固相萃取与气相色谱⁃质谱法联用测定食用植物油和含脂肪食品中氯丙醇酯的方法验证研究

doi:10.19586/j.2095-2341.2022.0077

生物技术进展 ›› 2023, Vol. 13 ›› Issue (1): 22-29.DOI: 10.19586/j.2095-2341.2022.0077

固相萃取与气相色谱⁃质谱法联用测定食用植物油和含脂肪食品中氯丙醇酯的方法验证研究

盛蕖(), 张涵, 万悦, 占艳, 焦玲玲, 卫杨帆, 王超, 程胜()

黄石市疾病预防控制中心，湖北黄石 435000

收稿日期:2022-05-15 接受日期:2022-07-12 出版日期:2023-01-25 发布日期:2023-02-07
通讯作者: 程胜
作者简介:盛蕖 E-mail:shengquHSCDC@163.com；

Method Validation Research for the Determination of Chloropropanol Esters in Edible Vegetable Oil and Fatty Food by Solid⁃phase Extraction and Gas Chromatography⁃mass Spectrometry

Qu SHENG(), Han ZHANG, Yue WAN, Yan ZHAN, Lingling JIAO, Yangfan WEI, Chao WANG, Sheng CHENG()

Huangshi Center for Disease Control and Prevention，Hubei Huangshi 435000，China

Received:2022-05-15 Accepted:2022-07-12 Online:2023-01-25 Published:2023-02-07
Contact: Sheng CHENG

摘要/Abstract

摘要：

氯丙醇酯是国际上广泛关注的食品加工过程污染物，其水解产物氯丙醇对人体（特别是婴幼儿）危害风险较大。采用固相萃取与气相色谱-质谱（gas chromatography-mass spectrometry,GC-MS）联用技术，对食用植物油和含脂食品中的氯丙醇酯[3-氯-1,2-丙二醇脂肪酸酯（简称3-MCPD酯）和2-氯-1,3-丙二醇脂肪酸酯（简称2-MCPD酯）]进行检测。该方法准确度高（3-MCPD酯和2-MCPD酯的平均回收率分别为98.9%和96.5%)、灵敏度高(3-MCPD酯和2-MCPD酯的检出限分别为0.042 mg·kg^-1和0.058 mg·kg^-1)、重现性好(相对标准偏差均低于5%)。76批次监测样品中，3-MCPD酯和2-MCPD酯的含量分别为0.042~4.865 mg·kg^-1(平均值为0.773 mg·kg^-1)和0.058~2.592 mg·kg^-1(平均值为0.469 mg·kg^-1)。经机构间的协同验证和英国FAPAS样的能力验证，2种氯丙醇酯在0.200~3.000 mg·kg^-1范围内线性良好，为进一步研究奠定了基础，同时也为食品加工企业严格控制生产过程建立了一种可行的检测方法。

关键词: 氯丙醇酯, 食用植物油, 含脂肪食品, 气相色谱-质谱法

Abstract:

The chloropropanol esters were internationally concerned as pollutants in food processing， its hydrolysates （chloropropanols） has a great risk of harm to human body （especially infants）. Therefore， the solid-phase extraction and gas chromatography-mass spectrometry （GC-MS） was used to determining 3-monochloropropane-1，2-diol ester （3-MCPD ester） and 2-monochloropropane-1，3-diol ester （2-MCPD ester） in edible vegetable oil and fatty food. The method had good accuracy （the average recoveries of 3-MCPD ester and 2-MCPD ester were 98.9% and 96.5%， respectively） and sensitivity （the detection limits for 3-MCPD ester and 2-MCPD ester were 0.042 and 0.058 mg·kg^-1， respectively）. Repeatability and reproducibility were satisfactory （the relative standard deviation was below 5%） for all analytes. The concentration of 3-MCPD ester and 2-MCPD ester in 76 batches of monitored samples were in the range of 0.042~4.865 mg·kg^-1 （the average was 0.773 mg·kg^-1） and 0.058~2.592 mg·kg^-1 （the average was 0.469 mg·kg^-1） respectively. Verified by institutions co-verification and proficiency testing of Food Analysis Performance Assessment Scheme （FAPAS） samples， the two chloropropanol esters showed good linearity in the range of 0.200~3.000 mg·kg^-1. The results layed a foundation for further research and established a feasible detection method for food processing enterprises to control the manufacturing process strictly.

