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.     

Migration of fluorochemical paper additives from food-contact paper into foods and food simulants

Fluorochemical-treated paper was tested to determine the amount of migration that occurs into foods and food-simulating liquids and the characteristics of the migration. Migration characteristics of fluorochemicals from paper were examined in Miglyol, butter, water, vinegar, water-ethanol solutions, emulsions and pure oil containing small amounts of emulsifiers. Additionally, microwave popcorn and chocolate spread were used to investigate migration. Results indicate that fluorochemicals paper additives do migrate to food during actual package use. For example, we found that microwave popcorn contained 3.2 fluorochemical mg kg^-1 popcorn after popping and butter contained 0.1 mg kg^-1 after 40 days at 4°C. Tests also indicate that common food-simulating liquids for migration testing and package material evaluation might not provide an accurate indication of the amount of fluorochemical that actually migrates to food. Tests show that oil containing small amounts of an emulsifier can significantly enhance migration of a fluorochemical from paper.     

Migration of fluorochemical paper additives from food-contact paper into foods and food simulants

Fluorochemical-treated paper was tested to determine the amount of migration that occurs into foods and food-simulating liquids and the characteristics of the migration. Migration characteristics of fluorochemicals from paper were examined in Miglyol, butter, water, vinegar, water–ethanol solutions, emulsions and pure oil containing small amounts of emulsifiers. Additionally, microwave popcorn and chocolate spread were used to investigate migration. Results indicate that fluorochemicals paper additives do migrate to food during actual package use. For example, we found that microwave popcorn contained 3.2 fluorochemical mg kg^?1 popcorn after popping and butter contained 0.1 mg kg^?1 after 40 days at 4°C. Tests also indicate that common food-simulating liquids for migration testing and package material evaluation might not provide an accurate indication of the amount of fluorochemical that actually migrates to food. Tests show that oil containing small amounts of an emulsifier can significantly enhance migration of a fluorochemical from paper.     

Migration kinetics of four photo-initiators from paper food packaging to solid food simulants

ABSTRACT

The migration behaviour of four photo-initiators (BP, EHA, MBP and Irgacure 907) was studied by ‘printing’ onto four different food-packaging materials (Kraft paper, white cardboard, Polyethylene (PE)-coated paper and composite paper) and tracking movement into the food simulant: Tenax-TA (porous polymer 2,6-diphenyl furan resin). The results indicated that the migration of the photo-initiators was related to the molecular weight and log K_o/w of each photo-initiator. At different temperatures, the migration rates of the photo-initiators were different in papers with different thicknesses. The amount of each photo-initiator found in the food was closely related to the food matrix. The Weibull model was used to predict the migration load into the food simulants by calculating the parameters τ and β and determining the relationship of the two parameters with temperature and paper thickness. The established Weibull model was then used to predict the migration of each photo-initiator with respect to different foods. A two-parameter Weibull model fitted the actual situation, with some deviation from the actual migration amount.     

食品包装纸中紫外吸收剂向固态模拟物的迁移行为

研究4种紫外吸收剂,即2-(2’-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑(UV-327)、2-(2-羟基-5-甲基苯基)苯并三氮唑(UV-P)、2-羟基-4-甲氧基二苯甲酮(UV-9)和2-羟基-4-正辛氧基二苯甲酮(UV-531)在50、75℃和100℃3个温度条件下从食品包装牛皮纸迁移到固态食品模拟物Tenax~?中的迁移规律和影响因素。结果表明:随着温度的升高,紫外吸收剂的迁移速度加快,迁移量增加。此外,不同紫外吸收剂本身的物理化学性质(相对分子质量、油水分配系数等)也对其迁移规律和平衡迁移率产生了重要影响。在上述实验的基础上建立数学模型,以达到预测迁移量的目的。数据证明,所构建的模型可很好地预测在达到迁移平衡前,紫外吸收剂从牛皮纸迁移到Tenax~?中的迁移量。     

Migration of a UV stabilizer from polyethylene terephthalate (PET) into food simulants

The migration characteristics of the UV stabilizer Tinuvin 234 (2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl)phenol) into food simulants has been measured from polyethylene terephthalate (PET) using HPLC with UV detection. Ethanol/water, isooctane and a fractionated coconut oil simulant (Miglyol®) were used as food simulating solvents. The migration characteristics were measured at temperatures in the range of 40-70°C. Diffusion coefficients were determined to be in the range of 1 × 10^-14 cm² s^-1 to 1 × 10^-18 cm² s^-1. At 40°C, the amount of migration into 95% ethanol after 10 days was 2 μg dm^-2. Isooctane is determined to be a good fatty food simulant that provides similar results for PET to those of fatty foods.     

