Time‐ and temperature‐dependent migration studies of Irganox 1076 from plastics into foods and food simulants

The study provides an exhaustive set of migration data for octadecyl 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate (Irganox 1076) from low‐density polyethylene (LDPE) in several food matrices. Irganox 1076 was used as a model migrant because it represents one of the typical substances used as an antioxidant in food packaging polymers. Kinetic (time‐dependent) migration studies of Irganox 1076 were performed for selected foodstuffs chosen with different physical–chemical properties and in relation to the actual European food consumption market. The effect of fat content and of the temperature of storage on the migration from plastic packaging was evaluated. The results show that migration increased with fat content and storage temperature. All data obtained from real foods were also compared with data obtained from simulants tested in the same conditions. In all studied cases, the kinetics in simulants were higher than those in foodstuffs. The work provides data valuable for the extension of the validation of migration model developed on simulants to foodstuffs themselves.     

纳米银-聚乙烯复合包装中银对2 种抗氧化剂向食品模拟物迁移的影响

探究纳米银-聚乙烯复合包装中纳米银成分的存在对2 种抗氧化剂（Irganox1076和Irgafos168）向食品模拟物迁移规律的影响。将含有抗氧化剂的聚乙烯包装膜和同时含有抗氧化剂与纳米银的复合包装膜裁成正方形若干,分别浸泡于正己烷和体积分数95%乙醇溶液2 种食品模拟物中,密封后在20、40 ℃以及70 ℃条件下进行迁移实验。食品模拟物中2 种抗氧化剂的加标回收率在79.3%～108.0%之间,相对标准偏差在0.7%～5.3%之间。2 种抗氧化剂的迁移会随着迁移温度的升高以及迁移时间的延长而增加直至达到迁移平衡,且其在正己烷模拟物中的迁移量大于在体积分数95%乙醇模拟物中的迁移量;含纳米银聚乙烯塑料比不含纳米银聚乙烯塑料中的抗氧化剂向食品模拟物中的迁移量小,表明纳米银成分的存在可以抑制包装中的抗氧化剂向食品模拟物中的迁移。     

纳米银-聚乙烯复合包装中助剂对银向食品模拟物迁移的影响

为探究纳米银-聚乙烯复合包装中添加剂对纳米银颗粒向食品模拟物迁移的影响,在20、40 ℃和70 ℃条件下分别将空白纳米银聚乙烯复合包装和含有助剂（抗氧化剂1076、抗氧化剂168、光稳定剂622和光稳定剂944）的纳米银聚乙烯复合包装在3 g/100 mL乙酸溶液和体积分数50%乙醇溶液两种食品模拟物中浸泡1～30 h,然后蒸干定容并用电感耦合等离子体质谱测定银的含量。结果表明：食品模拟物中银的加标回收率在84.19%～115.69%之间,相对标准偏差在3.21%～8.75%之间;在8 h内塑料中的添加剂会促进银向两种食品模拟物的迁移;同时银的迁移率会随着迁移温度的升高和迁移时间的增加而增大直至平衡;平衡时,塑料中的添加剂反而阻碍银向这两种食品模拟物的迁移;银在酸性模拟物中的迁移率大于在酒精类模拟物中的迁移率。     

Effect of high‐pressure processing on the migration of antioxidant Irganox 1076 from polypropylene film into a food simulant

The effect of high‐pressure processing (HPP) on the migration behaviour of a typical antioxidant, Irganox 1076, from polypropylene (PP) flexible structures was studied. Initial concentrations of Irganox 1076 in polypropylene (PP) were 2.0 and 5.0 mg g^?1. The migration experiments were carried out on high‐pressure treated and non‐treated polypropylene pouches containing either 95 or 10% ethanol aqueous food simulating liquids (FSL) for 20 days at 40 and 60 °C. After the contact period, concentrations of Irganox in PP and FSL were measured to determine migration behaviour. The results showed that there was no significant difference in the concentration of Irganox 1076 migrating from PP, and into the FSL for pressure‐treated vs non‐treated samples. No significant concentration differences were found in non‐treated (control) samples and those treated for 5 and 10 min. However, there was a storage time effect on the migration level. There was also a significant migration effect on the migration of Irganox between the two different food simulants, and an increase in the HPP temperature increased the rate of migration. Copyright © 2004 Society of Chemical Industry     

