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.     

Tailoring fatty food simulants made from solvent mixtures (1): comparison of methanol, ethanol and isopropanol behaviour with polystyrene

To investigate the use of solvent mixtures as test media replacing olive oil in migration tests, the interaction of polystyrene with mixtures composed of various amounts of tert.butyl acetate (mimicking the ester functions of oil) and of a low molecular weight alcohol (methanol, ethanol and isopropanol as inert co-solvent) was studied, using FTIR. Isopropanol, which has a lesser tendency to form hydrogen bonds in the plastic, can be used as main component of alternative fatty test media, its aggressiveness to polystyrene being tailored by adjusting the concentration of tert.butyl acetate. Concentrations below 20% seem useful on the basis of the mechanism of displacement of the alcohols.     

Food aroma partition between packaging materials and fatty food simulants

By means of thermal desorption experiments, the partition equilibrium (partition coefficient, K) was analysed for six food aroma components (d-limonene, n-decane, ethyl caproate, phenylethanol, n-hexanol and hexanal) between three sealable polymer films suitable for direct food contact (ultra-low density polyethylene, ULDPE; ionomer, ION; and polyester, PET) and four fatty food simulants (ethanol 95% , EtOH; sunflower oil, Oil; n-heptane, HEP; and iso-octane, OCT). The results showed that aroma scalping is highly dependent on the fatty food simulant utilized. Polar aroma components were more sorbed into polymers in the presence of a non-polar fatty food simulant, and vice versa. K values in the presence of Oil were always between those in EtOH and in HEP or OCT. In general, PET was the packaging film which showed the lowest partition coefficient for non-polar components while ULDPE showed the lowest partition for polar aromas. The partition equilibrium of mixed d-limonene, ethyl caproate, and n-hexanol was also determined. The differences in K values between isolated aromas and mixed aromas were small. In general, the most sorbed aroma showed increased partition by mixture while the partition of the least sorbed was reduced.     

Migration of additives from polymers into food simulants: numerical solution of a mathematical model taking into account food and polymer interactions

The principle of a computing program describing precisely the migration of additives from a polymer into a food simulant is presented. As six parameters are used to fit the simulant sorption and additive extraction kinetics, the parameters have been determined by independent experiments. Owing to the complicated coupling between the liquid and additive diffusion processes, migration kinetics cannot be obtained by a mathematical resolution of kinetic equations, but they must be calculated by numerical analysis. The method is applied to a UV absorber in polypropylene migrating into glyceryl tripelargonate, a pure triglyceride, of which behaviour and average molecular weight are similar to official fatty food simulants. Properly designed experiments validate the model used to fit the migration kinetics. The possibility of erasing any parameters is also discussed.     

Alternative fatty food simulants for migration testing of polymeric food contact materials.

The amounts of substances migrating from plastics into foodstuffs with high fat contents are in most cases higher than in foodstuffs with water contents. This increase in migration commonly is due to the higher solubility of the migrating organic compounds in fat compared to water. The increase in migration is not necessarily due to an increase in the substance's diffusion coefficient due to interactions between the fat and the plastic as is often assumed. Ethanol is a good simulant for fatty foods because it has little interaction with many plastics, e.g. polyolefins, migrants are readily soluble in it, and because it is easy to work with analytically. The utilizable limits of ethanol and ethanol/water mixtures as food simulants are developed from the physical background of diffusion. The use of ethanol and ethanol/water mixtures is supported by published experimental migration results.     

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.     

Cadmium and lead concentrations in acid food simulants: the values of validation parameters are predominantly affected by interspecific differences of utensils

The obvious toxicity of cadmium and lead is at the basis of compulsory concentration determinations for lixiviation solutions of ceramic and earthenware household receptacles such as cups, plates, bowls and others. Concentrations in the food simulant which exceed 0.100 +/- 0.005 mg Cd dm-2 and 1.00 +/- 0.05 mg Pb dm-2 for flat receptacles, 0.500 +/- 0.025 mg Cd l-1 and 5.00 +/- 0.25 mg Pb l-1 for low volume (< 5 l) receptacles and 0.250 +/- 0.025 mg Cd l-1 and 2.50 +/- 0.25 mg Pb l-1 for high volume (> 5 l) receptacles are not acceptable and measures were taken by the EU member state authorities to enforce these norm concentrations. Generally, the uncertainty on the results forwarded by the legislation amounts to 5%. This value does not at all match the pronounced variability observed for several 'identical' trade samples, but rather represents the inherent variability of spectrometric analyses alone. Considering that the coefficients of variation can be as high as approximately 30%, either the ranges of acceptable concentrations or the maximal allowable concentrations should be corrected. Aware of the negative health effects of heavy metal contamination and of the risk increase due to dietary intake, a downward adjustment of the acceptable concentration ranges to 0.07 mg Cd dm-2 +/- 12%, 0.30 mg Cd l-1 +/- 12% and 0.10 mg Cd l-1 +/- 12% and to 0.8 mg Pb dm-2 +/- 13%, 4.0 mg Pb l-1 +/- 13% and 1.50 mg Pb l-1 +/- 13% is suggested.     

