食品金属包装材料中化学物的迁移研究进展

基于目前关于食品用金属包装材料中有毒有害物质迁移研究还基本空白的现状,本文介绍了金属包装材料中的潜在迁移情况,并着重介绍了重金属、双酚类物质和三聚氰胺等潜在迁移物及其研究现状,探讨了金属包装材料中化学物迁移研究的一般过程,为后期金属罐内有害物质的迁移研究和食品包装行业的危害分析和关键控制点(HACCP,Hazard Analysis and Critical Control Point)管理提供依据.     

食品用金属罐中5种游离酚的迁移水平研究

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。     

酸性食品模拟物对金属罐甲醛迁移的适用性研究

建立食品模拟物中甲醛的迁移量和真实食品中甲醛含量的HPLC测定方法，调查了60℃、10 d迁移条件下4%(体积分数)乙酸对涂层金属罐的腐蚀情况。以环氧涂层中典型的挥发性物质甲醛为研究对象，研究了6种食品模拟物模拟21种金属罐装酸性食品的适用性。结果表明，在模拟食品长期贮存条件(60℃,10 d)下，19%的金属罐灌装乙酸溶液后发生了腐蚀；对于发生乙酸腐蚀的空罐样品，建议采用5 g/L柠檬酸作为此类产品用空罐中甲醛迁移量的食品模拟物。对于未发生乙酸溶液腐蚀的空罐样品，采用3 g/L与5 g/L柠檬酸及10%(体积分数)乙醇作为食品模拟物会导致超过80%的酸性罐装食品中甲醛含量的低估，此时推荐4%(体积分数)乙酸作为此类产品用空罐的甲醛迁移量测试的食品模拟物。     

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

采用4 种食品模拟物包括超纯水、30 g/L乙酸水溶液、10%乙醇水溶液和异辛烷对食品金属罐中4 种双酚物（包括双酚A、双酚F、双酚A二缩水甘油醚和双酚F二缩水甘油醚）迁移情况进行研究,并建立半经验的双酚物迁移规律数学模型。结果表明：4 种双酚物同时在10%乙醇溶液中出现最大迁移,且贮存温度和时间对迁移量变化有显著影响。根据模拟实验得到的迁移数据和Fick第二定律建立数学模型,初步确定扩散系数DP,再根据DP估计得到包材的特征参数AP的范围为35.38～48.48。     

液相色谱-串联质谱法测定金属罐中三(壬基酚)亚磷酸酯的迁移量

目的 建立液相色谱-串联质谱法检测金属罐中三(壬基酚)亚磷酸酯迁移量的分析方法。方法 金属罐经水、4%乙酸、10%乙醇、20%乙醇、50%乙醇等食品模拟物迁移后, 过滤, 采用大气压化学电离(atmosphere pressure chemical ionization, APCI)和多反应监测模式(multiple reaction monitoring, MRM)进行检测, 外标法定量。结果 三(壬基酚)亚磷酸酯在10~500 μg/L范围内呈现良好的线性关系, 相关系数不低于0.9997, 检出限为0.005 mg/L, 测定结果的相对标准偏差不大于5%(n=6), 加标回收率为94.20%~106.40%。结论 该方法准确、精密度好, 可用于金属罐中三(壬基酚)亚磷酸酯迁移量的快速检测。     

金属食品罐内涂层中双酚类物质的迁移及检测研究进展

鉴于双酚A及其他双酚类物质作为食品罐内涂层材料有潜在的毒性与危害,中国、欧盟、美国等国家均已严格限制它们在金属食品罐内涂料中的使用。本文介绍双酚A、双酚A二缩水甘油醚、双酚F、双酚F二缩水甘油醚的结构、应用、危害、检测方法及迁移结果,并简述固相萃取在样品前处理中的应用。     

