Fractionation of extracts from paper and board food contact materials for in vitro screening of toxicity

Paper and board used as food contact materials (FCMs) are chemically complex matrices, partly due to the naturally occurring substances in paper and board, but also due to the chemical treatment of the paper used to make it suitable for food contact. In order to assure the safety of packaging materials, information on the exposure as well as on the toxicity of substances in the packaging must be obtained. This study describes a comprehensive method for the extraction and fractionation of substances present in paper and board FCMs for further investigation by in vitro testing and chemical analysis. The extraction efficiency and the fractionation process were validated by determining recoveries in extracts from paper and board fortified with five surrogates of known concentration. The recoveries for the five surrogates were between 20% and 104% in the raw extract and between 21% and 109% after extraction and fractionation. The fractionation both reduces the number of compounds to be identified and works as a sample clean-up by reducing matrix effects. Raw extracts and fractions from two paper and board FCMs were furthermore tested in the aryl hydrocarbon receptor (AhR) reporter gene assay. Both raw extracts and two of the fractions of the raw extracts gave a positive response in the AhR assay. The strategy of extraction followed by fractionation offers a powerful tool in order to make the workflow for screening FCMs for potentially adverse effects more efficient.     

食品接触材料纸和纸板中非故意添加物质分析方法的研究进展

食品接触材料含有非故意添加物质可能来源于反应副产物、低聚物、降解过程、包装材料与食品之间的化学反应、生产原料中的杂质。在这篇综述中,综述非故意添加物质的定义、非故意添加物质的分析方法。纸和纸板中的非故意添加物质主要来自印刷油墨、粘合剂、上浆剂和表面涂料。通常针对已知的非故意添加物质进行靶标分析,而采用非靶标分析法分析未知的非故意添加物质。本文主要对食品接触材料纸和纸板中非故意添加物质分析方法的研究进展进行了概述,旨在给国内相关研究提供参考,并有助于后续食品接触材料纸和纸板中非故意添加物质分析工作的开展。     

Potential for short-term migration of mineral oil hydrocarbons from coated and uncoated food contact paper and board into a fatty food simulant

ABSTRACT

Mineral oil hydrocarbons (MOH) are widely used in the food industry for applications such as printing inks, additives, adhesives, and processing aids for food additives. Recently, the migration of MOH from food contact paper and board into foods has raised public health concerns. In this study, a total of 110 food contact paper and board samples, including baking and cooking paper (23), baking cups (28), food packaging bags (22), lunch boxes (8), party plates (26), and straws (3) were evaluated to quantify the content and short-term migration levels of MOH. The MOH were separated into mineral oil saturated hydrocarbons (MOSH)/polyolefin oligomeric saturated hydrocarbons (POSH) and mineral oil aromatic hydrocarbons (MOAH) via a validated on-line liquid chromatography?gas chromatography?flame ionisation detection (LC–GC–FID) technique. The coating materials of the sample products comprised polyethylene, polypropylene, polyethylene terephthalate, and silicone. The effects of the coating materials on the content and migration of MOH/POSH were evaluated. Quantitative analysis of the MOH in the samples showed that the MOSH/POSH and MOAH content varied widely, ranging from 16 to 5626 mg kg^?1 for MOH, regardless of the coating materials. Short-term migration of MOSH/POSH was observed only in samples with polyolefinic coatings, such as polyethylene and polypropylene, in experiments conducted at 25 °C for 10 min, although the extent of MOAH migration for all samples was at the trace level. The migration of MOSH/POSH was detected within the range of 0.93 to 62.3 μg L^?1 in 22 samples, and the migration of MOAH was detected within the range of 0.80 to 2.6 μg L^?1 in only 4 samples. These results demonstrate that although the short-term migration potential of MOH is generally negligible, the migration of MOSH/POSH into wet fatty foods can be accelerated by polyolefinic coatings, even within a very short time.     

