RRLC-MS/MS同时测定食品接触材料中9种双酚类化合物迁移量
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摘要
建立了高分离度快速液相色谱-串联质谱(RRLC-MS/MS)法同时测定食品接触材料中9种双酚类化合物的迁移量。样品经不同类型食品模拟物浸泡后,用Oasis HLB固相萃取柱净化,Agilent poroshell 120 SB-C18柱(2.1 mm×100 mm×2.7μm)分离,以甲醇和0.1 mmol/L乙酸铵水溶液为流动相进行梯度洗脱,在电喷雾负离子模式(ESI~-)和多反应监测(MRM)模式下进行分析。结果表明,在优化的实验条件下,9种双酚类化合物的线性关系良好,相关系数(R~2)均大于0.99,检出限为0.01～0.2μg/kg,定量限为0.05～1.0μg/kg,在低、中、高3个加标水平下的回收率为76.9%～113.1%,相对标准偏差为1.9%～6.7%。本方法灵敏、准确、可靠、快速,能满足食品接触材料中9种双酚类化合物迁移量的检测需求。
A method of rapid resolution liquid chromatography-tandem mass spectrometry(RRLC-MS/MS) was developed for the simultaneous determination of the migration of 9 bisphenols(bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, tetrabromobisphenol A, hexafluorobisphenol A, bisphenol AP, bisphenol BP) in food contact materials. Different types of food simulants(4% acetic acid,50% ethanol,isooctane) were used for migration test to simulate different types of food, such as acidic foods, alcoholic foods and oils. After the migration test, 10 mL of 4% acetic acid soaking solution were directly put in to solid phase extraction cartridge which had been pretreated, while 10 mL of 50% ethanol or isooctane soaking solution were dried by nitrogen in the water bath of 45 ℃, re-dissolved in 2 mL methanol, and fixed to 10 mL by water before purification. An Oasis HLB solid phase extraction cartridge(200 mg/6 mL) was applied for purification. The separation was performed on an Agilent poroshell 120 SB-C18 column(2.1 mm×100 mm×2.7 μm) by using methanol and 0.1 mmol/L ammonium acetate as mobile phases with gradient elution. The electrospray ionization source in negative ion(ESI~-) mode was used for the determination of the 9 bisphenols under the multiple reaction monitoring(MRM) mode. The results verified that, under the optimized experimental conditions, satisfactory linearities of the 9 bisphenols were obtained with correlation coefficients(R~2) higher than 0.99. The limits of detection(LOD) and quantitation(LOQ) of the 9 bisphenols were in the range of 0.01-0.2 μg/kg and 0.05-1.0 μg/kg, respectively. The average recoveries of 9 bisphenols ranged from 76.9% to 113.1% at three spiking levels, and the relative standard deviations(RSDs) were between 1.9% and 6.7%. The method is sensitive, accurate, reliable and rapid, and can fully meet the requirements for the simultaneous determination of migration of the 9 bisphenols in food contact materials and products. 60 samples of different types of food contact materials and products, including polycarbonate buckets, baby bottles, cups, food cans and food metal covers, were analyzed by the method. The results showed that bisphenol A and bisphenol F were found in food simulant soaking solution of 4 and 1 food metal covers, respectively. The test results indicate that bisphenols may be present in certain food contact materials and products, and also can be transferred to food in the process of product use.