高温下白卡纸中二苯甲酮和1-羟基环己基苯基甲酮向食品模拟物质的迁移

研究了在70℃和90℃下,采用直接浸泡法使白卡纸中的固化剂二苯甲酮（BP）和1-羟基环己基苯基甲酮（HCH）向水、3%乙酸、15%乙醇、50%乙醇、95%乙醇等食品模拟物质迁移,采用高效液相色谱仪（HPLC）分别检测迁移后模拟物质中的迁移量。结果表明两种固化剂在0.64⁴0mg/L的质量浓度范围内呈良好线性,相关系数不小于0.9995。温度越高,迁移时间越长,迁移量也越大;随着乙醇浓度的增高,BP、HCH的迁移量也增加;对于3%乙酸,BP和HCH迁移率最小。      

PVC密封圈中环氧大豆油向食品模拟物迁移量的测定

建立了气相色谱-质谱法（GC-MS）对食品玻璃包装瓶盖聚氯乙烯（Polyvinyl chloride polymer,PVC）密封圈中环氧大豆油（Epoxidized soybean oil,ESBO）向食品模拟物迁移量的检测方法。以蒸馏水和橄榄油为模拟物,在40℃条件下浸泡瓶盖240h,经甲酯化和衍生化,以11,14-二环氧二十烷酸乙酯为内标物,通过测定环氧亚油酸（18∶2 2E）衍生物的含量,进而定量测定ESBO的迁移量。结果表明:ESBO在0.5⁵0.0mg/kg的浓度范围内线性关系好,R2大于0.993,回收率在92.8%¹03.9%之间,RSD为0.9%⁸.0%（n=6）,检出限（LOD）为0.2mg/kg,定量限（LOQ）为0.5mg/kg,方法精密度好,灵敏度高,定性定量准确。最后,应用其对24种不同PVC密封圈中的ESBO迁移量进行测定,水基模拟物中ESBO的迁移量符合法规EC 10/2011限量,而在油脂模拟物中测得含量在0.7⁵01.8mg/kg之间,其中7种超过了限量要求。      

国内外食品接触用纸安全管理现状与分析

食品接触用纸安全是保障食品安全的重要组成部分。目前,欧盟、美国和中国关于食品接触用纸安全管理基本搭建了涵盖原材料控制、生产过程监管和产品检测的全程管理模式。本文通过介绍欧盟、美国和中国关于食品接触用纸安全管理的基本要求、食品接触用纸生产用物质和食品接触用纸安全卫生要求,对食品接触用纸安全管理现状进行了综述。通过对比欧盟、美国和中国关于食品接触用纸相关法规及标准,分析各个国家和地区食品接触用纸的安全管理模式,针对各管理模式的相同点和不同点进行综合比较,旨在深入、全面了解各国关于食品接触用纸的安全管理模式和发展趋势,分析其中可被我国在完善食品接触用纸安全管理模式中所用的先进内容和经验。     

食品接触材料中多环芳烃在食品模拟物中的迁移规律研究

采用气相色谱-质谱联用法,对食品接触材料中多环芳烃在水、乙酸(体积分数为3%)、乙醇(体积分数为10%)和异辛烷等4种食品模拟物中的迁移规律进行了研究,研究迁移量与实验的温度、时间和模拟物属性等参数的关系。结果表明:模拟物的属性对迁移行为有显著影响,迁移量随温度的升高和时间的增加而变大。     

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.     

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.     