高压液相色谱法测定纸质食品接触材料中亚甲基双硫氰酸酯的迁移量

目的 建立纸质食品接触材料中亚甲基双硫氰酸酯迁移量的高压液相色谱测定方法。方法 食品模拟物(水、3%乙酸-水溶液、10%乙醇-水溶液和橄榄油)中的亚甲基双硫氰酸酯通过高压液相色谱进行分离, 采用二极管阵列检测器进行测定。水基食品模拟物直接进样, 油基食品模拟物经乙腈萃取后进样, 外标法定量。结果 3种水基食品模拟物中, 亚甲基双硫氰酸酯在0.5~50 mg/L范围内线性关系良好, 定量下限为0.5 mg/L, 平均回收率为88.2%~97.4%, 相对标准偏差为0.44%~6.54%; 油基食品模拟物中, 亚甲基双硫氰酸酯在1.0~20 mg/kg范围内线性关系良好, 定量下限为1.0 mg/kg, 平均回收率为99.3%~104.7%, 相对标准偏差为0.75%~3.15%。结论 该方法准确、简便、快速, 可用于纸质食品接触材料中亚甲基双硫氰酸酯迁移量的实际检验工作。     

食品接触材料的安全卫生问题及检验标准 现状分析

食品接触材料导致的食品安全问题逐渐引起了社会各界的广泛关注。本文以聚合物型食品接触材料为例,简述了该领域在理化检验、不规范使用方面的安全卫生问题,尤其对现行的检测标准的适用性、操作性存在的问题进行了分析。建议企业应加强生产工艺管理,关注行业标准变化调整生产;相关机构加快标准的修订,对于某些较为模糊的条款应结合实际进一步细化,检测标准的更新应充分考虑产品实际的用途,特定物质的限量标准应满足行业发展的需求和人民群众健康安全的基本要求。     

Test procedures for obtaining representative extracts suitable for reliable in vitro toxicity assessment of paper and board intended for food contact

This paper describes the use of a suite of extraction procedures applicable to the assessment of the in vitro toxicity of paper/board samples intended for food-contact applications. The sample is extracted with ethanol, water, or exposed to modified polyphenylene oxide (Tenax®) for fatty, non-fatty and dry food applications, respectively. The water extracts are directly suitable for safety assessment using in vitro bioassays. The ethanol extracts of the paper/board and of the exposed Tenax require pre-concentration to give acceptable sensitivity. This is because the in vitro bioassays can tolerate only a small percentage of added organic solvent before the solvent itself inhibits. The extraction procedures have been selected such that they mimic the foreseeable conditions of use with foods and that they are also fully compatible with the battery of in vitro biological assays for the safety assessment of the total migrate. The application of the extraction protocols is illustrated by the results for one of the many paper/board samples provided by the BIOSAFEPAPER project industrial platform members. The assessment indicated that this sample should not be considered as suitable for use with fatty foodstuffs but was suitable for dry and non-fatty foods. Information subsequently received from the manufacturer revealed that this was a non-food-grade product included in the project to test the capabilities of the bioassay procedures. The selection criteria for the test conditions and the suite of methods developed have been prepared in Comité Européen de Normalisation (CEN) format and is currently being progressed by CEN/TC172 as a European Standard.     

食品接触纸质包装材料中有害物质的迁移及潜在危害的研究进展

食品接触用纸是指在正常或可预见的使用条件下,预期与食品接触的各种纸及制品,包括涂蜡纸、纸浆模塑制品及食品加工烹饪用纸等。由于在加工处理过程中需要加入各种添加剂,其本身所含的助剂、单体、低聚体、降解物等化学残留物就可能通过吸收、溶解、扩散等途径迁移到食品中,污染食品,造成一定的食品安全隐患。本文通过对比国内外相关法规与标准对纸质食品接触材料检测项目、限量指标和检测标准等方面的规定,对食品接触纸质包装材料中有害物质的迁移及其潜在危害进行总结,并对食品接触纸质包装材料中有害物质全氟辛烷磺酸(perfluorooctane sulfonates,PFOS)、全氟辛酸(perfluorooctanoic acid,PFOA)、荧光增白剂、特定芳香胺(specific aromatic amines,PAAs)、甲醛、五氯苯酚、丙烯酰胺、重金属、光引发剂的迁移及其潜在危害进行综述。     

食品包装用纸卫生状况调查分析

了解全国食品用纸包装产品安全现状以及存在的行业问题,进一步规范食品用纸包装产品质量监管。方法 随机抽取不同种类纸包装样品,对各样品中溶剂残留、蒸发残渣、重金属等指标进行检测分析和风险评估。结果 食品用纸包装容器中苯系物残留和多环芳烃残留比较严重。多环芳烃残留检出率达到99%,苯系物残留中,苯残留检出率达到100%,甲苯残留达到76%。结论 目前食品纸包装材料溶剂残留量检出率较高,存在一定的产品质量安全风险,暴露出行业监管的问题。     

