Determination of Trace Rare Earth Elements in Tungsten-Molybdenum Ore by Inductively Coupled Plasma-Mass Spectrometry with Microwave Digestion System
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摘要:
钨钼矿和稀土均是重要战略资源，评估钨钼矿中稀土元素含量对矿产中稀土资源开发利用具有重要意义。钨钼矿样品前处理时碱熔熔剂会引入盐分基体，酸溶法钨钼元素易水解和产生稀土氟化物。本文拟建立一种在微波中以混合酸体系实现快速消解，结合电感耦合等离子体质谱法（ICP-MS）准确分析钨钼矿中16种稀土元素的分析方法。样品采用硝酸-氢氟酸-高氯酸-盐酸体系在微波中进行处理，随后赶酸至黏稠状并以柠檬酸-盐酸溶液温热溶解络合钨钼，避免在酸性环境下钨钼易发生水解及产生稀土氟化物等问题；利用ICP-MS在线加内标及动能歧视策略对样品分析稀土元素进行实时校正，降低基体效应、多原子离子等干扰的影响。该方法精密度RSD<2.0%（n=7），检出限为0.0002～0.0087µg/g，加标回收率为80.0%～114.0%，样品测试平均值与标准物质标准值对数误差的绝对值|ΔlgC|≤0.1，符合地质矿产行业要求。应用该方法分析钨钼矿标准物质（GBW07239和GBW07238）和三种实际样品，结果表明标准物质中16种稀土元素含量在标准值范围；应用于分析河南钨钼矿中稀土元素测定值在0.198～41.2µg/g之间，与吉林辉钼矿石中0.013～5.53µg/g和云南钨矿石石英片岩0.68～107.0µg/g、电气石岩0.071～2.11µg/g相较，具有空间分布特征和岩石种类差异研究意义。
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关键词:
- 钨钼矿 /
- 稀土元素 /
- 微波消解 /
- 电感耦合等离子体质谱法 /
- 动能歧视
Abstract:BACKGROUND Tungsten-molybdenum ore and rare earth are both important strategic resources. It is of great significance to evaluate the contents of rare earth elements in tungsten-molybdenum ore for the development of rare earth resources in minerals. During the pretreatment of tungsten and molybdenum ore samples, the alkali melting flux will introduce the salt matrix, and the tungsten and molybdenum elements in an acid dissolution condition are easy to hydrolyze into tungstic acid and molybdic acid and produce rare earth fluoride.
OBJECTIVES To establish an analytical method for accurate determination of the 16 rare earth elements including La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc, in tungsten-molybdenum ore by inductively coupled plasma-mass spectrometry (ICP-MS).
METHODS Tungsten-molybdenum ore samples were fast digested by microwave with four acid system (HNO3-HF-HClO4-HCl) in a high temperature and high-pressure environment. Then the digestion acid solution was evaporated to the viscous state, and the mixed solution (citric acid-hydrochloric acid) was used to dissolve the complexed tungsten and molybdenum at warm temperature, which effectively avoided the introduction of salt matrix in the pretreatment of tungsten-molybdenum ore samples. The problem of tungsten and molybdenum easily hydrolyzing into tungstic acid and molybdic acid was also solved, and rare earth fluoride in an acid environment was produced. Online internal standard and kinetic energy discrimination (KED) strategy were used in real-time to calibrate the sample analysis by ICP-MS, which solved the interference problems of matrix effect and polyatomic ions in the analysis process.
RESULTS The 16 rare earth element contents of tungsten molybdenum standard material (GBW07239 and GBW07238) and real samples (1#, 2# and 3#) was efficiently measured. The results showed that the concentrations of 16 rare earth elements were within the scope of the standard value, the contents of real samples were 0.198-41.2µg/g. Relative standard deviation (RSD) of method precision was lower than 2.0%, the method detection limit was 0.0002-0.0087µg/g, and the spiked recovery of real samples was between 80.0% and 114.0%. The absolute value of the logarithmic error between the average value of sample testing and the standard value of reference materials| ΔlgC|≤0, meet the requirements of the geological and mineral industry. The measured contents of rare earth elements in tungsten-molybdenum ore sampled from Henan are 0.198-41.2µg/g, compared with 0.013-5.53µg/g in molybdenite ore from Jilin, 0.68-107.0µg/g in tungsten ore (quartz schist) from Yunnan and 0.071-2.11µg/g in tungsten ore (tourmaline) from Yunnan. The content distribution of rare earth elements has spatial distribution characteristics and research significance for differences in rock types.
CONCLUSIONS The tungsten-molybdenum ore samples are completely dissolved by microwave with the four-acid system. This method satisfies the requirements of the geology and mineral industry and can provide reference for the analysis technology of trace rare earth elements in tungsten-molybdenum ore for high-throughput sample analysis capability.
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表 1 ICP-MS仪器工作参数
Table 1. Instrument operation parameters of ICP-MS.