A method of rapid resolution liquid chromatography-tandem mass spectrometry(RRLC-MS/MS) was developed for the simultaneous determination of the migration of 9 bisphenols(bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, tetrabromobisphenol A, hexafluorobisphenol A, bisphenol AP, bisphenol BP) in food contact materials. Different types of food simulants(4% acetic acid,50% ethanol,isooctane) were used for migration test to simulate different types of food, such as acidic foods, alcoholic foods and oils. After the migration test, 10 mL of 4% acetic acid soaking solution were directly put in to solid phase extraction cartridge which had been pretreated, while 10 mL of 50% ethanol or isooctane soaking solution were dried by nitrogen in the water bath of 45 ℃, re-dissolved in 2 mL methanol, and fixed to 10 mL by water before purification. An Oasis HLB solid phase extraction cartridge(200 mg/6 mL) was applied for purification. The separation was performed on an Agilent poroshell 120 SB-C18 column(2.1 mm×100 mm×2.7 μm) by using methanol and 0.1 mmol/L ammonium acetate as mobile phases with gradient elution. The electrospray ionization source in negative ion(ESI~-) mode was used for the determination of the 9 bisphenols under the multiple reaction monitoring(MRM) mode. The results verified that, under the optimized experimental conditions, satisfactory linearities of the 9 bisphenols were obtained with correlation coefficients(R~2) higher than 0.99. The limits of detection(LOD) and quantitation(LOQ) of the 9 bisphenols were in the range of 0.01-0.2 μg/kg and 0.05-1.0 μg/kg, respectively. The average recoveries of 9 bisphenols ranged from 76.9% to 113.1% at three spiking levels, and the relative standard deviations(RSDs) were between 1.9% and 6.7%. The method is sensitive, accurate, reliable and rapid, and can fully meet the requirements for the simultaneous determination of migration of the 9 bisphenols in food contact materials and products. 60 samples of different types of food contact materials and products, including polycarbonate buckets, baby bottles, cups, food cans and food metal covers, were analyzed by the method. The results showed that bisphenol A and bisphenol F were found in food simulant soaking solution of 4 and 1 food metal covers, respectively. The test results indicate that bisphenols may be present in certain food contact materials and products, and also can be transferred to food in the process of product use.
引文
[1] Commission Regulation (EU) No 10/2011, Official Journal of the European Union, 2011.
[2] GB 9685—2016. 食品安全国家标准食品接触材料及制品用添加剂使用标准[S]. 北京:中国标准出版社,2016.
[3] KITAMURA S, SUZUKI T, SANOH S, et al. Comparative study of the endocrine-disrupting activity of bisphenol and 19 related compounds[J]. Toxicological Sciences, 2005, 84(2): 249-259.
[4] ROSENMAI A K, DYBDAHL M, PEDERSEN M, et al. Are structural analogues to bisphenola safe alternatives?[J]. Toxicological Sciences, 2014, 139(1): 35-47.
[5] XIAN Y P, WU Y L, DONG H, et al. Dispersive micro solid phase extraction (DMSPE) using polymer anion exchange (PAX) as the sorbent followed by UPLC-MS/MS for the rapid determination of four bisphenols in commercial edible oils[J]. Journal of Chromatography A, 2017, 1 517: 35-43.
[6] GALLO P, PISCILTTANO I D M, ESPOSITO F, et al. Determination of BPA, BPB, BPF, BADGE and BFDGE in canned energy drinks by molecularly imprinted polymer cleaning up and UPLC with fluorescence detection[J]. Food Chemistry, 2017, 220: 406-412.
[7] 勾新磊,高峡,胡光辉,等. 超高效液相色谱-串联质谱法同时测定塑料包装矿泉水中11种双酚类化合物[J].色谱,2014,32(9):988-991. GUO Xinlei, GAO Xia, HU Guanghui, et al. Simultaneous determination of 11 bisphenols in plastic bottled drinking water by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2014, 32(9): 988-991(in Chinese).
[8] WANG Q, ZHU L Y, CHEN M, et al. Simultaneously determination of bisphenol A and its alternatives in sediment by ultrasound-assisted and solid phase extractions followed by derivatization using GC-MS[J]. Chemosphere, 2017, 169: 709-715.
[9] ZHAO R S, WANG X, YUAN J P, et al. Highly sensitive determination of tetrabromobisphenol A and bisphenol A in environmental water samples by solid-phase extraction and liquid chromatographytandem mass spectrometry[J]. Journal of Separation Science, 2010, 33: 1 652-1 657.