Analysis for organic residues from aids to polymerization used to make plastics intended for food contact

Polymers intended for food contact use have been analysed for organic residues which could be attributed to a range of substances employed as polymerization aids (e.g. initiators and catalysts). A wide range of polymers was extracted with solvents and the extracts analysed by gas chromatography-mass spectrometry (GC-MS). The overwhelming majority of substances identified were not derived from aids to polymerization but were oligomers, additives and adventitious contaminants. However, a small number of substances were identified as initiator residues. These included tetramethylsuccinonitrile (TMSN) which was observed in two polymers and it derived from recombination of two azobisisobutyronitrile (AIBN) initiator radicals. Methyl benzoate, benzoic acid, biphenyl and phenyl benzoate were detected in one poly(methyl methacrylate) sample and in two polyvinylchlorides and they are thought to be derived from benzoyl peroxide initiator. TMSN was subsequently targeted for analysis of poly-(methyl methacrylate) plastics using proton nuclear magnetic resonance spectrometry (¹     

Analysis of food packaging UV inks for chemicals with potential to migrate into food simulants

Ultraviolet (UV) inks are an alternative formulation system to the more usual paste or liquid inks (oils or solvents based) that dry mainly by evaporation or penetration into the printed substrate. Based on acrylic acid chemistry, UV inks dry (the exact term is 'curing') by the chemical process of photopolymerization. Their composition (acrylate monomers and oligomers together with photo-initiators) exposed to UV emission lamps on the printing press units enable the transformation of the freshly printed ink layer into a tack-free film. For UV inks intended for primary food packaging, special care has to be paid to potential migrating species like small photo-initiator molecules and acrylate monomers not cross-linked in the formed network. The paper presents chromatographic methods to ascertain the level of ink ingredients potentially available to migrate into food simulants (migration tests). GC/MS was employed to quantify the levels of photo-initiators or acrylic esters (acrylates).     

欧盟塑料食品接触材料新法规浅析

欧盟塑料食品接触材料新法规修改和细化了塑料食品接触材料的安全性要求,进行了更为详细、规范和合理的规定.本文介绍了欧盟塑料食品接触材料新法规的主要内容,及其与原塑料指令之间的变化,旨在全面、深入了解欧盟对塑料食品接触材料的管理模式和走向,分析其中可为我国食品接触材料管理所用的内容,为监管部门以及相关行业、企业提供参考.我国在修订GB 9685-2008、构建食品接触材料标准体系中也可以借鉴法规中的一些管理内容及管理思路.     

An internet compendium of analytical methods and spectroscopic information for monomers and additives used in food packaging plastics

An internet website (http://cpf.jrc.it/smt/) has been produced as a means of dissemination of methods of analysis and supporting spectroscopic information on monomers and additives used for food contact materials (principally packaging). The site which is aimed primarily at assisting food control laboratories in the European Union contains analytical information on monomers, starting substances and additives used in the manufacture of plastics materials. A searchable index is provided giving PM and CAS numbers for each of 255 substances. For each substance a data sheet gives regulatory information, chemical structures, physico-chemical information and background information on the use of the substance in particular plastics, and the food packaging applications. For monomers and starting substances (155 compounds) the infra-red and mass spectra are provided, and for additives (100 compounds); additionally proton NMR are available for about 50% of the entries. Where analytical methods have been developed for determining these substances as residual amounts in plastics or as trace amounts in food simulants these methods are also on the website. All information is provided in portable document file (PDF) format which means that high quality copies can be readily printed, using freely available Adobe Acrobat Reader software. The website will in future be maintained and up-dated by the European Commission's Joint Research Centre (JRC) as new substances are authorized for use by the European Commission (DG-ENTR formerly DGIII). Where analytical laboratories (food control or other) require reference substances these can be obtained free-ofcharge from a reference collection housed at the JRC and maintained in conjunction with this website compendium.     