食品用纸杯中光引发剂特定迁移量的气相色谱- 串联质谱测定方法

目的建立11种光引发剂类化合物食品用纸杯特定迁移量的气相色谱-串联质谱(gas chromatographytandem mass spectrometry,GC-MS/MS)检测方法。方法食品模拟物中的光引发剂类化合物经反相固相萃取柱富集净化后,采用中等级性的DM-17MS气相色谱柱进行分离;采用三重四极质谱的多反应监测模式(multiple reaction monitoring,MRM)对化合物进行定量测定。结果本方法可在17 min内完成11种目标化合物的色谱分离。11种光引发剂在低、中、高3个添加水平的回收率在65.0%~119.8%范围内,相对标准偏差为1.2%~10.6%(n=6),方法检出限为1~7μg/L,定量限为2~20μg/L。结论该方法灵敏度高,定量准确,适用于食品模拟物中光引发剂类物质特定迁移量的测定。     

有机涂层食品接触材料中甲醛在食品模拟物中迁移规律的研究

目的 研究了有机涂层食品接触材料中毒害物质甲醛在食品模拟物中的迁移规律。方法 根据产品的实际使用条件,以食品模拟物对样品进行模拟浸泡,以乙酰丙酮分光光度法对食品模拟物中甲醛迁移量进行测定。结果 在相同的使用条件下,酸性模拟物中甲醛的迁移量最大;在接触同种食品模拟物时,甲醛的迁移量随着高压灭菌时间的延长和灭菌温度的升高而增加;货架存放时间对甲醛的迁移量无明显影响。结论 通过对甲醛迁移规律的考察,得出了有机涂层食品接触中甲醛的迁移风险。     

Migration of perfluoroalkyl acids from food packaging to food simulants

A broad range of fluorochemicals is used to impart oil and water barrier properties to paper and paperboard food packaging. Many of the fluorochemicals are applied to paper and paperboard as complex mixtures containing reaction products and by-products and unreacted starting materials. This work primarily focussed on the determination of seven perfluorocarboxylic acids (PFCAs) in two commercially available food contact papers: a di-perfluoro-alkyloxy-amino-acid and a perfluoroalkyl phosphate surfactant. In addition, the migration of the PFCAs into five food simulants from two commercial packages was evaluated. All seven PFCAs were detected in the range of 700–2220 µg kg^?1 of paper, while three perfluoroalkyl sulphonates were under the LOD. Results from migration tests showed that migration depends on paper characteristics, time and food simulant. The percentage of migration after 10 days at 40°C ranged from 4.8% to 100% for the two papers and different food simulants.     

纸基微流控芯片技术在食品安全检测中的应用

食品安全关系到全人类的生存和发展。食品分析检测是保证食品安全的重要途径。传统的食品安全监测体系主要依赖于专业的仪器设备和操作,昂贵且费时,寻求简单、快捷、大众型的食品安全检测方法具有重大的现实意义。纸基微流控芯片技术作为一种简便、高效、低成本的检测手段,可以实现从样品处理到检测的微型化、自动化、集成化及便携化,因而在食品安全快速检测领域展现出强大的发展活力。本文着重介绍了纸质微流控芯片技术在食品成分、农药残留、致病菌、重金属、食品添加剂等食品安全检测方面已取得的一系列重要进展,并展望了其在食品安全分析中的应用前景。     

Migration of Ti from nano-TiO2-polyethylene composite packaging into food simulants

An analytical method based on ICP-MS was developed for the determination of Ti in food simulants (3% (w/v) aqueous acetic acid and 50% (v/v) aqueous ethanol). The method was used to determine the migration of Ti from nano-TiO₂-PE films used for food packaging into food simulants under different temperature and migration time conditions. The maximum migration amounts into 3% (w/v) aqueous acetic acid were 1.4 ± 0.02, 6.3 ± 0.5 and 12.1 ± 0.2 μg kg^?1 at 25, 70 and 100°C, respectively, while into 50% (v/v) aqueous ethanol, the maximum migration amounts were 0.5 ± 0.1, 0.6 ± 0.03 and 2.1 ± 0.1 μg kg^?1 at 25, 70 and 100°C, respectively. Increasing the additive content in the film promoted migration of nanoparticles. The results indicated that the migration of nanoparticles might occur via dissolution from the surface and cut edges of the solid phase (film) into the liquid phase (food simulant).     

