Occurrence State of Rare Earth Elements in the Paleo-Weathering Crust of the Tieling Formation, Northern Hebei Province by X-Ray Diffraction and Electron Probe Microanalysis
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摘要:
近年来发现的古风化壳型稀土矿具有稳定、易于开采等优点，由于对其元素赋存状态的研究程度较低，制约了矿床富集机理的研究。本文采用逐级化学提取、X射线粉晶衍射、重砂鉴定、电子探针等测试技术，对铁岭组古风化壳稀土元素的赋存状态进行了系统研究。逐级化学提取显示古风化壳中稀土元素主要以矿物相存在，约占总含量的99.38%。水溶相、离子相及胶态沉积相中的稀土元素分别占比0.01%、0.22%和0.39%；X射线衍射分析显示古风化壳样品中的伊利石、伊蒙混层等黏土矿物可能吸附了极少量稀土元素；电子探针测试结果显示古风化壳样品中的锐钛矿、白钛矿和重晶石中含有0.1%左右的Ce、Nd、Sm等轻稀土元素。初步认为：古风化壳中稀土元素主体以矿物相存在，一部分以类质同象赋存于锐钛矿、白钛矿和重晶石中，其余则可能以纳米级微细颗粒存在于锐钛矿表面以及大量的黏土矿物中。极少量的离子态稀土元素可能吸附于伊利石、伊蒙混层等黏土矿物表面；呈水溶相及胶态沉积相中的稀土元素含量极低。本文对古风化壳稀土元素赋存状态的研究有助于优化开发利用工艺，为稀土资源的选冶利用提供数据基础。
Abstract:In recent years, the discovered paleo-weathering crustal rare earth ores have the advantages of stability and easy mining. However, due to the low degree of research on their element occurrence state, the study of the enrichment mechanism of the deposits is restricted. In this paper, the occurrence state of rare earth elements in the paleo-weathering crust of the Tieling Formation was systematically studied by using the techniques of stepwise chemical extraction, X-ray diffraction, heavy minerals identification, and electron probe microanalysis. Stepwise chemical extraction shows that rare earth elements in the paleo-weathering crust mainly exist in mineral phases, accounting for about 99.38% of the total content. The rare earth elements in aqueous solution, ionic phase, and colloidal deposition phase account for 0.01%, 0.22% and 0.39%, respectively; X-ray diffraction analysis shows that a small amount of rare earth elements in the ionic adsorption state in the paleo-weathering crust samples may exist on the surface of clay minerals such as illite; electron probe microanalysis results show that the anatase, leucoxene and barite in the paleo-weathering crust samples contain about 0.1% of light rare earth elements such as Ce, Nd and Sm. In summary, it is preliminarily concluded that the main rare earth elements in the paleo-weathering crust exist in mineral phases, some of them exist in anatase, leucoxene and barite as similar images, and the rest may exist on the surface of anatase and a large number of clay minerals in nano-scale fine particles. A very small amount of ionic rare earth elements may be adsorbed on the surface of clay minerals such as illite and illite-smectite mixed layer. The content of rare earth elements in the water-soluble phase and colloidal sedimentary phase is very low. The study on the occurrence state of rare earth elements in the ancient weathering crust helps to optimize development and utilization technology and provides a theory for the selection and smelting utilization of rare earth resources.
