Application of Automated Mineral Identification and Characterization System to Identify Minerals and Occurrences of Elements in Jixiangyu Rare Earth Deposit of Eastern Liaoning
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摘要:
辽宁省已知的稀土矿类型较少，以往稀土矿床的勘查评价偏重于独居石砂矿和碱性岩型稀土矿，沉积变质型稀土矿涉及较少，其矿石学、矿物学研究程度偏低。本文以吉祥峪稀土矿床为研究对象，应用自动矿物识别和表征系统(AMICS)，结合高分辨率扫描电子显微镜(SEM)和高通量能谱仪(EDS)对矿石进行分析，获得吉祥峪稀土矿石中矿物化学成分、元素赋存状态及矿物共生组合关系。结果表明，矿石中稀土元素以La、Ce、Pr、Nd等轻稀土元素为主；主要稀土矿物为独居石(0.73%)、褐帘石(6.25%)、方铈石(0.25%)和磷灰石(类质同象)等；通过背散射图像结合光学显微镜观察得出矿石中的褐帘石、独居石、方铈石及磷灰石等具有较好的连生关系，这些矿物以单颗粒或聚粒结构与磁铁矿交叉镶嵌，或分布在磁铁矿边缘及间隙中。矿石中稀土矿物与磁铁矿密切共生，含量呈正相关，其原因可能为：①沉积富集。吉祥峪稀土矿位于辽吉裂谷的核部，裂谷为矿床提供了有利的沉积环境。②岩浆改造。岩浆热液可能与里尔峪一段变粒岩产生反应，使其中的稀土和铁元素集聚。③构造控制。吉祥峪稀土矿位于吉祥峪—算盘峪背斜核部穹隆之上，构造发育，断裂带和褶皱可能在地壳的应力作用下形成矿物质富集的通道，使矿质从深部运移至浅部。
Abstract:BACKGROUND In Liaoning Province, there are limited known types of rare earth deposits, and historically, exploration and evaluation efforts have mainly focused on monazite placer and alkaline rock type rare earth deposits. Less attention has been given to sedimentary metamorphic rare earth primary deposits. Previous studies have shown that the Jixiangyu rare earth deposit is categorized as a sedimentary metamorphic remodeling deposit related to ancient volcanic structures. The analysis of existing data and previous exploration results prove that this type of rare earth deposit has a considerable rare earth content with monazite and allanite. However, unresolved issues remain, such as the occurrence status of rare earth minerals and the feasibility of extracting and utilizing rare earth minerals.
OBJECTIVES To explore the metallogenic mechanism and unveil the formation process of rare earth deposits by identifying the types of rare earth minerals, investigating the occurrence and distribution of rare earth elements within minerals, and analyzing the composition, structure, and distribution characteristics of rare earth minerals and associated minerals.
METHODS The experimental testing was conducted at the Henan Provincial Rock and Mineral Testing Center. The experimental instruments used in this study included an ultra-high resolution field emission scanning electron microscope (Zeiss Sigma500), an electric cooling energy spectrometer (Bruker XFlash6610), and a set of AMICS automatic mineral identification and characterization systems. During the experiments, a high vacuum environment was maintained, with an accelerating voltage of 20kV and a beam current of 5nA. The working distance was set at 11.8mm, and the point analysis acquisition time reached 250kcps before stopping automatically.
RESULTS The primary rare earth minerals in the Jixiangyu rare earth deposit were identified as allanite, monazite, and cerianite, constituting 6.25%, 0.73%, and 0.25% of the total mineral content, respectively. Light rare earth elements such as La, Ce, Pr, and Nd were predominantly present, enriched in monazite, xenotime, and bastnaesite, with a minor occurrence of rare earth elements in the form of solid solutions within apatite. Gangue minerals include actinolite, quartz, plagioclase, potassium feldspar, sphene, and biotite. The rare earth minerals, including allanite, monazite, cerianite, and apatite exhibited interlocking structures with magnetite, occurring as single particles or clustered structures, and were distributed along the edges and gaps of magnetite, forming complex symbiotic relationships.
CONCLUSIONS The rare earth formation process can be attributed to the following factors: (1) Sedimentary enrichment: The Jixiangyu rare earth deposit is situated in the core area of the Liao Ji Rift, providing favorable sedimentary conditions for ore deposition. Over time, sediments accumulated, compacted, and underwent alteration, gradually releasing and enriching rare earth and iron elements, leading to formation of the ore deposit. (2) Magmatic modification: Magmatic hydrothermal fluids may have interacted with variolitic rocks from the Lieryu section, facilitating the simultaneous or interweaving mineralization of rare earth minerals and magnetite in the same geological environment, resulting in the activation and in situ enrichment of high background values of rare earth and iron elements. (3) Tectonic control: The Jixiangyu rare earth deposit is situated on the anticlinal structure of the Liaoning—Jilin Paleoproterozoic rift core where fault zones and folds may have acted as channels for mineral enrichment, facilitating the migration of minerals from deeper to shallower crustal regions.
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表 1 吉祥峪稀土矿床样品AMICS矿物定量分析结果
Table 1. Quantitative analysis results of minerals measured by AMICS in Jixiangyu rare earth deposit.