聚乳酸抗菌包装中麝香草酚在食品模拟物中迁移规律

研究麝香草酚/聚乳酸包装材料中的抗菌剂麝香草酚在食品模拟物中的迁移行为。在4、10、20、30 ℃条件 下分别将麝香草酚/聚乳酸包装材料浸入蒸馏水溶液、体积分数4%乙酸溶液、正己烷溶液、体积分数10%乙醇溶液 中,通过紫外分光光度法测定食品模拟液中麝香草酚迁移量,分析温度和食品模拟物对麝香草酚迁移量的影响,在 实验数据基础上,采用Piringer方程建立麝香草酚迁移模型,分析验证迁移模型的合理性。结果表明：麝香草酚迁 移量随着迁移温度升高和迁移时间延长而逐渐上升直至平衡,且在4 种食品模拟物中麝香草酚的迁移量大小顺序为： 正己烷＞10%乙醇＞4%乙酸＞蒸馏水;根据幂律方程发现麝香草酚的迁移机制符合Fick扩散定律,且迁移方程扩散系 数随迁移温度升高而增大,分配系数与之相反;Piringer方程能够较好地描述麝香草酚迁移行为。在迁移实验的基础 上构建数学模型,进一步完善基于聚乳酸食品包装材料的迁移理论,以期更好地预测食品包装中麝香草酚的迁移。     

Stability testing of selected plastics additives for food contact in EU aqueous, fatty and alternative simulants

Within the framework of the AIR3-CT94-2360 EUproject, the stability of three plastics additives in three EU aqueous and fatty food simulants and in two alternative simulants was studied under various timetemperature conditions. The additives tested were bis(2-ethylhexyl) adipate (DEHA), bis(2-ethylhexyl) phthalate (DEHP) and octadecyl 3-(3,5-di- tert -butyl4-hydroxyphenyl) propionate (Irganox 1076). The various test conditions included exposures of 10 days at 40 o C, 1h at reflux temperature for all aqueous simulants, 10 days at 40 o C and 1h 175 o C for the olive oil and 2 days at 20 o C and 3h at 60 o C for the isooctane simulant. Following the exposure, the additive samples were extracted from aqueous simulants with hexane. A sonication step was necessary to ensure maximum extraction of control samples. In the case of the isooctane simulant, the samples were analysed directly from the simulant. The oil samples were extracted by acetonitrile. The extracts of samples exposed to various heat conditions as well as unexposed spiked controls and blanks were analysed by gas chromatography (GC) on a non-polar (5% -phenyl)-methylpolysiloxane capillary column with high temperature capabilities. The results showed that DEHA, DEHP and Irganox 1076 were stable at 40 o C and at reflux temperature in ethanolic or acidic aqueous simulants. The various additives were also stable in the organic isooctane simulant as well as in the fatty simulant olive oil. Studies on the stability of such additives used in food packaging are designed for regulatory purposes as an aid to decide whether the legislation should regulate limits for plasticizers based on a quantity in the food packaging itself or based on an ingested dose by the consumer.     

Kinetic migration studies from packaging films into meat products

One of the main concerns regarding safety of food packaging is the possible migration of chemical substances (monomers and other starting substances, additives, residues) from food contact materials into foods. To evaluate the effect of the fat content and of the temperature of storage on the migration from plastics packaging films into meat products as an important class of foodstuffs, the kinetic mass transport of a model migrant (diphenylbutadiene) from low density polyethylene (LDPE) film in contact with different meat products was investigated. From the data, the diffusion coefficients were calculated for the applied test conditions, by use of a mathematical model. The results showed that migration increased with fat content and storage temperature. Analysis of migration data corresponding to minced pork meat containing different amounts of fat, stored for 10 days at 25°C, revealed an excellent relationship between migration level and fat content. This behaviour was also found for other types of meat products (chicken and pork neck). A simplifying mathematical model was applied to derive effective diffusion coefficients in the polymer which, however, do take kinetic effects in the meat also into account. In the case of pork meat contact, the effective diffusion coefficients derived from mathematical modelling were ten times higher for storage at 25°C (1.88×10(-9)cm(2)s(-1)) than for storage at 5°C (1.2×10(-10)cm(2)s(-1)).     