Bio-based coatings as potential barriers to chemical contaminants from recycled paper and board for food packaging

Partition and diffusion experiments were carried out with paper and board samples coated with different biopolymers. The aim was to evaluate the physicochemical behaviour and barrier properties of bio-coatings against migration of typical contaminants from recycled paper packaging. Focus was directed towards water-based, renewable biopolymers, such as modified starches (cationic starch and cationic waxy starch), plant and animal proteins (gluten and gelatine), poured onto paper with an automatic applicator. Additionally, a comparison with polyethylene-laminated paper was performed. Microstructural observations of the bio-coated paper allowed the characterisation of samples. From the partitioning studies, considerable differences in the adsorption behaviour of the selected contaminants between bio-coated or uncoated paper and air were highlighted. For both the polar and non-polar compounds considered (benzophenone and diisobutyl phthalate, respectively), the lowest values of partition coefficients were found when paper was bio-coated, making it evident that biopolymers acted as chemical/physical barriers towards these contaminants. These findings are discussed considering the characteristics of the tested biopolymers. Diffusion studies into the solid food simulant poly 2,6-diphenyl-p-phenylene oxide, also known as Tenax^®, confirmed that all the tested biopolymers slowed down migration. The Weibull kinetic model was fitted to the experimental data to compare migration from paper and bio-coated paper. Values found for β, an index determining the pattern of curvature, ranged from 1.1 to 1.7 for uncoated and polyethylene paper, whereas for bio-coated papers they ranged from 2.2 to 4.9, corresponding to the presence of an evident lag phase due to barrier properties of the tested bio-coatings.     

气相色谱-质谱法测定食品接触材料润滑剂在脂类食品模拟物中迁移量

目的建立气相色谱-质谱法测定食品接触材料中润滑剂(油酸酰胺、硬脂酰胺、芥酸酰胺、山嵛酰胺)在脂类食品模拟物中迁移量的方法。方法采用异辛烷、95%乙醇、改性聚苯醚3种试验介质替代脂类食品试验,用三氟乙酸酐衍生后,采用气相色谱-质谱法测定。结果油酸酰胺、硬脂酰胺在0.2~20 mg/L范围内线性良好,芥酸酰胺、山嵛酰胺在1.0~30 mg/L范围内线性良好,方法定量限为0.026~0.14 mg/L,加标回收率为76.2%~97.3%,相对标准偏差(RSD)为1.2%~6.3%。结论本法简便、快速、准确,灵敏度及精密度较高,适用于食品接触材料中润滑剂在脂类食品模拟物中迁移量的测定。     

Migration of inorganic contaminants into dry food from packaging made from recycled paper and board.

A radiotracer method was applied to the measurement of inorganic contaminants migrating into food. The method was applied to the study of 10 samples of recycled paper and board. The only elements detected in the static migration test were zinc and iron, at concentrations close to the detection limit. Samples of rice, oats, custard powder, mushrooms and fries showed that traces of these elements had migrated from the packaging. The migration was limited to less than 1%, with the exception of the mushrooms, where the decomposition of the food had resulted in a 12.5% transfer of zinc from the mushroom bag after 8 days, equivalent to migration of 0.022 mg dm(-2). Shaking had no effect on migration, except in one case of custard powder where migration occurred at a level equivalent to 0.002 mg dm(-2). The maximum migration determined in the present study was 4.8 microg zinc and 2.6 microg iron, which is negligible when compared with the recommended daily intakes of 15 and 14 mg, respectively. When Tenax was tested as a food simulant, no zinc was detected (< 0.001 mg dm(-2)), although slight migration (0.001 mg dm(-2)) occurred into food.     

Simultaneous analysis and exposure assessment of migrated bisphenol analogues,phenol, and p-tert-butylphenol from food contact materials

ABSTRACT

A simple, rapid, and novel liquid chromatography tandem-mass spectrometry (LC-MS/MS) method was developed and validated to determine levels of eight bisphenol analogues (A, S, F, B, P, AF, AP, and Z), phenol, and p-tert-butylphenol migrated from food contact material (FCM) into food simulants. Method validation showed acceptable values in terms of linearity, precision, and accuracy. The limits of detection and quantification were 0.53–29.6 and 1.77–29.6 μg L^?1, respectively. Water, 4% acetic acid, 50% ethanol, and n-heptane were employed as food simulants for the migration tests, and the proposed method was applied to 234 articles of 11 FCMs including polycarbonate, polyethersulfone, polypropylene, and polyethyleneterephthalate, obtained from domestic markets and manufacturers in Korea. Only phenol was found in the FCMs poly(cyclophexane-1,4-dimethylene terephthalate), polylactide, and thermoplastic polyurethane. Eight bisphenol analogues and p-tert-butyl phenol were not found in any samples. Using the obtained migration results, the estimated daily intake (EDI) of phenol was calculated. Exposure assessments were carried out to compare the EDI with the tolerable daily intake (TDI), showing a low percentage (0.18%) of the TDI reported. This is the first study to examine eight bisphenol analogues and two phenols simultaneously in FCMs using the LC-MS/MS.     

