Migration Model of Toxic Metals from Ceramic Food Contact Materials into Acid Food

Migration studies of lead and cadmium from ceramic food contact materials into acid food simulants were conducted under various time–temperature conditions to investigate the kinetics of the leaching of lead and cadmium. A mathematical model based on one‐dimensional Fickian diffusion theory was derived in order to describe the migration behaviour of lead and cadmium. Moreover, diffusion coefficients of toxic metals were obtained by fitting the short‐time (24 h) migration data to the model. Comparisons of model solutions with experimental data obtained from the medium‐time tests (up to 600 h) and long‐time tests (up to 130 days) were carried out to verify the proposed model and the values of diffusion coefficients obtained from the short‐time test. Results show that the model fits the experimental data obtained under 20 and 40°C well but fails to fit the experimental data at 60°C. This indicates a change of the migration mechanisms from ion exchange to glass network dissolution as a result of higher temperature. Furthermore, results of migration experiments also reveal that the effects of temperature on the diffusion of lead and cadmium follow the Arrhenius law and that the leaching amounts of lead and cadmium decrease with pH value of the food simulant. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrospray Ionization‐Mass Spectrometry Analysis Reveals Migration of Cyclic Lactide Oligomers from Polylactide Packaging in Contact with Ethanolic Food Simulant

Electrospray ionization‐mass spectrometry analysis revealed rapid migration of cyclic oligomers from polylactide (PLA) packaging when stored in contact with 96% ethanol. The mass losses in contact with water, 3% acetic acid, 10% ethanol and isooctane were 3 to 5 times smaller and no migration of cyclic oligomers was observed. The presence of cyclic oligomers in the original PLA films and their solubility in ethanol, thus, explains the rapid mass loss for PLA in contact with ethanolic food simulant. On prolonged ageing no further mass loss was observed in 96% ethanol, whereas mass loss in aqueous food simulants increased because of hydrolysis of PLA matrix or the cyclic oligomers to water‐soluble linear products. The mass losses were generally somewhat smaller for the stereocomplex material compared with the poly‐l ‐lactide materials. Similar trend was observed for solvent uptakes, which is easily explained by the higher degree of crystallinity and stronger secondary interactions in the stereocomplex material. The use of ethanol as a fatty food simulant for PLA materials could, thus, lead to overestimation of the overall migration values. Copyright © 2012 John Wiley & Sons, Ltd.     

气相色谱-质谱法测定食品接触耐高温材料中氯苯和对二氯苯迁移量

目的利用气相色谱-质谱联用法测定食品接触耐高温材料中氯苯类物质(氯苯、对二氯苯等)的迁移量。方法从水基、酸性、醇类、油基等食品模拟物的迁移试验中得到的样品,通过正己烷或甲醇等有机溶剂萃取后,提取液中的氯苯类物质经由键合聚乙二醇的毛细管柱分离,最终在质谱中进行检测分析。结果在优化萃取溶剂、色谱柱等检测条件下,该方法可有效测定食品模拟物中氯苯、对二氯苯等物质的迁移量,在0.05~50 mg/kg(水性模拟物)或0.2~50 mg/kg(油性模拟物)的范围内线性良好,检出限可达到0.02 mg/kg(水性模拟物)或0.1 mg/kg(油性模拟物),回收率在87.6%~113.2%之间,相对标准偏差小于10%(n=6)。结论建立了食品接触材料中氯苯和对二氯苯迁移量的气相色谱-质谱联用方法,该方法简单、快捷、准确,满足了食品接触材料中氯苯类物质日常检验的要求。     

中国和欧盟酸性食品模拟物对食品接触材料迁移量的差异性分析

目的 对中国和欧盟分别规定的不同酸性食品模拟物进行差异分析,并对2种不同酸性食品模拟物的迁移试验结果差异进行考察。方法 选取4类典型的酸性食品(共123种)进行pH测试,分别以3%(质量分数)的乙酸和4%(体积分数)的乙酸为食品模拟物对食品接触材料及制品进行迁移试验,并测试样品的总迁移量、甲醛迁移量、三聚氰胺迁移量、双酚A迁移量和重金属(锑)迁移量,比较样品在2种不同酸性食品模拟物中的迁移量差异。结果 pH测试结果表明,中国生产的4类酸性食品的pH范围为2.3~5.1,国外生产的4类酸性食品的pH范围为2.49~4.88,pH<5对4类酸性食品的pH覆盖率均大于或等于pH<4.5。迁移结果表明,在大多数情况下,食品接触材料在4%(体积分数)的乙酸中的迁移量,无论是总迁移量还是特定迁移量都大于或等于在3%(质量分数)的乙酸中的迁移量,食品接触材料在3%(质量分数)的乙酸中的迁移量高于在体积分数4%的乙酸的情况极少。结论 根据研究结果,中国采用pH<5定义酸性食品符合中国人的餐饮习惯,酸性食品覆盖性更广,更具合理性。迁移量测试结果表明,4%(体积分数)的乙酸是比3%(质量分数)的乙酸更为严苛的食品模拟物,因此对于国外出口中国的食品接触材料,即使已经按照欧盟标准采用3%(质量分数)的乙酸进行了迁移量测试,在进口到国内时还应用4%(体积分数)的乙酸按照中国相关标准再次进行迁移量测试,以满足中国标准的相关要求。     