聚碳酸酯水桶中5种酚类物质的残留量检测以及迁移风险评估

目的利用超高效液相色谱法研究聚碳酸酯水桶(polycarbonate, PC)中5种酚类物质(苯酚、双酚A、对叔丁基苯酚、对枯基苯酚和2,4-二叔丁基苯酚)的残留量并对迁移风险进行评估。方法利用溶解-沉淀法对30批PC水桶中的酚类物质进行提取。参考GB 31604.1-2016《食品安全国家标准食品接触材料及制品迁移试验通则》和GB 5009.156-2015《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》对PC水桶进行迁移试验。利用超高效液相色谱法对提取液和迁移试液中的酚类物质进行定性和定量分析。结果在线性范围0.02～5mg/L内,线性系数均大于0.999,加标回收率在82%～109%之间,相对标准偏差范围为0.6%～5.2%(n=3)。30批饮用水桶中,各酚类物质的检出率分别为73%、93%、50%、43%和93%。食品模拟物为水的迁移实验中,只有苯酚和双酚A有检出,且数值都小于国家标准中的限量值。结论 5种酚类物质在PC水桶中的迁移风险都较小,研究可为PC产品的质量控制和酚类物质风险监测提供技术基础。     

外卖餐具中16种合成酚类抗氧化剂的迁移测定

摘 要：目的 测定外卖餐具中16种合成酚类抗氧化剂(Synthetic phenolic antioxidants, SPAs)的含量,分析外卖餐具中这类污染物的迁移行为。方法 本研究通过液相/气相色谱串联三重四极杆质谱联用技术,测定了6大类不同品牌外卖餐具中16种SPAs的含量,分别以纯净水、4%醋酸(v/v)、10%乙醇水溶液(v/v)、50%乙醇水溶液(v/v)和95%乙醇水溶液(v/v)为食品模拟物,开展不同品牌外卖餐具中主要SPAs的迁移实验。结果 外卖餐具中均可以检出一种以上SPAs,其中丁基化羟基甲苯及其代谢物的含量和检出率最高,2,4-二叔丁基苯酚和新兴化合物2,2''-亚甲基双-(4-甲基-6-叔丁基苯酚)次之,然而2,4-二叔丁基苯酚是外卖餐具最主要的迁移物。 结论 外卖餐具中合成酚类抗氧化剂广泛存在。 2,4-二叔丁基苯酚在外卖餐具中大量迁出,其健康危害需要引起足够关注。     

高效液相荧光法对5种罐装食品模拟物中双酚类化合物的迁移分析

双酚A及双酚类环氧衍生物是一种内分泌干扰物,易从金属罐头涂层迁移到食品内容物中。本文建立了一个高效液相色谱-荧光检测法同时检测罐头模拟物中14种双酚类化合物的分析方法。在10～1000ng/mL质量浓度范围,双酚A和各双酚类环氧衍生物的响应峰面积与其相应浓度呈良好相关性,最低检出限在1.41～3.66ng/mL之间;在10～250ng/mL添加水平范围内,平均回收率在72.55%～102.79%之间,日内和日间相对标准偏差均小于10%。之后将此方法应用于测定食品罐头中该双酚类化合物在不同食品模拟物中的迁移情况。     

食品包装迁移物双酚类物质稳定性与转化规律的研究

选用三片罐食品迁移物双酚A二环氧甘油醚(BADGE)及其6种双酚类物质衍生物为实验对象,探究了这些物质在模拟物体系中经不同灭菌方式后的稳定性以及各物质的转化产物。在此基础上,选取不同的储藏条件来进一步研究各物质之间的转化规律。结果表明:BADGE、BADGE·H_2O和BADGE·HCl在常压灭菌后以及储藏过程中会发生水合,转化成相应的水化物。BADGE·2HCl、BADGE·2H_2O和BADGE·H_2O·HCl在常压条件下,性质比较稳定。BADGE·HCl、BADGE·2HCl和BADGE·H_2O·HCl在经过高压灭菌后,三种氯化物在醇性模拟液中,会转变为BADGE及其水化物。本研究为金属包装材料中双酚类物质的迁移分析提供参考依据。     

Migration of bisphenol-A diglycidyl ether (BADGE) and its reaction products in canned foods

