气相色谱-三重四极杆质谱法测定染发剂中14种N-亚硝胺类化合物

doi:10.3969/j.issn.2097-2806.2023.11.013

摘要/Abstract

摘要：

建立了气相色谱-三重四极杆质谱法测定染发剂中N-亚硝基乙基异丙胺等14种N-亚硝胺类化合物含量的方法。样品采用QuEChERS法前处理，经聚乙二醇石英毛细管柱HP-INNOWAX（30 m×0.25 mm×0.25 μm）程序升温分离，在多反应监测（MRM）模式下分析，含量计算为外标法。结果表明，14种亚硝胺在5~100 μg/L范围内线性关系良好（r>0.998），检出限和定量下限分别为0.2~1.5 μg/L和0.6~5 μg/L。在25，50，100 μg/kg加标水平下，染发剂基质的平均回收率为83.8%~122.8%，相对标准偏差（RSD）小于11%（n=6）。采用该方法测定市售染发产品，结果发现1批样品中含有N-甲基-N-亚硝基苯胺，含量为31 μg/kg。该方法前处理简单高效，专属性强，灵敏度高，准确性好，可用于染发剂中14种亚硝胺的筛查和含量测定。

关键词: 气相色谱-三重四极杆质谱法, 染发剂, N-亚硝胺类化合物

Abstract:

A gas chromatography-tandem mass spectrometry （GC-MS/MS） method was established for the simultaneous detection of 14 N-nitrosamines （N-nitrosodimethylamine, N-nitrosoethylmethylamine, N-nitrosodiethylamine, N-nitrosoethylisopropylamine, N-nitrosodiisopropylamine, N-nitrosoethylpropylamine, N-nitrosodipropylamine, N-nitrosodibutylamine, N-nitrosomethylaniline, nitrosoethylphenylamin, N-nitrosopiperidine, N-nitrosopyrrolidine, N-nitrosomorpholine, N-nitrosodiphenylamine） in hair dyes. Pretreating based on QuEChERS method, the analytes were separated by polyethylene glycol quartz capillary gas chromatographic column HP-INNOWAX （30 m×0.25 mm×0.25 µm） following the GC temperature program. Mass spectrometric ionization was undertaken in electron impact （EI） ionization mode, and the MS detector was operated in multiple reaction monitoring （MRM） mode including quantitative ion pair and qualitative ion pair for all analytes. The correlation coefficients of the standard calibration curves are greater than 0.998 in the range of 5-100 μg/L. The limits of detection are 0.2-1.5 µg/L, and the limits of quantification are 0.6-5 µg/L, respectively. The average recoveries of 14 N-nitrosamines range from 83.8% to 122.8% at the spiked levels of 25, 50 and 100 µg/kg, with the relative standard deviations （RSDs） less than 11% （n=6）. N-nitroso-n-methylaniline is detected at the level of 31 µg/kg in one hair dye sample. The developed method is simple, rapid, exclusive, sensitive, accurate and precise. This method can be applied in the identification and quantitative of 14 N-nitrosamines in hair dyes.

Key words: gas chromatography-tandem mass spectrometry, hair dyes, N-nitrosamines

中图分类号:

TQ658

张静, 赖俊敏, 李思源, 严小红, 丁怡, 张起辉. 气相色谱-三重四极杆质谱法测定染发剂中14种N-亚硝胺类化合物[J]. 日用化学工业（中英文）, 2023, 53(11): 1334-1339.

Zhang Jing, Lai Junmin, Li Siyuan, Yan Xiaohong, Ding Yi, Zhang Qihui. Determination of 14 N-nitrosamines in hair dyes using gas chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2023, 53(11): 1334-1339.

