ICP-MS/MS法测定儿童彩妆类化妆品中的7种元素

doi:10.3969/j.issn.2097-2806.2025.01.012

摘要/Abstract

摘要：

建立了电感耦合等离子体串联质谱法（ICP-MS/MS）测定儿童彩妆类化妆品中7种元素的含量测定方法。样品经硝酸-氢氟酸的消解酸体系破坏、超级微波消解法进行消解，采用ICP-MS/MS法同时测定儿童彩妆类化妆品中硼（B）、钛（Ti）、锗（Ge）、钼（Mo）、锡（Sn）、锑（Sb）、碲（Te）7种元素的含量，选用铑（Rh）作为内标。分别以霜类、粉类、口红类为基质进行方法学考察，结果表明，所测元素在各自质量浓度范围内线性关系良好，相关系数均大于0.996 7。在2个加标水平下，三种基质的平均回收率范围分别为81.1%~104.6%、84.0%~116.0%、80.8%~113.1%，RSD分别为2.2%~7.5%、0.5%~7.1%、0.8%~7.3%。该方法采用硝酸-氢氟酸体系、超级微波消解法进行样品前处理，应用ICP-MS/MS技术对儿童彩妆类化妆品中元素进行含量测定，解决了不同类型样品尤其是组成复杂、基质干扰大的彩妆类样品在元素检测中的难题，为各类化妆品的样品前处理和元素分析提供了新思路，填补了现有法定标准中尚未建立的7种元素检测方法的空白。

关键词: 电感耦合等离子体串联质谱法（ICP-MS/MS）, 超级微波消解, 氢氟酸, 儿童彩妆, 元素分析

Abstract:

A method for the determination of 7 elements in children’s makeup by inductively coupled plasma tandem mass spectrometry （ICP-MS/MS） was established. The sample was destroyed by a digestion acid system of nitric acid-hydrofluoric acid and digested by a super microwave digestion method. ICP-MS/MS was used to simultaneously determine the contents of 7 elements in children’s cosmetics, including boron （B）, titanium （Ti）, germanium （Ge）, molybdenum （Mo）, tin （Sn）, antimony （Sb）, and tellurium （Te）. Rhodium （Rh） was selected as the internal standard and an internal standard method was used for quantitative analysis. Methodological studies were conducted using cream-based, powder-based and lipstick-based cosmetic as matrices. The results show that 7 elements have good linear relationship within their respective mass concentration ranges, with correlation coefficients greater than 0.996 7. At the two spiked levels, the average recoveries in three matrices are 81.1%-104.6%, 84.0%-116.0%, and 80.8%-113.1%, respectively, and the average relative standard deviations are 2.2%-7.5%, 0.5%-7.1%, and 0.8%-7.3%, respectively. This method uses a digestion acid system of nitric acid-hydrofluoric acid and a super microwave digestion method for sample pretreatment. And ICP-MS/MS technology is applied to determine the contents of elements in children’s cosmetics, solving the problem of element detection in different types of samples, especially those with complex composition and large matrix interference. It provides new ideas for sample pretreatment and element analysis of various cosmetics, filling the gap of 7 elements detection methods that have not yet been established in the existing legal standards.

Key words: ICP-MS/MS, super microwave digestion, hydrofluoric acid, children’s makeup, elemental analysis

中图分类号:

TQ658

吴莉, 庞庆林, 张妤琳, 耿悦, 陈民辉. ICP-MS/MS法测定儿童彩妆类化妆品中的7种元素[J]. 日用化学工业（中英文）, 2025, 55(1): 98-103.

Li Wu, Qinglin Pang, Yulin Zhang, Yue Geng, Minhui Chen. Determination of 7 elements in children’s makeup by ICP-MS/MS[J]. China Surfactant Detergent & Cosmetics, 2025, 55(1): 98-103.

