气相色谱-串联质谱法同时测定食品中的氯丙醇酯和缩水甘油酯
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摘要
建立了一种气相色谱-串联质谱仪(GC-MS/MS)同时测定多种油脂类食品中3-氯丙醇酯(3-MCPDE),2-氯丙醇酯(2-MCPDE)和缩水甘油酯(GE)的检测方法。通过试验对样品提取、酯交换、衍生化,以及GC-MS/MS检测条件进行了优化,采用建立的GC-MS/MS方法对植物油、焙烤类食品、油炸膨化类食品以及奶粉四类食品中3-MCPDE,2-MCPDE和GE进行检测,方法的定量限在四类食品中分别为10、20、50和100μg/kg。方法的总体平均回收率范围为68.9%~116.5%,相对标准偏差(RSDn=6)为2.11%~13.90%,结果表明样品在较宽的线性范围内,呈良好线性相关,相关系数(R)大于0.99。本方法提取效率高,净化效果好,检测灵敏度和准确度高,能够满足日常工作中植物油类、奶粉类、油炸膨化食品类和焙烤食品类等基质中3-MCPDE、GE和2-MCPDE的定性定量检测。
A gas chromatography-tandem mass spectrometry(GC-MS/MS) method was established for the simultaneous determination of 3-chloropropanol ester(3-MCPDE), 2-chloropropanol ester(2-MCPDE) and gycidyl ester(GE) in various fatty foods in this study. The 3-MCPDE, 2-MCPDE and GE in vegetable oils, bakery foods, fried-puffed foods and milk powder were determined by GC-MS/MS after the optimization of extraction, transesterification and derivatization of samples and conditions of GC-MS/MS. The limits of quantitation(LOQs) of the four types of food products were 10, 20, 50 and 100 μg/kg, respectively, and the total mean recoveries were in the range of 68.9% ~116.5% with the relative standard deviation(RSD n=6) of 2.11%~13.90%. The results showed that the samples had good linear correlation within a wide linear range, and the correlation coefficients(R) were higher than 0.99. The proposed method had the advantages of high extraction efficiency, good purification effect, high detection sensitivity and accuracy, which could be used for qualitative and quantitative determination of 3-MCPDE, 2-MCPDE and GE in vegetable oils, milk powder, fried-puffed foods and bakery foods.
A gas chromatography-tandem mass spectrometry(GC-MS/MS) method was established for the simultaneous determination of 3-chloropropanol ester(3-MCPDE), 2-chloropropanol ester(2-MCPDE) and gycidyl ester(GE) in various fatty foods in this study. The 3-MCPDE, 2-MCPDE and GE in vegetable oils, bakery foods, fried-puffed foods and milk powder were determined by GC-MS/MS after the optimization of extraction, transesterification and derivatization of samples and conditions of GC-MS/MS. The limits of quantitation(LOQs) of the four types of food products were 10, 20, 50 and 100 μg/kg, respectively, and the total mean recoveries were in the range of 68.9% ~116.5% with the relative standard deviation(RSD n=6) of 2.11%~13.90%. The results showed that the samples had good linear correlation within a wide linear range, and the correlation coefficients(R) were higher than 0.99. The proposed method had the advantages of high extraction efficiency, good purification effect, high detection sensitivity and accuracy, which could be used for qualitative and quantitative determination of 3-MCPDE, 2-MCPDE and GE in vegetable oils, milk powder, fried-puffed foods and bakery foods.
