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.     

水产品来源的甲醛膳食暴露评估初步研究

应用MonteCarlo模拟技术定量评估我国人群通过食用水产品途径的甲醛膳食暴露状况。结果表明,我国城乡普通居民通过食用水产品途径的甲醛暴露水平较低,且通过食用水产品途径城市人群摄入甲醛面临的健康风险高于农村人群;不同年龄群体的膳食暴露量存在差异,幼年消费者(2～13岁)的暴露量均高于成年人;7岁前,女孩的暴露水平高于男孩,7岁后,男孩的暴露水平高于女孩。我国普通居民仅通过食用水产品途径摄入甲醛对人体健康状况造成风险的可能性不大,但是幼儿、儿童是食用水产品途径甲醛暴露的敏感性群体,应在后续的风险管理过程中应给予足够的关注和重视。     

Exposure of the Irish population to PBDEs in food: consideration of parameter uncertainty and variability for risk assessment

Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants used to retard the ignition and/or spread of fire. PBDEs are used in various consumer products, such as textiles, mattresses and TV screens. This study presents a chemical risk assessment for the Irish population based on exposure to PBDEs from food. Special regard is given to the influence of parameter uncertainty and variability on the margins of safety. To quantitatively model uncertainty and variability in concentration data and variability in consumer behavior, a hierarchical probabilistic model was constructed. This model was evaluated using a two-dimensional Monte Carlo simulation (2D-MCS) approach. By considering uncertainty and variability in concentration data, margins of safety (MOS) were derived that are lower by a factor of ～2 compared to MOS based on dose estimates that only consider variability. The lowest MOS is 7.5?×?10⁴ for BDE-99, with impaired spermatogenesis as toxic endpoint. Assuming an MOS of 10⁴ as acceptable, we conclude that there is no significant risk for human health through intake of contaminated food. To investigate whether additional measurements could improve the quality of dose estimates, the statistic “uncertainty-to-variability (UVR)” was developed. By applying the UVR to our dose estimates, we show that, in our case, the datasets contain little uncertainty and additional measurements would not significantly improve the quality of dose estimates.     

Monte Carlo模拟对面制品中铝膳食暴露风险的概率评估

结合常见市售面制品中铝的残留量监测结果,采用Crystal Ball软件建立非参数概率评估模型,对居民面制品来源的铝膳食暴露量进行了初步评估。结果表明,所有面制品样品的铝残留量均值为15.5 mg/kg,最高检出值为1437.7 mg/kg,超标率为8.5%。不同类别面制品中铝的残留量差异具有统计学意义(p<0.05),以油炸类面制品的铝残留量均值最高,为22.7 mg/kg。不同年龄人群面制品来源的铝膳食日暴露量的P99百分位数分别为青少年(6~17岁):男性103.89/女性116.47 μg/(kg·d);青年(18~44岁):男性66.36/女性79.36 μg/(kg·d);中年(45~59岁):男性68.23/女性72.41 μg/(kg·d);老年(≥60岁):男性73.80/女性78.89 μg/(kg·d),低于每日可耐受摄入量(ADI)285.7 μg/(kg·d),风险指数最大值为0.41,小于1。面制品来源的铝膳食暴露风险在可接受范围内,普通居民通过面制品摄入铝的健康风险较低。     

HS-GC/MS method development and exposure assessment of volatile organic compounds from food packaging into food simulants

ABSTRACT

A simultaneous headspace-gas chromatography/mass spectrometry (HS-GC/MS) method was developed and validated to determine the migration of 12 volatile organic compounds (methanol, acetone, methylethylketone, ethylacetate, isopropylalcohol, benzene, toluene, ethylbenzene, xylene, cumene, propylbenzene, and styrene) from food contact materials into food simulants (water, 4% acetic acid, 50% ethanol, and n-heptane). The limits of detection and quantification were 0.007–0.201 mg L^?1 and 0.023–0.668 mg L^?1, respectively. The method was applied to 205 samples of paper/paperboard, polyethylene, polypropylene, polystyrene, and polyethylene terephthalate. The estimated daily intake (EDI) was calculated using the migration results. Exposure assessments were carried out to compare the EDI to the tolerable daily intake (TDI); the results indicated that the EDI of styrene represented only a small percentage (8.0%) of the TDI. This analytical method will be a useful tool to examine levels of various volatile compounds migrating from food packaging to food simulants using HS-GC/MS method.     

