Assessing the safety of co-exposure to food packaging migrants in food and water using the maximum cumulative ratio and an established decision tree

Food contact materials can release low levels of multiple chemicals (migrants) into foods and beverages, to which individuals can be exposed through food consumption. This paper investigates the potential for non-carcinogenic effects from exposure to multiple migrants using the Cefic Mixtures Ad hoc Team (MIAT) decision tree. The purpose of the assessment is to demonstrate how the decision tree can be applied to concurrent exposures to multiple migrants using either hazard or structural data on the specific components, i.e. based on the acceptable daily intake (ADI) or the threshold of toxicological concern. The tree was used to assess risks from co-exposure to migrants reported in a study on non-intentionally added substances (NIAS) eluting from food contact-grade plastic and two studies of water bottles: one on organic compounds and the other on ionic forms of various elements. The MIAT decision tree assigns co-exposures to different risk management groups (I, II, IIIA and IIIB) based on the hazard index, and the maximum cumulative ratio (MCR). The predicted co-exposures for all examples fell into Group II (low toxicological concern) and had MCR values of 1.3 and 2.4 (indicating that one or two components drove the majority of the mixture’s toxicity). MCR values from the study of inorganic ions (126 mixtures) ranged from 1.1 to 3.8 for glass and from 1.1 to 5.0 for plastic containers. The MCR values indicated that a single compound drove toxicity in 58% of the mixtures. MCR values also declined with increases in the hazard index for the screening assessments of exposure (suggesting fewer substances contributed as risk potential increased). Overall, it can be concluded that the data on co-exposure to migrants evaluated in these case studies are of low toxicological concern and the safety assessment approach described in this paper was shown to be a helpful screening tool.     

食品接触塑料材料及制品中高关注化合物的高分辨质谱分析技术研究进展

食品接触塑料材料及制品向食品可能发生的高关注化合物迁移一直是食品接触材料安全研究和合规管理的重点。这些高关注化合物分为有意添加物和非有意添加物。由于塑料食品接触材料高关注化合物来源复杂,迁移水平低且相当数量是未知的物质,在缺乏完整的化学物结构数据库、质谱谱图数据库以及标准品等情况下,对这些物质的鉴定和定量测定一直是食品接触材料安全分析所面临的重大技术挑战。近年来,基于气相色谱、液相色谱与各种高分辨率质谱联用的分析技术被视为一种有效手段,逐渐应用于对食品接触材料中高关注化合物的鉴定和定量分析。本文重点介绍近年来针对食品接触塑料高关注化合物分析的高分辨精确质谱(high resolution mass spectrometry, HRMS)分析技术进展,包括迁移试验条件、前处理技术、数据采集以及数据处理技术等。并总结应用HRMS技术所分析的不同食品接触塑料中的高关注化合物,以期为食品接触塑料的风险评估和管理工作提供参考。     

Migration from printing inks in multilayer food packaging materials by GC-MS analysis and pattern recognition with chemometrics

Inks and varnishes used in food packaging multilayer materials can contain different substances that are potential migrants when packaging is in contact with food. Although printing inks are applied on the external layer, they can migrate due to set-off phenomena. In order to assess food safety, migration tests were performed from two materials sets: set A based on paper and set B based on PET; both contained inks. Migration was performed to four food simulants (EtOH 50%, isooctane, EtOH 95% and Tenax^®) and the volatile compounds profile was analysed by GC-MS. The effect of presence/absence of inks and varnishes and also their position in the material was studied. A total of 149 volatile compounds were found in migration from set A and 156 from set B materials, some of them came from inks. Quantitative analysis and a principal component analysis were performed in order to identify patterns among sample groups.     

Food and beverage can coatings: A review on chemical analysis,migration, and risk assessment

The internal surface of food and beverage cans is generally covered with polymeric coatings to preserve food and protect metal substrate from corrosion. Coating materials are complex formulations that contain different starting substances (e.g., monomers, prepolymers, additives, etc.) and in addition during the manufacture of the material several compounds can be formed (e.g., reaction products, degradation products, etc.). These substances have the potential to migrate into the food. Many of them have not been identified and only some have been toxicologically evaluated. This article aims to provide a comprehensive review on the analytical methods used for the identification of potential migrants in can coatings. The migration and exposure to chemicals migrating from can coatings are also reviewed and discussed so far, which is essential for risk assessment. Moreover, a brief section on the current status of the legislation on varnishes and coatings for food contact in Europe is also presented. Liquid chromatography coupled to diode array and fluorescence detectors and particularly to mass spectrometry and gas chromatography–tandem mass spectrometry seem to be the techniques of choice for the identification of potential migrants in can coatings. Some studies have reported migration levels of BPA (bisphenol A) and BADGE (bisphenol A diglycidyl ether) and derivatives exceeding the specific migration limits set in the European legislation. On the whole, low dietary exposure to migrants from can coatings has been reported. However, it is interesting to highlight that in these studies the combined exposure to multiple chemicals has not been considered.     

