In situ Quantitative Analysis of Chemical Composition of Lithium and Beryllium Minerals by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry
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摘要:
锂、铍是当前全球战略性关键金属，采用激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）建立分析方法可以实现微区原位定量分析天然矿物样品中的锂、铍元素含量，为锂铍资源高效利用以及赋存状态的研究提供分析技术支撑。锂辉石和绿柱石等矿物是提取锂、铍元素的主要原料，微区分析常用的电子探针方法对于能量较低的轻元素难以准确定量，而LA-ICP-MS方法亟待改进降低非基体匹配校准带来的基体效应提高分析的准确度和精密度。本文探讨了仪器工作条件（同位素选择及计数模式、载气He气流速、样品气Ar气流速、束斑直径、能量密度大小）和数据处理方法（外部标准物质、内标元素）对定量结果精密度和准确度的影响。实验结果表明：He 和Ar气体流速不仅会影响锂、铍信号强度，而且适当降低载气He流速（0.6L/min）可以减小相对误差。增加束斑直径虽可以将数据精密度提高10%以上，但是对于准确度影响不大；对于绿柱石这类硬度高的透明矿物应提高能量密度（相对强度＞75%，通量＞2.7J/cm2）以保证产生稳定剥蚀信号。测定7Li时选择现有标准物质中含量较高的GSE-1G校准、9Be选择NIST610校准，以Al作为内标补偿元素，计算结果相对误差较小。LA-ICP-MS方法通过调整仪器工作条件和数据处理方法，可以降低基体差异，提高数据准确度，解决微区原位准确定量分析锂、铍轻元素的难题，为锂、铍资源的勘探开发和高效利用提供有力的技术支撑。但是也亟待开发高锂、铍含量的微区标准物质，解决因现有标准物质与样品中含量差异造成的基体效应来进一步提高数据质量。
Abstract:Lithium and beryllium are the strategic key metals and the minerals such as spodumene and beryl are the main raw materials for extracting lithium and beryllium elements. In order to accurately analyze the minerals by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), the quantitative analytical procedure needs to be improved to reduce the matrix effect caused by non-matrix matching calibration. In the research, a New Wave 193nm ArF excimer laser and an Element Ⅱ high resolution inductively coupled plasma-mass spectrometer were used and the working parameters of the instrument optimized. The analytical results show that Li and Be light elements can quantitatively be determined by the suggested method. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202305310072 .-
Key words:
- LA-ICP-MS /
- lithium mineral /
- beryllium mineral /
- gas flow /
- laser spot size
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表 1 锂辉石和绿柱石样品参考值
Table 1. Reference values of spodumene and beryl samples.
样品 Li2O
（%）BeO
（%）SiO2
（%）Al2O3
（%）数据来源 锂辉石 8.06 − 64.52 27.42 理论值 锂辉石L1 7.89 − 61.54 26.34 Li采用大气压液体阴极辉光放电光谱仪测定；Si、Al采用XRF测定 锂辉石K32 7.92 − 64.15 27.12 中国地质科学院矿产资源所电子探针微束分析实验室提供参考数值 绿柱石 − 13.97 67.04 18.99 理论值 绿柱石B1 − 12.80 63.77 18.12 Be采用碱熔结合ICP-OES测定；Si采用EMPA测定；Al采用XRF测定 绿柱石C12 − 13.85 64.32 18.65 中国地质科学院矿产资源所电子探针微束分析实验室提供参考数值 注：“−”表示无数据，下表同。 
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表 2 典型LA-ICP-MS仪器工作参数
Table 2. The typical operating conditions for LA-ICP-MS.
等离子体质谱系统 激光剥蚀系统 冷却气（Ar）流速 16.25L/min 激光波长 193nm、213nm 辅助气Ar）流速 0.93L/min 能量密度 50%、75%、100% 样品气（Ar）流速 0.7～0.9L/min 激光频率 8Hz RF功率 1300W 载气（He）
流速0.6～0.8L/min 分辨率 300（低分辨率） 束斑直径 30μm、60μm、90μm 检测模式 计数（Counting），
模拟（Analog）
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表 3 He流速对锂辉石和绿柱石化学成分定量分析的影响
Table 3. Effect of He on quantitative analysis of spodumene and beryl chemical composition.
