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。     

纳米铜/聚丙烯复合膜中铜向食品模拟物的迁移及其对膜性能的影响

当纳米包装材料与食品接触时,纳米成分可能会迁移到食品中,由于对纳米成分的毒性研究还不充分,可能引发食品安全问题。通过电感耦合等离子体发射光谱仪(inductively coupled plasma optical emission spectrometer, ICP-OES)探究了时间、温度、纳米铜含量、偶联剂、伽马射线辐照、循环使用及乙酸食品模拟物浓度对纳米铜/聚丙烯复合膜中铜向模拟物中迁移的影响,并对比复合膜迁移前后性能的变化。结果表明:复合膜中铜向模拟物中迁移的迁移率随时间和温度的增加而增大,直至平衡;循环使用的复合膜中铜在每次循环时的迁移能力与纳米铜含量有关;伽马射线辐照、乙酸食品模拟物的浓度增大使铜的迁移量显著增大;迁移后复合膜的机械性能较稳定,微观形貌和粗糙度随迁移行为有所变化。     

塑料包装材料化学物迁移试验中食品模拟物的选用

人们对健康的广泛重视引发了国际社会对食品安全的普遍关注。塑料包装材料化学物向食品的迁移与食品安全息息相关,美国FDA、欧盟EC等就此进行了广泛而深入的理论与试验研究。本文综述了包装材料化学物迁移试验中应用的食品模拟物并对其选用作了分析。     

影响聚丙烯塑料中抗氧剂BHA向食品中迁移规律因素研究

食品包装材料中有害化学物的迁移是污染食品和危害人们身体健康的主要途径之一,研究影响有害物质向食品中迁移规律的因素可有效降低食品包装材料对食品的污染风险。试验研究了含BHA的聚丙烯母料的比表面积和模拟液的溶解度参数对BHA向模拟液中迁移规律的影响,并把Scatchard-Hilderbrand热力学理论模型预测平衡分配系数(D_(r0))与试验值(D_r)进行比较分析,研究结果表明:模拟液中BHA的浓度符合C_t=a(1-e~(-b t))方程式,且塑料比表面积越大,迁移速率和迁移平衡分配系数(模拟液/塑料)越大,同时模拟液的溶解度参数与塑料的溶解度参数差值越小,其迁移速率越大,迁移平衡分配系数的试验值与Scatchard-Hilderbrand热力学理论模型计算值越接近。     

影响金属罐内涂中化学迁移物分配系数的因素

利用迁移平衡试验,研究BPA、BADGE在不同温度和不同食品模拟液下的迁移分配,分析讨论温度、食品模拟液和化学物分子结构对金属罐内涂环氧树脂中化学物分配系数的影响。结果表明:温度升高,分配系数减小;化学物分子结构越复杂,分配系数越大;食品模拟液身极性、对材料的溶胀及对化学物溶解性等对分配系数影响比较显著。     

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。     

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。     

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...     

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。     

影响聚丙烯塑料中抗氧剂1076向食品中迁移规律因素研究

有害化学物的迁移是食品包装材料污染食品和危害人们身体健康的主要途径之一,研究影响有害物质向食品中迁移规律的因素可有效降低食品包装材料对食品的污染风险。论文研究了含1076的聚丙烯母料的比表面积和模拟液的极性对抗氧剂1076向模拟液中迁移规律的影响,并把Scatchard-Hilderbrand热力学理论模型预测平衡分配系数(D_(r0))与实验值(D_r)进行比较分析,研究结果表明:模拟中1076的浓度(C_r)和浸泡时间(t)符合Ct=a(1-e~(-bt))方程式,且塑料比表面积(S)越大,迁移速率和迁移平衡分配系数(模拟液/塑料)越大,1076向乙醇模拟液中迁移的平衡分配系数(D_r)与比表面积(S)符合方程ln Dr=—3.93+2.21e~(-57.67S),平衡分配系数实验值与SatchardHilderbrand热力学理论模型计算值随模拟液的溶解度参数变化趋势完全一致,实验值与计算值的比值随模拟液与聚丙烯的溶解度参数差值减小而增大,即模拟液的极性越接近聚丙烯,实验值越接近Scatchard-Hilderbrand热力学理论模型平衡分配系数计算值。     

Use of a food-consumption database with packaging information to estimate exposure to food-packaging migrants: expoxidized soybean oil and styrene monomer