Properties of nisin‐incorporated polymer coatings as antimicrobial packaging materials

Nisin was incorporated into binder solutions of acrylic polymer and vinyl acetate‐ethylene co‐polymer, and then coated on to paper. Diffusive migration of incorporated nisin and the antimicrobial activity of the polymer coatings were investigated in order to understand the way of controlling nisin migration and the extent of microbial suppression by the coated paper. Vinyl acetate–ethylene co‐polymer exhibited a faster rate and higher degree of migration into aqueous food simulant solutions compared to acrylic polymer, and also exhibited a higher degree of suppression against Micrococcus flavus ATCC 10240 inoculated into the microbial medium. Addition of NaCl, sugar and citric acid to water significantly reduced the rate of diffusion of nisin in the case of acrylic polymer, while only slight change was observed due to the additive for vinyl acetate‐ethylene co‐polymer. The simulant type slightly affected the equilibrated migration level of nisin. When the nisin‐incorporated coatings were in contact with pasteurized milk and orange juice at 10°C, significant suppression of total aerobic bacteria and yeasts was observed without any noticeable difference between the two types of coatings. Copyright © 2002 John Wiley & Sons, Ltd.     

食品接触材料PVC中32种增塑剂在4种食品模拟物中的迁移规律研究

在不同的条件下,将含有已知量增塑剂的PVC薄膜,在水、乙酸(体积分数为3%)、乙醇(体积分数10%)和橄榄油等4种食品模拟物中浸泡,在规定的时间点抽取一定量的浸泡液,采用气相色谱-质谱法测定增塑剂含量,研究迁移量及迁移率与时间、温度、模拟食品属性、增塑剂初始浓度及包装材料厚度等参数的关系。结果表明:食品模拟物的食品属性对增塑剂的迁移行为有显著影响;增塑剂溶出种类数、迁移量和迁移率随温度升高显著增加;薄膜厚度增加,则增塑剂迁移量大,迁移率降低;薄膜中增塑剂初始浓度高,则迁移量大,迁移率低。     

Evaluating the potential of nanoparticles for controlling zinc stearate release from low‐density polyethylene into food simulants

The present study addressed the effect of polymer nanocomposites with different loading contents of fume silica (nanospheres) and nanoclay (nanosheet) on migration of zinc stearate from packaging materials into food simulants. Specific migration levels of zinc stearate from neat low‐density polyethylene (LDPE) and LDPE/nanocomposites into two food simulants stored at 40°C for 10 days were determined by gas chromatography coupled with flame ionization detector. Differential scanning calorimetry (DSC) analysis showed that incorporation of nanoparticles, especially at 1 wt% loading level of nano silica, noticeably increased degree of crystallinity, which significantly reduced water vapour permeability. Nanocomposites had a lower migration of zinc stearate in comparison with neat polymer. Additionally, results of this study revealed that physical properties of the food simulant had dominant effect on migration of zinc stearate.     

食品接触用银制品中8种重金属元素迁移量研究

目的考察重金属含量、食品模拟物、迁移温度和迁移时间这4个因素对食品接触用银制品中Ag,As,Pb,Cd,Cr,Ni,Sb,Zn迁移量的影响。方法试样按照充填浸泡和全浸泡的方法分别浸泡于乙酸(体积分数为4%)、乙醇(体积分数为10%,50%,95%)食品模拟物中,浸泡迁移完成后提取10 mL浸泡液用ICP-AES测定。结果8种重金属元素中Ag,Cr,Ni,Zn被检出,重金属元素迁移量随着该元素在食品接触用银制品中含量的增高而增高;乙醇(体积分数为10%,50%,95%)食品模拟物中重金属元素迁移量较低,体积分数为4%的乙酸食品模拟物中重金属元素迁移量明显增高;8种金属元素的迁移量随着浸泡温度的升高和浸泡时间的延长而逐渐增高。结论食品接触用银制品中8种重金属元素的迁移量与该元素在银制品中的含量有关,食品接触用银制品在接触酸性食品时存在较大质量安全隐患,很容易造成食品中Ag,Cr含量超标。为提高银制餐具的贸易销售提供了理论支持,为监管部门及时发现产品潜在安全风险提出了合理建议,也为食品接触用银制品中重金属元素迁移量的限量指标提供了数据参考。     