Effect of ionizing radiation on the physicochemical and mechanical properties of commercial monolayer flexible plastics packaging materials

The effect of γ-radiation doses (5, 10, 30 kGy) on the mechanical properties, gas and water vapour permeability, infrared (IR) spectra, and overall migration into aqueous and alternative fatty food simulants of commercial monolayer flexible packaging films ethylene vinyl acetate (EVA), high-density polyethylene (HDPE), polystyrene (PS), bi-axially oriented polypropylene (BOPP), low-density polyethylene (LDPE) and Ionomer was studied. For comparison purposes, respective non-irradiated (control) films were also studied. The results showed that radiation doses of 5, 10 and 30 kGy did not induce any statistically significant changes in the permeability of all studied films to gases (oxygen and carbon dioxide) and water vapour. Likewise, IR spectra of all studied films showed no significant differences after all absorbed doses. The mechanical properties (tensile strength, percentage elongation at break and Young's modulus) of all studied films remained unaffected after absorbed doses of 5 and 10 kGy. In contrast, the tensile strength of HDPE, BOPP and Ionomer films irradiated at a dose of 30kGy decreased. In addition, the percentage elongation at break of LDPE and Ionomer films irradiated at a dose of 30 kGy decreased while Young's modulus of all samples remained unaffected. All mechanical properties of PS and EVA films remained unaffected after radiation at 30 kGy. Radiation (all absorbed doses) resulted in no statistically significant differences in overall migration values into distilled water for all studied films. For 3% aqueous acetic acid, absorbed doses of 5 and 10 kGy did not affect overall migration values of all investigated samples with the exception of the Ionomer film, for which the overall migration value decreased at 10 kGy. An absorbed dose of 30 kGy caused an increase in BOPP overall migration values and a decrease in Ionomer overall migration values. In contrast, a dose of 30 kGy induced no changes in overall migration values of EVA, HDPE, LDPE and PS films into the same simulant. There were no statistically significant differences in overall migration values of EVA, PS and LDPE films into iso-octane for all absorbed doses. In contrast, a dose of 30 kGy resulted in an increase in overall migration values of BOPP and a respective decrease in HDPE and Ionomer films.     

食品接触塑料中添加剂迁移模型研究进展

食品接触塑料在加工过程中会引入很多小分子添加剂,在与食品接触过程中可能迁移到食品中,并随着食品进入人体对身体健康构成一定的危害。对于食品接触塑料及其制品的安全性评价大多是基于材料中小分子添加剂在食品及食品模拟物中迁移量的检测,而这些检测费时、费力并消耗大量的人力、物力及化学试剂。但是,结合迁移模型可以预测、推算其迁移规律和迁移量。本文论述了国内外食品接触塑料中小分子添加剂的迁移模型的研究现状和进展,重点介绍了确定性模型及非确定模型的研究及需要解决的理论问题,展望了迁移理论模型研究的发展前景。     

食品接触塑料中初级芳香胺检测方法研究进展

初级芳香胺是一类毒性较强的致癌物质,可通过皮肤、胃肠道和呼吸道进入人体,导致机体细胞的DNA功能和结构发生变化,严重者可引发人体输尿管癌、肾癌、膀胱癌等恶性疾病。塑料作为一种常见的食品接触材料,广泛用于食品包装、食品工具等。食品接触塑料中残留的初级芳香胺会在与食品接触的过程中向食品迁移,由此对食品安全和人身健康造成威胁。本文对国内外食品接触塑料中初级芳香胺的检测标准与相关的法规进行了对比,重点综述了近几年所报道的在食品接触塑料中初级芳香胺检测方法,包括高效液相色谱法、气相色谱.质谱法和液相色谱一质谱法等;对各种方法的前处理、仪器条件及优缺点等进行了分析;同时展望了食品接触塑料中初级芳香胺检测方法的发展趋势,以期为相关科技工作者提供参考。     

Mobility of alpha-tocopherol and BHT in LDPE in contact with fatty food simulants.

The migration/sorption behaviour of butylated hydroxytoluene (BHT) and alpha-tocopherol was studied in packaging material in contact with fatty food simulants. Two low-density polyethylene (LDPE) films, containing either BHT or alpha-tocopherol as antioxidants, were stored in contact with sunflower oil or 95% (v/v) ethanol. The antioxidant content was monitored in the films throughout a period of 7 weeks. The migration of alpha-tocopherol into the food simulants was slower than that of BHT. Since alpha-tocopherol was transferred from the film to the simulant to a lesser extent, it is considered to be a more stable antioxidant than BHT when used in an LDPE film in contact with 95% ethanol or sunflower oil.     