图/表 4

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参考文献 16

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序号	化合物名称	分子式	保留时间/min	母离子（m/z）	子离子（m/z）	碰撞能/eV
1	N-亚硝基二甲胺（N-nitrosodimethylamine, NDMA）	C₂H₆N₂O	6.02	74	44.1*, 42.1	3, 20
2	N-亚硝基甲乙胺（N-nitrosoethylmethylamine, NMEA）	C₃H₈N₂O	6.62	88	43.1*, 42.1	10, 10
3	N-亚硝基二乙胺（N-nitrosodiethylamine, NDEA）	C₄H₁₀N₂O	7.02	102	85*, 44.1	3, 15
4	N-亚硝基乙基异丙胺（N-nitrosoethylisopropylamine, NEiPA）	C₅H₁₂N₂O	7.55	116	44.1*, 99.1	20, 18
5	N-亚硝基二异丙胺（N-nitrosodiisopropylamine, NDiPA）	C₆H₁₄N₂O	7.98	130.1 88	88* 71	3, 12
6	N-亚硝基乙基正丙基胺（N-nitrosoethylpropylamine, NEPA）	C₅H₁₂N₂O	8.16	116	44.1*, 99.1	20, 18
7	N-亚硝基二正丙胺（N-nitrosodipropylamine, NDPA）	C₆H₁₄N₂O	9.460	130	113.1*, 43.1	3, 15
8	N-亚硝基二正丁胺（N-nitrosodibutylamine, NDBA）	C₈H₁₈N₂O	12.54	116 158	99.1* 99.1	3, 8
9	N-亚硝基-N-甲基苯胺（N-nitrosomethylaniline, NMPhA）	C₇H₈N₂O	12.65	106.1	77*, 79	21, 9
10	N-亚硝基-N-乙基苯胺（Nitrosoethylphenylamine, NEPhA）	C₈H₁₀N₂O	12.67	121.1 106.1	106.1* 79	15, 9
11	N-亚硝基哌啶（N-nitrosopiperidine, NPIP）	C₅H₁₀N₂O	12.740	114	84*, 97	10, 10
12	N-亚硝基吡咯烷（N-nitrosopyrrolidine, NPYR）	C₄H₈N₂O	12.99	100	70*, 68	5, 12
13	N-亚硝基吗啉（N-nitrosomorpholine, NMOR）	C₄H₈N₂O₂	13.34	116	86.1*, 56	2, 13
14	N-亚硝基二苯胺（N-nitrosodiphenylamine, NDPhA）	C₁₂H₁₀N₂O	16.32	169	168*, 167	20, 36

化合物	线性回归方程	相关系数（r）	线性范围/（μg/L）	LOD/（μg/L）	LOQ/（μg/L）
NDMA	y=3 468 x+177	0.998 5	5~100	0.2	0.6
NMEA	y=1 500 x+734	0.998 7	5~100	0.5	1.5
NDEA	y=1 351 x+517	0.999 9	5~100	0.2	0.6
NEiPA	y=512 x-39	0.999 3	5~100	1.5	5
NDiPA	y=1 404 x+390	0.999 0	5~100	0.5	1.5
NEPA	y=150 x+61	0.998 4	5~100	1.5	5
NDPA	y=595 x+124	0.998 9	5~100	0.2	0.6
NDBA	y=1 436 x-202	0.999 5	5~100	0.5	1.5
NMPhA	y=9 301 x-470	0.999 7	5~100	0.5	1.5
NEPhA	y=7 684 x-695	0.999 9	5~100	0.5	1.5
NPIP	y=1 809 x+639	0.999 9	5~100	0.2	0.6
NPYR	y=775 x+4	0.998 6	5~100	0.2	0.6
NMOR	y=2 871 x+446	0.999 1	5~100	0.2	0.6
NDPhA	y=18 269 x+3 302	0.999 8	5~100	0.2	0.6

化合物	加标水平/（μg/L）	平均回收率/%	RSD/%
NDMA	5, 10, 20	96.5, 90.2, 84.1	5.2, 4.9, 2.6
NMEA	5, 10, 20	98.5, 92.6, 90.1	5.0, 2.5, 3.2
NDEA	5, 10, 20	94.0, 90.9, 87.9	3.6, 2.8, 3.4
NEiPA	5, 10, 20	110.5, 97.8, 92.4	4.6, 7.7, 4.3
NDiPA	5, 10, 20	92.5, 95.2, 91.7	4.3, 2.7, 1.1
NEPA	5, 10, 20	122.8, 108.5, 105.0	5.0, 11, 8.1
NDPA	5, 10, 20	94.9, 92.9, 90.5	1.6, 3.7, 3.1
NDBA	5, 10, 20	98.7, 89.7, 83.8	4.2, 3.9, 5.6
NMPhA	5, 10, 20	113.7, 112.1, 111.5	3.9, 4.7, 3.0
NEPhA	5, 10, 20	106.6, 104.3, 99.0	2.1, 1.9, 3.2
NPIP	5, 10, 20	89.3, 84.5, 84.7	1.7, 6.1, 3.5
NPYR	5, 10, 20	100.6, 95.1, 94.6	6.0, 5.7, 5.6
NMOR	5, 10, 20	99.3, 93.1, 88.5	3.2, 4.3, 2.5
NDPhA	5, 10, 20	98.5, 99.5, 93.5	6.5, 4.7, 3.5