Correlation of foodstuffs with ethanol–water mixtures with regard to the solubility of migrants from food contact materials

Today most foods are available in a packed form. During storage, the migration of chemical substances from food packaging materials into food may occur and may therefore be a potential source of consumer exposure. To protect the consumer, standard migration tests are laid down in Regulation (EU) No. 10/2011. When using those migration tests and applying additional conservative conventions, estimated exposure is linked with large uncertainties including a certain margin of safety. Thus the research project FACET was initiated within the 7th Framework Programme of the European Commission with the aim of developing a probabilistic migration modelling framework which allows one (1) to calculate migration into foods under real conditions of use; and (2) to deliver realistic concentration estimates for consumer exposure modelling for complex packaging materials (including multi-material multilayer structures). The aim was to carry out within the framework of the FACET project a comprehensive systematic study on the solubility behaviour of foodstuffs for potentially migrating organic chemicals. Therefore a rapid and convenient method was established to obtain partition coefficients between polymer and food, K_P/F. With this method approximately 700 time-dependent kinetic experiments from spiked polyethylene films were performed using model migrants, foods and ethanol–water mixtures. The partition coefficients of migrants between polymer and food (K_P/F) were compared with those obtained using ethanol–water mixtures (K_P/F’s) to investigate whether an allocation of food groups with common migration behaviour to certain ethanol–water mixtures could be made. These studies have confirmed that the solubility of a migrant is mainly dependent on the fat content in the food and on the ethanol concentration of ethanol–water mixtures. Therefore dissolution properties of generic food groups for migrants can be assigned to those of ethanol–water mixtures. All foodstuffs (including dry foods) when allocated to FACET model food group codes can be classified into a reduced number of food categories each represented by a corresponding ethanol–water equivalency.     

Interaction between plastics packaging materials and foodstuffs with different fat content and fat release properties

The migration of an addictive (phenolic antioxidant) from different types of plastic food packaging materials (low density polyethylene [LDPE], high density polyethylene [HDPE], polypropylene [PP], acrylonitrile-butadiene-styrene [ABS] and high-impact polystyrene [SB]) into low-calorie (reduced fat) foodstuffs has been determined under normal storage conditions, and shown in most cases to be equivalent to migration into normal foodstuffs. Certain exceptions are discussed and related to the fat-release properties of the particular foodstuffs. Additive transfer into low-calorie products, as well as into emulsions of fat and water, has been compared with that into aqueous acetic acid and test fat HB 307 under normal storage conditions and after 10 days at 40 degrees C. The transfer of antioxidant from plastics was found to decrease in the order LDPE, HDPE, PP, SB and ABS. Migration was found to be higher into pure fat and margarine than into mayonnaise. When comparing absorption from different emulsions of fat and water, the ranking for plastics was the same as the above with LDPE having a greater absorption than HDPE, except that ABS and PP had absorptions of the same order whilst it was significantly higher for SB. The type of emulsion was, however, found to have a greater influence on migration of the antioxidant from the polymer than on the fat absorption from the emulsion. The results are discussed in relation to earlier work and also with respect to the classification of foodstuffs.     

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.     

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.     

Migration behaviour of silicone moulds in contact with different foodstuffs

Various foodstuffs were prepared in silicone baking moulds and analyzed for siloxane migration using a previously developed and validated ¹H-NMR method. Meat loaf significantly exceeded the overall migration limit of 60 mg kg^?1 (10 mg sdm^?1) in the first and third experiment. The highest siloxane migration found in a meat loaf after preparation in a commercial mould was 177 mg kg^?1. In contrast, milk-based food showed very low or non-detectable migration (<2.4 mg kg^?1), even containing high fat levels. Similar results were achieved using 50% ethanol as the simulant for milk-based products, as defined in the Plastics Directive 2007/19/EEC. After solvent extraction of the moulds in simulating long-term usage, no further migration into the food was detectable, indicating that there is no significant formation of low molecular weight, potentially migrating siloxanes from the elastomer. During repeated usage, the moulds showed a high uptake of fat: up to 8.0 g fat per kg elastomer. Proper tempering of the moulds had a major influence on the migration properties of siloxanes into different foodstuffs. Non-tempered moulds with a high level of volatile organic compounds (1.1%) were shown to have considerably higher migration than the equivalent tempered moulds.     

Alternative fatty food simulants and diffusion kinetics of nylon 12 food packaging.

