基于LA-ICP-MS的软质样品定量分析研究进展

高天恒; 任同祥; 王松

doi:10.12338/j.issn.2096-9015.2022.0269

基于LA-ICP-MS的软质样品定量分析研究进展

doi: 10.12338/j.issn.2096-9015.2022.0269

中国计量科学研究院，北京 100029

基金项目: 中国计量科学研究院基本科研业务费重点领域项目（21-AKYZD2006-3）。

详细信息

作者简介:
高天恒（1998-），中国计量科学研究院在读硕士，研究方向：激光剥蚀等，邮箱：gaoth@nim.ac.cn

通讯作者:
任同祥（1980-），中国计量科学研究院研究员，研究方向：元素及同位素分析，邮箱：rentx@nim.ac.cn

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出版历程
- 网络出版日期: 2023-02-04
- 刊出日期: 2023-01-18

Research Progress in Quantitative Analysis of Soft Samples Based on LA-ICP-MS

National Institute of Metrology, Beijing 100029, China

摘要

摘要: 激光剥蚀电感耦合等离子体质谱法（LA-ICP-MS）在近年来引起诸多关注，因为其能在准无损的条件下直接对固体样品分析，并且获得一定空间分辨率的原位元素浓度信息。然而由于元素分馏以及复杂的基质效应，LA-ICP-MS对于软质样品的定量分析仍具有挑战性。如要获得可靠可比的结果，相应的测量方案不仅需要使用经过验证的方法，还应建立基于标准物质的正确校正方法，从而实现测量结果的溯源性。本文通过分析2000年以来国内外研究团队发表的相关文献，介绍了LA-ICP-MS在三类不同软质样品测量中的常见测量策略，在此基础上通过汇总五个方面验证参数的情况，从方法精度、准确度、代表性三方面分析了定量方法的现状，并说明方法溯源性方面存在的问题。结果显示，基质匹配且同步测量的定量策略更有优势，另外受制于缺少完全基质匹配的CRM，领域内对于取样代表性及测量结果溯源性的研究并不充分。因此这两方面的相关内容，将会是未来利用LA-ICP-MS开展软质样品定量分析方法研究时需要重点解决的问题。国内在软质标准物质的合成方法和利用同位素稀释法实现测量结果溯源性等方面开展了一些研究，但依然有一系列问题尚待解决。
- 软质样品 /
- LA-ICP-MS /
- 校正策略 /
- 测量 /
- 方法验证 /
- 溯源性
Abstract: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has gained significant attention in recent years due to its capability to directly analyze solid samples under quasi-nondestructive conditions, and to provide in-situ elemental concentration information with a certain spatial resolution. However, quantitative analysis of soft samples by LA-ICP-MS remains a challenge due to elemental fractionation and complex matrix effects. To obtain reliable and comparable results, the corresponding measurement protocol not only requires the use of verified methods, but also the establishment of correct calibration methods based on standards, thus enabling the traceability of measurement results. This paper reviews relevant literature published by domestic and foreign research teams since 2000, and introduces the common measurement strategies of LA-ICP-MS for three different types of soft samples. By summarizing the verification parameters of the five methods, the current situation of quantitative methods is analyzed from three aspects: method precision, accuracy, and representativeness. The paper also highlights the problem of method traceability. The results show that the quantification strategy that matches the matrix and is synchronized with the measurement is more advantageous. However, the lack of a fully matrix-matched certified reference material (CRM) limits the research on sampling representativeness and traceability of measurement results. Therefore, these two aspects will be the key problems to be addressed in the future when using LA-ICP-MS to carry out quantitative analysis methods of soft samples. Although some researchers have conducted studies on the synthesis method of soft standard and the traceability of measurement results by isotope dilution method, there are still several issues that need to be resolved.
- soft sample /
- LA-ICP-MS /
- calibration strategy /
- measurement /
- method verification /
- traceability

HTML全文

图 1 软质样品的常见定量策略及5个评价参数

Figure 1. Common quantification strategies for soft samples and five evaluation parameters

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图 2 使用n个验证参数开展方法评价的文章的占比情况

Figure 2. The proportion of articles using n validation parameters for method evaluation

