Migration of perfluoroalkyl acids from food packaging to food simulants

A broad range of fluorochemicals is used to impart oil and water barrier properties to paper and paperboard food packaging. Many of the fluorochemicals are applied to paper and paperboard as complex mixtures containing reaction products and by-products and unreacted starting materials. This work primarily focussed on the determination of seven perfluorocarboxylic acids (PFCAs) in two commercially available food contact papers: a di-perfluoro-alkyloxy-amino-acid and a perfluoroalkyl phosphate surfactant. In addition, the migration of the PFCAs into five food simulants from two commercial packages was evaluated. All seven PFCAs were detected in the range of 700–2220 µg kg^?1 of paper, while three perfluoroalkyl sulphonates were under the LOD. Results from migration tests showed that migration depends on paper characteristics, time and food simulant. The percentage of migration after 10 days at 40°C ranged from 4.8% to 100% for the two papers and different food simulants.     

Migration of Ti from nano-TiO2-polyethylene composite packaging into food simulants

An analytical method based on ICP-MS was developed for the determination of Ti in food simulants (3% (w/v) aqueous acetic acid and 50% (v/v) aqueous ethanol). The method was used to determine the migration of Ti from nano-TiO₂-PE films used for food packaging into food simulants under different temperature and migration time conditions. The maximum migration amounts into 3% (w/v) aqueous acetic acid were 1.4 ± 0.02, 6.3 ± 0.5 and 12.1 ± 0.2 μg kg^?1 at 25, 70 and 100°C, respectively, while into 50% (v/v) aqueous ethanol, the maximum migration amounts were 0.5 ± 0.1, 0.6 ± 0.03 and 2.1 ± 0.1 μg kg^?1 at 25, 70 and 100°C, respectively. Increasing the additive content in the film promoted migration of nanoparticles. The results indicated that the migration of nanoparticles might occur via dissolution from the surface and cut edges of the solid phase (film) into the liquid phase (food simulant).     

Migration of fluorochemical paper additives from food-contact paper into foods and food simulants

Fluorochemical-treated paper was tested to determine the amount of migration that occurs into foods and food-simulating liquids and the characteristics of the migration. Migration characteristics of fluorochemicals from paper were examined in Miglyol, butter, water, vinegar, water-ethanol solutions, emulsions and pure oil containing small amounts of emulsifiers. Additionally, microwave popcorn and chocolate spread were used to investigate migration. Results indicate that fluorochemicals paper additives do migrate to food during actual package use. For example, we found that microwave popcorn contained 3.2 fluorochemical mg kg^-1 popcorn after popping and butter contained 0.1 mg kg^-1 after 40 days at 4°C. Tests also indicate that common food-simulating liquids for migration testing and package material evaluation might not provide an accurate indication of the amount of fluorochemical that actually migrates to food. Tests show that oil containing small amounts of an emulsifier can significantly enhance migration of a fluorochemical from paper.     

Migration of fluorochemical paper additives from food-contact paper into foods and food simulants

Fluorochemical-treated paper was tested to determine the amount of migration that occurs into foods and food-simulating liquids and the characteristics of the migration. Migration characteristics of fluorochemicals from paper were examined in Miglyol, butter, water, vinegar, water–ethanol solutions, emulsions and pure oil containing small amounts of emulsifiers. Additionally, microwave popcorn and chocolate spread were used to investigate migration. Results indicate that fluorochemicals paper additives do migrate to food during actual package use. For example, we found that microwave popcorn contained 3.2 fluorochemical mg kg^?1 popcorn after popping and butter contained 0.1 mg kg^?1 after 40 days at 4°C. Tests also indicate that common food-simulating liquids for migration testing and package material evaluation might not provide an accurate indication of the amount of fluorochemical that actually migrates to food. Tests show that oil containing small amounts of an emulsifier can significantly enhance migration of a fluorochemical from paper.     