食品接触材料及制品标签标准研究

深入分析了食品接触材料及制品标签标注存在的问题,提出了食品接触材料及制品标签标准关键要素及要求。     

食品接触材料及制品用油墨安全性管理模式研究

目的研究世界各国食品接触材料及制品用油墨的相关法律法规、指令及指南文件,为我国食品接触材料及制品用油墨产品标准的建立及油墨安全性管理模式的完善提供建议。方法收集世界各国相关法律法规、指令及指南文件,梳理、对比各种管理模式在应用范围、管理方法等方面的异同,研究其中可为我国油墨安全性管理所借鉴和参考的内容。结果总结出欧盟和德国、美国、日本等世界主要发达国家和地区油墨安全性管理模式及管理经验。结论建议我国应结合行业现状,针对不同种类油墨的安全性风险,适当参考其他国家管理经验,尽快建立食品接触材料及制品用油墨产品安全标准,同时鼓励行业协会积极参与油墨的安全性管理。     

食品接触材料及制品标签的常见问题

作为食品生产、流通重要的组成部分,食品接触材料及制品的安全性能越来越受到消费者的关注。2015年9月1日实施的GB/T 30643-2014《食品接触材料及制品标签通则》结合食品接触材料及制品的生产及流通特点,从产品名称、规格、日期、贮存条件、产品标准号、质量等级及使用说明等诸多方面对该类产品的标签标识进行了规范性要求。本文结合日常工作经验,对目前食品接触材料及制品标签存在的主要问题进行了梳理、归纳和分析,并对理解尚不统一的个别条款给出了建议,可为生产者完整、准确地标注标签提供参考。     

Migration of lead and arsenic from food contact paper into a food simulant and assessment of their consumer exposure safety

ABSTRACT

Paper is one of the most commonly used food packaging materials. During the production of packaging paper, it is possible for trace amounts of heavy metals to be incorporated as contaminants. These could migrate into food when packaging paper (food contact paper) is used for cooking, storing and eating. The aim of this study was to determine the migration of lead (Pb) and arsenic (As) from food contact paper into a food simulant and then to assess human safety through the estimated daily intake (EDI) with consumption factor. Migration tests were conducted for 310 samples using 4% acetic acid as a food simulant at 25°C for 10 min and at 95°C for 30 min. Concentrations of Pb and As in a food simulant were quantified by inductively coupled plasma mass spectrometry. LODs for Pb and As were 0.002 and 0.005 µg L^?1, respectively. The migration of Pb from food contact paper ranged from not detected (ND) to 17.5 μg L^?1 at 25°C for 10 min and from 0.10 to 25.6 μg L^?1 at 95°C for 30 min while As ranged from ND to 0.44 μg L^?1 at 25°C for 10 min and from ND to 0.87 μg L^?1 at 95°C for 30 min. The migration of Pb and As determined in this study confirm that the human exposure was within safe levels based on the EDI of food contact paper compared with the provisional tolerable weekly intake for Pb of 25 μg kg^?1 bw and for As of 15 μg kg^?1 bw.     

Updated evaluation of the migration of styrene monomer and oligomers from polystyrene food contact materials to foods and food simulants