图/表 5

表 1

表 2

表 3

表 4

表 5

参考文献 19

[1]	Luo Feiya, Su Zhe, Huang Xianglu, et al. The research progress of next generation risk assessment in safety evaluation of cosmetic ingredients[J]. China Surfactant Detergent & Cosmetics, 2023, 53 (1) :79-85.
[2]	Xiao Shuxiong, Zhou Zhiming, Liang Zhuye, et al. Safety problems of plant-derived cosmetic raw materials and relevant regulatory countermeasures[J]. China Food & Drug Administration Magazine, 2021 (1) : 42-47.
[3]	Yang Keyu, Tian Shaolei, Dong Jiangping, et al. Discussion on safety risks and inspection emphases of children’s cosmetics[J]. China Food & Drug Administration Magazine, 2023 (1) : 68-73.
[4]	Li Silong, Xu Weihong. Protecting the quality and safety of children’s cosmetics[J]. Legal System and Society, 2023 (3) : 44-46.
[5]	Gao Yuting, Cai Fei. Research progress on central neurotoxicity mechanism and prevention of trimethyltin chloride[J]. Chinese Pharmacological Bulletin, 2023, 39 (3) : 414-419.
[6]	Wang Yuting, Wu Hongye, Zeng Ming. Overview of toxic effect and clinical application of antimony compounds[J]. Chinese Journal of Pharmacology and Toxicology, 2018, 32 (12) : 979-986.
[7]	Chen Hongping, Cao Songle, Huang Ying, et al. Research progress on the toxic effects of heavy metal antimony on animals and humans[J]. Journal of Hunan University of Science and Engineering, 2023, 44 (3) : 18-22.
[8]	Wang Jinkun, Cao Jingjing, Zhang Yongchang. Advance in research on adverse effect of antimony on human health[J]. Occupational Health and Emergency Rescue, 2019, 37 (6) : 601-604.
[9]	Hu Liping, Lv Jing, Peng Kailiang, et al. Research progress on the toxicity of tellurium and its compounds[J]. Journal of Health Toxicology, 2002, 16 (2) : 120-123.
[10]	Wang Jian, Du Hongfeng, Gao Zhiqiang, et al. Synchronizing determination of tin and mercury in food, water, cosmetics and organisms sample by atomic fluorescence spectrometry[J]. Chinese Journal of Health Laboratory Technology, 2008, 18 (7) : 1249-1251, 1268.
[11]	Zhou Xia, Wang Yanhua, Jiang Xinjie, et al. Simultaneous determination of arsenic, antimony, lead and mercury in cosmetics by microwave digestion-atomic fluorescence spectrometry[J]. China Surfactant Detergent & Cosmetics, 2019, 49 (11) : 764-768.
[12]	Zhu Li, Liu Mingli, Yin Lihu, et al. Rapid detection of Pb, Hg, As, Sb in cosmetics by X-ray fluorescence elemental technology[J]. Chinese Journal of Pharmaceutical Analysis, 2014, 34 (10) : 1842-1846.
[13]	He Shuang, Xun Zhiqing, Lin Yiyun, et al. Determination of total content of tin in cosmetics by super microwave digestion coupled with ICP-MS[J]. Flavour Fragrance Cosmetics, 2017 (6) : 39-42.
[14]	Sun Xiuping, Gao Chaoyong, Zhang Yulomg, et al. Study on digestion methods for determination of rare-earth elements in soil by ICP-MS[J]. Chemical Research and Application, 2021, 33 (7) : 1403-1409.
[15]	Gu Yuxiang, Xu Hongbing, Ge Yu, et al. Study on the effect of methods of digestion of cosmetic samples on their results of determination of antimony, cadmium, chromium and neodymium by ICP-AES[J]. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2010, 46 (9) : 1031-1033.
[16]	Wang Fengrong, Liu Fangmei, Zhang Yuelin, et al. The optimization analysis of silicon dioxide detection by hydrofluoric acid method[J]. World Nonferrous Metals, 2020 (20) : 123-125.
[17]	Wang Jiansen, Xi Gaiqing. Improvement of hydrofluoric acid volatilization method for determining silica dioxide in quartz[J]. Hebei Chemical Industry, 2005 (1) : 62-63.
[18]	Tu Guorong, Wang Wushang, Zhang Lixing, et al. Application of nanometer titanium dioxide and composite natural ultraviolet absorbents in sun screening cosmetics[J]. Fine Chemicals, 2001, 18 (7) : 379-381.
[19]	Wu Mingyue, Li Kejian, Ma Yilong, et al. Application of nano TiO, ZnO in cosmetics sunscreen field[J]. Guangdong Chemical Industry, 2021, 48 (5) : 69-74.