There is no set protocol for completing refined exposure assessments of food-packaging migrants in the European Union. One novel method that could be used to provide more realistic exposure assessments and also reduce uncertainty in the exposure estimation could be the use of food consumption surveys that also have packaging information. The aim of the current study was to estimate exposure to two food-packaging migrants (expoxidized soybean oil (ESBO) and styrene monomer) using a food-consumption database that collected packaging information. The Irish National Children's Food Survey (NCFS) was completed in 2003-04 and it collected information on the type and amount of food consumed by 594 Irish children aged 5-12 years, in addition to the type of packaging used for these foods. The Irish Food Packaging Database (IFPD) was completed in parallel to this food consumption survey and recorded exact information on the contact layer used for the packaging. In a database that combined information from the NCFS and the IFPD, the packaging materials that could contain the target migrants were identified. If a food was packaged in a material that could contain the migrant, it was assumed that the migrant was present in the food. For the exposure assessment of ESBO the 90th percentile migration values of ESBO in foods derived from the literature were used. This was similar to a method as used by the European Food Safety Authority (EFSA) in their exposure assessment of ESBO for adults. Two scenarios of styrene exposure were undertaken in this study. In the first scenario the 90th percentile migration value for styrene found in foods was used; in the second scenario the maximum level of styrene found in foods was used. These migration values were derived from the literature. The mean intake of ESBO for Irish children was 0.023 mg kg^-1 body weight day^-1, which is well below the tolerable daily intake (TDI) of 1 mg kg^-1 body weight day^-1 set by the Scientific Committee for Food (SCF) in 1999. The food group that contributed most to ESBO intake was tomato sauces packed in glass jars with polyvinyl chloride (PVC)-lined metal lids (46.8%). For styrene, the mean intake was 0.122 µg kg^-1 body weight day^-1 when using the 90th percentile migration values and 0.169 µg kg^-1 body weight day^-1 when using the maximum migration values. These estimated intakes are below the provisional maximum tolerable daily intake (PMTDI) of 40 µg kg^-1 body weight day^-1, which was established by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) in 1984. Therefore, the estimated intakes of the two migrants are not of concern for Irish Children and uncertainty is reduced in the assessment due to the fact that information is available on the type of foods consumed the type of packaging used for these foods.     

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.     

Trace contamination of foods by migration from plastics packaging—A review

Plastic packaging often contains many components in addition to the base polymer. Additives are required both for the manufacturing process to give acceptable results and for the finished product to have the desired characteristics. Furthermore, decomposition products may arise from these additives, while the base polymer itself will contain monomer and oligomers in addition to traces of constituents of the polymerisation mixture (such as catalysts) and any decomposition products arising from these. Printing inks, laminates and their adhesives further complicate the picture. Consequently, the final product can contain a multitude of components at all levels from traces to perhaps 20–30% by weight.Where these components are of low molecular weight, a potential exists for their migration into packaged foods. It is essential, therefore, that manufacturers and users of plastic packaging intended for food contact be aware of the chemical nature of the range of potential migrants expected from a given polymer/additive/food system and have some understanding of the underlying mechanisms and kinetics of migration.This paper presents an overview of current knowledge of migration. After an outline of the physical basis of migration, the concept of—and problems inherent in—measuring overall migration are described, followed by a discussion of selected specific migrants.Although information on contamination from residual monomers forms the bulk of the available literature on specific migrants, migration of other base polymer constituents and of non-volatile plastics additives and their decomposition products can be of importance and is reviewed here.     

食品包装PE材料中荧光增白剂迁移规律的分析

以PE塑料薄膜为研究对象,采用高效液相色谱法研究食品包装塑料材料中荧光增白剂在纯水、乙酸、乙醇、植物油4?种不同模拟物中的迁移规律,研究荧光增白剂溶出量与食品接触介质、乙酸质量浓度、乙醇体积分数、浸泡温度以及处理时间等因素的关系。结果表明：纯水基质食品模拟物对香豆素类荧光增白剂有一定溶解性,酸性食品模拟物相比于水模拟物有更强的溶解性,而含醇类食品模拟物和脂肪类食品模拟物对大部分荧光增白剂都具有较好的溶解效果;荧光增白剂的溶出量随着乙酸和乙醇含量的增加而增加;较高的温度对塑料包装材料中荧光增白剂的迁移溶出具有显著影响,并且随着接触时间的延长,塑料包装材料中的荧光增白剂向食品中迁移的可能性也不断增大。     

Comparison of isopropanol and isooctane as food simulants in plasticizer migration tests.