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图 3 软质样品LA测量中RSD与R²的常见范围

Figure 3. Common ranges of RSD and R² in LA measurement of soft samples

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图 4 具有SI溯源性新方法原理示意图^[62]

Figure 4. Schematic diagram of the new method with traceability to the International System of Units (SI)

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表 1 三类软质样品的定量分析方法研究

Table 1. Research on quantitative analysis methods of three types of soft samples

序号	标准物质及样品^a	关注元素^b	仪器^c	定量分析要素^d	溯源性^e	校正方法	引文
1	1.BCRCRM680 聚烯烃薄膜	Ti、Cr、Cu、Br、Sr、Cd、Ba、Pb （C）	LA-ICP-QMS（Thermo Elemental Plasma Quad 3&New Wave Research LUV, 266 nm）	4.最小取样量m_min，5%=50 µg ~ 20 mg 5.XRF	1.样品为CRM	内标及分馏系数归一化	[23]
2	1.聚碳酸酯、聚乙烯	Pb、Cd、Hg （C）	LA-ICP-QMS（Perkin-Elmer ELAN 6000 ICP-MS &Microprobe laser ablation unit, 266 nm）	4.最小取样量m_min，5%=4 ~ 4000 mg 5.XRF		归一化至C内标	[24]
3	1.BAM-010H	Br、Pb、Cd、Cr （C）	LA-ICP-QMS（PerkinElmer Elan DRCII&Cetac-LSX213, 213 nm）	1. R²=0.9954 ~ 0.9995 2.RSD=8.9% ~ 20.3%	1.样品为CRM	归一化至C内标	[25]
4	1.EC681k、聚合物废料	Al、Si、Ca、Ti、Fe、Ba、As、Cd、Sb、Hg、Pb （Zn）	LA-ICP-QMS（Agilent 7500cs &Lambda Physics Compex, 193 nm）	2. RSD>20% 3.差异值平均为53% 5.XRF、湿化学法	1.NIST610、ERM681k外标	归一化至Zn内标	[7]
5	1.聚乙烯、聚丙烯、聚甲基丙烯酸酯 ERM680k、681k	As、Ba、Cd、Cr、Pb、Sr、Zn （C）	LA-ICP-QMS（Perkin Elmer ELAN DRC II & Cetac LSX-266, 266 nm）	1.R²=0.982 ~ 0.991(除Zn) 2.RSD=5% ~ 10%（Cr、Sr、Pb在1 μg∙g^-1级） 5.湿化学法	1.ERM680k、681k方法验证	归一化至C内标、干液滴外标	[15]
6	1.聚丙烯、聚乙烯 BCRCRM680、680k	Al、Ca、Mg、Ti、Zn、Si、As、Br、Cd、Cr、Hg、Pb、Sb （Sc、Y）	LA-ICP-QMS（7700X Agilent ICP-MS&Cetac LSX-213 G2+, 213 nm）	2.RSD=2.9% ~ 10.4% 5.湿化学法	1.ERM680k、681k方法验证	归一化至（Sc、Y）	[26]
7	1&2.聚甲基丙烯酸酯、聚酰亚胺、聚乙烯吡咯烷酮	Co、In、Pt	LA-ICP-QMS/LIBS（ThermoFisher Scientific iCAP& Applied Spectra J200, 266 nm）	2.通常RSD=5% 3.平均偏差4.4%	—	主成分回归校正	[27]
8	1.聚乙烯、聚丙烯、ABS、聚氯乙烯、聚酯	Br、Pb、Cd、Cr、Hg （C）	fsLA-ICP-MS (7700X Agilent ICP-MS&Fab Instruments N-Stage, 266 nm)	2.RSD=1.5% ~ 30% 3.偏差在30%以内	1.样品为CRM	内标校正	[28]
