ThO2 TiO2 SO3 Na2O MgO SiO2 Al2O3 TFeO MnO Cr2O3 Total Ti/[Ti+Fe] 类型 1 0.03 0.04 0.00 0.00 1.17 0.00 0.00 0.03 0.15 0.37 86.01 0.39 0.17 88.36 0.01 赤铁矿 2 0.00 0.00 0.05 0.01 4.23 0.00 0.00 0.00 0.11 0.16 85.36 0.00 0.05 89.96 0.04 3 0.02 0.00 0.00 0.04 29.15 0.01 0.03 0.20 0.25 0.43 61.96 0.00 0.12 92.21 0.27 钛赤铁矿 4 0.00 0.01 0.03 0.01 7.42 0.01 0.00 0.07 0.05 0.61 82.94 0.10 0.06 91.30 0.07 磁铁矿 5 0.02 0.01 0.00 0.00 12.73 0.00 0.03 0.12 0.07 0.76 77.36 0.31 0.10 91.52 0.11 钛磁铁矿 6 0.02 0.01 0.03 0.00 19.40 0.00 0.03 0.03 0.22 0.16 72.58 0.47 0.04 93.01 0.17 7 0.02 0.00 0.00 0.03 50.03 0.00 0.02 0.26 0.05 0.00 38.94 0.99 0.03 90.37 0.50 钛铁矿 8 0.04 0.03 0.01 0.03 53.02 0.00 0.02 0.61 0.09 0.20 40.09 0.31 0.10 94.54 0.51 9 0.04 0.04 0.00 0.02 55.18 0.00 0.01 0.04 0.00 0.01 37.47 2.60 0.05 95.46 0.53 10 0.06 0.03 0.00 0.05 54.42 0.00 0.01 0.07 0.00 0.02 36.15 6.23 0.07 97.11 0.54 11 0.38 0.05 0.04 0.04 61.32 0.02 0.13 0.10 0.48 0.28 27.60 0.20 0.06 90.69 0.63 白钛石 12 0.19 0.08 0.01 0.00 80.37 0.00 0.16 0.02 1.29 1.43 8.69 0.04 0.13 92.41 0.88 13 0.05 0.01 0.02 0.01 59.55 0.02 0.02 0.05 0.14 0.05 30.26 1.11 0.00 91.29 0.60 14 0.23 0.03 0.02 0.03 61.33 0.01 0.17 0.05 0.62 0.49 25.93 0.12 0.03 89.06 0.65 15 0.14 0.02 0.04 0.01 60.76 0.01 0.08 0.04 0.42 0.22 28.49 0.19 0.07 90.50 0.62 16 0.20 0.10 1.72 0.03 84.06 0.00 0.21 0.03 0.89 0.85 1.99 0.03 0.09 90.18 0.97 锐钛矿 17 0.09 0.02 0.00 0.00 91.16 0.00 0.02 0.20 0.07 0.03 1.57 0.00 0.01 93.17 0.98 18 0.01 0.00 0.00 0.00 97.36 0.00 0.00 0.02 0.00 0.00 1.16 0.03 0.01 98.60 0.99 注：TFeO为全铁含量，Ti/[Ti+Fe]为质量百分数换算成原子百分数的比值结果. 
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表 2 铁钛氧化物分类依据
Table 2. Classification basis of Fe-Ti oxides
矿物
名称TiO2
(%)[Ti]/
[Ti+Fe]形态 化学组成 钛铁矿 48~60 0.48~0.60 碎屑状、板状、叶片状 FeTiO3 钛磁
铁矿< 48 < 0.48 网格状、布纹状、块状 TiO2+Fe3O4 钛赤
铁矿< 48 < 0.48 胶状、它形 TiO2+Fe2O3 白钛石 60~90 0.6~0.9 胶状、叶片状、六边形 Fe2Ti3O9+FeO 锐钛矿 > 90 > 0.9 胶状、絮状、粒状 TiO2 金红石 > 90 > 0.9 网格状、针状、块状 TiO2 注：TiO2%为质量百分比.
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表 3 铁钛氧化物的矿物含量
Table 3. Mineral content of Fe-Ti oxides
样品号 深度(m) 矿物平均含量(μm2/mm2) 分带 钛铁矿 钛赤铁矿 钛磁铁矿 白钛石 金红石 锐钛矿 4-56-08-1 431.5 97.28 1 113.90 1 972.48 236.18 144.58 0.00
完全氧化亚带4-56-08-2 438.0 0.00 487.41 1 398.83 131.96 15.41 0.00 QC90-20 499.7 404.54 1 115.51 732.47 611.63 20.01 24.46 QC90-24 536.0 76.08 279.96 318.78 152.13 408.35 134.13 5-56-25 278.5 0.00 32.65 40.14 47.63 87.54 130.38 4-56-08-09 331.3 6.23 164.83 498.42 0.00 218.24 8.97 4-56-08-10 342.6 45.91 34.81 543.09 72.96 479.72 6.52 部分氧化亚带 4-56-08-11 333.3 123.93 277.47 244.51 40.16 585.02 0.00 5-56-41-7 232.8 4.52 3.63 425.56 0.00 84.91 44.41 4-17-120 301.6 598.55 263.85 1 515.53 224.97 43.40 77.42 4-WT3-U6 467.5 0.00 0.00 2.61 64.02 393.46 0.00 微弱氧化亚带 5-56-41-15 350.2 14.39 460.26 0.00 61.29 424.35 47.69 4-56-08-03 300.4 0.00 0.00 0.00 293.63 1631.33 30.68 4-56-08-08 299.4 10.95 0.00 24.14 15.25 147.74 820.37 4-11303-8 301.7 16.06 0.00 1 028.87 85.62 170.14 780.02 4-WT3-U2 420.6 0.00 0.00 0.00 126.24 46.27 256.73 过渡带 4-WT3-U3 500.8 37.89 84.41 0.00 768.58 419.21 241.08 4-56-08-4 316.8 44.42 0.00 0.00 124.58 369.02 647.01 4-56-08-5 317.4 130.52 0.00 105.79 192.27 1 072.48 908.48 IV29-02-01 405.1 12.45 0.00 3.78 220.33 224.53 324.06 4-17-120 431.0 0.00 0.00 0.00 202.15 137.54 33.59 5-56-25 288.2 0.00 0.00 0.00 0.00 371.01 484.67 4-14911-2 240.2 282.02 0.00 92.70 817.94 1 569.09 119.00 还原带 4-14911-3 257.5 216.37 0.00 162.34 1 185.02 1 658.66 9.78 4-11303-9 306.4 0.00 0.00 125.66 0.00 8 347.40 718.32 QC17-22 221 7 095.41 0.00 0.00 2 316.66 3 398.43 944.86 QC17-34 272.3 15.82 0.00 0.00 109.35 417.26 164.55
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