[10] 张明,唐访良,徐建芬,等. UPLC-MS/MS法同时测定地表水中6种双酚类化合物残留[J]. 质谱学报,2017,38(6):690-698. ZHANG Ming, TANG Fangliang, XU Jianfen, et al. Simultaneous determination of six bisphenol residues in surface water by UPLC-MS/MS[J]. Journal of Chinese Mass Spectrometry Society, 2017, 38(6): 690-698(in Chinese).
[11] SOSVOROVAA L K, CHLUPACOVA T, VITKU J, et al. Determination of selected bisphenols, parabens and estrogens in human plasma using LC-MS/MS[J]. Talanta, 2017, 174: 21-28.
[12] 张圣虎,张易曦,吉贵祥,等. 高效液相色谱-串联质谱法测定儿童和成人尿液中双酚A、四溴双酚A 和辛基酚[J]. 分析化学,2016,44(1):19-24. ZHANG Shenghu, ZHANG Yixi, JI Guixiang, et al. Determination of bisphenol A, tetrabromobisphenol A and 4-tert-octylphenol in child and adult urine samples using high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2016, 44(1): 19-24(in Chinese).
[13] 胡小键,张海婧,王肖红,等. 固相萃取液相色谱串联质谱法检测尿中双酚类和卤代双酚类物质[J].分析化学,2014,42(7):1 053-1 056. HU Xiaojian, ZHANG Haijing, WANG Xiaohong, et al. Determination of bisphenolic and halogenated bisphenolic compounds in human urine by high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2014, 42(7): 1 053-1 056(in Chinese).
[14] SPAGNUOLO M L, MARINI F, SARABIA L A, et al. Migration test of Bisphenol A from polycarbonate cups using excitationemission fluorescence data with parallel factor analysis[J]. Talanta, 2017, 167: 367-378.
[15] OCA M L, SARABIA L A, HRRRERO A, et al. Optimum pH for the determination of bisphenols and their corresponding diglycidyl ethers by gas chromatography-mass spectrometry. Migration kinetics of bisphenol A from polycarbonateglasses[J]. Journal of Chromatography A, 2014, 1 360: 23-38.
[16] OCA M L, ORTIZ M C, HERRERO A, et al. Optimization of a GC/MS procedure that uses parallel factor analysis for the determination of bisphenols and their diglycidyl ethers after migration from polycarbonate tableware[J]. Talanta, 2013, 15: 266-280.
[17] GB 31604.1—2015. 食品安全国家标准食品接触材料及制品迁移试验通则[S]. 北京:中国标准出版社,2015.
[18] GB 5009.156—2016. 食品安全国家标准食品接触材料及制品迁移试验预处理方法通则[S]. 北京:中国标准出版社,2016.
[2] GB 9685—2016. 食品安全国家标准食品接触材料及制品用添加剂使用标准[S]. 北京:中国标准出版社,2016.
[3] KITAMURA S, SUZUKI T, SANOH S, et al. Comparative study of the endocrine-disrupting activity of bisphenol and 19 related compounds[J]. Toxicological Sciences, 2005, 84(2): 249-259.
[4] ROSENMAI A K, DYBDAHL M, PEDERSEN M, et al. Are structural analogues to bisphenola safe alternatives?[J]. Toxicological Sciences, 2014, 139(1): 35-47.
[5] XIAN Y P, WU Y L, DONG H, et al. Dispersive micro solid phase extraction (DMSPE) using polymer anion exchange (PAX) as the sorbent followed by UPLC-MS/MS for the rapid determination of four bisphenols in commercial edible oils[J]. Journal of Chromatography A, 2017, 1 517: 35-43.