Antioxidants and their migration into food simulants on irradiated LLDPE film

Effects of γ-irradiation on residual and migration levels of antioxidants, tris-(2,4-di-tert-butylphenyl) phosphite (Irgafos 168) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076), and their radiolysis products were investigated in the linear low density polyethylene (LLDPE) packaging samples treated at doses from 0 to 200 kGy. The content of Irgafos 168 was not detected in 5 kGy treated samples and the content of Irganox 1076 decreased by 34.9% from the initial level in 10 kGy treated samples. The radiolysis products, 2,4-di-tert-butylphenol (2,4-DTBP), 1,3-di-tert-butylbenzene (1,3-DTBB), and toluene were identified and their concentrations gradually increased as the irradiation dose increased. Migration of Irgafos 168 from the LLDPE pouch into food simulants, distilled water, acetic acid (4 ml/100 ml distilled water) or ethanol (20 ml/100 ml distilled water), was not detected at dose levels up to 200 kGy while that of the Irganox 1076 was detected in a decreasing mode with increasing dose.     

热力学数学模型对塑料中化学物向食品模拟液中迁移平衡时分配系数的预测研究

目的分配系数能够直接反映出塑料包装材料中有害化学物向食品迁移的水平,研究分配系数与塑料包装材料、迁移物及食品(模拟物)三者之间的关系有重要意义。方法以Scatchard-Hildebrand统计热力学理论为基础,从热力学平衡角度分析了化学物在包装材料/食品体系中的迁移和分配过程,建立了一个预测化学物迁移平衡时分配系数的热力学数学模型。通过所建立的初级数学模型对聚乙烯薄膜中四种抗氧化剂,即2,6-二叔丁基-4-甲基苯酚(BHT)、二丁基羟基茴香醚(BHA)、Irganox1010和Irganox1076向脂肪类食品模拟物异辛烷迁移平衡时状态进行模拟计算,并与已公开发表的实验数据进行了对比。结果聚乙烯薄膜中四种抗氧剂向异辛烷中迁移平衡的分配系数模拟值与实验值随温度变化趋势一致。结论该热力学模型符合迁移理论,对PE/抗氧剂/脂肪类食品体系分配系数的预测有一定的适用性。     

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。     

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.     

Migration of Chemical Compounds from Packaging Polymers during Microwave,Conventional Heat Treatment,and Storage

Polymeric packaging protects food during storage and transportation, and withstands mechanical and thermal stresses from high‐temperature conventional retort or microwave‐assisted food processing treatments. Chemical compounds that are incorporated within polymeric packaging materials to improve functionality, may interact with food components during processing or storage and migrate into the food. Once these compounds reach a specified limit, food quality and safety may be jeopardized. Possible chemical migrants include plasticizers, antioxidants, thermal stabilizers, slip compounds, and monomers. Chemical migration from food packaging is affected by a number of parameters including the nature and complexity of food, the contact time and temperature of the system, the type of packaging contact layer, and the properties of the migrants. Researchers study the migration of food‐packaging compounds by exposing food or food‐simulating liquids to conventional and microwave heating and storage conditions, primarily through chromatographic or spectroscopic methods; from these data, they develop kinetic and risk assessment models. This review provides a comprehensive overview of the migration of chemical compounds into food or food simulants exposed to various heat treatments and storage conditions, as well as a discussion of regulatory issues.     