铝塑复合食品包装中的铝向食品模拟物的迁移研究

建立了基于电感耦合等离子体质谱法（ICP-MS）,铝塑复合食品包装中的铝向食品模拟物迁移量的测定方法。采用两种食品模拟物（3%（w/v）乙酸、水）,利用迁移机使食品模拟物与铝塑食品包装材料单面接触,在温度27±2、45、70℃下进行迁移实验,采用电感耦合等离子体质谱仪对食品模拟物中的铝元素进行测定,得出迁移规律。随着迁移时间的延长,铝的最大迁移量都在增加;在实验温度区间,随着温度的升高,铝的迁移量也随之增加至迁移平衡。本方法适合用于铝塑复合食品包装中的铝向3%（w/v）乙酸溶液和蒸馏水两种食品模拟物迁移后的检测。      

Migration of dehydroabietic and abietic acids from paper and paperboard food packaging into food-simulating solvents and Tenax TA

An investigation was undertaken to establish the concentration in paper products of dehydroabietic (DHA) and abietic (AA) resin acids, present in rosin, which are major toxicants of pulp- and paper-mill effluent. Their migration was studied from paper and paperboard products into various food-simulating solvents and the substitute fatty food simulant Tenax TA (modified polyphenylene oxide). DHA and AA were detected in five of 10 virgin paper products and in all 10 recycled paperboard products for food-contact use at concentrations of 14-500 and 110-1200 µg/g, respectively. In virgin paper products, the highest migration was into 95% ethanol or heptane, with negligible or no migration into other solvents. In recycled paperboard products, migration was highest into 95% ethanol, but was also observed into 20% ethanol, water and heptane. Migration to Tenax TA was also observed and the migration level increased with time. The maximum migration levels of DHA and AA into food simulants were 0.853 and 3.14 µg/g, respectively. The results suggest that, in the worst case, the daily intake of DHA and AA from paper and paperboard products was 50 times lower than the tolerable daily intake of rosin.     

Migration of melamine from can coatings cross-linked with melamine-based resins,into food simulants and foods

Resins based on melamine-formaldehyde and related analogues such as methylolated melamine are used to cross-link coatings used inside food cans and on the metal closures of glass jars. Thirteen commercially coated cans and closures representing 80% of the European market were tested using simulants under realistic industrial heat-processing conditions for canned and jarred foods. The food simulants and the retort conditions used were 3% acetic acid for 1?h at 100°C and 10% ethanol for 1?h at 130°C. The highest migration level seen for melamine into simulant was 332?µg?kg^?1. There was no detectable migration of the melamine analogues cyanuric acid (<1?µg?kg^?1) or ammelide (<5?µg?kg^?1) from any sample. Twelve of the thirteen samples released no detectable ammeline (<5?µg?kg^?1) but the coating giving the highest release of melamine did also release ammeline at 8?µg?kg^?1 with the higher of the two process temperatures used. Migration experiments into food simulant and foods themselves were then conducted using two experimental coatings made using amino-based cross-linking resins. Coated metal panels were exposed to the food simulant 10% (v/v) aqueous ethanol and to three foodstuffs under a range of time and temperature conditions both in the laboratory and in a commercial food canning facility using proprietary time and temperature conditions. The highest migration into a food was 152?µg?kg^?1 from the first coating processed for a long time at a moderate sterilisation temperature. The highest migration into simulant was also from this coating at 220?µg?kg^?1 when processed at 134°C for 60?min, dropping to 190?µg?kg^?1 when processed at 123°C for 70?min. Migration from the second coating was quite uniformly two to three times lower under all tests. These migration results were significantly higher than the levels of melamine extractable using 95% ethanol at room temperature. The experiments show that commercial canning and retorting can be mimicked in an acceptable way using laboratory tests with an autoclave or a simple pressure cooker. The results overall show there is hydrolytic degradation of the melamine cross-linked resins to release additional melamine. There is a strong influence of the temperature of heat treatment applied with foods or simulants but only a minor influence of time of heating and only a minor influence, if any, of food/simulant acidity.     

