Sequence and Genetic Mechanism of Nano-Micron Spinel Exsolution from Panzhihua V-Ti Magnetite Deposit
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摘要: 钛磁铁矿内部尖晶石出溶体的成分组成和形成机制对估算磁铁矿固溶体的成分以计算铁钛氧化物的氧逸度-温度具有重要意义.为了探究攀枝花钒钛磁铁矿中尖晶石的成因及形成机制，运用岩相观察和各种微区原位观测手段，系统研究了各类尖晶石的矿物学特征.尖晶石的粒度在纳微米之间，有3种类型：第1种为钛磁铁矿晶界处不规则的大颗粒尖晶石，Mg#为60~70；第2种为钛磁铁矿颗粒内部的粒状尖晶石，Mg#为71~77；第3种为沿钛磁铁矿（100）方向定向分布的尖晶石片晶，Mg#为75~77.3类尖晶石分别与磁铁矿主晶具有相同的取向关系：{111}Mag//{111}Spl，{110}Mag//{110}Spl和{100}Mag//{100}Spl.3类尖晶石均是磁铁矿主晶的出溶体，钛磁铁矿晶界处及其内部的粒状尖晶石的形成与某些晶体缺陷关系密切，是在降温过程中较早出溶的产物，尖晶石片晶在两者之后以旋节分解出溶形成.Abstract: Detailed characterization and formation mechanism of the spinel exsolution in titanomagnetite is crucial for reconstructing the composition of magnetite solid solution precursor and for application to the Fe-Ti oxide oxythermometer. The chemical composition, topographic characteristics and crystallographic relationships of spinel exsolution were studied systematically to probe into its sequence and genetic mechanism through petrographic observation and the integrated use of in-situ microanalysis methods. The results show that there are three output forms of the spinel exsolution. One spinel exsolution is on the edge of the titanomagnetite with Mg# range from 60-70. Another is granular spinel exsolution distributing dispersedly with big particle-size, with Mg# range from 71-77. The third spinel exsolution is present as lamellae parallelling to the {100} of the titanomagnetite with Mg# range from 75-77. Three different types of spinel exsolution are all the magnesia-alumina spinel and have close-packed oxygen planes and directions parallel to those in the host magnetite with {111}Mag//{111}Spl, {110}Mag//{110}Spl and {100}Mag//{100}Spl respectively. Analysis suggests that three different types of spinel exsolution are all the product of the magnetite solid solution in the process of slow cooling with different sequence and genetic significance. The granular spinel exsolution in the titanomagnetite and the spinel exsolution on the edge of the titanomagnetite are related to some crystallographic defects in titanomagnetite and exsolved at the early stages of exsolution. The spinel lamellae exsolved in the way of spinodal decomposition parallelling to {l00}.
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Key words:
- Panzhihua /
- nano-micron /
- spinel exsolution /
- sequence /
- genetic mechanism
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图 1 中国西南攀枝花-西昌地区区域地质图及峨眉山大火成岩省分布
Fig. 1. Generalized geological map of the Pan-Xi area, Emeishan large igneous province, SW China showing the distribution of mafic-ultramafic intrusions that host Fe-Ti oxide mineralization
图 3 矿石结构和构造
a, b.稀疏浸染状构造矿石；c.稠密浸染状构造矿石；d.致密块状构造矿石；e.海绵陨铁结构：钛磁铁矿和硫化物以他形集合体充填在先结晶的顽火辉石和透辉石颗粒之间；f.海绵陨铁结构：钛磁铁矿他形集合体充填在先结晶的顽火辉石和透辉石颗粒之间；g.粒状镶嵌结构：钛磁铁矿呈近等轴的粒状，粒度相似，以自形或半形直线镶嵌接触，脉石矿物呈不规则状充填在其颗粒之间；Di.透辉石；Mgn.镁铝尖晶石；Po.磁黄铁矿；Tmt.钛磁铁矿
Fig. 3. Textures and structures of ores
图 4 钛磁铁矿内部的尖晶石出溶体形貌特征
尖晶石形貌照片在东北大学研究院分析测试中心拍摄完成；Mgn.镁铝尖晶石
Fig. 4. The morphology of the magnesia-alumina spinel exsolutions inside the titanomagnetite
图 5 钛磁铁矿粒间的尖晶石出溶体形貌特征
Mgn.镁铝尖晶石；Po.磁黄铁矿；Tmt.钛磁铁矿
Fig. 5. The morphology of the magnesia-alumina spinel exsolution on the edge of the titanomagnetite
图 6 磁铁矿主晶及其内部和边缘尖晶石的晶体关系