塑料食品接触材料中非有意添加物检测方法研究进展

食品接触材料(Food contact materials, FCMs) 与食品安全密切相关。FCMs能有效保护食品,防止其腐败变质,但在生产过程中可能会由于一些原因引发食品安全问题,其中从FCMs中迁移出的非有意添加物(non intentionally added substance,NIAS)成为影响食品安全的重要因素而引起社会各界的广泛关注。由于NIAS非常复杂,且相当数量未知,其检测成为我国乃至全球食品接触材料安全评价的关键点及难点。在这篇综述中,以塑料食品接触材料和NIAS为主,介绍塑料材料中的NIAS来源、种类、国内外相关法律法规、近年来研究现状以及分析方法,最后对NIAS检测以及Orbitrap高分辨质谱检测技术的未来发展方向进行了展望。     

毒理学关注阈值方法在食品接触材料风险评估中的应用

食品接触材料中包含诸多有意添加的化学助剂,在生产和使用过程中还会引入大量非有意添加物。食品接触材料中的有意和非有意添加物质种类繁多,难以得出所有物质完整的毒理学数据;而且食品接触材料中存在一些低暴露量的物质,它们对人体造成的风险较小而不必要进行传统的风险评估。毒理学关注阈值（threshold oftoxicological concern,TTC）方法作为一种新的风险评估工具,可以对缺乏完整毒理学数据且暴露量较低的化学物质进行风险评估。本文综述TTC方法对食品接触材料中的物质（结构确定和结构未知的物质）进行风险评估的具体应用。对结构已知的物质,可以参照欧洲国际生命科学学会（European International Life Sciences Institute,ILSI）专家组提出的TTC决策树方法;对于未鉴定结构的物质,可以引用一个分步分析的方法,得出未知物质是否需要进行安全关注。本文还指出了TTC方法在食品接触材料风险评估中应用的难点和今后需解决的问题,可为食品接触材料中缺乏毒性数据物质的风险评估提供依据。     

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。     

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。     

基于FT-IR和GC-MS分析市售PLA吸管中挥发性物质

通过傅里叶变换红外光谱法对收集的市售聚乳酸（polylactic acid，PLA）吸管样品进行成分鉴定，采用气相色谱-质谱（gas chromatography-mass spectrometry，GC-MS）法对吸管样品进行非靶向分析，结合保留指数、NIST谱库和MS-DIAL解卷积定性，利用物质数据库对化合物进行溯源和安全风险关注。结果表明，样品均为PLA或以PLA为基材，不同程度混合了聚己二酸/对苯二甲酸丁二醇酯和聚丁二酸丁二醇酯；GC-MS分析检测出41 种挥发性物质，顶空GC-MS检出173 种挥发性物质，主要为塑料添加剂以及可能来源于原材料的杀虫剂、洗涤剂等，部分物质安全性应当被重点关注。GC-MS和顶空GC-MS结果相互补充，有利于更准确地分析挥发性物质。本研究为市售PLA吸管中挥发性物质的分析及安全风险评估提供基础。     

体外生物测定法在食品接触材料安全性评价中的应用研究进展

体外生物测定法是利用酵母、细菌、细胞等进行的生物体外短期毒性实验,可以有效针对生物体某一特异性效应,评价测试物的危害性以及探索其毒性作用机制。由于体外生物测定法可以提供食品接触材料迁移物（混合物）整体实际危害的综合信息,因此,近年来被越来越多地应用于食品接触材料的危害评估,尤其集中在细胞毒性、遗传毒性和内分泌干扰这3 类毒理学终点。本文重点综述了这3 类体外生物测定方法的基本原理,以及近20年来其在食品接触材料提取物危害评价中的应用研究进展,以期为今后食品接触材料生物学安全性评价的相关研究提供理论参考。     

食品包装材料中有害物质迁移的研究进展

随着人们生活水平的提高,食品安全问题得到了广泛的关注。塑料、纸质、玻璃、金属和复合材料等食品包装材料中有害物质的迁移现已成为食品安全隐患的重要组成部分。食品包装材料中添加的功能性助剂以及包装印刷过程中使用含苯、正己烷、卤代烃等有害化工材料为主要原料的油墨、溶剂及辅料的迁移都得到了一定的研究。目前,国内研究多局限于塑料包装材料,而国外的研究相对全面。结合国内外的研究现状,对食品包装材料中有害物质的来源组成及其迁移的研究现状和趋势加以综述,为科研工作者的研究、食品包装行业的质量监控以及食品安全问题的妥善解决提供一定的理论基础和实践参考。     

