顶空气相色谱-质谱联用法同时测定食品用洗涤剂中的三种成分

doi:10.3969/j.issn.2097-2806.2024.08.016

摘要/Abstract

摘要：

建立了顶空气相色谱-质谱联用仪（HS-GC-MS）同时测定食品用洗涤中的甲醛、甲醇和1, 4-二噁烷的方法。方法对顶空进样的影响因素进行了单因素方差分析和正交试验，确定最优试验条件；选择强极性色谱柱SH-Rtx-Wax（30 m×0.32 mm×0.25 μm）进行分离；采用选择离子扫描（SIM）模式和外标法定量分析。实验结果表明，甲醛、甲醇和1, 4-二噁烷分别在8~200，8~200和2~50 μg/mL范围内线性关系良好，检出限（LOD）在0.10~0.60 μg/mL，定量限（LOQ）在0.29~1.78 μg/mL；对实际样品添加低、中、高三个水平进行加标回收和精密度试验，加标回收率在84.0%~101.9%，相对标准偏差（RSD）在0.5%~3.7%。该方法操作简单、灵敏度高、重复性好，能够满足食品用洗涤剂中甲醛、甲醇、1, 4-二噁烷同时测定的要求，同时也为我国食品用洗涤剂相关安全指标提供技术依据和参考。

关键词: 甲醛, 甲醇, 1, 4-二噁烷, 顶空, 气质联用, 食品, 洗涤剂

Abstract:

A method for simultaneous determination of methanal, methanol and 1, 4-dioxane in food detergents by headspace gas chromatography-mass spectrometry （HS-GC-MS） was established. The influencing factors of headspace sampling were analyzed by single factor variance analysis and orthogonal test to determine the optimal conditions. A strong polar column SH-Rtx-Wax （30 m×0.32 mm×0.25 μm） was selected for separation. Selective ion scanning （SIM） mode and external standard method were used for quantitative analysis. The results show that methanal, methanol and 1, 4-dioxane have good linear relationships in the ranges of 8-200 μg/mL, 8-200 μg/mL and 2-50 μg/mL, respectively. The limits of detection （LOD） are 0.10-0.60 μg/mL, and the limits of quantification （LOQ） are 0.29-1.78 μg/mL. The recovery and precision test of the actual samples are carried out at low, medium and high levels. The recovery rate is 84.0%-101.9% and relative standard deviation （RSD） is 0.5%-3.7%. The method is simple, sensitive and reproducible, which can meet the requirements of simultaneous determination of methanal, methanol and 1, 4-dioxane in food detergents, and also provide technical basis and reference for the relevant safety indicators of food detergents in China.

Key words: methanal, methanol, 1, 4-dioxane, headspace, gas chromatography-mass spectrometry, food, detergent

中图分类号:

TQ649

张颍,姚晨之,严方,李晓婷. 顶空气相色谱-质谱联用法同时测定食品用洗涤剂中的三种成分[J]. 日用化学工业（中英文）, 2024, 54(8): 1008-1014.

Ying Zhang,Chenzhi Yao,Fang Yan,Xiaoting Li. Simultaneous determination of three components in food detergents by headspace gas chromatography-mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2024, 54(8): 1008-1014.

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参考文献 16

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Number	Compound	CAS	Retention time/min	Precursor ion m/z	Daughter ion m/z
1	Methanal	50-00-0	1.330	30.00^*	29.00，31.00
2	Methanol	67-56-1	2.194	32.00	31.00^*，29.00
3	1, 4-Dioxane	123-91-1	4.771	88.00^*	58.00，43.00

Test number	A	B	C	Empty	Peak area （×10⁴）
Test number	A	B	C	Empty	Methanal	Methanol	1, 4-Dioxane
1	1	1	1	1	3.94	38.33	4.40
2	1	2	3	2	4.36	39.91	4.66
3	1	3	2	3	4.20	43.69	5.19
4	2	1	3	3	6.81	59.25	7.66
5	2	2	2	1	8.15	59.84	7.15
6	2	3	1	2	7.63	60.29	7.36
7	3	1	2	2	12.03	105.42	13.17
8	3	2	1	3	12.28	96.92	12.16
9	3	3	3	1	13.08	102.52	12.83

Compound	Linear range/（μg/mL）	Linear equation	r	LOD/（μg/mL）	LOQ/（μg/mL）
Methanal	8~200	Y=6.362×10²X+3.931	0.999 9	0.59	1.78
Methanol	8~200	Y=4.720×10³X+6.245×10³	0.999 9	0.34	1.02
1, 4-Dioxane	2~50	Y=2.354×10³X+5.746×10²	0.999 9	0.10	0.29

Compound	Add/μg	Sample 1			Sample 2			Sample 3
Compound	Add/μg	Original/μg	Recovery/%	RSD/%	Original/μg	Recovery/%	RSD/%	Original/μg	Recovery/%	RSD/%
Methanal	20.00	1.65	84.4±1.3	1.5	1.51	87.7±1.0	1.2	1.29	87.9±3.1	3.5
	40.00	1.65	84.0±0.7	0.8	1.51	88.6±1.8	2.1	1.29	84.7±1.1	1.2
	100.00	1.65	91.3±3.4	3.7	1.51	89.2±2.4	2.6	1.29	87.9±9.4	2.7
Methanol	20.00	0.00	97.6±1.3	1.3	0.00	99.3±0.5	0.5	0.00	94.9±2.6	2.7
	40.00	0.00	100.0±0.7	0.7	0.00	101.3±1.4	1.3	0.00	100.1±0.9	0.9
	100.00	0.00	98.8±4.6	2.3	0.00	101.9±1.1	1.1	0.00	101.1±2.4	2.3
1, 4-Dioxane	5.00	0.37	96.6±1.8	1.8	0.47	98.4±0.6	0.6	1.33	82.7±2.0	2.5
	10.00	0.37	96.2±0.7	0.7	0.47	97.5±1.8	1.8	1.33	85.2±1.0	1.1
	25.00	0.37	92.9±5.1	2.6	0.47	96.7±1.2	1.2	1.33	90.9±2.8	3.1

Sample	Measure/（μg/mL）
Sample	Methanal	Methanol	1, 4-Dioxane
1	1.65±0.19 （1.78）	ND	0.37±0.02
2	1.51±0.27 （1.78）	ND	0.47±0.02
3	1.29±0.33 （1.78）	ND	1.33±0.05
4	1.37±0.33 （1.78）	ND	ND
5	0.82±0.05 （1.78）	ND	ND
6	0.84±0.01 （1.78）	ND	ND
7	1.26±0.05 （1.78）	16.48±0.28	ND
8	0.71±0.07 （1.78）	ND	ND