The migration of laurolactam and cyclic di- and trimer of nylon 12 was assessed using three different films and five food simulants (olive oil, isooctane, 95% ethanol, 50% ethanol, water). Substitute test conditions for migration into olive oil according to European Union Directive EC/97/48 were applied using 95% ethanol and isooctane. Results showed that 95% ethanol overestimated while isooctane underestimated the respective migration into olive oil. Water was the best olive oil substitute, as migration of laurolactam into water and olive oil using the same temperature gave similar results. Additionally, diffusion kinetics of laurolactam were investigated by migration kinetic studies using isooctane and olive oil. Diffusion coefficients determined with isooctane were significantly higher than those found using olive oil. It was proved that isooctane had an interaction and olive oil was inert to the polymer. The diffusion conductance parameter, A(p), for nylon 12 determined using olive oil ranged from 0.3 to 0.6.     

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)).     

Time–temperature study of the kinetics of migration of DPBD from plastics into chocolate,chocolate spread and margarine

Migration of low molecular weight substances into foodstuffs is a subject of increasing interest and an important aspect of food packaging because of the possible hazardous effects on human health.The migration of a model substance (diphenylbutadiene) from low-density polyethylene (LDPE) was studied in foodstuffs with high fat contents: chocolate, chocolate spread and margarines (containing 61% and 80% fat).A simplifying mathematical model based on Fick’s diffusion equation for mass transport processes from plastics was used to derive effective diffusion coefficients which take also kinetic effects in the foods into account and to determine partition coefficients between plastic and food. With this model migration levels obtainable under other storage conditions can be predicted. The effective diffusion coefficients for both margarines stored at 5 °C (3.0–4.2 × 10⁻¹⁰ cm² s⁻¹) and at 25 °C (3.7–5.1 × 10⁻⁹ cm²  s⁻¹) were similar to each other, lower than for chocolate spread stored at 5 °C (9.1 × 10⁻¹⁰ cm² s⁻¹) and higher than the diffusion coefficient for chocolate stored at 25 °C (2.9 × 10⁻¹⁰ cm² s⁻¹). Good agreement was found between the experimental and the estimated data, allowing validation of this model for predicting diffusion processes in foodstuffs with high fat contents.     

Tailoring fatty food simulants made from solvent mixtures (2): determining the equivalent migration behaviour of olive oil and of solvents in the case of polyolefins

It is suggested that solvent mixtures consisting of an ester and of an inert solvent can be used as fatty food simulants capable of having the same migration behaviour as olive oil with plastics. Migration tests carried out with low-density polyethylene for 20 and 48h in an 8 and 5% mixture of tert-butyl acetate in ethanol respectively gave results equivalent to those obtained with olive oil after 10 days at 40°C. The use of solvent mixtures facilitated the analysis and improved detection limits, giving good repeatability. Furthermore, the more rapid migration in solvent mixtures can be particularly useful for industrial controls as alternative test methods.     

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.     

家用料理机Cr和Mn迁移规律及风险估计研究

目的研究市售家用料理机中重金属Cr和Mn迁移规律并对其进行风险评估。方法以市售家用料理机为研究对象,对不同材质料理机在不同的食品模拟物体系中(去离子水,4%乙酸溶液,10%乙醇溶液,50%乙醇溶液)重金属Cr和Mn向食品体系的迁移过程进行动力学分析与扩散模型分析,将Cr和Mn迁出浓度与我国现有标准中重金属限量值进行比较。结果在Cr和Mn迁出风险较高的4%乙酸溶液中,其迁移行为符合一级动力学过程,短期接触时部分迁移符合Fick扩散过程,长期接触时均符合Fick扩散过程。当迁移达到平衡时,4种模拟液中Cr和Mn元素的迁出浓度均低于生活饮用水中限量值。结论 Fick第二定律能较好地应用于料理机中Cr和Mn的迁移研究,在日常使用条件下料理机中Cr和Mn的迁移危害风险较低。     

Characterizing the migration of antioxidants from polypropylene into fatty food simulants

The migration (diffusion and equilibrium) processes of antioxidants (AOs) from polypropylene (PP) films of different thicknesses into n-heptane and 95% ethanol as fatty food simulants were analysed at 20, 37 and 60°C. Heptane fully extracted the AOs from the polymer while a partition equilibrium described the migration to ethanol. The kinetics of migration were also studied via the diffusion coefficients. As expected, diffusion was found to be faster when the polymer was in contact with heptane, due to polymer swelling by the solvent. The kinetics of the process in ethanol was described by different theoretical expressions which are discussed. Equations disregarding partition equilibrium failed to describe the process and the diffusion coefficient values obtained through them were much smaller than the actual ones and dependent on film thickness. The results also showed the significance of food simulant selection in the analysis of food-packaging interactions and migration variability with thickness.     