塑料食品包装材料中受限物迁移研究进展

塑料食品包装材料为了达到应有的机械强度,韧性,常常需要在包装材料中添加一些加工助剂,但这些加工助剂在包装材料包装食品的过程中,会迁移到食品中,从而对人体产生危害。本文综述了塑料食品包装材料中添加的四大类受限物质,包括增塑剂、抗氧化剂、热稳定剂以及紫外吸收剂,检索了在中国期刊全文数据库CNKI和Web of Science中相关文献的信息,系统地分类分析了查阅到的文献,并且介绍了4类添加剂的作用机制和目前国内国外对4类添加剂发生迁移的研究现状,比较了我国与发达国家关于4类受限物质的法律法规及迁移限量,提出了减少食品中受限物质迁移量的方法措施以及加强我国塑料食品接触材料中受限物质使用与管理的建议。     

Evaluating the migration of ingredients from active packaging and development of dedicated methods: a study of two iron-based oxygen absorbers

The behaviour of two commercial oxygen-scavenging products with respect to migration of active ingredients into foodstuffs was investigated. Migrants were identified, and by using appropriate analytical methods, migration was determined in a variety of liquid, solid or gelled food simulants and foods. Simulants were chosen to cover a range of water activities and viscosities. Foods and the gelled food simulant agar were packed with and without vacuum, and with the oxygen scavenger in various locations relative to the packed food. The main migrants, as identified by X-ray fluorescence spectrometry, infrared spectroscopy and scanning electron microscopy with energy-dispersive spectrometry were Na + and Cl - in non-acidic aqueous simulants, and Na + , Cl - and Fe 2+ in 3% acetic acid. Migration into aqueous simulants exceeded the current European Union limit for total migration from plastic materials (assumed to be currently applicable to these systems) and was probably excessive by any reasonable standard. However, neither oxygen scavenger appeared to release significant quantities of migrants into solid foods when the scavenger was properly located in the package and the packing process does not favour the contents becoming wet by water released from the food.     

Safety by design of printed multilayer materials intended for food packaging

ABSTRACT

Printing inks are commonly used in multilayer plastics materials used for food packaging, and compounds present in inks can migrate to the food either by diffusion through the multilayers or because of set-off phenomena. To avoid this problem, the right design of the packaging is crucial. This paper studies the safety by design of multilayer materials. First, the migration from four different multilayers manufactured using polyethylene terephthalate (PET), aluminium (Al) and polyethylene (PE) was determined. The structural differences among materials such as the presence of inks or lacquer coatings as well as the differences in layers position allowed the study of a safety-by-design approach. Sixty-nine different compounds were detected and identified; 49 of them were not included in the positive list of Regulation EU/10/2011 or in Swiss legislation and 15 belong to Cramer class III, which means that they have a theoretical high toxicity. Some of the compounds related to ink composition were pyrene, a compound commercially used to make dyes and dye precursors and the antioxidant Irganox 1300. The application of external lacquers decreased the concentration of some migrants but also brought the potential for new migrants coming from its composition. A final risk assessment of the material allowed evaluating food safety for different food simulants and confirm it.     

外卖食品接触材料中有害物质迁移研究进展

近年来外卖行业发展迅速,随之产生的食品接触材料安全问题也不容忽视。食品接触材料（FCM）由于反应副产物、低聚物、降解过程、包装材料与食品之间的化学反应或生产所用原料中的杂质而含有有害物质,在与食品接触时这些物质会迁移至食品中从而对人体造成危害。常见外卖食品接触材料为塑料与纸制品,其中含有塑化剂、抗氧化剂、光稳定剂等添加剂,而传统中式食品又以高温、高油食品为主,在使用一次性餐具盛装该类外卖食品时,添加剂极可能迁移到相关外卖食品中,具有较大的安全风险与隐患。本文对常见外卖食品接触材料中主要有害物质的性质、检测方法与迁移研究现状进行简述,了解外卖食品接触材料中有害物质的迁移情况,从而给外卖食品接触材料的安全监管提供一定的参考依据。     

