盐和糖含量对食品复合袋中二氨基二苯甲烷迁移的影响

采用液相色谱-质谱（liquidchromatography-massspectrometry,LC-MS）法检测二氨基甲苯（diaminotoluene,TDA）和二氨基二苯甲烷（diaminodiphenylmethane,MDA）同分异构体的迁移量。调查了市场上10种食品复合袋中TDA和MDA向4%乙酸的迁移水平。此外,将盐析、糖析辅助液液萃取与LC-MS结合,研究氯化钠和蔗糖对食品复合袋中2,4’-MDA和2,2’-MDA向10%乙醇溶液和水迁移的影响。结果显示：4,4’-MDA、2,4’-MDA和2,2’-MDA在4个样品中被测出,其中一个样品的MDA总迁移量超过10μg/kg。盐、糖的存在对2,4’-MDA和2,2’-MDA向10%乙醇溶液和水迁移产生显著影响（P<0.05）,迁移量随着食品模拟物中盐、糖质量浓度的增加（2、5、10、15、20 g/100 mL）显著降低（P<0.05）。对用于高盐、糖食品的包装迁移测试时,可能需要调整食品模拟物。     

金属涂层罐中三聚氰胺污染来源的研究

简要介绍了食品包装用金属涂层三片罐的加工工艺,研究了三片罐各工艺流程中三聚氰胺的迁移量。试验结果表明:内壁涂料是食品罐中三聚氰胺迁移的主要来源;由于制罐前半成品均为层叠堆放,外壁油墨的黏脏也是三聚氰胺污染的重要来源。     

聚对苯二甲酸乙二醇酯饮料瓶食品级循环再生料中锑的迁移行为

该研究探究聚对苯二甲酸乙二醇酯(polyethylene terephthalate, PET)饮料瓶和再生食品级再生聚对苯二甲酸乙二醇酯(regenerated polyethylene terephthalate, rPET)切片中锑迁移情况,及食品模拟液、温度对PET饮料瓶和rPET切片中锑迁移行为的影响。将PET饮料瓶和rPET切片样品在4%(体积分数)乙酸、10%(体积分数)和20%(体积分数)乙醇食品模拟液中完全浸泡,利用电感耦合等离子体质谱仪(inductively coupled plasma-mass spectrometry, ICP-MS)对PET饮料瓶和rPET切片中的锑进行定量分析。通过实验迁移量与迁移模型预测曲线拟合,分析不同食品模拟液和温度对迁移扩散系数的影响。结果表明,在60℃且达到迁移平衡时,rPET切片较PET饮料瓶中锑向不同食品模拟液中的迁移量均增加;对比3种食品模拟液,PET饮料瓶和rPET切片中锑向4%乙酸食品模拟液中扩散系数更高;在不同温度下,PET饮料瓶中锑向4%乙酸中迁移的实验测定值与迁移模型预测曲线拟合效果良好(拟合度达0.9以上),温...     

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。     

油墨溶剂在食品与塑料包装间分配系数测定

依据PRV(相位比)的原理,建立气-液-固三相平衡系统,利用顶空气相色谱法测定平衡时空气中丁酮、甲苯、乙酸丁酯的浓度,通过计算得到油墨中三种有害物质在六种聚合物(PE、PP、OPP/CPP、PET/CPP、PET/PE和PET/PA/CPP)和六种食品模拟液(蒸馏水、3%乙酸、6%乙酸、10%乙醇、40%乙醇和正己烷)之间的分配系数,研究发现PP吸附丁酮较PE多,而PE吸附甲苯和乙酸丁酯的能力要高于PP。丁酮、甲苯、乙酸丁酯迁移量随着模拟液浓度的增大而增大。三种物质都更容易迁移到代表脂肪类模拟物的正己烷中。     