Review of Mechanical Properties,Migration, and Potential Applications in Active Food Packaging Systems Containing Nanoclays and Nanosilver

The incorporation of nanomaterials into a range of polymeric materials shows great potential for developing new active food packaging systems. Although there are many suggested benefits of nanoparticles (NPs) in food packaging, there are also potential risks due to the possibility of such particles migrating into foodstuffs. This has obvious implications for human health and it may also negatively impact on marketing and consumer confidence. This review focuses on 2 particular types of nanomaterials: nanoclays and nanosilver, with a view to examining the effects of these on system mechanical properties (nanoclays) and antimicrobial efficacy (nanosilver). It further reports on the various migration studies, techniques for characterization, and measurement of NPs as well as the potential migration of NPs from packaging into foodstuffs. Assessment of the literature to date suggests there is an urgent need for further research in order to devise better NP detection methods and to determine the likelihood of their migration from packaging materials into foodstuffs.     

Additive migration from various plastics with different processing or properties into test fat HB 307

The migration of the antioxidant n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate from various plastics into the test fat HB 307 was investigated. Plastics from the following classes were included: high-impact polystyrene (HIPS), polypropylene (PP), high- and low-density polyethylene (HDPE and LDPE), and were found to have distinctly different properties--in particular, different densities, melt flow indices and structural characteristics. Each plastic was processed into test specimens such as pressed and extruded sheets, injection-moulded cups, deep-drawn tubs and blown bottles. The migration out of these specimens was investigated under identical test conditions. The results confirm that the amounts of additive migrating from the different classes of plastics into test fat HB 307 in general decrease in the order LDPE greater than HDPE greater than PP greater than HIPS. Moreover, it seems to be of great importance that the respective amounts of additive migrating from the injection-moulded cups, deep-drawn tubs and blown bottles into test fat were significantly lower in all cases than those from the corresponding pressed or extruded sheets. Presumably, this effect is mainly caused by orientation of the polymer molecules in the injection-moulded, deep-drawn or blown products. It is concluded that the migration of the antioxidant decreases with increasing density of the polymer and that the melt flow index (molecular weight) has hardly any influence. Migration from HIPS into fat increases with the content of impact modifier. In the case of the polyethylenes, the influence of processing on the migration rate decreases with decreasing density of the polymer.     

Antistatic finishing of plastics from food hygiene and toxicological viewpoints]

The authors investigated experimentally the migration behaviour of formed plastics with antistatic finish. The degree of molecular coating on the surface and the rate of diffusion of the antistatics used (ethoxylated amines and alkyl sulphonate) were calculated from the results of washing-off and continuous extraction experiments. The findings are indicative of a good depot effect, i.e. the antistatic action is steadily regenerated by secondary migration. Certain agents such as polyethylene glycol enhance diffusion whereby the values for the migration in normal polystyrene are increased; but this increase is acceptable from the viewpoint of safety. In impact polystyrene, the limiting value for total migration is largely exceeded so that considerable contamination may be expected when it comes in contact with foods. From the viewpoint of food-toxicology, there are concerns about the high specific migration values of alkyl sulphonate. For this reason, its use in the food sector should be limited to such cases where direct contact with foods is excluded.     

Migration modelling from food-contact plastics into foodstuffs as a new tool for consumer exposure estimation