尖晶石及主晶磁铁矿EBSD测试在中国地质大学(武汉)场发射扫描电镜实验室完成.a.磁铁矿主晶的赤平极射投影图(45点)；b.钛磁铁矿内部定向排列的小颗粒尖晶石片晶赤平极射投影图(3点)；c.钛磁铁矿内部形态复杂的较大颗粒尖晶石赤平极射投影图(7点)；d.钛磁铁矿边缘不规则大颗粒尖晶石的赤平极射投影图(5点)
Fig. 6. Crystallographic orientation of host magnetite and spinel from the first magnetite grain
图 7 磁铁矿主晶及其内部尖晶石的晶体关系
尖晶石及主晶磁铁矿EBSD测试在中国地质大学(武汉)场发射扫描电镜实验室完成.a.磁铁矿主晶的赤平极射投影图(31点)；b.钛磁铁矿内部形态复杂的较大颗粒尖晶石赤平极射投影图(18点)
Fig. 7. Crystallographic orientation of host magnetite and spinel from the second magnetite grain
图 8 钛磁铁矿粒间显微出溶结构场发射扫描电镜照片
Fig. 8. The analyses with SEM of the exsolution texture in titanomagnetite's edge
图 9 尖晶石在钛磁铁矿中的出溶序次原理
Fig. 9. Schematic diagrams illustrating the exsolution sequence with progressive cooling in titanomagnetite
表 1 钛磁铁矿内部粒状尖晶石出溶体电子探针分析数据
Table 1. The EPMA data of the spinel exsolutions in the titanomagnetite
矿物(%) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Na2O 0.04 0.03 0.04 0.03 0.02 0.04 0.05 0.05 0.05 0.056 0.00 0.01 0.01 0.00 0.02 MgO 21.31 21.53 20.76 21.36 21.11 21.30 21.78 21.54 21.18 21.52 18.66 23.43 21.63 22.09 19.35 Al2O3 65.83 65.72 64.54 65.66 65.36 65.52 66.47 66.60 66.22 66.78 58.18 60.57 63.82 63.66 61.30 SiO2 0.18 0.13 0.15 0.011 0.17 0.14 0.10 0.13 0.14 0.04 0.54 0.67 0.17 0.29 0.01 BaO 0.07 0.04 0.00 0.02 0.03 0.04 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 FeO 12.09 10.91 13.50 12.52 12.68 12.03 11.89 11.35 13.15 11.36 18.59 14.79 14.32 14.72 17.72 MnO 0.08 0.06 0.07 0.01 0.08 0.06 0.05 0.02 0.07 0.04 0.06 0.06 0.05 0.08 0.03 NiO 0.00 0.05 0.00 0.03 0.05 0.00 0.00 0.03 0.00 0.00 0.04 0.00 0.00 0.00 0.00 TiO2 0.66 0.44 0.24 0.18 0.21 0.25 0.32 0.38 0.26 0.47 0.06 0.34 0.13 0.00 0.00 Cr2O3 0.09 0.07 0.08 0.07 0.08 0.06 0.08 0.06 0.07 0.11 0.13 0.14 0.09 0.06 0.09 V2O5 0.13 0.07 0.04 0.01 0.05 0.03 0.11 0.08 0.12 0.13 0.10 0.06 0.06 0.04 0.07 Total 100.49 99.06 99.43 100.01 99.86 99.48 100.86 100.25 101.28 100.53 96.40 100.06 100.27 100.96 99.60 Na apfu 0.002 0.001 0.002 0.001 0.001 0.002 0.002 0.001 0.002 0.003 0.000 0.000 0.000 0.000 0.001 Mg 0.791 0.807 0.786 0.795 0.789 0.797 0.803 0.798 0.781 0.795 0.463 0.581 0.537 0.548 0.481 Al 1.932 1.946 1.932 1.933 1.931 1.937 1.936 1.950 1.931 1.951 1.141 1.188 1.252 1.249 1.203 Si 0.004 0.003 0.004 0.003 0.004 0.004 0.003 0.003 0.004 0.001 0.009 0.011 0.003 0.005 0.000 Ba 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 Fe2+ 0.235 0.202 0.218 0.207 0.223 0.206 0.204 0.209 0.225 0.212 0.281 0.154 0.204 0.189 0.284 Fe3+ 0.017 0.027 0.066 0.054 0.043 0.046 0.042 0.027 0.047 0.024 0.133 0.156 0.095 0.117 0.096 Mn 0.002 0.001 0.001 0.000 0.002 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.000 Ni 0.000 0.001 0.000 0.001 0.001 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.001 Ti 0.012 0.008 0.005 0.003 0.004 0.005 0.006 0.007 0.005 0.009 0.001 0.004 0.002 0.000 0.014 Cr 0.002 0.001 0.002 0.002 0.002 0.001 0.002 0.001 0.001 0.002 0.002 0.002 0.001 0.001 0.001 V 0.004 0.001 0.001 0.000 0.002 0.000 0.002 0.001 0.002 0.002 0.001 0.001 0.001 0.000 0.001 Mg# 75.23 76.86 71.07 73.38 73.31 74.30 75.06 76.18 72.55 76.28 60.67 69.29 69.91 69.19 63.33 DIA(μm) - - 43.0 47.8 38.5 27.0 16.0 20.0 32.0 10.6 - - - - - 注：尖晶石定量成分分析在中国地质科学院矿产资源研究所电子探针实验室完成.1~2测点为定向分布尖晶石片晶的成分数据；3~10测点为钛磁铁矿内部粒状尖晶石成分数据；11~13测点为钛磁铁矿颗粒边缘的大颗粒尖晶石成分数据；14~15测点为“鸟眼状”尖晶石的成分数据. 
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