仪器工作参数 设定值 仪器工作参数 设定值 射频功率 1400W 扫描方式 跳峰扫描 雾化气流速 1.25L/min 驻留时间 20.0ms 辅助气流速 1.00L/min 采样深度 2.70mm 冷却气流速 14.0L/min 氧化物离子产率 ＜1.0% 碰撞气流速 1.35mL/min 双电荷离子产率 ＜1.0% 
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表 2 微波升温消解程序
Table 2. Heating digestion procedure of microwave.
升温步骤 预加压
（MPa）升温时间
（min）设定温度
（℃）保温时间
（min）1 4.0 8.0 150 3.0 2 4.0 8.0 240 3.0 3 4.0 10.0 270 40.0
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表 3 分析元素的方法检出限、定量限和线性方程
Table 3. Method detection limit, quantitation limit and linear equation of analytical elements.
分析元素 线性方程 相关系数
r方法检出限
（µg/g）方法定量限
（µg/g）45Sc y=0.0019x+7.81×10−5 1.0000 0.0087 0.029 89Y y=0.0094x+13.6×10−5 1.0000 0.0015 0.0050 139La y=0.0197x+39.7×10−5 0.9999 0.0077 0.026 142Ce y=0.0107x+15.4×10−5 0.9999 0.0064 0.021 141Pr y=0.0275x+3.20×10−5 0.9999 0.0017 0.0057 146Nd y=0.0053x+4.50×10−5 0.9999 0.0058 0.019 149Sm y=0.0027x+2.52×10−5 1.0000 0.0024 0.0080 153Eu y=0.0112x+142×10−5 1.0000 0.0009 0.0030 160Gd y=0.0067x+48.9×10−5 1.0000 0.0025 0.0083 159Tb y=0.0263x+0.01021 0.9999 0.0054 0.018 164Dy y=0.0080x+4.56×10−6 1.0000 0.0005 0.0017 165Ho y=0.0276x+4.55×10−6 1.0000 0.0004 0.0013 170Er y=0.0054x+2.37×10−5 1.0000 0.0018 0.0060 169Tm y=0.0311x+1.50×10−6 1.0000 0.0002 0.0007 174Yb y=0.0108x+1.22×10−5 1.0000 0.0009 0.0030 175Lu y=0.0246x+7.93×10−5 1.0000 0.0005 0.0017 注：表中线性方程中x为元素浓度，y为元素信号响应值（cps）与内标元素信号响应（cps）的均值比值。
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表 4 样品中分析元素测试结果（n=3）
Table 4. Results of analytical elements in the samples （n=3）.
分析元素 GBW07239 GBW07238 标准值（µg/g） 测定均值±SD（µg/g） ΔlgC 标准值（µg/g） 测定均值±SD（µg/g） ΔlgC 45Sc 8.40±0.80 8.57±0.37 0.01 3.40±0.30 3.14±0.08 −0.03 89Y 34.2±2.20 32.2±0.10 −0.03 11.4±1.20 11.1±0.42 −0.01 139La 37.4±1.90 36.0±0.24 −0.02 7.10±0.60 7.22±0.20 0.01 142Ce 60.3±3.30 62.4±0.93 0.02 20.8±1.80 19.7±0.28 −0.02 141Pr 7.40±0.60 7.29±0.56 −0.01 3.00±0.40 2.75±0.18 −0.04 146Nd 29.8±2.10 30.6±0.82 0.01 11.3±2.20 9.84±0.52 −0.06 149Sm 6.40±0.50 6.50±0.23 0.01 2.10±0.40 1.84±0.06 −0.06 153Eu 1.50±0.10 1.53±0.05 0.01 0.59±0.11 0.587±0.07 0.00 160Gd 5.80±0.40 5.70±0.07 −0.01 1.90±0.30 1.65±0.03 −0.06 159Tb 0.98±0.08 0.983±0.06 0.00 0.34±0.05 0.325±0.03 −0.02 164Dy 5.80±0.40 5.89±0.42 0.01 1.80±0.30 1.64±0.15 −0.04 165Ho 1.20±0.10 1.23±0.04 0.01 0.36±0.06 0.330±0.04 −0.04 170Er 3.20±0.40 3.35±0.35 0.02 1.00±0.20 0.837±0.04 −0.08 169Tm 0.44±0.06 0.491±0.01 0.05 0.14±0.03 0.117±0.004 −0.08 174Yb 2.80±0.30 3.00±0.13 0.03 1.00±0.20 0.857±0.03 −0.07 175Lu 0.41±0.06 0.416±0.02 0.01 0.16±0.05 0.118±0.007 −0.13
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表 5 样品元素含量、加标回收率和精密度测试结果
Table 5. Measured values, spiked recovery and precision of analytical elements in the environment samples.