9	2.共混聚合物薄膜	Fe、Zn、Rb、Y、Au （C、Co、Cu）	LA-ICP-QMS (7500cs Agilent ICP-MS&Kenelec Technologies New Wave UP213, 213 nm)	2.RSD=0.84% ~ 4.30% 3.偏差-30% ~ +25%	—	内标校正	[20]
10	1.BAM-H010 2.共混聚合物薄膜	Pb （Bi）	LA-ICP-QMS (XSERIES 2 Thermo Scientific ICP-MS&Kenelec Technologies New Wave UP213, 213 nm)	2.线间RSD<3% 3.量值一致	1.BAM-H010方法验证 2.同位素稀释法	内标校正	[29]
11	2.明胶	As、Gd	LA-ICP-QMS (7900X Agilent ICP-MS &Teledyne Analyte G2, 193 nm)	4.5 μm光斑下RSD<2.2%	—		[30]
12	2.琼脂糖	B、Na、Mg、P、S、K、Ca、Cr、Mn、Fe、Ni、Cu、Zn、As、Rb、Sr、Cd、Ba、Pb （C）	LA-ICP-QMS （7700X Agilent ICP-MS&Coherent GeoLas , 193 nm）	1.R²>0.991 2.RSD<10% 3.平均相对误差小于10%	1.CRM方法验证	内标校正	[31]
13	2.聚甲基丙烯酸 2-羟乙酯薄片、载玻片	Li、Co、Rb、La、Tl	LA-ICP-QMS （7700X Agilent ICP-MS&ESI NWR193, 193 nm ArF）	1.R²>0.99 2.RSD=5.5% ~ 8.1% 3.偏差小于3.8% 5.湿化学法	—	干液滴外标	[16]
14	3.大脑切片	P、S、Fe、Cu、Zn (U、Th)	LA-HR-ICP-MS （ELEMENT Thermo HR-ICP-MS&（未注明厂家Nd:YAG 213 nm））	1.R²=0.9995 2.RSD=2% ~ 3% 3.准确度2% ~ 3%	—	内标校正、匀浆添加外标	[32]
15	3.大脑切片	Zn、Cu、Pb	LA-HR-ICP-MS （ELEMENT Thermo HR-ICP-MS&CETAC LSX 200, 266 nm）	1.R²>0.994	—	匀浆添加外标	[33]
16	3.大脑切片	P、Fe （C）	LA-ICP-QMS （8800Agilent ICP-MS&NewWave NWR213, 213 nm）	1.R²=0.9849（Fe）	—	内标校正、匀浆添加外标	[34]
17	3.大鼠肝脏	Fe、Cu	LA-ICP-QMS （iCAP Qc Thermo ICP-MS&CETAC LSX-213 G2⁺, 213 nm）	1.R²>0.995 2.RSD<7.1%	—	明胶外标	[35]
18	3.肝脏	Fe、Cu、Zn	LA-ICP-QMS （iCAP Qc Thermo ICP-MS&CETAC LSX-213 G2⁺, 213 nm）	1.R²=0.995-0.999 2.RSD=5.1%-9.8%	—	明胶外标	[36]
19	3.大鼠肾脏	U	LA-ICP-QMS （iCAP Q Thermo ICP-MS&CETAC Analyte Excite, 193 nm）	1.R²=0.993 2.RSD=5% ~ 25% 5.溶液同位素稀释法	2.溶液法通过同位素稀释溯源至SI	明胶内标、匀浆外标	[37]
20	3.小鼠脑	Fe、Cu、Zn （C）	LA-ICP-QMS （7700X Agilent ICP-MS &CETAC LSX-213, 213 nm）	2.RSD<8.9% 5.μ-XRF、ID-MS	2.稀释法溯源至SI	归一化至C、液滴ID	[38]
21	3.羊脑	Fe （Rh）	LA-HR-ICP-MS （ELEMENT 2 Thermo HR-ICP-MS&（ESI NWR213, 213 nm））	1. R²=0.9978 2.RSD=15%	2.在线加标稀释法溯源至SI	归一化至Rh、在线双稀释	[39]
注：a:1代表传统聚合物；2代表人工合成的软质标准物质；3代表生物软质样品。b: 括号内为内标。c: 括号内为仪器型号。d: 包括1.线性相关系数R²；2.相对标准偏差RSD；3.系统误差；4.取样代表性；5.方法验证。e：“-”为文章中缺失内容。

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