Key words: chloropropanol esters, edible vegetable oil, fatty food, GC-MS

中图分类号:

TS207

盛蕖, 张涵, 万悦, 占艳, 焦玲玲, 卫杨帆, 王超, 程胜. 固相萃取与气相色谱⁃质谱法联用测定食用植物油和含脂肪食品中氯丙醇酯的方法验证研究[J]. 生物技术进展, 2023, 13(1): 22-29.

Qu SHENG, Han ZHANG, Yue WAN, Yan ZHAN, Lingling JIAO, Yangfan WEI, Chao WANG, Sheng CHENG. Method Validation Research for the Determination of Chloropropanol Esters in Edible Vegetable Oil and Fatty Food by Solid⁃phase Extraction and Gas Chromatography⁃mass Spectrometry[J]. Current Biotechnology, 2023, 13(1): 22-29.

图/表 11

参考文献 30

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目标物	保留时间/min	定性离子/(m·z^-1)	定量离子/(m·z^-1)
3-MCPD	14.737	289 253 453	289
2-MCPD	15.138	289 253	289
d5-3-MCPD	14.521	257 294 278	257
d5-2-MCPD	14.908	257 294	257

目标物	保留时间/min	定性离子/(m·z^-1)	定量离子/(m·z^-1)
3-MCPD	14.737	289 253 453	289
2-MCPD	15.138	289 253	289
d5-3-MCPD	14.521	257 294 278	257
d5-2-MCPD	14.908	257 294	257

化合物	线性方程	相关系数(R²)	线性范围/(mg·kg^-1)	LOD/(mg·kg^-1)	LQD/(mg·kg^-1)
3-MCPD酯	y=0.4339x+0.148	0.9994	0.200~4.000	0.042	0.140
2-MCPD酯	y=0.3866x-0.014	0.9993	0.200~4.000	0.058	0.193

化合物	线性方程	相关系数(R²)	线性范围/(mg·kg^-1)	LOD/(mg·kg^-1)	LQD/(mg·kg^-1)
3-MCPD酯	y=0.4339x+0.148	0.9994	0.200~4.000	0.042	0.140
2-MCPD酯	y=0.3866x-0.014	0.9993	0.200~4.000	0.058	0.193

机构编号	目标物	线性范围 /（mg·kg^-1）	LOD /(mg·kg^-1)	加标水平 /(mg·kg^-1)	平均回收率 /%	相对偏差 /%
1	3-MCPD酯	0.100~3.000	0.030	2.00	90.1	3.9
1	2-MCPD酯	0.100~3.000	0.030	2.00	98.8	5.8
2	3-MCPD酯	0.100~3.000	0.030	2.00	103.9	9.9
2	2-MCPD酯	0.100~3.000	0.030	2.00	104.8	9.7
3	3-MCPD酯	0.100~3.000	0.030	2.00	89.9	9.1
3	2-MCPD酯	0.100~3.000	0.030	2.00	100.9	8.3
4	3-MCPD酯	0.100~3.000	0.030	2.00	94.9	7.9
4	2-MCPD酯	0.100~3.000	0.030	2.00	104.9	6.8
5	3-MCPD酯	0.200~4.000	0.042	0.50	82.9	4.2
5	2-MCPD酯	0.200~4.000	0.058	0.50	94.8	6.7

固相萃取与气相色谱⁃质谱法联用测定食用植物油和含脂肪食品中氯丙醇酯的方法验证研究

Method Validation Research for the Determination of Chloropropanol Esters in Edible Vegetable Oil and Fatty Food by Solid⁃phase Extraction and Gas Chromatography⁃mass Spectrometry