Migration of substances from food packaging materials to foods

The employment of novel food packaging materials has increased the number of occurring hazards due to the migration from packaging material to the packaged food. Although polymers have mainly monopolized the interest of migration testing and experimentation, recent studies have revealed that migration also occurs from "traditional" materials generally considered to be safe, such as paper, carton, wood, ceramic, and metal. The regulations and the directives of the EU tend to become stricter in this respect. The emphasis is on reaching a consensus in terms of food simulants and testing conditions for migration studies. Furthermore, the list of hazardous monomers, oligomers, and additives continues to augment in order to ensure that the consumer safety is in current agreement with the HACCP, which is continuously gaining ground.     

采用ICP-MS研究聚酯类食品包装材料中锑向食品模拟物的迁移规律

目的 建立聚酯(PET)和4种食品模拟物中锑的电感耦合等离子体质谱(ICP-MS)测定方法.用该方法研究PET中的锑向水、10％(V/V)乙醇溶液、3％(W/V)乙酸水溶液和精炼橄榄油4种食品模拟物迁移的行为与浸泡时间、温度、食品模拟物属性、锑初始含量等参数的关系.方法 在不同的温度下,将不同的PET浸泡于食品模拟物中,于一定的时间点吸取少量浸泡液,用ICP-MS测定其含量.结果 ICP-MS方法回收率在94.3％ ～96.1％之间,相对标准偏差在1.38％ ～3.31％之间.结论 锑迁出量随温度升高而增加;随着时间的延长,锑迁出量逐渐增加,一定时间后达到迁移平衡;大部分PET材料本底含量越高迁出量越高;PET中锑易于在酸性食品模拟物中迁出,应少食用PET包装的酸性食品.     

有机涂层食品接触材料中甲醛在食品模拟物中迁移规律的研究

目的 研究了有机涂层食品接触材料中毒害物质甲醛在食品模拟物中的迁移规律。方法 根据产品的实际使用条件,以食品模拟物对样品进行模拟浸泡,以乙酰丙酮分光光度法对食品模拟物中甲醛迁移量进行测定。结果 在相同的使用条件下,酸性模拟物中甲醛的迁移量最大;在接触同种食品模拟物时,甲醛的迁移量随着高压灭菌时间的延长和灭菌温度的升高而增加;货架存放时间对甲醛的迁移量无明显影响。结论 通过对甲醛迁移规律的考察,得出了有机涂层食品接触中甲醛的迁移风险。     

UV油墨光引发剂EDB在食品软包装中的迁移分析

为研究UV油墨光引发剂4-二甲氨基苯甲酸乙酯（EDB）在食品软包装中的迁移行为,制作了实际印刷、直接污染和蹭脏污染三种包装试样,分别以3%（w/v）乙酸、10%（v/v）乙醇和95%（v/v）乙醇作为酸性、酒精类和脂类食品模拟液,研究了EDB的迁移和残留行为。结果表明,光引发剂EDB在三种包装试样中都发生迁移。在三种食品模拟液中,EDB向95%乙醇中的迁移量最大,且初始迁移速率最快,说明EDB更容易向脂类模拟物迁移。温度越高,迁移量越大,达到平衡的时间越短。      

PVC密封圈中环氧大豆油向食品模拟物迁移量的测定

建立了气相色谱-质谱法（GC-MS）对食品玻璃包装瓶盖聚氯乙烯（Polyvinyl chloride polymer,PVC）密封圈中环氧大豆油（Epoxidized soybean oil,ESBO）向食品模拟物迁移量的检测方法。以蒸馏水和橄榄油为模拟物,在40℃条件下浸泡瓶盖240h,经甲酯化和衍生化,以11,14-二环氧二十烷酸乙酯为内标物,通过测定环氧亚油酸（18∶2 2E）衍生物的含量,进而定量测定ESBO的迁移量。结果表明:ESBO在0.5⁵0.0mg/kg的浓度范围内线性关系好,R2大于0.993,回收率在92.8%¹03.9%之间,RSD为0.9%⁸.0%（n=6）,检出限（LOD）为0.2mg/kg,定量限（LOQ）为0.5mg/kg,方法精密度好,灵敏度高,定性定量准确。最后,应用其对24种不同PVC密封圈中的ESBO迁移量进行测定,水基模拟物中ESBO的迁移量符合法规EC 10/2011限量,而在油脂模拟物中测得含量在0.7⁵01.8mg/kg之间,其中7种超过了限量要求。      