元素
（以氧化物计，%）He气流速
（L/min）锂辉石L1（n=6）激光波长193nm 锂辉石K32（n=10）激光波长213nm 内标法
610 I.S.1σ 归一法
610M.N.1σ 内标法
610 I.S.1σ 归一法
610M.N.1σ Li2O 0.6 7.11 0.72 7.39 0.62 7.90 0.33 7.92 0.28 0.7 7.10 0.27 7.76 0.86 10.34 0.37 9.67 0.38 0.8 7.63 0.28 7.86 0.25 10.20 0.70 9.62 0.63 SiO2 0.6 61.54 − 64.09 1.48 64.15 − 64.28 0.96 0.7 61.54 − 63.99 0.83 64.15 − 61.12 0.96 0.8 61.54 − 63.43 0.41 64.15 − 61.15 0.88 Al2O3 0.6 27.11 1.73 28.20 1.18 27.37 0.13 27.40 0.95 0.7 26.68 0.88 27.90 0.69 29.33 1.41 28.80 0.85 0.8 27.52 0.50 28.36 0.36 29.34 1.41 28.81 0.94 元素
（以氧化物计，%）He气流速
（L/min）绿柱石C12（n=6）激光波长193nm 绿柱石C12（n=8）激光波长213nm 内标法
610 I.S.1σ 归一法
610M.N.1σ 内标法
610 I.S.1σ 归一法
610M.N.1σ BeO 0.6 14.65 0.56 14.86 0.41 14.44 1.21 14.87 1.38 0.7 15.45 0.74 15.35 0.57 15.11 0.44 15.71 0.97 0.8 13.72 0.77 14.06 0.68 21.15 1.67 19.96 3.22 SiO2 0.6 63.77 − 64.76 0.79 63.77 − 62.55 1.32 0.7 63.77 − 63.39 0.75 63.77 − 62.05 1.63 0.8 63.77 − 65.14 0.90 63.77 − 58.93 2.97 Al2O3 0.6 18.84 0.58 19.10 0.64 20.10 0.28 20.57 1.10 0.7 19.07 0.72 19.79 0.41 19.11 0.88 20.27 0.79 0.8 18.69 0.29 19.29 0.38 20.86 1.33 19.24 0.84
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表 4 样品气Ar流速对锂辉石和绿柱石化学成分定量分析的影响
Table 4. Effect of sample gas Ar on quantitative analysis of spodumene and beryl chemical composition.
元素
（以氧化物计，%）Ar气流速
（L/min）锂辉石L1（n=6） 绿柱石B1（n=6） 内标法
610 I.S.1σ 归一法
610M.N.1σ 内标法
610 I.S.1σ 归一法
610M.N.1σ Li2O 0.7 7.59 0.05 7.74 0.12 − − − − 0.8 8.01 0.10 8.20 0.23 − − − − 0.9 7.99 0.32 7.99 0.46 − − − − 0.7 − − − − 13.54 0.17 13.97 0.31 BeO 0.8 − − − − 13.69 0.14 13.91 0.28 0.9 − − − − 13.48 0.14 13.80 0.26 SiO2 0.7 61.54 − 62.83 0.51 63.77 − 65.77 0.73 0.8 61.54 − 62.99 0.39 63.77 − 64.77 0.46 0.9 61.54 − 61.64 1.72 63.77 − 65.29 0.59 Al2O3 0.7 28.57 0.79 29.16 0.58 18.71 0.59 19.29 0.40 0.8 27.64 0.36 28.30 0.24 19.39 0.38 19.69 0.26 0.9 29.83 2.31 29.83 1.38 18.88 0.48 19.33 0.32
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表 5 激光束斑大小对锂辉石和绿柱石化学成分定量分析的影响
Table 5. Effect of spot size on the quantitative analysis of spodumene and beryl chemical composition.