[6] GALLO P, PISCILTTANO I D M, ESPOSITO F, et al. Determination of BPA, BPB, BPF, BADGE and BFDGE in canned energy drinks by molecularly imprinted polymer cleaning up and UPLC with fluorescence detection[J]. Food Chemistry, 2017, 220: 406-412.
[7] 勾新磊,高峡,胡光辉,等. 超高效液相色谱-串联质谱法同时测定塑料包装矿泉水中11种双酚类化合物[J].色谱,2014,32(9):988-991. GUO Xinlei, GAO Xia, HU Guanghui, et al. Simultaneous determination of 11 bisphenols in plastic bottled drinking water by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2014, 32(9): 988-991(in Chinese).
[8] WANG Q, ZHU L Y, CHEN M, et al. Simultaneously determination of bisphenol A and its alternatives in sediment by ultrasound-assisted and solid phase extractions followed by derivatization using GC-MS[J]. Chemosphere, 2017, 169: 709-715.
[9] ZHAO R S, WANG X, YUAN J P, et al. Highly sensitive determination of tetrabromobisphenol A and bisphenol A in environmental water samples by solid-phase extraction and liquid chromatographytandem mass spectrometry[J]. Journal of Separation Science, 2010, 33: 1 652-1 657.
[10] 张明,唐访良,徐建芬,等. UPLC-MS/MS法同时测定地表水中6种双酚类化合物残留[J]. 质谱学报,2017,38(6):690-698. ZHANG Ming, TANG Fangliang, XU Jianfen, et al. Simultaneous determination of six bisphenol residues in surface water by UPLC-MS/MS[J]. Journal of Chinese Mass Spectrometry Society, 2017, 38(6): 690-698(in Chinese).
[11] SOSVOROVAA L K, CHLUPACOVA T, VITKU J, et al. Determination of selected bisphenols, parabens and estrogens in human plasma using LC-MS/MS[J]. Talanta, 2017, 174: 21-28.
[12] 张圣虎,张易曦,吉贵祥,等. 高效液相色谱-串联质谱法测定儿童和成人尿液中双酚A、四溴双酚A 和辛基酚[J]. 分析化学,2016,44(1):19-24. ZHANG Shenghu, ZHANG Yixi, JI Guixiang, et al. Determination of bisphenol A, tetrabromobisphenol A and 4-tert-octylphenol in child and adult urine samples using high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2016, 44(1): 19-24(in Chinese).
[13] 胡小键,张海婧,王肖红,等. 固相萃取液相色谱串联质谱法检测尿中双酚类和卤代双酚类物质[J].分析化学,2014,42(7):1 053-1 056. HU Xiaojian, ZHANG Haijing, WANG Xiaohong, et al. Determination of bisphenolic and halogenated bisphenolic compounds in human urine by high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2014, 42(7): 1 053-1 056(in Chinese).
[14] SPAGNUOLO M L, MARINI F, SARABIA L A, et al. Migration test of Bisphenol A from polycarbonate cups using excitationemission fluorescence data with parallel factor analysis[J]. Talanta, 2017, 167: 367-378.
[15] OCA M L, SARABIA L A, HRRRERO A, et al. Optimum pH for the determination of bisphenols and their corresponding diglycidyl ethers by gas chromatography-mass spectrometry. Migration kinetics of bisphenol A from polycarbonateglasses[J]. Journal of Chromatography A, 2014, 1 360: 23-38.
[16] OCA M L, ORTIZ M C, HERRERO A, et al. Optimization of a GC/MS procedure that uses parallel factor analysis for the determination of bisphenols and their diglycidyl ethers after migration from polycarbonate tableware[J]. Talanta, 2013, 15: 266-280.
[17] GB 31604.1—2015. 食品安全国家标准食品接触材料及制品迁移试验通则[S]. 北京:中国标准出版社,2015.
[18] GB 5009.156—2016. 食品安全国家标准食品接触材料及制品迁移试验预处理方法通则[S]. 北京:中国标准出版社,2016.