引文
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[3]S Macmahon,TH Begley,GW Diachenko.Occurrence of3-MCPD and glycidyl esters in edible oils in the United States[J].Food Additives&Contaminants Part A,2013,30(12):2081-2092
[4]J Leigh,S Macmahon.Occurrence of 3-monochloropropanediol esters and glycidyl esters in commercial infant formulas in the United States[J].Food Additives&Contaminants:Part A,2017,34(3):356-370
[5]AP Arisseto,WC Silva,GR Scaranelo,et al.3-MCPD and glycidyl esters in infant formulas from the Brazilian market:occurrence and risk assessment[J].Food Control,2017,77:76-81
[6]Hamlet C G,Said P A,Gray D A.Generation of Monochloropropanediols(MCPDs)in Model Dough Systems.1.Leavened Doughs[J].Journal of Agricultural&Food Chemistry,2004,52(7):2059-2066
[7]Lynch B S,Bryant D W,Hook G J,et al.Carcinogenicity of Monochloro-1,2-Propanediol(α-Chlorohydrin,3-MCPD)[J].International Journal of Toxicology,1998,17(1):47-76
[8]金青哲,王兴国.氯丙醇酯-油脂食品中新的潜在危害因子[J].中国粮油学报,2011,26(11):119-123JIN Qing-zhe,WANG Xing-guo.Chloropropanol esters in edible fats and oils-new potential risk factors[J].Journal of the Chinese Cereals and Oils Association,2011,26(11):119-123
[9]吴少明,傅武胜,杨贵芝.食用植物油中脂肪酸氯丙醇酯形成机制的研究进展[J].食品科学,2014,35(1):266-270WU Shao-ming,FU Wu-sheng,YANG Gui-zhi.Formation mechanism of 3-Chloropropane-1,2-diol esters in edible vegetable oil[J].Food Science,2014,35(1):266-270
[10]周红茹,金俊,杨娇,等.油脂中3-氯丙二醇酯形成的化学反应机制[J].中国粮油学报,2012,27(10):118-122ZHOU Hong-Ru,JIN Jun,YANG Jiao,et al.The chemical reaction mechanism of 3-MCPD esters formed in the oil[J].Journal of the Chinese Cereals and Oils Association,2012,27(10):118-122
[11]刘京,王瑛瑶,段章群,等.食用植物油中氯丙醇酯的形成途径与检测方法[J].食品科学,2013,34(21):375-378LIU Jing,WANG Ying-yao,DUAN Zhang-qun,et al.Forrmation pathways and detection methods of chlorine propanol esters in edible vegetable oil[J].Food Science,2013,34(21):375-378
[12]A Ermacora,K Hrn?i?ík.Development of an analytical method for the simultaneous analysis of MCPD esters and glycidyl esters in oil-based foodstuffs[J].Food Additives&Contaminants Part A,2014,31(6):985-994
[13]M Küsters,U Bimber,S Reeser,et al.Simultaneous determination and differentiation of glycidyl esters and3-monochloropropane-1,2-diol(MCPD)esters in different foodstuffs by GC-MS[J].Journal of Agricultural Food Chemistry,2011,59(11):6263-6270
[14]A Ermacora,K Hrncirik.A novel method for simultaneous monitoring of 2-MCPD,3-MCPD and glycidyl esters in oils and fats[J].Journal of the American Oil Chemists Society,2013,90(1):1-8
[15]K Miyazaki,K Koyama,H Sasako,et al.Indirect method for simultaneous determinations of 3-Chloro-1,2-propanediol fatty acid esters and glycidyl fatty acid esters[J].Journal of the American Oil Chemists Society,2012,89(8):1403-1407
[16]J K Leigh,S Macmahon.Extraction and Liquid Chromatography-Tandem Mass Spectrometry Detection of3-Monochloropropanediol Esters and Glycidyl Esters in Infant Formula[J].Journal of Agricultural&Food Chemistry,2016,64(49):9442-9451
[17]Zuzana Zelinkova,Anupam Giri,Thomas Wenzl.Assessment of critical steps of a GC/MS based indirect analytical method for the determination of fatty acid esters of monochloropropanediols(MCPDEs)and of glycidol(GEs)[J].Food Control,2017,77:65-75
[18]苗雨田,杨悠悠,王浩,等.气相色谱-质谱法测定食用油中3-氯丙醇酯[J].中国粮油学报,2016,31(11):135-139MIAO Yu-tian,YANG You-you,WANG Hao,et al.Determination of 3-chloropropanol-1,2-diol(3-MCPD)Esters in edible oil by gas chromatography and mass spectrometry[J].Journal of the Chinese Cereals and Oils Association,2016,31(11):135-139
