Migration of plasticizersphthalates,bisphenol A and alkylphenols from plastic containers and evaluation of risk

This study investigates the potential migration of plasticisers, plastic components and additives from several plastic water bottles. Compounds studied were phthalates (dimethyl phthalate, di-n-butyl phthalate, benzylbutyl phthalate, bis(2-ethylhexyl) phthalate), bis(2-ethylhexyl) adipate, octylphenol, 4-nonylphenol and bisphenol A. Polycarbonate (PC), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene terephthalate (PET) and polystyrene (PS) plastics used in the water bottling sector were tested using three kinds of total or specific migration tests: (1) standard method UNE-EN ISO 177; (2) ultrasonic forced extraction; and (3) standard method UNE-EN 13130 UNE-EN 13130. 2005. Materials and articles in contact with foodstuffs – plastics substances subject to limitation. Part 1: guide to test methods for the specific migration of substances from plastics to foods and food stimulants and the determination of substances in plastics and the selection of conditions of exposure to food simulants.  [Google Scholar]-1. In addition, bottled waters contained in different plastic materials were analysed to determine the potential migration of target compounds in real conditions. In all cases, samples were solid-phase extracted using Oasis HLB 200?mg cartridges and analysed using GC-MS in scan-acquisition mode. Bisphenol A and 4-nonylphenol were detected in incubated samples, indicating that migration from food plastics can occur at the experimental conditions tested. The total daily intake was calculated according to the levels detected in bottled water and the assessment of the consumers’ risk was evaluated taking into consideration toxicological and legislative values.     

Contents of plasticizers in cap-sealing for bottled food and their migration into food

Plasticizers in cap-sealing for bottled foods were analyzed. Twenty-three domestic samples and 80 imported samples, a total of 103 samples, were tested. Among them, 93 contained chloride, and 62 contained di(2-ethylhexyl) phthalate (DEHP), diisodecyl phthalate, O-acetyl tributyl citrate, diacetyllauroyl glycerol, di(2-ethylhexyl) adipate, diisononyl phthalate or dicyclohexyl phthalate. Twelve samples with DEHP-containing caps were further tested for plasticizer levels in the foods. Higher DEHP was detected in oily and fluid food specimens. However, the intake of plasticizers calculated based on usual food consumption did not exceed the tolerable daily intake level in any of the cases. A food sample containing the highest level of DEHP was stored under various conditions, and DEHP that migrated from the cap-sealing into the food was determined. Shaking the bottles increased migration of DEHP into foods.     

Concentrations of phthalates in bottled water under common storage conditions: Do they pose a health risk to children?

Of recent concern is the migration of phthalates from plastic products such as Polyethylene Terephthalate (PET) bottles into the water contain. These concerns should be addressed, especially considering the steady growth of the consumption of bottled water and the toxicological effects of phthalates. In this regard, special attention should be paid to children's consumption because of their particular susceptibility to the effects of phthalates.The aim of this study was to determine the concentrations of phthalates, including dibutyl phthalate (DBP), butyl benzyl phthalate (BBP) and bis(2-ethylhexyl) phthalate (DEHP), in bottled water and to estimate the health risk of endocrine disrupting chemicals due to water intake in children for the first time.Migration of phthalates was investigated in PET-bottled water under various storage conditions using gas chromatography–mass spectroscopy. A phthalate exposure assessment was performed to characterize their risk to the children's health via a calculated hazard quotient (HQ).It seems that increase in the temperature and the duration of storage affect phthalate migration, but the level of DEHP in bottled water was always very low and does not exceed 26.83% of the U.S. EPA maximum concentration limit (MCL). In particular, phthalate migration was not substantial at low temperatures (< 25 °C) and freezing conditions and the most abundant phthalate (DEHP) was not more than 10.6% MCL.The estimated child intake ranged from 0.01 μg/kg/day for BBP to 0.24 μg/kg/day for DEHP. Estimated phthalate intakes are generally in the safe range and exposure decreased with increasing age. Toxicological risk assessment of the maximum concentrations measured revealed a maximum HQ of 0.012 in the worst condition. Furthermore, a negligible carcinogenic risk of 6.5 × 10^− 7 for DEHP was observed. Consequently, risk evaluation showed that bottled water is safe for consumption by children.     

