高效液相色谱-电感耦合等离子体质谱法测定化妆品中的6种砷形态

doi:10.3969/j.issn.2097-2806.2026.07.016

摘要/Abstract

摘要：

为准确评估化妆品中不同砷形态的健康风险，建立了一种高效液相色谱-电感耦合等离子体质谱法（HPLC-ICP-MS）测定化妆品中砷胆碱（AsC）、砷甜菜碱（AsB）、三价砷[As（Ⅲ）]、二甲基砷（DMA）、一甲基砷（MMA）和五价砷[As（Ⅴ）]6种砷形态含量的检测方法。样品经1%硝酸+1%抗坏血酸溶液于80 ℃超声辅助提取，提取液经正己烷脱脂净化后，采用磷酸二氢铵（pH 8.5）为流动相，阴离子交换色谱-梯度洗脱法进行分析。结果表明：6种砷形态化合物在10 min内实现完全分离，在1~100 μg/L质量浓度范围内标准曲线的线性相关系数（r ²）均大于0.996，检出限范围0.9~1.6 μg/kg，定量限范围2.9~5.0 μg/kg，回收率范围86.2%~102.1%，精密度（RSD）范围1.8%~4.3%，日内稳定性1.5%~3.7%，日间稳定性2.1%~4.3%。该方法回收率、精密度、稳定性和准确性良好，适用于化妆品中6种砷形态化合物的同时测定，同时有效填补了《化妆品安全技术规范》（2015年版）关于砷形态项目检测的空白，为进一步建立和完善化妆品标准化体系研究提供了技术支撑。

关键词: 化妆品, 砷形态, 高效液相色谱-电感耦合等离子体质谱法, 检测, 方法

Abstract:

To accurately assess the health risks of different arsenic species in cosmetics, a method was developed using high-performance liquid chromatography-inductively coupled plasma mass spectrometry（HPLC-ICP-MS）for the simultaneous determination of six arsenic species: arsenocholine（AsC）, arsenobetaine（AsB）, arsenite[As（III）], dimethylarsinic acid（DMA）, monomethylarsonic acid（MMA）, and arsenate [As（V）]. The samples were extracted with an ultrasonic-assisted treatment at 80 ℃ by using a 1% nitric acid-1% ascorbic acid solution, followed by the purification with n-hexane for defatting. The analysis was then performed by anion-exchange chromatography with gradient elution, by employing ammonium dihydrogen phosphate（pH 8.5）as the mobile phase. The results showed that the six arsenic species were completely separated within 10 min. The standard curves were linear over the mass concentration range of 1-100 μg/L, with correlation coefficients（r ²）greater than 0.996. The limits of detection ranged from 0.9 to 1.6 μg/kg, and the limits of quantification ranged from 2.9 to 5.0 μg/kg. Recovery rates ranged from 86.2% to 102.1%, with precision（RSD）ranges of 1.8%-4.3%. Intra-day and inter-day stabilities were 1.5%-3.7% and 2.1%-4.3%, respectively. The proposed method exhibits good recovery rate, precision, stability, and accuracy, which is suitable for routine determination of six arsenic species in cosmetics. Moreover, it effectively addresses the current gap in the “Safety and Technical Standards for Cosmetics”（2015 Edition）regarding the arsenic speciation, and provides an essential technical support for the future refinement of cosmetic regulatory standards.

Key words: cosmetics, arsenic species, HPLC-ICP-MS, determination, method

中图分类号:

TQ658

杨亚瑞, 李永盼, 任胜楠, 王琳, 李丹丹, 雒丽丽. 高效液相色谱-电感耦合等离子体质谱法测定化妆品中的6种砷形态[J]. 日用化学工业（中英文）, 2026, 56(7): 968-976.

Yarui Yang, Yongpan Li, Shengnan Ren, Lin Wang, Dandan Li, Lili Luo. Determination of six arsenic species in cosmetics by high-performance liquid chromatography-inductively coupled plasma mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2026, 56(7): 968-976.

图/表 10

参考文献 24

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Time/min	?（Mobile phase A）/ %	?（Mobile phase B）/ %	Flow rate/（mL/min）
0	100	0	1.0
4.0	100	0	1.0
4.1	0	100	1.0
7.0	0	100	1.0
7.1	100	0	1.0
10	100	0	1.0

Operating parameters	Set values	Operating parameters	Set values
radio-frequency coil power/W	1 550	auxiliary gas flow rate/（L/min）	0.8
detector voltage/V	-1 650/+825	coolant gas flow rate/（L/min）	14
nebulizer gas flow rate/（L/min）	1.064	acquisition time/s	600
collision gas flow rate（He）/（mL/min）	4.586	measurement mode	collision mode（KED）

Extraction solution	Recoveries/%
Extraction solution	AsC	AsB	As（Ⅲ）	DMA	MMA	As（Ⅴ）
1% nitric acid + 1% ascorbic acid	85.9-96.2	88.3-93.6	87.2-93.1	86.8-93.8	86.5-89.7	88.7-94.6
nitric acid-simulated gastric fluid	70.5-89.3	65.2-81.3	63.8-79.3	76.2-85.1	62.3-79.5	60.5-90.3
pure water	26.1-63.5	36.5-78.6	65.2-80.6	45.6-90.2	39.5-62.3	42.8-61.5

Extraction method	Recoveries/%
Extraction method	AsC	AsB	As（Ⅲ）	DMA	MMA	As（Ⅴ）
ultrasound with heating	87.2-93.5	88.2-93.1	87.4-92.3	86.9-95.3	86.4-92.8	89.2-97.3
shaking with heating	45.2-82.3	68.3-86.4	72.3-88.6	80.6-91.2	76.1-83.6	75.6-88.2
heating alone	61.2-81.2	62.1-85.7	75.1-84.3	71.2-85.1	59.3-76.4	66.5-85.1

Compound	Linear range/ （μg/L）	Linear equation	Correlation coefficient （r ²）	Limit of detection/ （μg/kg）	Limit of quantification/ （μg/kg）
AsC	1.0-100.0	Y = 6 204.153X+134.265	0.996	1.1	3.5
AsB	1.0-100.0	Y = 8 171.123X+315.128	0.997	1.3	4.1
As（Ⅲ）	1.0-100.0	Y = 7 171.643X+602.198	0.998	1.5	4.6
DMA	1.0-100.0	Y = 6 504.493X+394.281	0.996	1.3	4.1
MMA	1.0-100.0	Y = 5 312.698X+882.960	0.998	0.9	2.9
As（Ⅴ）	1.0-100.0	Y = 3 067.674X+1 318.615	0.999	1.6	5.0