分析元素 样品1#
含量测定均值±SD
（µg/g，n=3）样品2#
含量测定均值±SD
（µg/g，n=3）样品3#
含量测定均值±SD
（µg/g，n=3）样品1#
（n=7）
RSD（%）样品1#
加标量样品1#加标浓度均值
（n=2）加标回收率
（%）45Sc 5.79±0.24 12.4±0.24 10.4±0.12 0.90 0.5 6.22 86.0 5.0 10.4 92.2 25.0 31.3 102.0 89Y 20.6±0.34 28.2±1.03 41.2±0.23 0.36 0.5 21.0 80.0 5.0 25.9 106.0 25.0 47.7 108.0 139La 12.8±0.60 24.5±0.35 27.5±1.57 0.79 0.5 13.3 100.0 5.0 18.0 104.0 25.0 37.6 99.2 142Ce 12.5±0.49 35.8±1.56 28.1±1.65 0.83 0.5 13.0 100.0 5.0 17.3 96.0 25.0 35.6 92.4 141Pr 3.50±0.12 10.4±0.54 5.92±0.31 0.67 0.5 3.92 84.0 5.0 8.41 98.2 25.0 27.3 95.2 146Nd 10.2±0.42 23.2±1.15 23.2±1.27 0.67 0.5 10.6 80.0 5.0 14.9 94.0 25.0 33.3 92.4 149Sm 3.67±0.10 5.39±0.28 5.35±0.25 0.97 0.5 4.13 92.0 5.0 9.03 107.0 25.0 31.1 110.0 153Eu 0.744±0.02 1.18±0.07 1.27±0.07 1.13 0.5 1.27 105.0 5.0 6.19 109.0 25.0 28.1 109.0 160Gd 3.26±0.01 5.54±0.19 5.39±0.26 0.65 0.5 3.67 82.0 5.0 8.71 109.0 25.0 29.4 105.0 159Tb 0.485±0.01 0.886±0.03 0.899±0.03 1.00 0.5 1.01 105.0 5.0 5.87 108.0 25.0 26.4 104.0 164Dy 3.09±0.03 5.35±0.15 4.48±0.24 0.65 0.5 3.64 110.0 5.0 8.51 108.0 25.0 29.0 104.0 165Ho 0.627±0.01 1.10±0.05 1.23±0.03 0.69 0.5 1.19 113.0 5.0 5.90 105.0 25.0 26.3 103.0 170Er 1.78±0.04 3.19±0.14 3.44±0.05 0.81 0.5 2.34 112.0 5.0 6.96 104.0 25.0 27.1 101.0 169Tm 0.198±0.01 0.462±0.02 0.477±0.01 1.17 0.5 0.708 102.0 5.0 5.35 103.0 25.0 25.2 100.0 174Yb 1.45±0.07 3.02±0.11 2.19±0.11 0.88 0.5 2.02 114.0 5.0 6.55 102.0 25.0 26.2 99.0 175Lu 0.213±0.01 0.441±0.02 0.461±0.01 0.65 0.5 0.759 109.0 5.0 5.56 107.0 25.0 26.3 104.0
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表 6 酸体系消解效果对比
Table 6. Comparison for digestion effect of acid systems.
酸种类 是否赶酸 复溶酸种类 消解效果 2mL硝酸+6mL盐酸 否 - 消解后底部有大量沉淀 2mL硝酸+4mL盐酸+2mL氢氟酸 否 - 消解后底部有少量沉淀 2mL硝酸+1mL盐酸+4mL氢氟酸+1mL高氯酸 否 - 消解后底部有微量沉淀 2mL硝酸+1mL盐酸+4mL氢氟酸+1mL高氯酸 是 硝酸溶液 消解后及复溶后底部有微量沉淀 2mL硝酸+1mL盐酸+4mL氢氟酸+1mL高氯酸 是 盐酸溶液 消解后有微量沉淀，复溶后溶液略有浑浊 2mL硝酸+1mL盐酸+4mL氢氟酸+1mL高氯酸 是 盐酸+柠檬酸溶液 消解后有微量沉淀，复溶后溶液澄清
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表 7 微波消解条件优化
Table 7. Optimization for digestion conditions of microwave.
预加氮气压力
（MPa）工作温度
（℃）保持时间
（min）样品消解效果 4.0 260 40 消解复溶后有微量沉淀 4.0 270 40 消解复溶后溶液澄清 4.0 280 40 消解复溶后溶液澄清 4.0 270 20 消解复溶后有微量沉淀 4.0 270 60 消解复溶后溶液澄清 3.0 270 40 消解复溶后有微量沉淀 5.0 270 40 消解复溶后溶液澄清
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表 8 样品元素分析质量数及内标元素
Table 8. Mass number of analytical elements in the samples and internal standard elements.
分析元素 质量数 内标元素 分析元素 质量数 内标元素 镧La 139 Rh 镝Dy 164 Ir 铈Ce 142 Rh 钬Ho 165 Ir 镨Pr 141 Rh 铒Er 170 Ir 钕Nd 146 Rh 铥Tm 169 Ir 钐Sm 149 Ir 镱Yb 174 Ir 铕Eu 153 Ir 镥Lu 175 Ir 钆Gd 160 Ir 钇Y 89 Rh 铽Tb 159 Ir 钪Sc 45 Rh
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