建立了食品用金属罐中苯酚、双酚A、间甲基苯酚、邻甲基苯酚、4-叔丁基苯酚迁移量的超高效液相色谱结合荧光检测器的分析方法,并开展了食品用金属罐中相关游离酚的迁移水平分析。5种游离酚在0.010~0.500 mg/L的范围内线性关系良好;在水、4%乙酸溶液、10%乙醇溶液和玉米油4种不同模拟物中加标回收率为70.2%~118.7%,平均回收率为90.7%,精密度范围为0.9%~7.2%(n=6);5种游离酚的检出限范围为0.001~0.010 mg/L。该方法准确性高、重现性好,可用于食品用金属罐中游离酚迁移量的检测分析。对6类共49种食品用金属罐采用6种不同食品模拟物浸泡,依照迁移实验条件进行游离酚迁移量分析。结果显示,除4-叔丁基苯酚之外,其他各游离酚的迁移量与总游离酚迁移量均处于限量值之内,双酚A对总游离酚的迁移量贡献最大。不同种类模拟物以及不同涂层、不同罐型条件下,5种游离酚的迁移量与检出率存在一定差异。
A analytical method of ultra-high performance liquid chromatography with fluorescence detector was established to detect migration of phenol, bisphenol A, methylphenol, o-methylphenol, and 4-tert-butylphenol from metal cans intend to contact with food, and the migration risk of related free phenols in metal cans was investigated. The 5 free phenols had a good linear relationship between 0.010 mg/L and 0.500 mg/L. In 4 different simulants of water,4% acetic acid,10% ethanol solution and corn oil, the recovery rate was in the range of 70.2%~118.7% and the average was 90.7%. The range of accuracy was 0.9%~7.2%(n=6). The detection limits ranged between 0.001~ 0.010 mg/L for 5 free phenols in 4 different simulants. The method has high accuracy and good reproducibility and can be used for analysis of free phenol migration in metal cans intend to contact with food. A total of 49 kinds of metal cans were soaked by corresponding food simulants, and the migration of free phenol was analyzed according to the migration experimental conditions. The migration risk of each free phenol and total amount of free phenol were within the safe limit except 4-tert-butylphenol, and bisphenol A was biggest contributors to the total migration amount of free phenol. Migration and detection rate of 5 kinds of free phenol vary under the conditions of different simulation, coating and can type.
[1] 李婷,柏建国,刘志刚,等. 食品金属包装材料中化学物的迁移研究进展[J]. 食品工业科技, 2013,34(15):380-383,389.
[2] 何明枫,周建伟,刘东红. 食品罐内涂层中双酚A及其环氧衍生物的迁移及检测研究进展[J]. 食品工业科技, 2015 (1):381-385.
[3] LIN Q B, CAI L F, WU S J, et al. Migration of Bisphenol A and Bisphenol A diglycidyl-ether from can coatings into food simulants[J]. Asian Journal of Chemistry, 2015,27(8):3 013-3 018.
[4] GOODSON A, ROBIN H, SUMMERFIELD W, et al. Migration of bisphenol A from can coatings: Effects of damage, storage conditions and heating[J]. Food Additives & Contaminants, 2004,21(10):1 015-1 026.
[5] BUCULEI A, AMARIEI S, OROIAN M, et al. Metals migration between product and metallic package in canned meat[J]. LWT-Foos Science and Fechnology, 2014,58(2):364-374.
[6] NERIN C, ALFARO P, AZNAR M, et al. Compounds from multilayer plastic bags cause reproductive failures in artificial insemination[J]. Scientific Reports, 2014,4(6 184):649-652.
[7] 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.
[8] European Commission. (EU) No 213/2018 of 12 February 2018 on plastic materials and articles intended to come into contact with food[S]. Brussels Official Journal of European Communities, 2018.
[9] 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.
[10] GB 4806.10—2016. 食品安全国家标准食品接触用涂料及涂层[S]. 北京:中国标准出版社, 2016.
[11] GB 31604.46—2016.食品安全国家标准食品接触材料及制品游离酚的测定和迁移量测定[S]. 北京:中国标准出版社, 2016.
[12] SUN C,LEONG L P,BARLOW P J,et al.Single laboratory validation of a method for the determination of Bisphenol A,Bisphenol A diglycidyl ether and its derivatives in canned foods by reversed-phase liquid chromatography[J]. Journal of Chromatography A, 2006, 1 129(1): 145-148.
[13] ERRICO S, BIANCO M, MITA L, et al. Migration of bisphenol A into canned tomatoes produced in Italy: dependence on temperature and storage conditions.[J]. Food Chemistry, 2014,160(10):157-164.
[14] XIA Y, RUBINO M. Kinetic study of bisphenol A migration from low-density polyethylene films into food simulants[J]. Industrial & Engineering Chemistry Research, 2015,54(14):150403092206008.
[15] 潘生林,童捷,翟苏婉,等. 出口内涂罐包装的游离酚GC-MS法迁移分析[J].包装学报, 2015,7(2): 43-46,58.
[16] 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.
[17] GB 31604.10—2016. 食品安全国家标准食品接触材料及制品 2,2-二(4-羟基苯基)丙烷(双酚A)迁移量的测定[S]. 北京:中国标准出版社, 2016.
[18] CHANG Y, NGUYEN C, PARANJPE V R, et al. Analysis of bisphenol A diglycidyl ether (BADGE) and its hydrolytic metabolites in biological specimens by high-performance liquid chromatography and tandem mass spectrometry[J]. Journal of Chromatography B, 2014, 965: 33-38.
[19] KAWAMURA Y, ETOH M, HIRAKAWA Y, et al. Bisphenol A in domestic and imported canned foods in Japan[J]. Food Additives & Contaminants: Part A, 2014, 31(2): 330-340.
[20] 冯怡,汪仕韬,卫荣,等. 食品包装污染物双酚类物质在食品模拟体系中的迁移规律研究[J].食品科学, 2014,35(5): 101-106.
