Electron Probe Quantitative Analysis of HREE-V-Aluminosilicate Minerals
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摘要:
产自广东省梅州市玉水铜矿的景文矿，属于含水、重稀土-矾-铝硅酸盐矿物(简写为HREE-V-铝硅酸盐矿物)，其化学结构式为Y2Al2V24+(SiO4)2O4(OH)4，该矿物在全球属首次发现，暂未开展相关研究。相对于含轻稀土矿物，含重稀土矿物在电子探针分析过程中，当被高压电子束轰击时，被激发出来的特征X射线线系繁多，线系之间分布更加密集，彼此之间相互重叠的现象也更为严重，要获得理想数据的难度很大，是亟待解决和突破的技术难题。本文对该矿物进行了精细的电子探针定量分析，获得理想的化学成分数据，为新矿物命名提供了理论数据技术支撑。通过对实验方法的探索和总结获得以下结果：①利用15kV加速电压、100nA束流对试样进行全元素扫描，以此确定出17种元素；②在定量分析过程中，对重叠峰进行了剥离；③利用仪器软件中的Zoom-Peak ID程序，选择出17种元素的分析线系、精确的峰位及上下背景值；④选取合适的标样及测试时间等定量分析条件，最终获得理想的定量分析结果(平均总量97.41wt%)。上述四条也是确保获得理想定量分析数据的关键因素。
Abstract:BACKGROUND Jingwenite, Y2Al2V24+(SiO4)2O4(OH)4), from Yushui Copper Mine, Meizhou City, Guangdong Province, is a type of HREE-V hydrated aluminosilicate minerals. Since its discovery, no research has been done. During electron probe microanalysis (EPMA) for HREE minerals, many characteristic X-ray lines are excited when samples are bombarded by a high-voltage electron beam. The lines are not only numerous, but also seriously overlap with each other. It is very difficult to obtain optimal data, and it is a technical problem that needs to be solved.
OBJECTIVES To obtain ideal chemical composition data by fine quantitative analysis of the mineral by EPMA to provide theoretical data technical support for the naming of the new mineral.
METHODS Full element wave spectrum scanning for Jingwenite by JEOL JXA-8530F Plus.
RESULTS (1) 17 elements were identified by wave dispersive scanning with an accelerating voltage of 15kV and a beam current of 100nA; (2) Stripping overlapped peak during the quantitative analysis; (3) Peak positions, upper and lower background values of 17 elements were set by Zoom-Peak ID program in quantitative analysis; (4) The ideal quantitative analysis results (total 97.41wt%) were obtained by selecting appropriate standard samples and testing dwell time.
CONCLUSIONS The above four items are key factors to ensure ideal quantitative analysis data.
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表 1 HREE-V-铝硅酸盐矿物电子探针分析条件
Table 1. Analysis conditions of HREE-V-aluminiosilicate minerals by electron probe microanalyzer
序号 元素 分光晶体 峰位L(mm) 线系 峰位/背景测量时间(s) 标样 峰位干扰描述 标样溯源 1 Si TAP 77.322 Kα1 10/5 Albite 被Lu的Lβ1干扰，Bg-避开Si Kβ，Bg+避开YLL 美国国家标准委员会 2 Al TAP 90.577 Kα1 10/5 Hornblende 没有干扰 3 Ti LiFH 191.178 Kα1 20/10 Hornblende 没有干扰 4 Fe LiFH 134.751 Kα1 30/15 Hornblende 没有干扰，Bg-避开Dy Lα1，Bg+避开Tb Lα1 5 F LDE1 85.105 Kα1 10/5 Apatite 没干扰，计数率低 6 Nd LiFH 164.668 Lα1 30/15 REE-2 没干扰，计数率低 7 Sm LiFH 152.842 Lα1 20/10 REE-2 计数率低，注意与Y Kβ5区分 8 Gd LiFH 142.452 Lα1 20/10 REE-1 没干扰，计数率低 9 Tb LiFH 137.576 Lα1 30/15 REE-1 没干扰，计数率低 10 Dy LiFL 132.693 Lα1 20/10 REE4 没干扰，Bg+注意避开Fe Kα 11 Er LiFL 124.058 Lα1 20/10 REE4 被Tb Lβ4干扰 12 Tm LiFL 120.030 Lα1 30/15 REE-1 被Sm Lg1干扰 13 Yb LiFL 116.190 Lα1 30/15 REE-2 没干扰，计数率低 14 Ho LiFL 114.536 Lβ1 20/10 REE-4 Lα1被Gd Lβ1干扰 15 Lu LiFL 98.757 Lβ1 30/15 REE-2 Lα1被Ho Lβ3、Dy Lβ2, 15干扰 16 Y PETJ 206.590 Lα1 20/10 YPO4 没有干扰 图卢兹大学 17 V PETJ 80.128 Kα1 20/10 Ca3(VO4)2 被Ti Kβ5干扰，与Ti Kβ1, 3区分 国家标准化管理委员会 注：测量时间如“10/5”表示峰位10s，背景5s。 
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表 2 定量分析过程中所用标样成分原始数据及监测数据