[19]李秋红,江秀明,肜雅婵,等.气相色谱法检测植物油中3-氯丙醇酯[J].食品安全质量检测学报,2016,7(4):1715-1719LI Qiu-hong,JIANG Xiu-ming,RONG Ya-chan,et al.Determination of 3-chloropropane-1,2,-diol ester in oils by gas chromatography[J].Journal of Food Safety and Quality,2016,7(4):1715-1719
[20]Alice Thürer,Michael Granvogl.Direct Detection Techniques for Glycidyl Esters[M].Elsevier Inc.:2014
[21]A Garballo-Rubio,J Soto-Chinchilla,A Moreno,et al.Anovel method for the determination of glycidyl and3-monochloro-propanediol esters in fish oil by gas chromatography tandem mass spectrometry[J].Talanta,2017,165:267
[22]AP Arisseto,PFC Marcolino,AC Augusti,et al.Contamination of Fried Foods by 3-Monochloropropane-1,2-diol Fatty Acid Esters During Frying[J].Journal of the American Oil Chemists Society,2017,94(3):449-455
[23]C-III 18(09),Ester-bound3-chloropropane-1,2-diol(3-mcpd esters)and glycidol(glycidyl esters)determination of fats and oils by GC-MS[S]DGF Standard Method
[24]C-VI 18(10),Fatty-acid bound 3-chloropropane-1,2-diol(3-MCPD)and 2,3-expoipropane-1-ol(glycidol)determination in oils and fats by GC-MS(Differential measurement)[S]DGF Standard method
[25]Animal and vegetable fats and oils-Fatty-acid bound3-chloropropane-1,2-diol(3-MCPD)and 2,3-expoipropane-1-ol(glycidol)-Determination in oils and fats by GC/MS(Differential measurement)[S]ISO committee standard method
[26]GB 5009.191-2016,食品安全国家标准食品中氯丙醇及其脂肪酸酯含量的测定[S]GB 5009.191-2016,National food safety standards Determination of Chloropropanols and Chloropropanol Esters in food[S]
[2]ZelinkováZ,SvejkovskáB,Velísek J,et al.Fatty acid esters of 3-chloropropane-1,2-diol in edible oils[J].Food Additives&Contaminants,2006,23(12):1290-1298
[3]S Macmahon,TH Begley,GW Diachenko.Occurrence of3-MCPD and glycidyl esters in edible oils in the United States[J].Food Additives&Contaminants Part A,2013,30(12):2081-2092
[4]J Leigh,S Macmahon.Occurrence of 3-monochloropropanediol esters and glycidyl esters in commercial infant formulas in the United States[J].Food Additives&Contaminants:Part A,2017,34(3):356-370
[5]AP Arisseto,WC Silva,GR Scaranelo,et al.3-MCPD and glycidyl esters in infant formulas from the Brazilian market:occurrence and risk assessment[J].Food Control,2017,77:76-81
[6]Hamlet C G,Said P A,Gray D A.Generation of Monochloropropanediols(MCPDs)in Model Dough Systems.1.Leavened Doughs[J].Journal of Agricultural&Food Chemistry,2004,52(7):2059-2066
[7]Lynch B S,Bryant D W,Hook G J,et al.Carcinogenicity of Monochloro-1,2-Propanediol(α-Chlorohydrin,3-MCPD)[J].International Journal of Toxicology,1998,17(1):47-76
[8]金青哲,王兴国.氯丙醇酯-油脂食品中新的潜在危害因子[J].中国粮油学报,2011,26(11):119-123JIN Qing-zhe,WANG Xing-guo.Chloropropanol esters in edible fats and oils-new potential risk factors[J].Journal of the Chinese Cereals and Oils Association,2011,26(11):119-123
[9]吴少明,傅武胜,杨贵芝.食用植物油中脂肪酸氯丙醇酯形成机制的研究进展[J].食品科学,2014,35(1):266-270WU Shao-ming,FU Wu-sheng,YANG Gui-zhi.Formation mechanism of 3-Chloropropane-1,2-diol esters in edible vegetable oil[J].Food Science,2014,35(1):266-270
[10]周红茹,金俊,杨娇,等.油脂中3-氯丙二醇酯形成的化学反应机制[J].中国粮油学报,2012,27(10):118-122ZHOU Hong-Ru,JIN Jun,YANG Jiao,et al.The chemical reaction mechanism of 3-MCPD esters formed in the oil[J].Journal of the Chinese Cereals and Oils Association,2012,27(10):118-122