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参考文献 30

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机构编号	目标物	参考值 /(mg·kg^-1)	合格范围 /(mg·kg^-1)	测定均值 /(mg·kg^-1)	相对偏差 /%
1	3-MCPD酯	1.610	1.130~2.090	1.490	8.2
1	2-MCPD酯	0.708	0.470~0.947	0.940	5.9
2	3-MCPD酯	1.610	1.130~2.090	1.400	1.6
2	2-MCPD酯	0.708	0.470~0.947	0.800	3.7
3	3-MCPD酯	1.610	1.130~2.090	1.280	8.4
3	2-MCPD酯	0.708	0.470~0.947	0.830	5.4
4	3-MCPD酯	1.610	1.130~2.090	1.300	9.1
4	2-MCPD酯	0.708	0.470~0.947	0.800	9.5
5	3-MCPD酯	0.586	0.352~0.821	0.594	0.3

方法萃取	目标物	样品类型	萃取条件	衍生条件	LOD	LOQ	加标回收率%	参考文献
SPME	3-MCPD	液体水解植物蛋白	PDMS, 27 ℃，30 min	0.25 mg PBA，90 ℃， 5 min	3.87 ng·g^-1	-	74.6~111.0	[29]
MSPE	3-MCPD	食用油	20 mg Fe₃O₄磁性纳米颗粒与30 µL 水混合，涡旋3 min；用1 mL乙酸乙酯解吸	30 µL TMSI，15 µL 吡啶，25 ℃， 10 min	1.1 ng·g^-1	3.6 ng·g^-1	70.0~104.9	[30]
PLE	3-MCPD	烘焙制品	70 µL BSTFA，1 g硅藻土，1 500 psi，70 ℃ 3 min，90 s洗脱，乙酸乙酯，80%的淋洗体积，1个静态循环	—	0.5 µg·kg^-1	1.7 µg·kg^-1	86.2~109.0	[18]
DLLME	3-MCPD	大豆、饮料等	2 mL乙腈, 100 µL三氯甲烷，50 µL HFBI，30 ℃ 5 min超声	—	0.6 ng·mL^-1	1.9 ng·mL^-1	97.0~105.0	[20]
SPE	3-MCPD	油及其制品、谷物制品、特殊营养用食品	1 mL甲醇钠，硅藻土，40 mL正己烷，80 mL无水乙醚洗脱	50 μL HFBI，75 ℃， 30 min	0.042 mg·kg^-1	0.140 mg·kg^-1	96.5%	本研究
SPE	2-MCPD	油及其制品、谷物制品、特殊营养用食品	1 mL甲醇钠，硅藻土，40 mL正己烷，80 mL无水乙醚洗脱	50 μL HFBI，75 ℃， 30 min	0.058 mg·kg^-1	0.193 mg·kg^-1	98.9%	本研究

食品类别	样品种类	样品数	3-MCPD酯		2-MCPD酯
食品类别	样品种类	样品数	平均值 /(mg·kg^-1)	范围 /(mg·kg^-1)	平均值 /(mg·kg^-1)	范围 /(mg·kg^-1)
合计		76	0.773	0.042~4.865	0.469	0.058~2.592
油及其制品	大豆油	6	0.257	0.075~0.817	0.122	0.080~0.157
(n=25)	花生油	5	1.007	0.888~2.170	0.612	0.068~1.326
	菜籽油	4	0.367	0.081~1.007	0.244	0.123~0.560
	调和油	6	0.407	0.042~0.885	0.252	0.058~0.589
	橄榄油	4	0.562	0.042~1.198	0.346	0.055~0.741
谷物及其制品	面包	8	1.250	0.087~2.577	0.623	0.338~1.331
(n=38)	饼干	6	1.353	0.029~2.424	0.709	0.088~1.195
	糕点	5	0.497	0.042~1.057	0.285	0.051~0.516
	方便面	6	0.958	0.576~1.575	0.792	0.220~1.162
	麻花	5	0.68	0.323~0.927	0.781	0.452~1.241
	油条	8	1.832	0.311~4.865	0.969	0.296~2.592
特殊营养用食品	乳及乳制品	8	0.406	0.042~1.325	0.174	0.011~0.463
(n=13)	特殊膳食	5	0.478	0.059~1.532	0.191	0.033~0.620