Migration Characteristics under Long‐term Storage and a Combination of UV and Heat Exposure of Poly(Amide)/Poly(Ethylene) Composite Films for Food Packaging

The migration behaviour of polymer films in contact with food simulants is of high importance in terms of consumer protection. Legal regulations require compliance with specific and overall migration limits that are tested by standardized testing conditions. The testing of a polymer film generally takes place shortly after the manufacturing process and decides about the conformity or non‐conformity of the polymer film with the legal requirements. For film and food producers as well as for end users, it is of great interest that the conformity of a film is ensured over its complete lifetime and that environmental influences do not affect the migration behaviour inadequately. In this work, we have investigated (I) the long‐term storage behaviour of a poly(amide)/poly(ethylene) film over a storage period of 40 months with respect to the overall migration rate. This rate is decreasing over the storage period for the chosen food simulant. This means that the material characteristics concerning the overall migration of the poly(amide)/poly(ethylene) film were preserved over the lifetime of the film and even improved with regard to the overall migration potential. Additionally, (II) the migration behaviour was investigated under a combination of ultraviolet and heat exposure. A significant increase in the overall migration rate of 36.8% compared with the standardized migration conditions of 10 days at 40°C was observed. The specific migration of caprolactam, however, did not show a significantly different migration behaviour compared with the standardized migration conditions.     

食品接触材料聚乙烯和聚丙烯中9种抗氧化剂在食品模拟物中的迁移规律研究

在不同条件下,将含有已知量抗氧化剂的聚乙烯和聚丙烯薄膜,在水、乙酸(3 g/L)、体积分数为10%,50%和95%的乙醇等5种食品模拟物中浸泡,在规定的时间点抽取一定量的浸泡液,采用超高效液相色谱法检测抗氧化剂含量,研究了迁移量及迁移率与时间、温度、模拟物属性、抗氧化剂初始浓度和聚丙烯材料的厚度等参数的关系。结果表明:食品模拟物的属性对抗氧化剂的迁移行为影响最大;迁移量和迁移率随温度的升高而增加;材料厚度增加,则抗氧化剂迁移量增加,而迁移率降低;薄膜中抗氧化剂初始浓度越高,则迁移量越大,迁移率越低。     

Migration of Tinuvin P,a UV stabilizer,from PET bottles into fatty‐food simulants

Tinuvin P migration from Polyethyleneterephthalate (PET) bottles was investigated using several fatty‐food simulants such as olive oil, soybean oil, n‐heptane and iso‐octane, at exposure conditions of 2–10 days at 40°C (total immersion). The stability of several UV stabilizers (BHT, Cyasorb UV 5411, Tinuvin P, Tinuvin 326 and Tinuvin 327) in n‐heptane and iso‐octane was also studied. After 10 days at 40°C, losses of 6% and 10% in iso‐octane and n‐heptane respectively, were verified for Tinuvin P. Other UV stabilizers at the same experimental conditions showed higher losses (up to 30% for Tinuvin 327). These results confirm that, when carrying out specific migration studies, the stability of the substance of interest should be established in the food simulant to avoid underestimating the real migration behaviour. In order to quantify UV stabilizer migration, n‐heptane and iso‐octane solutions were concentrated and directly analysed by SIM mode GC–MS. For olive and soybean oils, Tinuvin P was isolated using size‐exclusion chromatography and quantified by SIM mode GC–MS. Iso‐octane proved to be a more suitable fatty‐food simulant than n‐heptane for the migration study of Tinuvin P from PET. Higher levels of Tinuvin P migrated to olive and soybean oils rather than to n‐heptane. These results suggest that the MERCOSUL recommended official methods for specific migration studies should be revised, since the migration levels using n‐heptane as a fatty‐food simulant could be underestimated when compared to edible oils. Copyright © 1999 John Wiley & Sons, Ltd.     