Due to the 2011 labelling of styrene monomer as “reasonably anticipated to be a human carcinogen” by the National Institutes of Health’s National Toxicology Program (NTP) and the controversy over whether styrene oligomers mimic the physiological effects of estrogen, an updated review of styrene monomer and oligomers in food and food contact materials (FCMs) was performed. The concentrations of styrene monomer and oligomers were determined in 24 polystyrene (PS) products and ranged from 9.3 to 3100 mg kg^–1 for the styrene monomer, 130–2900 mg kg^–1 for the sum of three styrene dimers, and 220–16,000 mg kg^–1 for the sum of six styrene trimers. Foods in contact with PS packaging had styrene monomer concentrations ranging from 2.6 to 163 ng g^–1; dimer concentrations from the limit of quantitation (LOQ) to 4.8 ng g^–1 and trimer concentrations were all below the LOQ (2 ng g^–1). Diffusion coefficients (D_p) and partition coefficients (K) were also calculated for styrene dimers and trimers. The results presented here indicate that styrene monomer concentrations in foods have not significantly changed since the 1980s and monomer concentrations in food packaging quantified in this study were all below USFDA limits. Although styrene dimers and trimers are present in higher concentrations in PS FCMs than the monomer, their migration to food is limited because of their high K values (4 × 10² to 2 × 10⁶) and their low diffusion coefficients in PS products. Additionally, diffusion coefficients calculated using USFDA-recommended food simulants and Arrhenius plots describing the temperature dependence of styrene dimers and trimers can be used in future calculations of dietary intake of the styrene oligomers.     

Migration of bisphenol A and benzophenones from paper and paperboard products used in contact with food

Migration of bisphenol A (BPA) and benzophenones, i.e., benzophenone (BZ), 4-(dimethylamino)benzophenone (DMAB), Michler's ketone (MK) and 4,4'-bis(diethylamino)benzophenone (DEAB), from 21 paper and paperboard products (15 recycled paperboard boxes and 6 virgin paper products) used in contact with food was examined. Migration levels of compounds from recycled paperboard were compared under various food-simulating conditions. BPA showed the highest migration into 20% ethanol and benzophenones into 95% ethanol. No compounds migrated from virgin paper products, but compounds did migrate into food simulants from recycled paperboard food boxes. BPA migrated into 20% ethanol from all recycled paperboard food boxes between 1.0 and 18.7 ng/mL. Into 95% ethanol, migration of BZ was observed in 8 samples (1.0-18.9 ng/mL), DMAB in 12 samples (1.2-3.7 ng/mL), MK in 13 samples (1.9-9.0 ng/mL), and DEAB in 13 samples (1.0-10.6 ng/mL). The highest migration level was 27.2 ng/mL and most of the migration levels were below 10 ng/mL. These values are sufficiently low compared with the TDI and NOAEL levels. Moreover, the amount of food in daily meals that comes into contact with paperboard products is relatively small. Consequently, it was concluded that there was no safety concern regarding the tested compounds in recycled paperboard food boxes.     

Safety evaluation of food contact paper and board using chemical tests and in vitro bioassays: role of known and unknown substances

In vitro toxicological tests have been proposed as an approach to complement the chemical safety assessment of food contact materials, particularly those with a complex or unknown chemical composition such as paper and board. Among the concerns raised regarding the applicability of in vitro tests are the effects of interference of the extractables on the outcome of the cytotoxicity and genotoxicity tests applied and the role of known compounds present in chemically complex materials, such as paper and board, either as constituents or contaminants. To answer these questions, a series of experiments were performed to assess the role of natural substances (wood extracts, resin acids), some additives (diisopropylnaphthalene, phthalates, acrylamide, fluorescent whitening agents) and contaminants (2,4-diaminotoluene, benzo[a]pyrene) in the toxicological profile of paper and board. These substances were individually tested or used to spike actual paper and board extracts. The toxic concentrations of diisopropylnaphthalenes and phthalates were compared with those actually detected in paper and board extracts showing conspicuous toxicity. According to the results of the spiking experiments, the extracts did not affect the toxicity of tested chemicals nor was there any significant metabolic interference in the cases where two compounds were used in tests involving xenobiotic metabolism by the target cells. While the identified substances apparently have a role in the cytotoxicity of some of the project samples, their presence does not explain the total toxicological profile of the extracts. In conclusion, in vitro toxicological testing can have a role in the safety assessment of chemically complex materials in detecting potentially harmful activities not predictable by chemical analysis alone.     

食品接触材料塑料制品标签标识存在的问题及改进意见

食品接触材料制品作为在正常使用条件下,各种已经或预期可能与食品或食品添加剂接触、或其成分可能转移到食品中的材料和制品,是百姓日常生活中十分常见且必需的产品。而塑料制品则占到了其中的绝大多数。随着这几年百姓与政府对食品接触材料安全的重视,其产品本身的质量得到了较大幅度的提高,但产品标签标识却依然存在较多的问题。本文结合日常工作经验,对目前食品接触材料塑料制品标签标识存在的问题进行整理分析,并提出改进意见。