高压液相色谱法测定食品接触材料水性模拟液中2,4-二羟基二苯甲酮

目的 探讨高压液相色谱法测定食品接触材料水性模拟液中2,4-二羟基二苯甲酮的方法。方法 食品接触材料经水、10%乙醇(v/v)、20%乙醇(v/v)、50%乙醇(v/v)以及3%乙酸(w/v)5种不同水性模拟液提取后, 以Agilent HC-CN为分析柱, 甲醇: 水(55: 45, v/v)为流动相, 经UV检测器(?=290 nm) 进行定量分析。结果 5种不同水性模拟液中2,4-二羟基二苯甲酮在0.5~10.0 mg/L浓度范围内线性关系均良好(r=0.9999), 检测限(S/N=3)均为0.02 mg/L。在低、中、高3个不同添加水平下进行加标回收实验, 2,4-二羟基二苯甲酮的平均回收率为84.0%~96.9%, RSD(n=6)为0.85%~4.60%。结论 本方法简单、快速、准确, 完全能够满足食品接触材料日常检验的需要。     

Determination of low levels of aziridine in official EU food simulants by capillary gas chromatography

 An analytical method for the determination of the specific migration of aziridine (ethyleneimine) into food simulants at trace levels is described. The method comprises a two-phase (aqueous-organic solvent) derivatization procedure with 4-fluorobenzoyl chloride, using propyleneimine as an internal standard. The derivatization reaction is accomplished very quickly and the organic layer containing the derivatized imine is analysed by capillary gas chromatography using selective nitrogen detection (nitrogen-phosphorus detector). The detection limits of the method were lower than 5 μg/kg in the food simulant. Received: 5 June 1996     

Determination of bisphenol A in, and its migration from, PVC stretch film used for food packaging

Bisphenol A (BPA) is used as an additive in polyvinyl chloride (PVC) products, including stretch films used for food packaging. The BPA contents were investigated of several brands of stretch film bought locally but marketed internationally or throughout Spain and which were presumably produced at different manufacturing plants. Their major components were identified by FTIR (Fourier Transform Infrared Spectrometry) and horizontal attenuated total reflectance, and the migration of BPA from these materials into the standard European Union food simulants was determined by high-performance liquid chromatography (HPLC) using both fluorescence (FL) and ultraviolet (UV) detection, the identity of the analyte being confirmed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The two HPLC detection methods had different detection limits (30 μg l^-1 for UV, 3 μg l^-1 for FL), but afforded virtually identical BPA determinations for the samples tested. BPA contents ranging from 40 to 100 mg kg^-1 were found in three of the five PVC-based films analysed, and a content of 500 mg kg^-1 was found in a fourth; for these determinations, extraction into acetonitrile was used. In standard tests of migration into water, 3% acetic acid and olive oil over 10 days at 40°C, migration from a given film was in all cases greatest into olive oil. Migration from the films with non-zero BPA contents ranged from 3 to 31 μg dm^-2, values higher than those reported for many other food-contact materials, but lower than the European Union specific migration limit for BPA. PVC stretch film nevertheless may make a significant contribution to contamination of foodstuffs by BPA, and should be taken into account in estimating BPA intake or exposure to this substance.     

水产品活性包装和智能包装技术的研究进展

水产品贮藏品质对加工保藏技术的要求以及国内消费者对水产品加工食品质量安全的存疑促进了水产品活性包装和智能包装技术的发展。活性包装技术通过包装材料吸收不利保藏的成分,或释放有利保藏的成分,或发挥涂膜抗菌、抗氧化作用,对水产品起到防腐保鲜的作用。智能包装技术通过标签指示剂、信息溯源提高产业链管理效率以及减少消费者对水产品品质和安全的担心。虽然国内外在水果、蔬菜、奶制品等食品上已有新包装技术的应用,但是我国水产品活性包装和智能包装的工业化尚在起步阶段。本文总结了主要的活性包装和智能包装技术,并总结了新包装技术在国外水产品上的应用,以期为我国未来水产品新包装的发展提供借鉴参考。     

Application of the yeast comet assay in testing of food additives for genotoxicity

Different kinds of additives are widely applied in food industry. The rationale for their use is preservation, coloring or sweetening of diverse foods. Though it has been proven that some additives possess cytotoxic effect they are still used in practice. As a justification of their use is being their low concentration of application. We have used the method of Comet assay to detect minimal concentrations at which a group of selected food additives could damage DNA. Five substances, commonly added in foods and one in pharmaceutical drugs showed DNA damaging effectively at concentrations lower than that used in practice. Additionally, we have compared the sensitivity of higher eukaryotic cells with yeast to genotoxic effect of these compounds. The higher sensitivity of yeast cells revealed by the comet assay was undoubtedly demonstrated.