淋膜纸杯中Al、Mg向酸性食品模拟物的迁移及数学模拟

为了研究淋膜纸杯中Al和Mg向酸性食品中的迁移规律以及数学模拟软件模拟迁移的有效性,对8种淋膜纸杯样品采用湿法消解的方法消解,之后利用电感耦合等离子体原子发射光谱(ICP-OES)检测8种淋膜纸杯中Al和Mg的初始含量及其向酸性食品模拟物(3%乙酸溶液)中迁移的量。淋膜纸杯中Al和Mg的初始含量分别为841.6～3 482.0,179.1～19 720.1mg/kg。在迁移条件为40℃/12h,8种样品中Al和Mg向3%乙酸溶液中迁移量分别为0.077～0.212,0.065～0.862mg/kg,而在70℃/8h下8种样品中Al和Mg向3%乙酸溶液中迁移量分别为0.074～0.180,0.064～2.209mg/kg,淋膜层低密度聚乙烯(LDPE)的厚度、迁移温度和时间以及纸的厚度和密度都能影响2种金属元素的迁移。使用迁移模拟软件AKTS-SML对8种淋膜纸杯样品进行迁移模拟,扩散系数采用Piringer模型,纸与LDPE之间的分配系数设置为1 000,LDPE与食品模拟物(3%乙酸)之间的分配系数设置为1,Al和Mg在40℃/12h下迁移模拟结果分别为0.760～3.075,0.162～17.750mg/kg;70℃/8h下迁移模拟结果分别为0.757～3.059,0.161～17.660mg/kg,软件模拟的迁移结果比试验所得到的都要高,迁移模拟结果在一定程度上能取代Al和Mg的迁移试验,确保消费者安全。     

PVC密封圈中环氧大豆油向食品模拟物迁移量的测定

建立了气相色谱-质谱法(GC-MS)对食品玻璃包装瓶盖聚氯乙烯(Polyvinyl chloride polymer,PVC)密封圈中环氧大豆油(Epoxidized soybean oil,ESBO)向食品模拟物迁移量的检测方法。以蒸馏水和橄榄油为模拟物,在40℃条件下浸泡瓶盖240h,经甲酯化和衍生化,以11,14-二环氧二十烷酸乙酯为内标物,通过测定环氧亚油酸(18∶2 2E)衍生物的含量,进而定量测定ESBO的迁移量。结果表明:ESBO在0.5~50.0mg/kg的浓度范围内线性关系好,R2大于0.993,回收率在92.8%~103.9%之间,RSD为0.9%~8.0%(n=6),检出限(LOD)为0.2mg/kg,定量限(LOQ)为0.5mg/kg,方法精密度好,灵敏度高,定性定量准确。最后,应用其对24种不同PVC密封圈中的ESBO迁移量进行测定,水基模拟物中ESBO的迁移量符合法规EC 10/2011限量,而在油脂模拟物中测得含量在0.7~501.8mg/kg之间,其中7种超过了限量要求。     

微流控纸芯片在食品安全快速检测中的应用

微流控纸芯片,又称纸芯片,是用纸张代替了传统的微流控基底材料并将生化反应微缩于几平方厘米大小的纸上,构成的微型实验室分析系统。由于其低成本、便携性、热稳定性等优势,在质量控制与快速检测领域展现出了独特的创新和潜力。本文综述了纸芯片近几年在食品质量安全快速检测方面的研究进展,主要介绍了传统二维纸芯片制备过程中选择的纸质基材、微流控芯片亲水/疏水材料与技术和表面改性,深入三维结构纸芯片的流体通道构造,通道微阀、折叠等流体控制方式;重点介绍了2016—2022年纸芯片在食品质量安全快速检测方面(农兽药残留检测、致病菌检测、农药残留检测和食品掺假鉴别)的最新应用进展,并讨论其在未来的发展趋势与目前所面临的挑战,以期为纸芯片在食品安全检测领域的发展提供有效参考。