Assessing human exposure to phthalic acid and phthalate esters from mineral water stored in polyethylene terephthalate and glass bottles

Phthalic acid and phthalate esters are of growing interest due to their significant usage and potential toxicity. Polyethylene terephthalate (PET) and glass are both widely used materials for bottled drinking water. In this study, phthalic acid (PhA), bis(2-ethylhexyl) phthalate (DEHP), dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiisoBP) and dibutyl phthalate (DBP) were analysed in a large number of Italian bottled water samples. These samples showed different concentrations of phthalates are nearly 20 times higher in samples bottled in PET than those from glass bottles with total levels of phthalates of 3.52 and 0.19 µg l^-1, respectively. However, the observed levels do not represent a significant exposure pathway when considering the US Environmental Protection Agency (USEPA) reference dose (an estimate of a daily oral exposure to the human population, including sensitive subgroups, that is likely to be without an appreciable risk of deleterious effects during a lifetime). In addition, no significant correlation was found between the phthalate concentrations and the physicochemical properties of the different water samples, apart from the still/sparkling water parameter for the PET samples. In this instance, slightly higher concentrations were observed for the PET bottled still water samples than for the sparkling water samples, although no explanation has been found yet.     

Assessing human exposure to phthalic acid and phthalate esters from mineral water stored in polyethylene terephthalate and glass bottles

Phthalic acid and phthalate esters are of growing interest due to their significant usage and potential toxicity. Polyethylene terephthalate (PET) and glass are both widely used materials for bottled drinking water. In this study, phthalic acid (PhA), bis(2-ethylhexyl) phthalate (DEHP), dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiisoBP) and dibutyl phthalate (DBP) were analysed in a large number of Italian bottled water samples. These samples showed different concentrations of phthalates are nearly 20 times higher in samples bottled in PET than those from glass bottles with total levels of phthalates of 3.52 and 0.19 µg l^?1, respectively. However, the observed levels do not represent a significant exposure pathway when considering the US Environmental Protection Agency (USEPA) reference dose (an estimate of a daily oral exposure to the human population, including sensitive subgroups, that is likely to be without an appreciable risk of deleterious effects during a lifetime). In addition, no significant correlation was found between the phthalate concentrations and the physicochemical properties of the different water samples, apart from the still/sparkling water parameter for the PET samples. In this instance, slightly higher concentrations were observed for the PET bottled still water samples than for the sparkling water samples, although no explanation has been found yet.     

Quantification of Six Phthalates and One Adipate in Luxembourgish Beer Using HS-SPME-GC/MS

A simple, low-cost and sensitive method for the determination of six phthalate acid esters (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate and dioctyl phthalate) and one adipate (bis(2-ethylhexyl) adipate) in beer has been developed using head-space solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to mass spectrometry (GC/MS). SPME conditions were optimised, and optimum extraction parameters were found to be 95 °C at 100 min, without addition of NaCl. Matrix interference was avoided by using a deuterated internal standard (ISTD). Limits of detection ranged from 0.006 to 0.590 μg/L. The method showed good linearity with coefficients of determination ranging from 0.963 to 0.999 and satisfactory accuracy (74–101 %) and repeatability (3.56–27.86 %) values. The method was applied to 15 samples of beer from Luxembourgish breweries, stored in different containers (can, glass and aluminium bottle), and phthalates were detected in all samples with concentrations as high as 61.56 μg/L for total phthalates. The exact origins of phthalates in beer were difficult to determine from the data in this study, though the brewing and bottling process seems to be a major contributor.     

Material labeling of soft plastic toys and plasticizers in polyvinyl chloride products

We investigated the labeling and content of plasticizers of soft plastic toys. First, we investigated material labeling in 96 products purchased in fiscal years 2000 and 2001. Among these products, 43% of those purchased in fiscal 2000 and 68% of those purchased in fiscal 2001 were labeled. We then investigated the kinds and amounts of plasticizers in 73 soft polyvinyl chloride (PVC) toys. Three kinds of phthalates and six other kinds of plasticizers were detected in the soft PVC toys. Diisononyl phthalate, di(2-ethylhexyl) phthalate, diisononyl adipate, and O-acetyl tributyl citrate were detected at high frequency, and in large amounts. The average total content of all plasticizers was 280 mg/g for the products purchased in fiscal 2000 and 227 mg/g for those in fiscal 2001. In fiscal 2001, antioxidants, 4-nonylphenol, and bisphenol A were investigated in addition to plasticizers.     