纸塑包装中PCBs的迁移模型及效果评价

多氯联苯化合物种类繁多,无法逐一进行冗长的迁移试验,迁移模型不仅可以简化迁移研究,而且概括性强,适用范围广。文章基于"有限包装-有限食品"模型,考虑纸层与塑料层间的扩散系数,忽略其间分配系数的差异,建立迁移预测模型。并以Brandsch模型估算扩散系数,以定义式粗算分配系数,并分析迁移试验值与模拟预测情况的差异。对比结果显示,试验值变化的整体趋势与模型预测结果相符。迁移量均随着时间的延长而增加,且平衡时的迁移量随着温度的升高而加大,大多预测值明显略高于试验值。     

食品接触材料中多环芳烃在食品模拟物中的迁移规律研究

采用气相色谱-质谱联用法,对食品接触材料中多环芳烃在水、乙酸(体积分数为3%)、乙醇(体积分数为10%)和异辛烷等4种食品模拟物中的迁移规律进行了研究,研究迁移量与实验的温度、时间和模拟物属性等参数的关系。结果表明:模拟物的属性对迁移行为有显著影响,迁移量随温度的升高和时间的增加而变大。     

陶瓷食品包装材料中铅、镉向真实食品的迁移研究

陶瓷食品包装容器中的有害重金属铅、镉向食品的迁移会造成食品污染进而危害消费者身体健康。本文通过制备含有铅、镉这两种重金属元素的陶瓷样品,使之分别在20℃和40℃的条件下与白酒、黄酒、醋和酸豆角汁这四种真实食品接触一定时间来研究这两种重金属的迁移行为。结果表明:铅、镉迁移量随着温度的升高而增加,并且迁移速率也与温度成正比;铅、镉的迁移量受食品的pH影响,pH越低,迁移量越高;铅的迁移量还与酒精度成反比,酒精度越高,铅的迁移量越少。      

端视ICP-AES法测定食品用塑料包装容器在四种食品模拟物中有害元素迁移量

建立了端视电感耦合等离子体原子发射光谱(ICP-AES)法测定食品用塑料包装容器在4种食品模拟物中有害元素铅、镉、铬、砷、锑和锗迁移量的分析方法。研究了不同食品模拟物试液的处理方法以及仪器工作参数对铅、镉、铬、砷、锑和锗测定信号的影响,消除了乙醇基质的严重抑制干扰,并优化了ICP-AES测定条件。铅、镉、铬、砷、锑和锗的检出限分别为0.0025、0.00023、0.00016、0.0033、0.0032、0.0030mg/L,测定低限:以蒸馏水、3%乙酸、10%乙醇作食品模拟物时分别为0.010、0.0010、0.0010、0.010、0.010、0.010mg/L;以精制橄榄油作食品模拟物时分别为0.020、0.0020、0.0020、0.020、0.020、0.020mg/L。加标回收率在92.0%～98.8%,相对标准偏差在1.69%～7.64%(n=8)。方法灵敏、简便、快速、准确,适用于进出口食品用塑料包装容器中有害元素迁移量的快速测定。     

Assessment of the migration potential of nanosilver from nanoparticle-coated low-density polyethylene food packaging into food simulants

