利用激光剥蚀（LA）-ICP-MS快速测定熔融玻璃片的稀土元素含量的方法以及华南木子店岩石样品的应用实例

路志伟; 高世新; 王达

doi:10.3969/j.issn.2097-0013.2025.02.018

利用激光剥蚀（LA）-ICP-MS快速测定熔融玻璃片的稀土元素含量的方法以及华南木子店岩石样品的应用实例

成都理工大学地球与行星科学学院，行星科学国际研究中心，四川成都 610000

详细信息

作者简介: 路志伟（1995—），男，成都理工大学在读研究生，主要从事同位素地球化学方面的研究，E-mail：346465754@qq.com

通讯作者: 王达（1991—），男，研究员，主要从事早期地球和同位素地球化学方面的研究，E-mail：da.wang@cdut.edu.cn

中图分类号: O657；P584

收稿日期: 2025-04-02

修回日期: 2025-04-23

刊出日期: 2025-06-30

Rapid Determination of Rare Earth Element Content in Molten Glass Sheets Using Laser Ablation (LA) - ICP-MS and an Application Example of Rock Samples from Muzidian, South China

Research Center for Planetary Science, School of Earth and Planetary Sciences, Chengdu University of Technology, Chengdu 610000, Sichuan, China

More Information

Corresponding author: WANG Da, da.wang@cdut.edu.cn

Received Date: 02 April 2025

Revised Date: 23 April 2025

Publish Date: 30 June 2025

摘要

摘要:
传统溶液进样SN-ICP-MS技术测定微量元素存在耗时较长、交叉污染风险及难溶矿物是否完全溶解等问题，本文针对XRF（X射线荧光光谱仪）主量元素测试的玻璃片，建立了一种利用193 nm ArF准分子激光剥蚀系统（LA）与ICP-MS联用快速分析样品微量元素丰度的方法。根据硼酸锂熔融玻璃片样品的特点，优化了激光参数，系统比较了选择不同内标元素和不同基质外部参考标准对分析结果的影响。实验结果表明，采用Ca为内标、NIST612为外标的校正策略，可在GSR系列花岗岩、安山岩、玄武岩等8种标样中获得高精度稀土元素数据（相对偏差SD<10%，相对标准偏差RSD<10%）。与前人利用飞秒激光系统的分析结果对比显示，193 nm准分子激光在稀土元素分析中具有相似的可靠性，但在过渡金属元素（如Sc）分析上存在局限性。将该方法应用于华南木子店地区基性-超基性岩样品，其LA-ICP-MS与SN-ICP-MS的稀土数据相对偏差≤12%，验证了方法的实用性。本研究提出的硼酸锂熔融玻璃制备结合准分子激光分析技术，显著简化了前处理流程（样品总用量约0.6 g），规避了酸消解和稀释过程中的交叉污染风险，为开展全岩稀土元素地球化学研究提供了一个高效手段。
- 原位微区 /
- 硅酸盐玻璃 /
- LA-ICP-MS /
- 微量元素 /
- REE
Abstract:
Due to the limits of the conventional solution nebulization SN-ICP-MS method for trace element measurement such as relatively long data-return time, potential risk of contamination, and the difficulty of digesting refractory, this study developed a new method for the trace element measurement of XRF glass bead using a 193 nm ArF laser ablation (LA) system coupled with Q-ICP-MS. Based on the sample matrix of LiBrO₃ glass, we optimized the laser parameters and systematically evaluated the effects of different internal and external standards for data normalization. Our experimental results revealed that the use of Ca as the internal standard and NIST612 as the external standard yielded the best trace element data for eight reference materials of different lithologies including granite, andesite, and basalt (relative deviation <10%, RSD <10%). Compared with the results using femtosecond laser systems, our experiments show similar precision and accuracy for REE data, however, limitations persisted for transitional metals (e.g., Sc). We also presented a case study of mafic rocks in the Muzidian area of the South China Block, our data showed a ≤12% relative deviation between LA-ICP-MS and SN-ICP-MS REE data, which confirmed the utility of this method. In summary, our proposed highly efficient trace element analytical protocol based on the XRF glass bead requires a relatively small amount of sample (approximately 0.6 g, depending on the size of the glass bead). Also avoids the risk of inter-sample contamination during conventional chemical procedures, which yielded comparable quality of whole-rock REE data with the conventional solution-based methods.
- in situ microanalysis /
- Silicate glass /
- LA-ICP-MS /
- trace elements /
- REE

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图 1 不同内标对样品GSR-1测试精度相对偏差（RD）的影响

Figure 1.

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图 2 基质匹配和非基质匹配外标对玄武岩样品GSR-3 分析准确度的影响

Figure 2.

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图 3 稀土元素测试平均值与参考值的相对偏差（RD）（a、b）及稀土元素分析相对标准偏差（RSD）（c、d）

Figure 3.