矿物名称 质量分数
(%)面积百分比
(%)统计面积
(μm2)颗粒数
(个)统计相对误差
(%)矿物标准分子式［29-30］ 褐帘石 6.25 6.62 3386157.37 809 0.14 (Ce，Ca)(Ce，La)(Nd，Pr)(Fe2+，Fe3+)(Al，Mg)[Si2O7][SiO4]O(OH) 独居石 0.73 0.57 289757.48 105 0.35 (Ce，La，Ca，Fe，Th，Nd，Pr)[SiO4] [PO4] 方铈石 0.25 0.50 257590.30 78 0.06 (Ce3+，Th，Fe，Pr，Nd)O2 磷灰石 5.73 7.22 3696466.51 861 0.10 FeFe2O4 磁铁矿 63.48 48.95 25056614.78 1891 0.07 Ca5[PO4]3(F，OH) 阳起石 7.61 9.94 5088796.43 524 0.11 Ca2Na(Mg，Fe)5(Al，Fe3+)[(Si，Al)4O11]2(OH)2 石英 7.36 11.16 5713847.71 1218 0.08 SiO2 钙铁榴石 0.01 0.01 70.14 1 2.00 Ca3Fe2[SiO4]3 斜长石 2.14 3.25 1663198.10 288 0.16 Na[AlSi3O8] 榍石 0.39 0.44 227134.51 301 0.20 CaTi[SiO4]O 锆石 0.01 0.01 1928.91 12 0.58 Zr(SiO4) 绿泥石 0.14 0.19 99300.33 166 0.18 Fe3 2+[Si4O10](OH)2(Mg，Al，Fe，Si)3(OH)6 钾长石 2.20 3.41 1743721.36 134 0.21 K[AlSi3O8] 黑云母 0.51 0.65 334115.41 344 0.15 K(Fe，Al)3AlSi3O10(F，OH)2 未知矿物 3.20 6.36 3255145.74 4728 0.05 / 孔隙 / 0.73 371809.84 22084 0.06 / 
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表 2 褐帘石能谱分析结果
Table 2. Energy spectrum analysis results of allanite.
样品编号 质量分数(%) O Fe Si Ca Al Mg Ce La Nd Pr XT02-07 37.43 16.07 11.74 7.76 5.27 0.59 11.06 6.95 2.04 1.08 XT02-13 35.73 15.11 12.31 7.76 5.50 0.59 11.60 7.81 2.33 1.25 XT02-29 38.23 15.73 11.30 8.39 5.02 0.41 10.94 7.07 1.94 0.98 XT02-30 37.13 17.78 11.63 8.06 5.17 0.47 10.27 6.18 2.31 1.00 XT02-31 36.85 16.50 12.80 7.41 6.17 0.82 9.77 6.17 2.26 1.25 XT02-32 37.03 17.08 11.49 8.39 4.99 0.42 10.48 6.58 2.54 1.00 平均值 37.07 16.38 11.88 7.96 5.35 0.55 10.69 6.79 2.24 1.09
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表 3 方铈石能谱分析结果
Table 3. Energy spectrum analysis results of cerianite.
样品编号 质量分数(%) Ce O Fe Si P Pr Nd Ca Th Al La Mn Mg XT02-38 57.32 17.24 8.32 3.63 3.96 3.84 2.80 1.36 / 1.53 / / / XT02-39 52.73 16.46 8.53 4.17 3.58 4.15 2.35 1.29 / 1.75 / 3.95 1.04 XT02-54 45.70 23.43 13.12 4.25 2.71 0.98 1.13 1.79 1.95 2.04 2.02 / 0.89 XT02-61 53.13 25.81 5.44 4.38 3.06 1.30 1.36 1.04 2.02 1.11 1.35 / / XT02-62 66.35 15.50 4.47 2.79 3.22 1.65 1.59 1.02 1.61 / 1.80 / / XT02-63 55.86 21.51 6.37 2.63 4.07 2.56 1.83 1.57 2.84 0.74 / / / XT02-64 44.60 27.54 13.65 3.86 2.93 1.94 1.48 1.02 0.62 1.46 0.89 / / 平均值 53.67 21.07 8.56 3.67 3.36 2.35 1.79 1.30 1.29 1.23 0.87 0.56 0.28
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表 4 独居石能谱分析结果
Table 4. Energy spectrum analysis results of monazite.
样品编号 质量分数(%) O Ce La P Nd Pr Ca Fe Si Th XT02-06 27.53 24.44 17.99 14.39 7.11 2.49 2.20 2.20 0.93 0.72 XT-02-40 21.03 12.05 28.06 14.69 12.33 4.81 3.46 2.34 0.88 0.33 XT02-46 25.81 11.32 26.81 12.77 11.69 4.49 2.40 1.35 1.71 1.65 XT02-47 26.91 9.71 26.13 13.38 11.81 4.71 2.16 1.64 1.38 2.17 XT02-53 32.08 9.84 24.95 12.25 10.93 4.13 1.90 0.89 1.07 1.96 XT02-55 31.13 20.20 19.32 13.69 7.65 2.45 4.33 1.24 / / XT02-56 38.95 14.45 19.58 12.79 8.18 2.67 2.06 / 1.32 / XT02-68 39.31 14.25 18.25 11.32 6.91 2.53 3.14 2.85 0.54 0.90 XT02-69 30.77 26.29 16.70 15.64 7.28 2.30 / / / 1.02 XT02-71 27.88 27.67 17.08 13.91 7.96 2.16 / 0.27 0.65 2.43 XT02-73 28.40 28.23 18.51 14.91 6.78 1.99 / 0.30 / 0.88 XT02-74 26.63 27.20 17.16 14.08 7.92 2.07 / 0.39 1.01 3.55 XT02-75 28.00 27.00 17.16 14.73 7.52 2.08 / 0.82 0.77 1.91 XT02-76 26.93 28.47 18.32 15.59 7.42 2.06 / 0.38 1.01 / 平均值 29.38 20.08 20.43 13.87 8.68 2.92 1.55 1.05 0.81 1.25
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