果蔬用泡沫箱中挥发性有机物的迁移特性

目的 研究果蔬用聚苯乙烯泡沫箱中挥发性有机物的迁移情况,对食物接触泡沫箱后的安全性进行评估.方法 采集不同来源的泡沫箱,先用乙酸(体积分数为4％)和乙醇(体积分数为10％)对其进行模拟液迁移实验,然后选取迁移量较高的挥发性有机物进行实物迁移实验,检测挥发性有机物的迁移量.结果 模拟液的迁移实验中检出间二甲苯、对二甲苯、邻二甲苯、苯乙烯、乙苯和1,3-丁二烯均有不同程度的迁移,并且体积分数为10％的乙醇作为迁移液时迁移值较高,苯乙烯在体积分数为10％的乙醇中迁移量最高;实物迁移实验中邻二甲苯在橙子中未检出,苯乙烯在橙子中的迁移量随着温度的升高,贮藏时间越长,迁移量越高.菜心检出了邻二甲苯,并且迁移量同样随着温度和时间的增加而呈现上升趋势,樱桃番茄中未检出挥发性有机物的迁移.结论 泡沫箱中苯乙烯、邻二甲苯在模拟液中的迁移量较高,并且在较高温度、较长时间接触橙子和菜心后可能会大量迁移,对人体健康产生风险.     

食品接触用硅橡胶中危害物迁移的研究进展

目的综述食品接触用硅橡胶制品中潜在危害物的迁移研究现状,为相关法规的修订提供参考。方法介绍食品接触用硅橡胶中硅氧烷低聚物、N-亚硝胺类物质及金属元素向食品模拟物和真实食品的迁移研究进展,并提出可减少硅橡胶制品中潜在危害物的建议。结论食品接触用硅橡胶制品中的硅氧烷低聚物易向油性食品模拟物和高脂肪含量的食品发生迁移,且分子量较小的硅氧烷低聚物更容易发生迁移;硅橡胶奶嘴中的N-亚硝胺类物质会向人工唾液中发生迁移;硅橡胶制品中的金属会向酸性食品模拟物发生迁移。这些物质迁移到食品中会存在健康隐患,故需要减少食品接触用硅橡胶制品中潜在危害物的含量,并进一步完善相关法规。     

Suitability of alternative fatty food simulants to study the effect of thermal and microwave heating on overall migration of plastic packaging

The suitability of alternative fatty food simulants on overall migration determination under thermal treatment and microwave heating were analysed for different plastic materials commonly used for packs subjected to thermal treatment or microwave heating. Elevated temperature and microwave heating increased overall migration. The results demonstrated that polymer–simulant affinity plays a large role in determining the suitability of the alternative simulant. For PA/PE, ethanol 95% represented the best alternative fatty food simulant to reproduce overall migration with olive oil. PVC presented a high overall migration. Microwave heating increased migration up to 45 mg/dm². For PVC, isopropanol was able to reproduce olive oil even after microwave heating. For PP, none of the alternative fatty food simulants were able to reproduce overall migration with olive oil. PP presented high inert behaviour. Microwave heating did not produce a significant increase in overall migration; meanwhile, the time of exposure produced a more significant migration. Copyright © 2004 John Wiley & Sons, Ltd.     

发泡聚苯乙烯中苯乙烯的迁移研究

采用单面浸泡的方式,以蒸馏水和体积分数为95%的乙醇为食品模拟液,研究发泡聚苯乙烯(EPS)中苯乙烯(ST)在不同温度(25,45,65℃)和不同浸泡时间(1~240 h)下的迁移情况。结果表明:在蒸馏水食品模拟液中,很难检测到苯乙烯的迁移;在体积分数为95%的乙醇食品模拟液中,苯乙烯的迁移量要明显高于其在蒸馏水中的迁移量;25,45,65℃条件下,EPS中ST在体积分数为95%的乙醇食品模拟液中的扩散系数分别为5.08×10-9,1.29×10-8,6.78×10-8 cm2/s,对应的活化能为53.9 k J/mol。     

Migration of alkylbenzenes from packaging into food and Tenax®

Alkylbenzenes (alkyl chain C₁₀–C₁₃) are used as solvent components in certain offset printing inks. Alkylbenzenes were identified from 10 out of 15 samples of offset‐printed food packaging made of board. Printed hamburger collars intended for hamburger restaurants had exceptionally high contents of alkylbenzenes (70–500 mg/kg). Most of the collars had varnish on both the printed surface and the non‐printed food contact surface. Migration of alkylbenzenes from the hamburger collar into a roll was 2 mg/kg. In another test, in which Tenax^® was used as simulant, the effect of a varnish layer on the food contact surface was studied. It was found that the varnish layer reduced migration by about 70%. Tests with Tenax^® as a food simulant resulted in higher migration than in tests with rolls. The European Commission has published a risk assessment report on alkylbenzenes. The report concludes that there is no need for further testing or for risk reduction measures beyond those which are currently applied. However, consumer exposure was calculated without taking into account the possibility of oral exposure to alkylbenzenes migrating from food packagings. The migration of alkylbenzenes thus merits further study. Copyright © 2001 John Wiley & Sons, Ltd.     