Bisphenol-A diglycidyl ether (BADGE) is used as an additive or starting agent in coatings for cans. The presence of hydrochloric acid in the organosol (PVC-based) lacquers results in formation of chlorohydroxy compounds of BADGE. These compounds, as well as BADGE itself, are potential migrants into the preserved food and are of toxicological concern. In the present investigation the presence of BADGE and the chlorohydroxy compounds (BADGE.HCl and BADGE.2HCl) in various kinds of canned foods from 30 brands have been determined by HPLC with fluorescence detection. BADGE was found in levels up to 5.1mg/kg in the food and only in food from cans containing BADGE.HCl and BADGE.2HCl in the lacquers. BADGE was found both in fish in oil and in fish in tomato sauce, however, the highest amounts were found in the fatty foodstuffs. BADGE.HCl and BADGE.2HCl were found in concentrations up to 2.4mg/kg and 8.3mg/kg, respectively. Unlike BADGE, BADGE.2HCl was found in similar concentrations in fish in oil and in fish in tomato sauce. In aqueous and acidic foodstuffs BADGE readily hydrolyses into mono- and dihydrolysed products (BADGE.H₂O and BADGE.2H₂O). In this study BADGE.H₂O was not found in any food sample, whereas BADGE.2H₂O was found in levels up to 2.6mg/kg. The Scientific Committee for Food (SCF) of the European Commission has proposed that a limit of restriction of 1mg/kg food shall include BADGE itself and BADGE.H₂O, BADGE.HCl, BADGE.2HCl and BADGE.HCL.H₂O. The present results indicate that the migration of BADGE.HCl and BADGE.2HCl, compounds with almost no data on toxicity, implies a greater problem than BADGE.H₂O and BADGE.2H₂O.     

The determination of monomers and oligomers from polyester-based can coatings into foodstuffs over extended storage periods

The polymeric coating used in metal packaging such as cans for foods and beverages may contain residual amounts of monomers used in the production of the coating, as well as unreacted linear and cyclic oligomers. Traditionally, although designed for use with plastic food contact materials, food simulants have been used to determine the migration of monomers from coatings into foodstuffs. More recently, food simulants have also been used to determine oligomeric species migrating from can coatings. In the work reported here, the migration of both monomers and oligomers from polyester-based can coatings into food simulants and foodstuffs, some of which were towards the end of their shelf-life, is compared. The concentrations of monomers and selected oligomers in canned foods at the end of their shelf life were found to be significantly lower than those in food simulants, which in turn was lower than those in the extraction solvent acetonitrile.     

食品罐内壁涂层中双酚A-二缩水甘油醚双水合物的迁移特性的数值仿真与实验研究

对金属罐内壁涂层中的有害物质(双酚A-二缩水甘油醚双水合物,以下简称BADGE·2H2O)向食品模拟液在给定条件下的迁移特性进行了数值仿真,并与对应条件下的实验结果进行了对比、分析。结果表明:温度、初始浓度、涂层厚度对物质迁移的影响较大;对于给定的温度,温度越高,则迁移达到平衡时所需要的时间越短,迁移量越大;对于给定的初始浓度和涂层厚度,初始浓度越大,涂层厚度越厚,则迁移量越大;同时,在不同温度下,BADGE·2H2O从食品罐内壁涂层向水性模拟液迁移的数值解与实验值最大差值为0.023μg/mL。数值仿真与实验结果有较好的一致性。     

Bisphenol A (BPA) and its source in foods in Japanese markets

The determination of bisphenol A (BPA) and/or bisphenol A diglycidyl ether (BADGE) in foods sold in Japanese markets and in water leached from six epoxy resin cans with similar diameters was carried out using high-performance liquid chromatography (HPLC) with electrochemical detection (LC/ECD), LC-mass spectrometric detection (LC/MS) and LC-tandem mass spectrometric detection (LC/MS/MS). BPA concentrations were 0-842 ng g^-1 for 48 canned foods, 0-14 ng g^-1 for 23 foods in plastic containers, and 0-1 ng g^-1 for 16 foods in paper containers. No BADGE was detected in three canned foods. There was no difference in leaching concentrations of BPA into glycine buffers at pHs 8 and 11, and water. The amounts of BPA leached into water from six epoxy resin cans held at 121°C for 20 min were almost the same as the cans' contents and were much higher than the amounts leached from cans held at or below 80°C for 60 min. The amount leached depended on the type of can, but not on the amount of BADGE leached from the cans. Considerably more BPA than BADGE leached to water from six cans. Two cans whose contents had high concentrations of BPA showed no BADGE leaching even at 121°C, suggesting the different kinds of epoxy resin can linings from others. The results imply that the main source of human exposure to BPA is food from cans with linings that contain high percentages of BPA as an additive or an unforeseen contaminant.     