元素	霜类回收率/%		粉类回收率/%		口红类回收率/%
元素	2 mL HNO₃	1.5 mL HNO₃- 0.5 mL HF	2 mL HNO₃	1.5 mL HNO₃- 0.5 mL HF	2 mL HNO₃	1.5 mL HNO₃- 0.5 mL HF
B	89.3	92.3	143.6	79.0	148.3	99.3
Ti	148.0	105.8	92.3	89.5	65.6	113.1
Ge	75.3	95.2	24.7	98.9	66.0	89.4
Mo	6.3	102.4	22.1	98.4	42.1	99.9
Sn	-11.4	111.0	12.1	112.9	9.1	88.1
Sb	0.0	93.9	0.1	103.4	0.6	87.3
Te	16.5	90.2	34.3	96.3	77.3	104.1

模式	霜类回收率/%	霜类RSD/%	粉类回收率/%	粉类RSD/%	口红类回收率/%	口红类RSD/%
47 Ti [No Gas]	70.5	12.4	82.3	7.1	90.0	14.0
47 Ti [He]	107.1	3.5	88.0	6.7	88.0	2.2
47→47 Ti [H₂]	108.9	5.4	91.0	5.8	105.8	2.1
47→47 Ti [NH₃]	109.9	10.9	99.6	8.4	71.4	10.0
47→63 Ti [O₂]	105.8	2.0	100.4	4.9	105.3	2.4

编码	元素种类	线性方程	相关系数（r）	线性范围/（μg/L）	检出限/（mg/kg）	定量限/（mg/kg）
1	B	y=2.16×10^-4x-4.09×10^-5	0.999 9	2~100	0.12	0.40
		y=1.91×10^-4x-8.89×10^-6	0.999 4	50~5 000	1.2	3.9
2	Ti	y=2.45×10^-2x+8.94×10^-4	0.996 7	50~5 000	0.089	0.30
3	Ge	y=4.17×10^-4x-5.08×10^-7	1.000 0	1~100	0.001 5	0.005 0
4	Mo	y=1.60×10^-3x+5.38×10^-7	0.999 8	1~100	0.006 5	0.022
5	Sn	y=1.30×10^-3x+2.00×10^-6	0.999 8	1~100	0.011	0.037
6	Sb	y=1.50×10^-3x-1.03×10^-6	0.999 7	1~100	0.002 9	0.009 7
7	Te	y=2.50×10^-5x	0.999 6	1~100	0.002 7	0.009 0

编号	元素	霜类/（mg/kg）	粉类/（mg/kg）	口红类/（mg/kg）
1	B	0.73~17 009	<3.9~20 038	<0.40~4.1
2	Ti	6 890~101 270	103~140 998	<0.30~17 814
3	Ge	<0.005 0~0.31	0.21~2.1	<0.005 0~0.47
4	Mo	<0.022~0.74	<0.022~6.1	<0.022~0.36
5	Sn	<0.037~46	0.090~6 210	<0.037~131
6	Sb	<0.009 7~0.96	<0.009 7~7.7	<0.009 7~1.1
7	Te	<0.009 0~0.021	<0.009 0~0.90	<0.009 0