In the last 25 years, plastics have faced a massive demand in packaging technology due to their desirable properties, such as flexibility, light weight, etc. Moreover, their packaging applications have spread in the area of food and pharmaceutical products. Much concern has arisen from that fact as most of these plastics contain high amounts of additives which tend to migrate when they come into contact with liquid or solid surrounding media. Plasticized PVC is one of the most popular polymers in packaging technology and at the same time is subject to criticism for the high concentration levels of plasticizer in most of its applications. In an attempt to carry out simple and realistic migration tests, many investigators used simple organic substances which simulate as much as possible the behaviour of foods towards plasticizer migration. Much of our previous work intended to examine migration of dioctyl phthalate (DOP) from PVC sheets into some simple surrounding media, such as methanol, white spirit, paraffin oil, etc. The present work is focused on the examination of the plasticizer migration into two promising food simulants, namely isopropanol and isooctane. Radioactivity measurements were employed in order to detect quantitatively the plasticizer which had migrated into the surrounding liquid. In contrast to similar studies, the phenomenon of migration was studied until equilibrium was reached.     

纳米塑料复合食品包装中的纳米成分及其迁移研究进展

在塑料食品包装中加入纳米材料可以实现很好的机械性、气体阻隔性或抗菌性等优良性能。然而在与食品 接触的过程中这些纳米材料也有可能迁移到食品中,从而对消费者的健康产生威胁,甚至对市场及消费者信心造成 负面影响。对纳米材料进行迁移研究是对其进行风险评估的重要一环,已经得到国内外学者的广泛关注。本文综述 了纳米塑料复合包装的种类、在食品包装中应用较多的纳米材料及其作用,并详细分析了食品包装中纳米材料向食 品或食品模拟物迁移的研究。结果表明：食品包装中纳米材料向食品或食品模拟释放的量较小,但到目前为止,关 于它们是否会以纳米形态释放出来仍然没有达成统一意见。另外,微波处理、塑料助剂的添加可以影响纳米材料的 释放。     

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)。     

Migration and sorption phenomena in packaged foods

Rapidly developing analytical capabilities and continuously evolving stringent regulations have made food/package interactions a subject of intense research. This article focusses on: (1) the migration of package components such as oligomers and monomers, processing aids, additives, and residual reactants in to packaged foods, and (2) sorption of food components such as flavors, lipids, and moisture into packages. Principles of diffusion and thermodynamics are utilized to describe the mathematics of migration and sorption. Mathematical models are developed from first principles, and their applicability is illustrated using numerical simulations and published data. Simulations indicate that available models are system (polymer‐penetrant) specific. Furthermore, some models best describe the early stages of migration/sorption, whereas others should be used for the late stages of these phenomena. Migration‐ and/or sorption‐related problems with respect to glass, metal, paper‐based and polymeric packaging materials are discussed, and their importance is illustrated using published examples. The effects of migrating and absorbed components on food safety, quality, and the environment are presented for various foods and packaging materials. The impact of currently popular packaging techniques such as microwavable, ovenable, and retortable packaging on migration and sorption are discussed with examples. Analytical techniques for investigating migration and sorption phenomena in food packaging are critically reviewed, with special emphasis on the use and characteristics of food‐simulating liquids (FSLs). Finally, domestic and international regulations concerning migration in packaged foods, and their impact on food packaging is briefly presented.     

纸质食品包装材料的矿物油迁移研究进展

食品中的矿物油污染物是指石油来源的C10~C50烃类化合物, 包括烷烃矿物油(mineral oil saturated hydrocarbons, MOSH)和芳烃矿物油(mineral oil aromatic hydrocarbons, MOAH)2大类。近年来的研究表明, 食品中的矿物油污染物主要来源于食品的回收纸包装材料迁移。本文综述了国外近十年来纸质包装材料的矿物油迁移研究情况, 包括纸质包装材料迁移的矿物油分析方法——液相色谱-气相色谱联用法; 矿物油迁移至食品的2种方式: 气态扩散迁移和包装材料接触迁移; 降低矿物油迁移的技术方法, 即食品包装纸质材料的回收工艺, 向包装纸质中添加活性炭等吸附剂以及增加阻隔层以阻挡矿物油的迁移。旨在为相关企业和机构提供数据与技术参考。