气相色谱-质谱法测定化妆品中苯甲酸酯类和对羟基苯甲酸酯类16种防腐剂

doi:10.3969/j.issn.1001-1803.2023.02.016

Abstract

Abstract:

A method for the determination of benzoate and paraben preservatives in cosmetics by gas chromatography-mass spectrometry （GC-MS） was established. The sample was extracted by saturated sodium chloride and ethyl acetate, then the supernatant was fixed to volume with acetonitrile after centrifugation. The extracted solution was separated by the chromatographic column of HP-5ms （30 m×250 μm×0.25 μm）. The determination was carried out under the mode of selected ion monitoring （SIM） and the external standard method was used for quantitative determination. All the 16 preservatives show good linearity in the corresponding range, the LOD and LOQ of benzoates are 0.3 μg/g and 1 μg/g, respectively, and the LOD and LOQ of parabens are 0.6 μg/g and 2 μg/g, respectively. Three types of cosmetics are selected to verify the accuracy and precision of the method at two levels. The average spiked recoveries of the 16 preservatives are 85.4%-113.8%, and the corresponding relative standard deviations （RSDs, n=6） ≤10.9%. The use frequency of methylparaben and propylparaben in 50 baby cosmetics are 50% and 36%, respectively, and the maximum contents are lower than the limit of relevant requirements.

Key words: cosmetics, gas chromatography-mass spectrometry （GC-MS）, benzoate, paraben, preservatives

CLC Number:

TQ658

Lü Wen, Zhang Jingya, Hu Bei, Liu Hong, Huang Wei. Determination of 16 preservatives of benzoates and parabens in cosmetics by GC-MS[J].China Surfactant Detergent & Cosmetics, 2023, 53(2): 239-244.

Figures/Tables 7

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References 16

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编号	化合物	CAS	保留时间/min	定量离子/（m/z）	定性离子/ （m/z）
1	MB	93-58-3	6.459	105	77，51，136
2	EB	93-89-0	7.239	105	77，51，122
3	IPB	939-48-0	7.588	105	77，51，123
4	PB	2315-68-6	8.258	105	77，51，123
5	IBB	120-50-3	8.930	105	77，51，123
6	BB	136-60-7	9.558	105	77，51，123
7	PHB	93-99-2	13.779	105	77，51，65
8	MP	99-76-3	10.790	121	65，152，93
9	EP	120-47-8	12.188	121	65，138，93
10	IPP	4191-73-5	12.631	121	65，138，93
11	PP	94-13-3	13.391	121	65，138，93
12	IBP	4247-02-3	13.902	121	65，138，93
13	BP	94-26-8	14.230	121	65，138，93
14	AP	6521-29-5	14.866	121	65，138，93
15	PHP	17696-62-7	15.894	121	65，214，93
16	BEP	94-18-8	16.278	121	65，228，91

化合物	线性范围/（μg/mL）	线性方程	相关系数	LOD/ （μg/g）	LOQ/ （μg/g）
MB	0.05~25	y=1 234.49x+196.13	0.999 7	0.3	1
EB		y=1 055.69x+41.62	1.000 0
IPB		y=1 180.95x+75.32	0.999 2
PB		y=1 217.37x-183.72	0.999 2
IBB		y=1 170.20x-132.60	0.999 8
BB		y=1 048.99x-132.32	0.999 7
PHB		y=1 447.59x-58.09	0.998 7
MP	0.1~50	y=506.50x-283.44	0.998 7	0.6	2
EP		y=544.14x-224.71	0.999 2
IPP		y=513.16x-240.96	0.999 2
PP		y=528.90x-236.30	0.998 7
IBP		y=636.78x-231.83	0.999 1
BP		y=492.80x-276.60	0.999 5
AP		y=470.39x-239.25	0.998 9
PHP		y=221.09x-99.38	0.998 3
BEP		y=154.70x-72.88	0.999 0

化合物	加标量/（μg/g）	霜		乳		水
化合物	加标量/（μg/g）	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
MB	20	104.8	5.4	87.6	0.3	102.6	1.4
MB	200	100.8	0.9	104.1	4.2	89.5	6.6
EB	20	111.1	9.2	92.8	1.5	100.8	1.1
EB	200	105.8	4.6	109.7	3.0	93.9	6.1
IPB	20	106.6	9.0	90.9	0.7	92.2	4.8
IPB	200	105.2	0.5	108.0	3.1	93.8	7.3
PB	20	112.1	7.0	91.5	1.9	95.9	6.0
PB	200	107.4	2.5	111.6	3.5	93.2	6.7
IBB	20	110.6	9.6	94.7	1.6	94.1	6.7
IBB	200	103.9	3.3	107.1	3.6	93.0	7.1
BB	20	113.5	10.8	94.5	1.5	95.6	8.2
BB	200	103.5	2.7	105.3	3.0	91.8	6.8
PHB	20	102.0	9.1	91.5	5.7	86.0	8.4
PHB	200	95.1	5.4	86.0	4.0	90.1	3.9
MP	40	103.9	10.3	103.9	4.0	85.4	3.5
MP	400	113.8	5.8	104.9	3.1	105.9	4.7
EP	40	106.4	9.0	108.7	3.2	96.6	2.9
EP	400	109.9	5.1	105.1	4.4	101.9	7.8
IPP	40	104.1	10.5	100.2	4.9	108.6	4.9
IPP	400	101.5	3.6	108.8	5.9	93.5	9.9
PP	40	107.4	10.4	109.8	7.1	103.5	5.6
PP	400	93.6	3.9	98.8	3.3	100.4	9.7
IBP	40	98.0	10.2	99.3	5.7	101.1	2.4
IBP	400	92.1	5.1	92.1	3.1	92.3	7.2
BP	40	101.4	10.0	99.2	3.2	89.8	7.8
BP	400	96.5	6.5	96.4	5.7	93.2	8.6
AP	40	100.2	10.8	106.3	3.9	86.9	4.5
AP	400	102.1	10.1	103.1	4.7	94.8	8.8
PHP	40	100.7	9.0	105.0	6.2	85.7	8.2
PHP	400	101.7	9.2	103.1	3.8	104.8	8.5
BEP	40	98.5	10.9	100.8	3.7	95.9	4.9
BEP	400	108.7	1.4	109.3	4.0	93.4	8.9

化合物	检出率/%	平均含量/%	最大含量/%	限度/%
MP	50	0.13	0.22	0.4
EP	4	0.03	0.05	0.4
PP	36	0.06	0.11	0.14
BP	4	0.02	0.04	0.14

Determination of 16 preservatives of benzoates and parabens in cosmetics by GC-MS

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