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表 1 稀土元素赋存状态逐级分离实验分析结果
Table 1. Analytical results of occurrence state of REEs in step-by-step separation test
REEs相态 REEs各相态含量
(×10−6)REEs各相态占比
(%)水溶相 0.017 0.01 离子相 1.24 0.22 胶体相 2.22 0.39 矿物相 560 99.38 全相 563.477 100.0 
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表 2 铁岭组古风化壳样品中的重矿物鉴定分析结果
Table 2. Identificatied results of heavy minerals in the paleo-weathering crust samples of the Tieling Formation
矿物名称 含量(%) 有用矿物及副矿物特征描述 赤褐铁矿 84.06 红褐色，棱角次棱角块状，不透明，弱金属光泽，中高硬度，部分有蚀变，粒径0.05～0.6mm 重晶石 3.02 无色、白色，板状，透明，珍珠光泽，低硬度，粒径0.03～0.5mm 锆石 2.60 粉色，次滚圆-滚圆柱状，透明-半透明，弱金刚-毛玻光泽，表面较粗糙，断口有溶磨痕迹，伸长系数1.2～2.0，粒径0.02～0.13mm，锆石磨圆度较高，分选性较好，略显搬运痕迹 磁铁矿 1.34 黑色，半自形八面体、次棱角块状，不透明，金属光泽，高硬度，粒径0.03～0.3mm 电气石 0.52 褐色，次滚圆柱状、粒状，透明，毛玻光泽，高硬度，粒径0.05～0.25mm 白钛矿 0.25 驼色、灰色，次滚圆粒状、扁粒状，不透明，瓷状光泽，中高硬度，粒径0.03～0.1mm 锐钛矿 0.16 灰蓝色、灰绿色、灰褐色，次滚圆粒状，半透明，油脂光泽，高硬度粒径0.03-0.1mm 金红石 0.11 暗红色、黑色，次滚圆柱状，微透明，油脂光泽，高硬度，粒径0.03～0.1mm 黄铁矿 0.01 铜黄色，棱角-次棱角块状、半自形次滚圆粒状、半自形立方体，不透明，金属光泽，高硬度，粒径0.05～0.3mm 榍石 0.01 浅褐黄色，次棱角块状，透明，油脂光泽，中高硬度，粒径0.05～0.25mm 其余矿物 7.92 石英、蚀变矿物
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表 3 铁岭组古风化壳样品中的重矿物电子探针分析结果(%)
Table 3. EPMA analysis results of heavy minerals in the paleo-weathering crust samples of the Tieling Formation
样品编号 K2O CaO TiO2 Na2O Ga2O3 MgO Al2O3 SiO2 La2O3 BaO CoO SO3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Eu2O3 FeO 合计 PTD-2-Rz1 0.017 − 98.025 0.045 0.099 − 0.013 0.01 − − − − − − − 0.049 − 0.091 98.349 PTD-2-Rz2 0.016 0.009 98.583 0.018 0.04 − 0.028 0.059 − − − − − − − − − 0.097 98.85 PTD-2 -Ant1 0.014 0.007 99.041 − − − 0.016 0.011 − − − − − − − 0.085 − 0.112 99.286 PTD-2- Ant2 − − 98.919 0.033 0.06 0.005 0.009 0.011 − − − − 0.069 − 0.053 − − 0.07 99.229 PTD-2-Ant3 0.013 − 98.849 − − − 0.026 0.076 − − − − 0.034 − − − 0.141 0.043 99.187 PTD-2- Ant4 0.024 0.01 99.381 − − 0.016 0.016 0.04 − − − − − − − 0.004 − 0.063 99.577 PTD-2-Btk1 0.047 0.035 94.471 − 0.12 0.007 0.266 0.808 − − − − − − − − − 1.857 97.611 PTD-2-Btk2 0.122 0.057 96.298 0.036 − 0.052 0.469 0.727 − − − − − − 0.039 − − 0.662 98.462 PTD-2-Btk3 0.014 0.03 95.658 0.006 − 0.007 0.179 0.315 − − − − 0.1 − 0.015 − 0.016 0.565 96.905 PTD-2- Btk4 0.001 0.028 96.167 − − 0.036 0.21 1.515 − − − − − − − − − 0.622 98.592 PTD-2 -Brt1 − 0.193 − 0.071 0.029 − 0.032 0.012 − 64.441 0.05 35.892 0.058 − 0.035 − 0.02 − 100.833 PTD-2-Brt2 − − − 0.032 0.092 − 0.027 − − 63.63 − 36.157 − − 0.046 0.027 − 0.007 100.018 PTD-2-Brt3 − 0.1 − 0.064 0.04 − 0.043 0.05 − 64.649 − 35.316 − − 0.095 − − 0.002 100.39 PTD-2-Brt4 − 0.09 − 0.073 − − 0.037 − − 65.395 0.023 34.686 − − 0.064 − − 0.012 100.39 注：“−”表示低于EPMA分析方法检出限，未检出。矿物代号： Rz—金红石； Ant—锐钛矿；Lm—褐铁矿；Brt—重晶石；Btk—白钛矿。
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