食品接触材料中多种添加剂迁移量的测定

目的建立食品接触材料中32种添加剂迁移量的高效液相色谱检测方法,调查市售塑料食品接触材料中32种添加剂的迁移水平。方法选取103批不同材质的塑料食品接触材料,采用异辛烷、乙醇(体积分数分别为50%,20%,10%)、质量分数为3%的乙酸浸泡样品,得到模拟液,用液相色谱仪分析,外标法定量。结果 DBP,DEHP,二苯酮,UV-1577,BHT,697,2246,BHEB和荧光增白剂184均有检出,其中11批PVC样品中DBP或DEHP、1批PP样品中二苯酮和1批PC样品中UV-1577的迁移量高于限量要求。上述添加剂在异辛烷模拟物中的检出率最高,在体积分数为50%的乙醇模拟物中有较低的检出率,在其他3种模拟物中均未检出。结论塑料食品接触材料不宜直接用于接触油类食品和浓度较高的酒类食品。PP材质中的二苯酮、PC材质中的UV-1577、PVC材质中的DBP和DEHP存在的潜在危害较大,应加强监管。     

Migration of Photoinitiators in Food Packaging: A Review

Photoinitiators are highly photoactive compounds included in the formulations of UV curing printing inks and varnishes. Twenty five of those photoinitiators can be found in the bibliography regarding food packaging migration and analytical methods with an increasing interest in the last 9 years because of the foodstuffs contamination with 2‐isopropylthioxanthone detected in 2005. An overview about migration of photoinitiators in food packaging is firstly given in terms of Rapid Alert System for Food and Feed notifications, mechanisms of migration, and specific migration limits. Besides set off, a migration model based on diffusion and partition coefficients is considered to analyse the factors affecting migration: physicochemical properties of the photoinitiator, characteristics of the foodstuffs and food simulants, temperature and packaging. Molecular weight, volatility, polarity and lipophilicity are considered as the main physicochemical properties of the photoinitiators playing a role in migration. In relation with the food packaging, information from published works is reviewed, taking into account the special migration behaviour of paper and cartonboard as well as the efficiency of different plastic films as barriers to avoid or reduce migration. Results of the application of the migration model are compared with reported data from the bibliography. Finally, the use of polymeric multifunctional photoinitiators is concluded as the best option for ultraviolet curing inks and varnishes to print food packaging. They have higher molecular weight together with fewer and lower volatility photodecomposition byproducts and a higher probability than conventional photoinitiators of being bound into the cured polymer matrix. Copyright © 2014 John Wiley & Sons, Ltd.     

食品接触塑料制品中1-己烯迁移量的测定

目的 研究食品接触用塑料制品中1-己烯特定迁移的测定方法,为制订相关检测标准、有害物质的检测与控制提供参考依据。方法 采用不同食品模拟物浸泡,再经顶空-气相色谱分析,研究顶空平衡温度、顶空平衡时间、色谱柱对1-己烯分析测试的影响。结果 在所选择的优化试验条件下,经色谱柱分离,在11 min内即可完成目标化合物的分离分析。1-己烯在0.5,1.5,3.0 mg/kg添加水平的回收率为86.0%～105.3%,相对标准偏差为1.5%～4.4%（n=6）,方法定量限为0.1 mg/kg。结论 该方法快速、准确、灵敏,适合食品接触用塑料制品在不同食品模拟物中1-己烯特定迁移量的测定。     

Investigations on Overall Migration of Various Plastic Materials and Articles Used in Contact with Foodstuffs

The results of overall migration tests for a wide range of plastic packagings and other domestic and imported articles made of plastic intended to come into direct contact with foodstuffs are presented. In these tests the simulants specified in Directive 85/572/EEC as well as isooctane and 95% ethanol (so called alternative substances) have been used. Checking the overall migration into the four simulants specified in the above mentioned Directive it was found that the limit (equal to 10 mg/dm² according to Directive 90/128/EEC) was exceeded in a few, very specific, cases. Comparison between overall migration from some articles into sunflower oil and isooctane was also examined. The results indicate that though the use of isooctane as an alternative substance significantly simplifies the testing procedure, exceeding an overall migration limit into isooctane is not equivalent to exceeding the limit of migration into sunflower oil. In such cases only migration into typical fatty food simulants can have a deciding meaning. © 1997 John Wiley & Sons, Ltd.