Dietary exposure to chemical migrants from food contact materials: A probabilistic approach

A two-dimensional probabilistic model has been developed to estimate the short-term dietary exposure of UK consumers to migrants from food packaging materials. The current EU approach uses a default scenario of assuming that all individuals are 60 kg weight and consume 1 kg of food packaged in the material of interest per day. Using four UK National Dietary and Nutrition Surveys comprising 4-7 day dietary records for different age groups and survey years, a sample representative of the UK population has been obtained consuming around 4200 different food items. Each survey provides records for around 2000 individuals and supplies detailed information on the consumption of food and data on sex, height and socio-economic status which may be used to analyse the exposure of selected groups within the community. As a result we are able to address the variation in consumption of food amongst individuals, and account for actual body weights providing a more accurate representation of the 'true' exposure. The migrants bisphenol A diglycidyl ether (BADGE), di-2-ethylhexyl adipate (DEHA) and styrene were considered as specimen compounds although the methodology employed has the flexibility to adapt to other migrants and packaging types and indeed other food contaminants. Exposure for each individual is estimated by calculating and summing the individual exposure from each item in their diet, and is repeated for all individuals in each survey to produce a distribution of exposures for the population. The packaging type of each food item is assigned by utilizing known packaging types from the database or, by sampling from a distribution based upon market share information. The parameters contributing towards the exposure from a packaged dietary item are migrant concentration and item weight. Distributions are used to represent the inherent variation and uncertainty affecting these parameters. Where data on concentrations for a particular type of food are lacking, expert judgement is used to extrapolate from available data for other food types. The model can also be run using only migration data for food simulants. In this case, concentrations expected for each of the food items are assigned based on the data for the relevant food simulant. The primary outputs of the model are distributions of estimated daily intakes for the selected population. Each distribution gives the variation across the population subject to the uncertain parameters sampled in that iteration of the model. Analysing the ensemble of distributions allows us to obtain the confidence limits around estimates for percentiles due to the uncertainties. The probabilistic approach allows sensitivity analysis to evaluate the relative importance of the input parameters and places confidence bounds on the outputs to show the effect of the uncertainties and the contribution of each food type toward the overall exposure.     

Assessment of uncertainty in a probabilistic model of consumer exposure to pesticide residues in food

The assessment of consumer exposure to pesticides is an important part of pesticide regulation. Probabilistic modelling allows analysis of uncertainty and variability in risk assessments. The output of any assessment will be influenced by the characteristics and uncertainty of the inputs, model structure and assumptions. While the use of probabilistic models is well established in the United States, in Europe problems of low acceptance, sparse data and lack of guidelines are slowing the development. The analyses in the current paper focused on the dietary pathway and the exposure of UK toddlers. Three single food, single pesticide case studies were used to parameterize a simple probabilistic model built in Crystal Ball™. Data on dietary consumption patterns were extracted from National Diet and Nutrition Surveys, and levels of pesticide active ingredients in foods were collected from Pesticide Residues Committee monitoring. The effect of uncertainty on the exposure estimate was analysed using scenarios, reflecting different assumptions related to sources of uncertainty. The most influential uncertainty issue was the distribution type used to represent input variables. Other sources that most affected model output were non-detects, unit-to-unit variability and processing. Specifying correlation between variables was found to have little effect on exposure estimates. The findings have important implications for how probabilistic modelling should be conducted, communicated and used by policy and decision makers as part of consumer risk assessment of pesticides.     

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。     

不同国家和国际组织食品接触材料的风险评估

通过对欧盟、美国、加拿大和我国食品接触材料的基本定义、食品接触材料风险评估需要递交的资料和暴露评估的介绍,了解不同国家或国际组织对食品接触材料的风险评估方法,从而对国际上食品接触材料的风险评估有更清晰的认识。     