A study on the migration of organic pollutants from recycled paperboard packaging materials to solid food matrices

Paper and board are widely used as food packaging materials, mainly for disposable products. As public interest in conservation of natural resources has accelerated in the past several years, the use of recycled paper and board has increased. Recycled fiber materials can be used in certain limits as food contact materials. The safety of recycled fiber-based materials for food contact applications is largely dictated by the ability of post-consumer contaminants to be absorbed into recycled materials and later released by the packaging material and trapped on the food. The present work was undertaken with the aim of investigating the physicochemical behavior of selected model contaminants on paper and board, in contact with foodstuffs thus producing a fundamental set of data about their mobility from recycled paper and board into foods. More specifically, the kinetics of migration of selected model contaminants (surrogates) from contaminated recycled paper packaging samples into dry foodstuffs with different fat content was studied using a method based on solvent extraction and GC-FID quantification. Results showed the ability of selected contaminants of various types and various volatilities to potentially transfer to dry foods. The proportion of substances migrated to food was strongly dependent on the nature of the paper samples, fat content of the food, chemical nature and volatility of the migrant. The highest level of migration of organic pollutants was observed for the substrate with the highest fat content. Furthermore, it is shown that contact time and temperature have a significant effect on migration of model contaminants into foods.     

Retention of α-tocopherol in low-density polyethylene (LDPE) and polypropylene (PP) in contact with foodstuffs and food-simulating liquids

Alpha-tocopherol occurs as a natural antioxidant in many foods and has also found use as a stabiliser in polymeric packaging materials. During storage of a food in contact with a plastic material, α-tocopherol may be released from the packaging material and transferred into the food. An active packaging application with the transfer of a substance, such as an antioxidant, from a packaging material to a food may help to prolong the shelf-life of the food. In this study, the retention of α-tocopherol in low-density polyethylene (LDPE) and polypropylene (PP) was investigated for contact with liquid foods with different fat contents and food simulants with different ethanol contents. The PP film exhibited excellent retention of α-tocopherol when in contact with all media, whereas some losses were observed from the LDPE film. A number of factors including fat, alcohol and organic acid contents of the various foodstuffs seemed to influence the loss of α-tocopherol from the LDPE film. © 1999 Society of Chemical Industry     

石墨烯/低密度聚乙烯复合包装膜中2种抗氧化剂向食品模拟物异辛烷的迁移

建立高效液相色谱法检测石墨烯/低密度聚乙烯复合食品包装薄膜中2种抗氧化剂(Irganox1076、Irgafos168)的方法。考察时间、温度以及石墨烯和石墨烯微片的存在对2种抗氧化剂向脂肪类食品模拟物异辛烷迁移的影响,同时分析2种不同抗氧化剂在迁移中的相互作用。结果表明,2种抗氧化剂的迁移会随着迁移温度的升高以及迁移时间的延长而增加直至达到迁移平衡;2种抗氧化剂之间存在协同作用,在迁移过程中会相互影响;石墨烯及石墨烯微片纳米粒子的团聚现象和吸附作用抑制了食品包装中的Irganox1076、Irgafos168两种抗氧化剂向异辛烷中的迁移。     

Migration of nanoparticles from plastic packaging materials containing carbon black into foodstuffs

Carbon black was investigated to assess and quantify the possibility that nanoparticles might migrate out of plastic materials used in the food packaging industry. Two types of carbon black were incorporated in low-density polyethylene (LDPE) and polystyrene (PS) at 2.5% and 5.0% loading (w/w), and then subjected to migration studies. The samples were exposed to different food simulants according to European Union Plastics Regulation 10/2011, simulating long-term storage with aqueous and fatty foodstuffs. Asymmetric flow field-flow fractionation (AF4) coupled to a multi-angle laser light-scattering (MALLS) detector was used to separate, characterise and quantify the potential release of nanoparticles. The AF4 method was successful in differentiating carbon black from other matrix components, such as extracted polymer chains, in the migration solution. At a detection limit of 12 µg kg^?1, carbon black did not migrate from the packaging material into food simulants. The experimental findings are in agreement with theoretical considerations based on migration modelling. From both the experimental findings and theoretical considerations, it can be concluded that carbon black does not migrate into food once it is incorporated into a plastics food contact material.     