One important aspect within the European Union's public healthcare is the exposure of consumers to undesirable chemicals in the diet. Food-contact materials (FCM) are one potential contamination source and therefore of particular interest for food exposure assessment. On the other hand, scientific investigations concerning the migration potential and behaviour of food-packaging materials have demonstrated that diffusion in and migration from FCM are foreseeable physical and, in principle, mathematically describable processes. Because of this situation and the current state-of-the-art in migration science, a research project was initiated within the 5th Framework Programme of the European Commission. This project, with the acronym 'FOODMIGROSURE' (European Union Contract No. 'QLK1-CT2002-2390') started on 1 March 2003, was due to last 3 years and had the participation of nine European project partners (see the project website: www.foodmigrosure.org). The aim of the project was to extend currently existing migration models (which have been demonstrated to be applicable for less complex matrices such as food simulants) to foodstuffs themselves. In this way, the project aims to provide a novel and economic tool for estimation of consumer exposure to chemicals migrating from food-contact plastic materials under any actual contact conditions. In addition, the project aims to increase knowledge of the mechanisms of diffusion of organic compounds in foodstuffs and provide data on the partitioning effects between FCM and foods. Today the latter aspect is increasingly regarded as a fundamental influence parameter for migration into foods. Based on the project achievements, a much better scientific basis is available to allow scientifically appropriate amendments of European Union Directive 85/572/EEC as well as to support further developments with the so-called Plastics Directive 2002/72/EC. The paper introduces the project and presents an overview of the project work progress.     

Migration from food contact plastics. Part I. Establishment and aims of the PIRA project

In the European Community regulatory approaches adopted by individual Member States to the control of food contact plastics differ markedly and, as a result, the European Commission has identified a need for harmonized legislation in this sector. The Commission requested its Scientific Committee for Food to advise on the toxicity of monomers and other starting substances used in the production of such plastics and the Committee's report has recently been published. It is apparent that, although some monomers have been studied in depth, for many little or no information was available to the Committee on either the levels migrating into food or their likely toxic effects. The Committee has requested that such information be provided within 3 years. Following discussions between the UK Ministry of Agriculture, Fisheries and Food, PIRA and companies involved in either the manufacture or use of food contact plastics, a Project has been established at PIRA to develop sensitive analytical procedures for the relevant UK-required monomers and to provide the required migration data. As a second part to this project the methodology for determining overall migration is being examined with a view to resolving existing experimental difficulties. The first analytical methods to be developed in the project are those for the determination or terephthalic acid and isophthalic acid. Residual levels of these monomers in plastics and the quantities migrating into food simulants and food have been shown to be very low.     

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。     

模拟液的极性对聚丙烯中抗氧化剂迁移的影响

研究了4种抗氧化剂BHA、BHT、Irganox1076、Irgafos168从聚丙烯塑料迁移至6种不同极性的模拟液时,模拟液极性对抗氧化剂迁移规律的影响。结果表明,抗氧化剂与聚丙烯塑料相溶性越差,与模拟液相溶性越好,迁移平衡分配系数越大;同时,模拟液极性越接近聚丙烯时,迁移扩散系数越高,扩散系数受分子量影响越小,反之,则迁移扩散系数受分子量影响较大,扩散系数随分子量的增大而减小;无水乙醇模拟液中,抗氧化剂分子量越大,平衡分配系数受温度影响越大,迁移焓变随分子量增大而增大,而正己烷模拟液中变化正好与之相反。     

Effect of microwave heating on the migration of dioctyladipate and acetyltributylcitrate plasticizers from food-grade PVC and PVDC/PVC films into olive oil and water

Migration of dioctyladipate (DOA) and acetyltributylcitrate (ATBC) plasticizers from plasticized Polyvinylchloride (PVC) and polyvinylidene chloride (PVDC/PVC (Saran) films into both olive oil and distilled water during microwave heating has been studied. The plasticizer migrating into olive oil and water was determined using an indirect GC method after saponification of the ester-type plasticizer (DOA or ATBC) and subsequent collection of the alcohol component of the ester, namely: 2-ethyl-1-hexanol and 1-butanol, respectively. Migration was dependent on heating time, microwave power setting, the nature of the food simulant and the initial concentration of the plasticizer in the film. Migration of DOA into olive oil reached equilibrium after heating for 10 min at full power (604.6 mg DOA/1). Migration into distilled water was 74.1 mg/1 after 8 min of microwave cooking at full power. The amount of ATBC migrating into olive oil reached equilibrium after heating for 10 min at full power (73.9 mg ATBC/1). Migration into distilled water was 4.1 mg/1 after heating at full power for 8 min. Control samples containing olive oil gave DOA migration values which were significantly higher than the upper limit for global migration (60 mg/1) set by the European Community. It is proposed that PVC should not be used in direct contact with food in the microwave oven, while Saran may be used with caution in microwave heating and reheating applications, avoiding its direct contact with high fat foodstuffs.