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。     

食品包装薄膜残留苯和甲苯在食品中的迁移研究

为了解食品包装薄膜溶剂残留的危害现状及包装各类食品的安全性,试验采用气相色谱法对市场中常见的9种食品包装薄膜中苯和甲苯的残留及两者在包装过程中对苹果、油条、煎饺、啤酒的迁移进行了研究。结果表明,未检出苯或甲苯的薄膜在其相应包装的食品中也未检出苯或甲苯;在苹果和啤酒中均为检出两者;迁移量与包装时间有密切关系,油条和煎饺在包装过程中的最初10min均未检出两者,包装60min时最大迁移量达到1.168mg/kg。     

蜜胺餐具中三聚氰胺单体的迁移规律研究

结合蜜胺餐具的实际使用情况,选用合适的食品模拟物进行迁移实验,采用LC-MS/MS法测定三聚氰胺迁移量,研究蜜胺餐具中三聚氰胺单体的迁移规律。重点考察了食品模拟物种类、接触时间、接触温度、乙酸浓度、乙醇浓度、重复使用和微波加热等迁移条件下蜜胺餐具中三聚氰胺迁移量的变化情况。结果表明酸性食品和牛奶中的三聚氰胺迁移风险较高,且需控制蜜胺餐具的使用温度、盛放时间、重复使用次数及微波加热功率和时间以降低密胺餐具中三聚氰胺迁移风险。     

食品包装用三聚氰胺成型品中甲醛迁移规律的研究

目的研究食品包装三聚氰胺成型品中甲醛迁移规律。方法采用盐酸苯肼分光光度法测定60、75和90℃三个模拟温度下甲醛从食品包装用三聚氰胺成型品中迁移至3%乙酸、15%乙醇两种模拟溶剂中的量。根据所得的实验数据,讨论了不同温度和不同食品模拟物的选择对甲醛迁移行为的影响,以及样本重复10次进行迁移实验时甲醛迁移量的变化规律。结果3%醋酸作为模拟溶剂的甲醛迁移量较15%乙醇作为模拟溶剂的高,且其迁移量随着模拟温度的升高而增多;3个温度下,2种模拟溶剂中单次迁移实验的甲醛迁移量均未超过我国国家标准的限量值和欧盟规定对其规定的特定迁移量(SML)2.5 mg.dm-2,而以3%醋酸作为模拟溶剂的甲醛的10次迁移实验的总量均超过欧盟对甲醛的特定迁移量。结论食品包装用三聚氰胺成型品不宜在酸性和高温条件下使用。     

蒸煮温度和模拟液对复合膜中甲苯迁移及阻隔性能的影响

采用顶空气相色谱法研究不同蒸煮条件和模拟液种类对双向拉伸尼龙薄膜/流延聚丙烯薄膜耐蒸煮复合膜中残留甲苯迁移及阻隔性能的影响。结果表明,随着蒸煮温度升高和处理时间的延长,不同模拟液中甲苯的迁移率逐渐增大;其迁移率大小依次为：5 g/100 mL氯化钠＞0.2 g/100 mL谷氨酸钠＞10 g/100 mL蔗糖＞蒸馏水;高温蒸煮导致调味品模拟液处理复合膜的氧气透过量和水蒸气透过量上升;红外光谱、差示扫描量热仪和扫描电子显微镜分析结果表明,高温、蒸馏水和氯化钠处理会破坏膜的内部结构,使其结晶度下降,分子间作用力减弱、导致其结构松散、膜的表面凹凸不平、出现扭曲现象。     

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。     

食品金属罐中14种双酚类物质迁移量的同时测定及杀菌过程对其迁移的影响

为了调查国内食品金属罐中双酚类物质的迁移水平,本文建立了同时测定食品金属罐中14种双酚类物质迁移量的高效液相色谱法,并研究了杀菌过程对双酚类物质迁移的影响及食品金属罐中双酚类物质的迁移规律.结果表明,14种双酚类物质在4种食品模拟物(4％体积乙酸、10％体积乙醇、50％体积乙醇和异辛烷)中线性关系良好,加标回收率为83...     