An experimental nanosilver-coated low-density polyethylene (LDPE) food packaging was incubated with food simulants using a conventional oven and tested for migration according to European Commission Regulation No. 10/2011. The commercial LDPE films were coated using a layer-by-layer (LbL) technique and three levels of silver (Ag) precursor concentration (0.5%, 2% and 5% silver nitrate (AgNO₃), respectively) were used to attach antimicrobial Ag. The experimental migration study conditions (time, temperature and food simulant) under conventional oven heating (10 days at 60°C, 2 h at 70°C, 2 h at 60°C or 10 days at 70°C) were chosen to simulate the worst-case storage period of over 6 months. In addition, migration was quantified under microwave heating. The total Ag migrant levels in the food simulants were quantified by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Mean migration levels obtained by ICP-AES for oven heating were in the range 0.01–1.75 mg l^?1. Migration observed for microwave heating was found to be significantly higher when compared with oven heating for similar temperatures (100°C) and identical exposure times (2 min). In each of the packaging materials and food simulants tested, the presence of nanoparticles (NPs) was confirmed by scanning electron microscopy (SEM). On inspection of the migration observed under conventional oven heating, an important finding was the significant reduction in migration resulting from the increased Ag precursor concentration used to attach Ag on the LDPE LbL-coated films. This observation merits further investigation into the LbL coating process used, as it suggests potential for process modifications to reduce migration. In turn, any reduction in NP migration below regulatory limits could greatly support the antimicrobial silver nanoparticle (AgNP)-LDPE LbL-coated films being used as a food packaging material.     

食品包装材料中邻苯二甲酸酯的迁移规律研究

目的研究不同食品包装材料中邻苯二甲酸酯(phthalate esters,PAEs)的迁移规律。方法采用气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)对不同温度、不同时间条件下PAEs从食品包装材料中向水、4%乙酸、50%乙醇与异辛烷食品模拟物中的迁移规律进行研究。结果 PAEs的迁移受食品模拟溶液、温度、时间、包装材料的影响。不同食品模拟物中迁移率为:异辛烷50%乙醇4%乙酸≈水;在同一种食品模拟物中,随着迁移时间延长和温度增加PAEs迁移量增大,温度越高迁移速率越快;食品包装材料的材质不同,PAEs含量不同,PAEs含量越高的包装材料迁移到食品中的量也越大。结论本研究可以为食品的加工生产、存储、运输过程的安全控制提供理论基础和方法依据。     

Migration of photoinitiators from paper to fatty food simulants: experimental studies and model application

The migration of five different photoinitiators from kraft paper to two fatty food simulants, Tenax^® and 95% ethanol, was investigated under different conditions. The effects of temperature and storage time, as well as the physicochemical properties of the photoinitiators on migration, were discussed. Mathematical models based on Fick’s second law generated from two cases, single- and two-side contacts, were applied to predict the migration behaviour from the paper to the food simulants. The partition coefficients estimated from the model decreased with temperature. The diffusion coefficients of the selected photoinitiators from the paper ranged from 1.55 × 10^–10 to 7.54 × 10^–9 cm² s^?1 for Tenax and from 2.79 × 10^–9 to 8.03 × 10^–8 cm² s^?1 for 95% ethanol. The results indicate that the applied model can predict the migration of photoinitiators in the initial short period before equilibrium, and the migration from paper to Tenax through a single-side contact demonstrated an especially high concordance.     

高温下白卡纸中二苯甲酮和1-羟基环己基苯基甲酮向食品模拟物质的迁移

研究了在70℃和90℃下,采用直接浸泡法使白卡纸中的固化剂二苯甲酮（BP）和1-羟基环己基苯基甲酮（HCH）向水、3%乙酸、15%乙醇、50%乙醇、95%乙醇等食品模拟物质迁移,采用高效液相色谱仪（HPLC）分别检测迁移后模拟物质中的迁移量。结果表明两种固化剂在0.64⁴0mg/L的质量浓度范围内呈良好线性,相关系数不小于0.9995。温度越高,迁移时间越长,迁移量也越大;随着乙醇浓度的增高,BP、HCH的迁移量也增加;对于3%乙酸,BP和HCH迁移率最小。