重庆市居民膳食中铬暴露水平及其健康风险评估

目的 评估重庆市居民膳食中铬暴露水平及潜在的健康风险。方法 利用2018—2021年重庆市9类共2 780份食品中铬含量监测数据,结合中国健康与营养调查项目2018年重庆市膳食调查数据（3 d 24 h膳食回顾法）,采用蒙特卡罗模拟估计重庆市居民膳食中铬暴露水平并评估其健康风险。结果 重庆市各类食物中铬平均含量范围为0.013 9~0.126 3 mg/kg,总体检出率为40.6%。铬平均含量以水产品及其制品最高,其次是特殊膳食用食品、叶菜类蔬菜和大米。重庆市居民膳食中铬每日平均暴露量范围为0.683~2.117 μg/kg·BW,高食物量消费人群的膳食暴露水平（P95）范围为1.165~3.597 μg/kg·BW。各年龄组人群的铬每日平均暴露量随年龄增加有降低的趋势,1~6岁人群的铬每日平均暴露量最高,60岁以上人群最低;男性铬平均暴露量高于女性;城市地区人群的铬平均暴露量高于农村地区。谷物及其制品对重庆市居民膳食中铬暴露的贡献率最高,达39.31%~49.13%,其次为蔬菜、肉及肉制品。各年龄、性别、地区组人群膳食中铬每日平均暴露量和P95暴露量占每日耐受摄入量（TDI）的比例均低于1。结论 重庆市居民膳食中铬暴露的健康风险较低,谷物及其制品、蔬菜、肉及肉制品是膳食中铬摄入的主要来源。     

超高效液相色谱-串联质谱法测定食品接触材料中油酸酰胺的迁移量

目的 建立超高效液相色谱-串联质谱法测定食品接触材料中油酸酰胺迁移量的分析方法。方法 按照GB 5009.156-2016《食品安全国家标准食品接触材料及制品迁移试验预处理方法通则》的要求配制5种食品模拟液,幵按照标准要求迚行浸泡试验,浸泡液经过滤后迚样,经过ZORBAX C_18(3.0mm×100mm,1.8μm)色谱柱分离,在正离子模式下以电喷雾电离多反应监测模式迚行定性和定量分析。结果 5种食品模拟物(4%乙酸、10%乙醇、20%乙醇、50%乙醇以及95%乙醇)中的油酸酰胺在0.25～5.0 mg/L浓度范围具有较好线性,相关系数(r2)均大于0.9990,方法检出限为0.001～0.002mg/L,方法定量限为0.003～0.005mg/L,油酸酰胺在3个浓度水平的加标回收率为90.3%～117.1%,相对标准偏差为0.20%～2.10%(n=6)。结论 该方法灵敏、准确,能够满足食品接触材料中油酸酰胺的迁移量的检测。     

Exposure of consumers to deoxynivalenol from consumption of white bread in Hungary

In view of the frequent occurrence of mycotoxins in cereals, a study was initiated to assess the exposure of the Hungarian adult population. Consumption data for 1360 individuals, based on a 3-day questionnaire, indicated that white bread accounted for the major intake of cereal-based products. Various cereal products were analysed for 16 mycotoxins by a LC/MS/MS multi-toxin method with LOD of 16?µg?kg^?1 and LOQ of 50?µg?kg^?1. Deoxynivalenol (DON) was most frequently detected, but no acetyl-deoxynivalenol was present in detectable concentrations. Consumer exposure was calculated with standard Monte Carlo probabilistic modelling and point estimates, taking into account bread consumption and DON contamination in independently taken wheat flour and wheat grain samples. Over 55% of cases the DON intake were below 15% of the provisional maximum tolerable daily intake (PMTDI) of 1?µg/(kg?bw)/day. However, in 5–15% of cases, the intake from bread consumption alone exceeded the PMTDI. Wheat grain data led to the higher percentage. Intakes estimated from both data sets were at or below the acute reference dose (ARfD) of 8?µg/(kg?bw)/day in 99.94–99.97% of cases.     

基于蒙特卡洛仿真的小麦仓储环节菌落总数风险评估方法

小麦是重要的粮食作物,对其食品安全问题的研究具有十分重要的意义。在小麦供应链中,小麦仓储环节是生物性危害物产生的高风险环节,应对其危害物的风险水平进行有效监控和预警。风险评估技术正被大力推动并用于评估因接触食物中的生物、化学或物理危害物而对健康生活造成的潜在危害和相关风险。考虑到已有定性和定量风险评估方法的优缺点以及缺少直观明确的风险度量指标等问题,本实验以小麦仓储环节中菌落总数为评估对象,研究一种针对生物性危害物的风险评估方法。首先,建立可以适应不同生长环境的菌落动态生长模型;在此基础上,基于蒙特卡洛仿真对小麦仓储环节中菌落总数概率分布进行定量预测;最后,提出风险度量指标“危害度”,并基于该指标对小麦仓储环节中菌落总数风险进行定量评价。该风险评估方法可以为风险管理和决策部门提供实时、直观的风险评估结果,给风险防控提供理论支持。