食品接触材料样品前处理和检测方法研究进展

近年来,食品接触材料中有害物质迁移导致的食品安全问题已经引起了社会各界的广泛关注。食品接触材料中有害物质具有种类多、来源广、成分复杂、未知性强等特点,选择合适的样品前处理方法结合快速、灵敏、准确以及多组分同时检测的分析检测方法是食品接触材料安全评价的关键。本文简要介绍了食品接触材料中有害物质的危害性,食品接触材料种类以及食品接触材料中非有意添加物的来源,重点评述了食品接触材料的样品前处理方法和分析检测方法,并对食品接触材料分析检测存在的问题及未来的发展趋势进行了分析和展望。     

液相色谱-串联质谱技术在食品药品安全分析领域的应用

液相色谱(liquid chromatogram,LC)在分离能力、灵敏度和专属性等方面有着巨大优势,与质谱(mass spectrometry,MS)联用后可以展现出强大的定性、定量分析能力,并已经在农兽药残留、非法添加、有毒物质研究等各领域得到广泛应用。本文对液相色谱-串联质谱(liquid chromatography-tandem mass spectrometry,LC-MS/MS)技术在食品相关国家标准,如农残、兽残、食品接触类材料,及《中华人民共和国药典(2015版)》中的应用进行了简单介绍,并介绍了本部门在食品安全、药品安全、食品接触类塑料制品残留物分析等领域取得的工作进展。     

Estimation of exposure to food packaging materials. 3: Development of consumption factors and food-type distribution factors from data collected on Irish children

There are many initiatives in Europe trying to refine the exposure assessment for food packaging migrants. In the USA, the US Food and Drug Administration (US FDA) uses food consumption and food-type distribution factors to aid the exposure assessment process and generate more realistic estimates of exposure. The present study developed food-consumption factors and food-type distribution factors for Irish children aged 5-12 years from data collected as part of a National Children's Food Survey (NCFS) completed in Ireland in 2003-04, combined with data from the 2003-05 Irish Food Packaging Database and from literature data on surface area-to-weight ratios for food packaging. Consumption factors are defined as the fraction of a person's diet likely to contact a specific food-contact material, while food-type distribution factors reflect the fraction of all food contacting each material that is aqueous, acidic, alcoholic or fatty. In this study, it was found that 'total plastics' had the highest consumption factor of 0.83, while 'total paper and board' had a factor of 0.13 and 'total metal and alloys' had a factor of 0.06. Although it is tentative to compare the US FDA factors with the factors derived in the current study, as the US FDA data are for the total US population, the consumption factor for 'total plastics' in the present study (0.83) was similar to that used by the US FDA (0.79). However, a large difference existed for the consumption factor for 'total metal and alloys' in the Irish data (0.06) and the US FDA data (0.2). In terms of the type of materials used for foods, glass was used mainly for acidic foods (0.67), while plastic was uniformly used for all food types. The food-contact area for plastic packaging for all foods consumed by children was 10.67 dm²/child day^-1, which is slightly lower than the proposed value for the average European consumer of 12.4 dm²/person day^-1. However, this should be expected, as children do not consume as much food as adults. When scenario exposure estimates were made, it was found that when using European Union assumptions, estimates were much larger than when using consumption factors and food-type distribution factors in the exposure assessment, even when conservative assumptions were employed for the consumption factor. This study highlights the potential use of consumption factors and food-type distribution factors in the refinement of the exposure assessment process and how these factors can be calculated using data collected as part of a national food survey.     

Mutagenicity assessment of food contact material migrates with the Ames MPF assay

ABSTRACT

A major challenge in the safety assessment of food contact materials (FCM) is the evaluation of unknown non-intentionally added substances (NIAS). Even though consumer exposure levels may be quantitatively low, these substances are considered to be of high toxicological concern if they act as DNA reactive mutagens. From a safety assessment perspective, it is therefore important to detect their presence in FCM migrates. The present study applied the Ames MPF assay to assess the mutagenicity of migrates obtained from 30 food contact material samples out of 3 categories: plastics, composite materials and coatings. As a food simulant, 95% ethanol (EtOH) had a superior performance to less volatile simulants when evaluating recovery rates of representative model substances in different volatility categories. To monitor possible interference of the FCM matrix with Ames MPF results, migrates were spiked with reference substances and recovery rates were established. Out of 30 samples tested, two caused significant inhibition of revertant formation in the presence of the spiking control. Overall detection limits of the applied test method were estimated by determination of the lowest effective concentrations (LEC) for 10 Ames-positive substances. Even though the current limits of detection are not sufficient to entirely fulfil regulatory and safety requirements, three out of 30 FCMs showed evidence of dose-dependent effects in the Ames MPF assay. Overall, the data obtained supported the relevance of testing FCM migrates for DNA reactive contaminants and showed the value of the Ames MPF assay for the safety assessment of FCMs.