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表 1 制作的玻璃熔片组成成分

Table 1. Composition of the produced glass melt

称量试剂	称量质量（g）
固体溶剂（45Li₂B₄O₇ + 10LiBO₂ + 5LiF）	6.0000±0.0002
硝酸铵（NH₄NO₃）	0.30±0.001
样品	0.6000±0.0001

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表 2 本次实验激光剥蚀系统和ICP-MS的操作条件

Table 2. Operating conditions for laser denudation systems and ICP-MS in this experiment

激光剥蚀系统（Teledyne Analyte Excite）		ICP-MS （Thermo Scientific）
激光类型	ArF准分子激光	射频功率	1550 W
激光波长	193 nm	冷却气(Ar)流速	14 L min⁻¹
能量密度	5 J/cm²	辅助气(Ar)流速	0.85 L min⁻¹
束斑直径	150 μm	载气(Ar)流速	1 L min⁻¹
频率	20 Hz	采样深度	5.5 mm
剥蚀模式	线扫模式	同位素驻留时间	10 ms
激光移动速度	10 μm/s	检测器模式	Dual
Cup gas (He)	0.3 L/min
Cell gas (He)	0.35 L/min

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表 3 木子店样品熔融玻璃主量元素XRF测定结果（%）

Table 3. Results of XRF determination of the main element of molten glass from Muzidian samples (mass %)

样品号	岩性	SiO₂	TiO₂	Al₂O₃	TFe₂O₃	MnO	MgO	CaO	Na₂O	K₂O	P₂O₅	烧失量	总量
M2-14	基性斜长角闪岩	46.68	3.748	13.14	17.31	0.28	5.26	8.47	2.90	1.176	0.380	0.20	99.55
M2-68	基性斜长角闪岩	47.42	0.618	8.43	13.12	0.21	16.13	9.03	0.98	1.994	0.169	1.33	99.42
M2-75	超基性岩	44.87	0.415	9.00	10.29	0.14	20.83	5.64	0.45	4.831	0.191	1.82	98.48

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表 4 采用本研究建立的方法和 SN-ICP-MS法测试的木子店样品稀土元素组成（×10⁻⁶）

Table 4. REE composition of Muzidian samples measured by the method established in this study and SN-ICP-MS method (×10⁻⁶)

元素	M2-14				M2-68				M2-75
元素	LA-ICP-MS法	SN-ICP-MS法	相对偏差RD(%)	偏差允许限Y_C(%)	LA-ICP-MS法	SN-ICP-MS法	相对偏差RD(%)	偏差允许限Y_C(%)	LA-ICP-MS法	SN-ICP-MS法	相对偏差RD(%)	偏差允许限Y_C(%)
Sc	33.93	35.82	5.28	21.81	26.19	26.32	0.47	22.79	24.70	24.36	−1.42	23.01
Y	54.01	52.37	−3.13	20.13	15.30	14.76	−3.63	24.93	10.86	11.27	3.57	26.37
La	33.24	34.63	4.02	21.89	20.45	21.14	3.28	23.76	10.75	11.24	4.37	26.41
Ce	77.56	83.88	7.53	18.89	44.88	44.55	−0.74	20.79	24.07	26.16	7.98	23.28
Pr	10.73	12.25	12.35	26.42	5.10	5.56	8.14	29.77	3.27	3.37	2.95	31.93
Nd	48.99	49.02	0.05	20.47	22.35	22.35	0.01	23.4	14.20	14.20	0.02	25.24
Sm	11.73	11.65	−0.63	26.04	4.29	4.26	−0.69	30.6	2.93	2.96	0.95	32.49
Eu	3.11	3.18	2.30	32.19	1.15	1.21	4.85	37.51	0.65	0.65	0.03	40.95
Gd	11.37	11.21	−1.37	26.17	3.70	3.62	−2.18	31.33	2.53	2.53	0.00	33.25
Tb	1.76	1.77	0.41	35.16	0.50	0.52	3.85	42.52	0.32	0.36	10.78	45.37
Dy	10.95	10.67	−2.63	26.33	3.03	3.03	0.01	32.32	2.05	2.15	4.49	34.34
Ho	2.23	2.04	−9.56	33.89	0.61	0.56	−8.21	41.3	0.42	0.42	0.14	43.68
Er	6.20	5.60	10.79	28.86	1.66	1.53	−8.22	35.48	1.18	1.14	−3.13	37.38
Tm	0.85	0.79	−6.95	39.29	0.21	0.21	−1.25	48.27	0.15	0.15	1.28	50.64
Yb	5.69	5.16	10.23	29.27	1.50	1.34	11.68	36.03	1.09	1.04	−4.77	37.85
Lu	0.83	0.76	−9.25	39.40	0.21	0.20	−5.77	48.36	0.15	0.16	6.91	50.73

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