Phthalate esters in bottled drinking water and their human exposure in Beijing,China

Phthalate esters (PAEs) have attracted much attention because of their ubiquity and toxicity. However, previous studies mainly focused on the occurrence of PAEs controlled by the Environmental Protection Agency and neglected most uncontrolled PAEs. In this study, the occurrence of 21 PAEs, including 6 controlled and 15 uncontrolled PAEs, was investigated in polyethylene terephthalate (PET)-bottled drinking water samples purchased from markets in Beijing. Seventeen PAEs were detected in all samples, with dibutyl phthalate, diisobutyl phthalate, and dimethyl phthalate as the predominant compounds. Correlation analysis suggested that PET bottles might be one of the potential sources of PAEs in PET-bottled drinking water. The human health risks assessments indicated little or no risks from four controlled PAEs in bottled water. In comparison, the risks of uncontrolled PAEs should be of greater concern for their ubiquities in bottled drinking water.     

Analysis of plasticizers in cap-sealing resins for bottled foods

A survey of plasticizers in cap-sealing resins for bottled foods has been undertaken. During 1997-1999 di-(2- ethylhexyl)phthalate (DEHP) was found in seven out of 21 samples on the Japanese domestic market and in 10 out of 61 imported samples as well as a further two samples which contained di-(2-ethylhexyl)adipate (DEHA). In the period 1993-1999, of the other plasticizers diacetyl lauroyl glycerol (DALG) was only detected in domestic samples whereas diisodecyl phthalate (DIDP) and diisononyl phthalate (DINP) were only in imported samples. It was observed overall that DEHP and DEHA were restricted to use in cap-sealing resins for bottled foods. Whilst phthalates, DEHA or DALG were detected in samples in 1993 and 1995, the investigation in 1997-1999 showed fewer samples in which these plasticizers were found.     

Development and application of a method for analysis of phthalates in ham sausages by solid-phase extraction and gas chromatography–mass spectrometry

A gas chromatography-mass spectrometry assay was developed and successfully applied for the determination of phthalates in ham sausage migrated from packaging film. The phthalates studied were dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), benzylbutyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DNOP) , with dibutyl adipate (DBA) as internal standard. The sample pre-treatments included extraction with n-hexane, solvent evaporation and reconstitution with acetonitrile before and after solid-phase extraction (SPE). The extraction and cleaning up procedure was carried out with cartridges containing dimethyl butylamine groups, which showed extraction efficiencies over 87.3%. The calibration curves obtained were linear with correlation coefficients greater than 0.99. The method proved to be accurate and precise for the six phthalates used. It was successfully applied to a study on the migration of phthalates from packaging PVC film into ham sausage.     

Survey of epoxidized soybean oil in cap sealing for bottled foods

Epoxidized soybean oil (ESBO) was surveyed in the 103 samples of cap sealing for bottled foods on the Japanese market. Most of the sealings were made of polyvinyl chloride, while a few were made of polyethylene or acrylic resin. All the sealings contained ESBO in the range of 0.006-42.4%. Sealings for baby food, jam, etc. contained higher levels of ESBO, though those for beverages contained lower levels. Sealings in lug caps and press-on twist caps contained higher levels of ESBO, though that in pilfer-proof caps contained lower levels. Some sealings in screw caps and lug caps also contained other plasticizers, for example, di-2-ethylhexyl phthalate and diisononyl phthalate, and their ESBO contents were 1/10 of those in sealings containing only ESBO. In this survey, ESBO was the most common plasticizer in cap sealing resin for bottled foods on the Japanese market.     