元素
（以氧化物计，%）束斑大小
（μm）锂辉石L1（n=6） 绿柱石B1（n=6） 内标法
610 I.S.1σ 归一法
610M.N.1σ 内标法
610 I.S.1σ 归一法
610M.N.1σ Li2O 30 7.22 0.15 8.43 1.75 − − − − 60 9.72 0.19 9.65 0.40 − − − − 90 8.21 0.15 8.40 0.33 − − − − BeO 30 − − − − 15.32 1.26 15.15 1.02 60 − − − − 12.86 0.13 13.23 0.28 90 − − − − 15.39 0.13 15.53 0.28 SiO2 30 61.54 − 62.78 0.44 63.77 − 63.12 1.04 60 61.54 − 61.08 0.59 63.77 − 65.65 1.02 90 61.54 − 63.02 0.41 63.77 − 64.37 0.37 Al2O3 30 27.94 0.66 28.49 0.49 20.39 0.53 20.17 0.39 60 29.20 0.98 28.97 0.73 19.10 1.26 19.65 1.01 90 27.58 0.64 28.23 0.51 18.33 0.31 18.50 0.25
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表 6 激光能量密度对锂辉石和绿柱石化学成分定量分析的影响
Table 6. Effect of laser fluence on the quantitative analysis of spodumene and beryl chemical composition.
元素
（以氧化物计，%）能量密度
（%）锂辉石K32（n=6） 绿柱石B1（n=6） 内标法
610 I.S.1σ 归一法
610M.N.1σ 内标法
610 I.S.1σ 归一法
610M.N.1σ Li2O 50 7.04 0.20 6.67 0.68 − − − − 75 7.11 0.13 7.02 0.20 − − − − 100 7.14 0.05 7.15 0.14 − − − − BeO 50 − − − − − − − − 75 − − − − 15.71 0.06 15.58 0.13 100 − − − − 13.45 0.15 13.85 0.40 SiO2 50 64.15 − 62.49 3.00 − − − − 75 64.15 − 63.39 0.42 63.77 − 63.21 0.37 100 64.15 − 64.21 0.49 63.77 − 65.67 0.31 Al2O3 50 30.91 3.08 30.42 2.31 − − − − 75 29.52 0.47 29.16 0.28 19.99 0.48 19.81 0.36 100 28.27 0.87 28.29 0.65 18.40 0.34 18.95 0.32
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表 7 不同外部标准物质和内标元素对锂辉石和绿柱石化学成分定量分析的影响
Table 7. Effects of external standards and internal standard element on the quantitative analysis of spodumene and beryl chemical composition.
元素
（以氧化物计，%）外部标准 锂辉石K32（n=6） 绿柱石B1（n=6） 内标法
I.S.相对误差
（%）内标法
I.S.相对误差
（%）Li2O NIST610 8.16 3.03 − − GSE-1G 7.96 0.50 − − CGSG-4 8.38 5.81 − − BeO NIST610 − − 13.45 5.01 GSE-1G − − 17.38 35.78 Al2O3 NIST610 28.27 4.24 18.40 1.65 GSE-1G 27.65 1.96 18.01 0.61 CGSG-4 30.65 13.02 − − 元素
（以氧化物计，%）内标元素 锂辉石K32（n=6） 绿柱石B1（n=6） 内标法
610 I.S.相对误差
（%）归一法
610M.N.相对误差
（%）内标法
610 I.S.相对误差
（%）归一法
610M.N.相对误差
（%）Li2O Si 8.19 3.41 8.11 2.39 − − − − Al 7.88 0.50 8.07 1.89 − − − BeO Si − − − − 13.08 2.19 13.54 5.78 Al − − − − 13.07 2.11 13.53 5.70
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