紫外分光光度法测定食品模拟物中六价铬和铝

建立食品模拟物中铝和六价铬的紫外分光光度测定方法。用含内涂层的金属饮料罐(两片罐和三片罐)分别盛装水、3%乙酸水溶液、10%乙醇水溶液,于40℃浸泡240h,得到食品模拟物。水、3%乙酸水溶液食品模拟物样品直接测定,10%乙醇水溶液食品模拟物经蒸发乙醇再测定。采用二苯碳酰二肼分光光度法测定六价铬,铬天青S分光光度法测定铝。六价铬的方法检出限为10ng/mL,方法回收率在82.0%～101%;铝的方法检出限为25ng/mL,回收率在82.2%～108%。该方法准确度高,操作简单。     

Chlorohydrins of bisphenol A diglycidyl ether (BADGE) and of bisphenol F diglycidyl ether (BFDGE) in canned foods and ready-to-drink coffees from the Japanese market

BADGE.2HCl and BFDGE.2HCl were determined in 28 samples of ready-to-drink canned coffee and 18 samples of canned vegetables (10 corn, 5 tomatoes and 3 others), all from the Japanese market. HPLC was used as the principal analytical method and GCMS for confirmation of relevant LC fractions. BADGE.2HCl was found to be present in one canned coffee and five samples of corn, BFDGE.2HCl in four samples of canned tomatoes and in one canned corn. No sample was found which exceeded the 1mg/kg limit of the EU for the BADGE chlorohydrins. However the highest concentration was found for the sum of BFDGE.2HCl and BFDGE.HCl.H₂O at a level of 1.5mg/kg. A Beilstein test confirmed that all cans containing foods contaminated with BADGE.2HCl or BFDGE.2HCl had at lest one part coated with a PVC organosol.     

Migration of styrene monomer, dimers and trimers from polystyrene to food simulants

Migration experiments with polystyrene were performed in two-sided contact with n-heptane and distilled water as the food simulants at temperatures of 10, 24 and 40, and 40, 60 and 90°C, respectively. The surface/volume ratios in the migration cell were set at 8.04 and 10.05 dm² l^-1 for n-heptane and distilled water, respectively. Styrene monomer, styrene dimers and styrene trimers migrating to the food simulants were determined by GC-FID analysis. Heptane fully extracted the styrene monomer and the oligomers from the polystyrene sheet, whereas in the distilled water only the migrated styrene trimers could be detected. To determine the apparent diffusion coefficient, the migration process was analysed based on Fick's law. The higher the molecular weight of the oligomers, the more significant the reduction in the diffusion coefficient. Higher molecular weight oligomers also had lower activation energy of diffusion when the temperature dependence of diffusivity was analysed by the Arrhenius equation. The diffusion coefficient of the trimers was much higher for heptane contact than for water. The activation energy of the diffusion of trimers for water contact was higher than that for heptane.     

纳米金属/金属氧化物-聚烯烃食品包装膜中纳米成分迁移的扩散系数估算

为探讨Fick第二定律是否符合聚烯烃食品包装膜中纳米成分向食品模拟物的迁移规律,根据已有实验数据,基于Crank模型进行拟合,估算纳米金属/金属氧化物-聚烯烃食品包装膜中纳米成分的扩散系数,并分析温度、聚烯烃、纳米成分和食品模拟物对扩散系数的影响。结果表明：纳米成分向食品模拟物的迁移符合Fick第二定律。温度升高促进纳米成分的迁移,且温度与纳米成分扩散系数的关系符合Arrhenius公式。不同聚烯烃结构对扩散系数的影响不同;聚丙烯3 种结构中,纳米铜和纳米氧化锌在均聚共聚聚丙烯中的扩散系数最大。不同纳米成分质量分数对其扩散系数的影响不同。纳米成分与食品模拟物、聚烯烃之间的溶解度差异也会影响其向食品模拟物迁移。     

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography-mass spectrometry (LC-MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4-14.3 µg kg^-1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg^-1 bw day^-1, which is below the Tolerable Daily Intake of 50 µg kg^-1 bw recently established by EFSA.