Table 2. Original data and monitoring data of components in standard sample by quantitative analysis
普通标样 稀土标样 成分 钠长石 角闪石 磷灰石 Ca3(VO4)2 成分 YPO4 REE1 REE2 REE4 原始数据(wt%) 监测数据(wt%) 原始数据(wt%) 监测数据(wt%) 原始数据(wt%) 监测数据(wt%) 原始数据(wt%) 监测数据(wt%) 原始数据(wt%) 监测数据(wt%) 原始数据(wt%) 监测数据(wt%) 原始数据(wt%) 监测数据(wt%) 原始数据(wt%) 监测数据(wt%) SiO2 68.14 67.98 40.37 40.46 0.34 0.19 - - SiO2 - - 26.96 26.89 27.7 27.07 28.34 28.33 Al2O3 19.77 19.75 14.9 15.23 - - - - Al2O3 - - 30.52 30.24 30.63 30.7 32.08 31.79 Na2O 11.46 11.13 2.6 2.52 0.23 0.22 - - CaO - - 25.16 25.12 25.26 25.38 26.45 26.27 K2O 0.23 0.22 2.05 1.96 - - - - Eu2O3 - - 4.20 4.25 - - - - CaO 0.38 0.16 10.3 10.24 54.02 54.24 48.13 48.72 Gd2O3 - - 4.46 4.46 - - - - FeO - - 10.92 10.52 - - - - Tb2O3 - - 4.35 4.45 - - - - TiO2 - - 4.72 4.71 - - - - Tm2O3 - - 4.35 4.31 - - - - MgO - - 12.8 13.07 - - - - Nd2O3 - - - - 4.26 4.25 - - MnO - - 0.09 0.10 - - - - Sm2O3 - - - - 4.26 4.22 - - P2O5 - - - - 40.78 40.69 - - Yb2O3 - - - - 4.26 4.33 - - F - - - - 2.94 2.97 - - Lu2O3 - - - - 4.26 4.06 - - V2O5 - - - - - - 51.5 51.39 Dy2O3 - - - - - - 4.36 4.21 Cl - - 0.41 0.33 - - Ho2O3 - - - - - - 4.41 4.31 总计 99.98 99.35 98.75 98.81 98.72 98.27 99.63 100.12 Er2O3 - - - - - - 4.36 4.24 P2O5 38.6 38.67 - - - - - - Y2O3 61.4 61.11 - - - - - - 总计 100 99.73 100 99.73 100 100.02 100 99.14
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表 3 HREE-V-铝硅酸盐矿物定量分析结果
Table 3. Quantitative analysis results of HREE-V-aluminiosilicate minerals
氧化物 原始点号测量值(wt%) 平均值(wt%) 平均D.L* (ppm) 85 86 87 88 89 90 91 93 94 95 96 VO2 24.18 25.68 24.43 25.84 28.03 26.14 25.88 24.95 25.05 25.74 25.38 25.57 153 Al2O3 11.9 11.38 12.06 12.13 12.52 12.38 12.18 12.6 13.02 12.8 12.69 12.12 176 SiO2 16.28 16.44 16.3 16.37 16.51 16.61 16.41 16.34 16.43 16.43 16.25 16.40 124 TiO2 3.72 3.08 3.45 1.21 ND 0.99 1.45 0.85 0.22 0.13 0.06 1.38 123 FeO** 0.60 0.45 0.52 1.44 0.75 0.71 0.91 1.80 1.79 1.29 1.33 1.05 128 F 0.09 0.10 0.07 0.18 0.09 0.05 0.15 0.26 0.28 0.19 0.19 0.02 211 Y2O3 24.8 24.17 24.78 25.36 25.17 25.08 25.51 25.44 24.49 22.98 22.57 24.58 205 Nd2O3 0.05 ND 0.04 0.05 0.03 0.02 0.01 0.01 ND 0.01 0.02 0.64 195 Sm2O3 0.08 0.06 0.06 0.13 0.10 0.05 0.10 0.13 0.07 0.04 0.06 0.31 236 Gd2O3 0.79 0.81 0.85 0.65 0.65 0.64 0.64 0.57 0.56 0.49 0.42 1.38 261 Tb2O3 0.24 0.37 0.40 0.22 0.30 0.33 0.35 0.36 0.34 0.24 0.25 3.24 288 Dy2O3 3.26 3.58 3.32 2.62 3.60 2.83 2.90 3.11 3.56 3.57 3.32 0.88 278 Ho2O3 0.80 1.05 0.95 0.66 0.96 0.82 0.84 0.81 0.91 0.84 1.02 3.62 624 Er2O3 3.50 3.65 3.50 3.07 3.47 3.42 3.28 3.36 3.82 4.28 4.47 0.63 306 Tm2O3 0.56 0.54 0.59 0.60 0.55 0.63 0.54 0.54 0.66 0.80 0.87 4.02 260 Yb2O3 3.70 3.80 3.55 3.99 3.26 4.01 3.69 3.52 3.74 5.18 5.83 2.58 277 Lu2O3 2.44 2.80 1.20 2.54 2.39 2.97 2.61 1.06 2.64 3.52 4.24 0.15 832 总计 96.95 97.9 96.02 96.95 98.33 97.66 97.38 95.59 97.46 98.45 98.87 97.41 - ∑R2O3 40.22 40.82 39.23 39.87 40.48 40.8 40.47 38.9 40.79 41.96 43.06 40.60 - VO2+TiO2 27.9 28.76 27.88 27.05 28.03 27.13 27.33 25.8 25.27 25.87 25.44 26.95 - 注：氧化物以wt%为单位，平均最低探测极限(D.L)以ppm为单位。“*”：表示在1σ下的11个数据元素平均最低探测极限。“**”：FeO表示Fe2+全铁。
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