Food and beverage can coatings: A review on chemical analysis,migration, and risk assessment

The internal surface of food and beverage cans is generally covered with polymeric coatings to preserve food and protect metal substrate from corrosion. Coating materials are complex formulations that contain different starting substances (e.g., monomers, prepolymers, additives, etc.) and in addition during the manufacture of the material several compounds can be formed (e.g., reaction products, degradation products, etc.). These substances have the potential to migrate into the food. Many of them have not been identified and only some have been toxicologically evaluated. This article aims to provide a comprehensive review on the analytical methods used for the identification of potential migrants in can coatings. The migration and exposure to chemicals migrating from can coatings are also reviewed and discussed so far, which is essential for risk assessment. Moreover, a brief section on the current status of the legislation on varnishes and coatings for food contact in Europe is also presented. Liquid chromatography coupled to diode array and fluorescence detectors and particularly to mass spectrometry and gas chromatography–tandem mass spectrometry seem to be the techniques of choice for the identification of potential migrants in can coatings. Some studies have reported migration levels of BPA (bisphenol A) and BADGE (bisphenol A diglycidyl ether) and derivatives exceeding the specific migration limits set in the European legislation. On the whole, low dietary exposure to migrants from can coatings has been reported. However, it is interesting to highlight that in these studies the combined exposure to multiple chemicals has not been considered.     

Migration of bisphenol A from can coatings—effects of damage, storage conditions and heating

Bisphenol A (BPA) is an important monomer used in the manufacture of epoxy resins for internal food can linings. Experiments were conducted to investigate the effects of different storage conditions and can damage on the migration of BPA to foods. These experiments were conducted in a systematic fashion by filling empty epoxyphenolic coated cans with four foods: soup, minced beef, evaporated milk and carrots and a food simulant (10% ethanol). Filled cans of each food type or simulant were then sealed and processed using appropriate conditions, before storage at three different temperatures: 5°C, 20°C and 40°C. For each of the storage regimes, 50% of the cans were dented to establish if this would lead to increased BPA migration. Cans were removed from these stocks at intervals of 1, 3 and 9 months storage at 5°C and 20°C or 10 days, 1 and 3 months at 40°C. Some initial problems of heterogeneity between samples was overcome by determining the amount of BPA in food as well as in the can lining. It was found that 80-100% of the total BPA present in the coating had migrated to foods directly after can processing by pilot plant filling with food or simulant, sealing and sterilization. This level was not changed by extended storage (up to 9 months) or can damage, indicating most migration was occurring during the can processing step. There was no noticeable difference, in this respect, between the different foods or the food simulant. Analysis of control samples (foods fortified with ∼0.1 mg kg^-1 BPA and contained in Schott bottles) showed that BPA was stable under both processing and storage. Experiments were also conducted to investigate the potential effects, on the migration of BPA from can coatings, of cooking or heating foods in the can prior to consumption. Food cans were purchased and the food either cooked or heated in the can. BPA was analysed prior to and after the heating/cooking process. It was concluded from the results that there were no appreciable differences in the BPA level before and after cooking or heating.     

The migration from the internal coatings of food cans; summary of the findings and call for more effective regulation of polymers in contact with foods: a review

The analysis of migrates from the internal coatings of food cans showed that the present regulation is not sufficient to ensure safety of food contact polymers. The migrates often consist of complex mixtures of reaction products and impurities, and their harmlessness cannot be deduced from the use of non-toxic starting substances compiled in positive lists. The regulation proposed herein asks producers to analyse the composition of the migrates. It includes an upper limit for the molecular weight (e.g. 1000Da) and thresholds defining concentrations in the foods down to which components must be identified and evaluated. Primarily considering feasibility at reasonable costs, thresholds of 30 mu g/kg for individual components and 300 mu g/kg for the sum of the unidentified materials are proposed. Producers must be able to demonstrate that the individual components or mixtures exceeding this limit, including reaction products with food components, have no toxic effect.     