[11]刘京,王瑛瑶,段章群,等.食用植物油中氯丙醇酯的形成途径与检测方法[J].食品科学,2013,34(21):375-378LIU Jing,WANG Ying-yao,DUAN Zhang-qun,et al.Forrmation pathways and detection methods of chlorine propanol esters in edible vegetable oil[J].Food Science,2013,34(21):375-378
[12]A Ermacora,K Hrn?i?ík.Development of an analytical method for the simultaneous analysis of MCPD esters and glycidyl esters in oil-based foodstuffs[J].Food Additives&Contaminants Part A,2014,31(6):985-994
[13]M Küsters,U Bimber,S Reeser,et al.Simultaneous determination and differentiation of glycidyl esters and3-monochloropropane-1,2-diol(MCPD)esters in different foodstuffs by GC-MS[J].Journal of Agricultural Food Chemistry,2011,59(11):6263-6270
[14]A Ermacora,K Hrncirik.A novel method for simultaneous monitoring of 2-MCPD,3-MCPD and glycidyl esters in oils and fats[J].Journal of the American Oil Chemists Society,2013,90(1):1-8
[15]K Miyazaki,K Koyama,H Sasako,et al.Indirect method for simultaneous determinations of 3-Chloro-1,2-propanediol fatty acid esters and glycidyl fatty acid esters[J].Journal of the American Oil Chemists Society,2012,89(8):1403-1407
[16]J K Leigh,S Macmahon.Extraction and Liquid Chromatography-Tandem Mass Spectrometry Detection of3-Monochloropropanediol Esters and Glycidyl Esters in Infant Formula[J].Journal of Agricultural&Food Chemistry,2016,64(49):9442-9451
[17]Zuzana Zelinkova,Anupam Giri,Thomas Wenzl.Assessment of critical steps of a GC/MS based indirect analytical method for the determination of fatty acid esters of monochloropropanediols(MCPDEs)and of glycidol(GEs)[J].Food Control,2017,77:65-75
[18]苗雨田,杨悠悠,王浩,等.气相色谱-质谱法测定食用油中3-氯丙醇酯[J].中国粮油学报,2016,31(11):135-139MIAO Yu-tian,YANG You-you,WANG Hao,et al.Determination of 3-chloropropanol-1,2-diol(3-MCPD)Esters in edible oil by gas chromatography and mass spectrometry[J].Journal of the Chinese Cereals and Oils Association,2016,31(11):135-139
[19]李秋红,江秀明,肜雅婵,等.气相色谱法检测植物油中3-氯丙醇酯[J].食品安全质量检测学报,2016,7(4):1715-1719LI Qiu-hong,JIANG Xiu-ming,RONG Ya-chan,et al.Determination of 3-chloropropane-1,2,-diol ester in oils by gas chromatography[J].Journal of Food Safety and Quality,2016,7(4):1715-1719
[20]Alice Thürer,Michael Granvogl.Direct Detection Techniques for Glycidyl Esters[M].Elsevier Inc.:2014
[21]A Garballo-Rubio,J Soto-Chinchilla,A Moreno,et al.Anovel method for the determination of glycidyl and3-monochloro-propanediol esters in fish oil by gas chromatography tandem mass spectrometry[J].Talanta,2017,165:267
[22]AP Arisseto,PFC Marcolino,AC Augusti,et al.Contamination of Fried Foods by 3-Monochloropropane-1,2-diol Fatty Acid Esters During Frying[J].Journal of the American Oil Chemists Society,2017,94(3):449-455
[23]C-III 18(09),Ester-bound3-chloropropane-1,2-diol(3-mcpd esters)and glycidol(glycidyl esters)determination of fats and oils by GC-MS[S]DGF Standard Method
[24]C-VI 18(10),Fatty-acid bound 3-chloropropane-1,2-diol(3-MCPD)and 2,3-expoipropane-1-ol(glycidol)determination in oils and fats by GC-MS(Differential measurement)[S]DGF Standard method
[25]Animal and vegetable fats and oils-Fatty-acid bound3-chloropropane-1,2-diol(3-MCPD)and 2,3-expoipropane-1-ol(glycidol)-Determination in oils and fats by GC/MS(Differential measurement)[S]ISO committee standard method
[26]GB 5009.191-2016,食品安全国家标准食品中氯丙醇及其脂肪酸酯含量的测定[S]GB 5009.191-2016,National food safety standards Determination of Chloropropanols and Chloropropanol Esters in food[S]