食品包装材料中双酚A迁移量的测定

建立采用高效液相色谱法对塑料食品包装材料中双酚A向食品模拟物迁移量的检测方法。使用4种食品模拟物：水、质量分数为4%乙酸溶液、体积分数30%的乙醇溶液和脂肪类模拟物(正己烷、异辛烷和橄榄油)。结果表明,双酚A在与食品塑料包装接触过程中,无论在何种情况下都会向食品模拟物中迁移,尤其向醇类模拟物中迁移最严重;在温度超过60℃时,双酚A向食品模拟物中的迁移率骤增;在微波加热条件,高火700W功率时双酚A向食品模拟物中的迁移速率最快。该方法检测限为0.3ng/mL,线性范围为0.5～100ng/mL,线性相关系数为0.9997,回收率在92.0%～102.4%之间,相对标准偏差≤2.84%(n=5)。     

Solubility determination as an alternative to migration measurements

Solubility values for six UV stabilisers (Cyasorb UV-1164, Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 327 and Tinuvin 1577) and five antioxidants (Irgafos 168, Irganox 1010, Irganox 3114, Irganox 3790 and Irganox 565) were determined in all the liquid food simulants (3% (m/V) acetic acid–water mixture, 10% (V/V), 20% (V/V), 50% (V/V) ethanol–water mixture and vegetable oil) proposed in European Union Regulation No. 10/2011/EC, as well as in fruit juice and cola drink. The applied method was obtained by modification of the method for the determination of water solubility as described in OECD guideline Test No. 105. By using ultrasonication and shorter equilibration time, the time demand of the solubility determinations were decreased notably. Solubility values proved to be lower than the specific migration limits (as specified in 10/2011/EC) at 25°C for almost all target compounds in food simulants A, B, C and D1 as well as in fruit juice and cola drink. The exceptions were Tinuvin P and Irganox 3790 in simulant D1. The solubility in food simulant D2 was higher than 1000 µg ml^–1 for all target compounds. These results show that the solubility of some additives in food simulants can be so low that it makes migration studies for certain additive–food simulant pairs dispensable.     

Efficiency of whole and skimmed powdered milk for trapping volatile compounds released from plastic containers in high-temperature applications

Plastic food containers used for high-temperature applications are not completely inert, and potentially harmful chemicals may be transferred to foodstuffs when such containers are heated. The aim of this work was to investigate the role of food fat content on the efficiency of trapping volatile organic compounds from heated plastic packaging. Relatively simple food matrices such as powdered skimmed and whole milk were evaluated with respect to their retention of several selected migrants: toluene, 1-octene, ethylbenzene, o-, m-, and p-xylene, styrene, and 1,4-dichlorobenzene released from containers made of polypropylene (random and copolymer), polycarbonate, and styrene-acrylonitrile copolymer, which are all commonly used in high-temperature applications. The analytical method (purge and trap gas chromatography and mass spectrometry) was optimized for each matrix. The developed procedure had detection limits of 0.01 to 1.2 ng, depending on the analyte and sample matrix, and both reproducibility and repeatability (expressed as relative standard deviation) were below 15%. This method was applied to the different plastic materials. The concentrations of the volatile compounds in both matrices were well below the established specific migration limits. Temperature and fat content of powdered milk were the most influential variables in mass transfer processes. These values were compared with those obtained with either Tenax TA (alternative test medium for fatty food simulants) or Porapak Q (another widely used sorbent). Similar results were found in skimmed powdered milk and Tenax TA, but significant differences were observed for whole powdered milk.     

食品和药品接触材料聚丙烯中添加剂及 物质迁移的液相色谱分析

聚丙烯(PP)塑料被广泛用在食品及药品的包装上,PP中有害物质的迁移现已成为食品及药品安全隐患的重要组成部分,当食品与包装材料直接接触时,残留在PP包装材料里的抗氧剂及分解产物可以迁移到食品中污染食品。由于食品的多样性,因此常用几种食品模拟液来代替食品在实验室各种控制条件下进行迁移试验,因为迁移到模拟液里的添加剂浓度非常小,其浓度的测定常使用灵敏度较高的高效液相色谱法。迁移受到很多因素的影响,比如:接触的时间温度、接触的方式、包装材料的类型、迁移物的性质等。本文综述了聚丙烯包装材料有害物质迁移的研究现状,为我国食品包装行业标准化体系的建立提供一定的理论依据。