Target and non-target analysis of migrants from PVC-coated cans using UHPLC-Q-Orbitrap MS: evaluation of long-term migration testing

A simple, rapid and sensitive method for analyzing multi-target and non-target additives in polyvinyl chloride (PVC) food can coatings using ultra-high-performance liquid chromatography coupled to quadrupole-orbital ion-trap mass spectrometry was developed. This procedure was used to study the behaviour of a cross-linking agent, benzoguanamine (BGA), two slip agents, oleamide and erucamide, and 18 other commonly used plasticisers including phthalates, adipates, sebacates, acetyl tributyl citrate and epoxidised soybean or linseed oils. This optimised method was used to detect these analytes in food simulants (water and 3% acetic acid) in a long-term migration test of PVC-coated food cans for a period ranging from 1 day to 1.5 years at 40°C. Although very low detection limits (5 ng ml^–1) were obtained for the majority of compounds, none of the monitored plasticisers and slip agents was detected in simulants extracted from cans over the period of the test. However, the presence of BGA in both aqueous food simulants was confirmed based on high-resolution mass spectrometry, product ion spectra and analysis of a reference standard. The BGA concentration in both simulants continued to increase with storage time: after 1.5 years storage in aqueous food simulants at 40°C, BGA was detected at concentrations up to 84 µg dm^–2. We believe this is the first study describing the long-term migration capacity of BGA from any vinyl coating material intended for use in PVC-coated food cans. Our results may have implications for migration test protocols for food cans that will be stored for extended time periods.     

Studies on the analytical method for epichlorohydrin from internal can coatings

An improved migration test was developed for determination of trace amounts of epichlorohydrin from internal can coatings. Eight kinds of sample cans, coated mainly with epoxy resin, for foods and beverages were prepared, and both their bodies and lids were tested for migration as follows. A body was filled with n-pentane and soaked for 2 hours at 25 degrees C. A lid was soaked in n-pentane (2 mL/cm2) for 2 hours at 25 degrees C. The test solution was analyzed by GC-FID and GC/MS using two DB-WAX capillary columns with different inside diameters. The limits of quantitation were 0.05 microgram/mL by GC-FID and 0.02 microgram/mL by GC/MS with selected ion monitoring. Recoveries of spiked epichlorohydrin were 99.9-104.5% at the level of 0.05 microgram/mL and 0.5 microgram/mL, with high precision. In this study, no epichlorohydrin was found to have migrated from any of the bodies and lids.     

Study on the migration phenomena of selected metals in canned fruits during long storage

Experimental studies were conducted on the migration of Fe, Sn, Ca, and Mg in canned fruits: black currant, cherry and strawberry. Three-piece-cans had been protected with different coatings and technics. Cans of 31 capacity with fruits were stored in ambient temperature (ca 20 °C) during 60 weeks. There was stated increasing dependence of storage time on concentration of Fe and Sn in cans. Contents of Ca and Mg in this time systematically decreased in cans due to adsorption process of these metals on internal coatings. Migration rate of Fe and Sn, as well as migration trends of Ca and Mg (adsorption process) are shown on figures. There are great differences among migration of Fe, Sn and migration trends of Ca and Mg. Both these phenomena are disadvantageous for quality of canned fruits.     

超高效液相色谱法同时测定食品塑料包装材料中紫外吸收剂和抗氧化剂的迁移量

目的建立食品塑料包装材料中限用紫外吸收剂(UV-0、UV-9、UV-71、UV-326、UV-327、UV-234)和抗氧化剂(2246、425、TH-1790、3114和1076)迁移量的超高效液相色谱(ultra performance liquid chromatography,UPLC)测定方法。方法优化仪器条件及模拟液萃取条件,考察超纯水、3%乙酸水(V:V)溶液、10%乙醇水(V:V)溶液及95%乙醇水(V:V)溶液等4种食品模拟物中紫外吸收剂和抗氧化剂的迁移量,并将建立的方法用于市售样品迁移量的检测。结果 11种目标物质在相应的浓度范围内线性关系良好,相关系数r~2大于0.9992,方法检出限为0.5~2.0 mg/L;平均加标回收率为81.2%~113.2%,相对标准偏差(n=6)为2.8%~8.5%。结论该检测方法灵敏、准确,满足欧盟指令(EU)No.10/2011和GB 9685-2008对食品塑料接触材料及制品中紫外吸收剂和抗氧化剂特定迁移量(SML)的限量要求,适用于食品塑料包装材料中紫外吸收剂和抗氧化剂的迁移量的测定。