食品塑料包装材料中邻苯二甲酸二（2-乙基己）酯的暴露评估

文中主要综述了食品塑料包装材料所用邻苯二甲酸酯类增塑剂中,邻苯二甲酸二（2-乙基己）酯（DEHP）的性质、来源、毒性及危害。提出了预防措施和建议,为食品塑料包装材料的安全陛以及包装食品的安全陛的相关研究提供参考依据。     

食用油中邻苯二甲酸酯和己二酸酯的GC-MS定量分析与迁移特性研究

采用有机溶剂超声萃取法对食用油中的邻苯二甲酸酯和己二酸酯进行提取,并对萃取溶剂和物料比进行优化,利用气相色谱-质谱-选择离子监测技术进行检测,同时研究不同温度条件下食用油中邻苯二甲酸酯和己二酸酯的定量迁移规律。结果表明,在优化实验条件下,21 种邻苯二甲酸酯和己二酸酯的平均回收率和精密度分别为82.74%～111.01%和2.56%～6.01%,方法检出限在0.28～14.25 μg/L之间,塑料桶装食用油中主要含有邻苯二甲基二甲酯、邻苯二甲基二丁酯、邻苯二甲基二（2-乙基己基）酯和己二酸二（2-乙基己基）酯,且在不同温度条件下,迁移量随着时间推移逐渐增加。     

应用气相色谱模拟分离软件快速检测火腿肠及肠衣中的塑化剂

利用气相色谱模拟分离软件,测定火腿肠及其肠衣中的塑化剂邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、 邻苯二甲酸二丁酯、邻苯二甲酸二环己酯、邻苯二甲酸二（2-乙基）己酯和邻苯二甲酸二正辛酯的含量。对比超声 提取和索式提取2 种前处理方法对样品中塑化剂的提取效果,确定了程序升温条件,采用外标法定量。结果表明： 6 种标准物质的标准曲线R2为0.996 7～0.998 8,最小检出限为0.04 mg/kg,相对标准偏差为5.0%～9.3%;索式提取 法的提取效果更显著,某些火腿肠和火腿肠肠衣中含有高含量的生殖致癌物邻苯二甲酸酯类物质。     

Stability testing of selected plastics additives for food contact in EU aqueous, fatty and alternative simulants

Within the framework of the AIR3-CT94-2360 EUproject, the stability of three plastics additives in three EU aqueous and fatty food simulants and in two alternative simulants was studied under various timetemperature conditions. The additives tested were bis(2-ethylhexyl) adipate (DEHA), bis(2-ethylhexyl) phthalate (DEHP) and octadecyl 3-(3,5-di- tert -butyl4-hydroxyphenyl) propionate (Irganox 1076). The various test conditions included exposures of 10 days at 40 o C, 1h at reflux temperature for all aqueous simulants, 10 days at 40 o C and 1h 175 o C for the olive oil and 2 days at 20 o C and 3h at 60 o C for the isooctane simulant. Following the exposure, the additive samples were extracted from aqueous simulants with hexane. A sonication step was necessary to ensure maximum extraction of control samples. In the case of the isooctane simulant, the samples were analysed directly from the simulant. The oil samples were extracted by acetonitrile. The extracts of samples exposed to various heat conditions as well as unexposed spiked controls and blanks were analysed by gas chromatography (GC) on a non-polar (5% -phenyl)-methylpolysiloxane capillary column with high temperature capabilities. The results showed that DEHA, DEHP and Irganox 1076 were stable at 40 o C and at reflux temperature in ethanolic or acidic aqueous simulants. The various additives were also stable in the organic isooctane simulant as well as in the fatty simulant olive oil. Studies on the stability of such additives used in food packaging are designed for regulatory purposes as an aid to decide whether the legislation should regulate limits for plasticizers based on a quantity in the food packaging itself or based on an ingested dose by the consumer.     

2018年吉林省部分地区市售食用植物油产品中塑化剂含量的检测结果分析

目的 了解2018年吉林省部分地区食用植物油产品中塑化剂的污染情况。方法 检测并分析食用植物油产品155批次, 依据GB 5009.271-2016《食品安全国家标准 食品中邻苯二甲酸酯的测定》(第二法 气相色谱-质谱法 外标法), 对产品中的邻苯二甲酸二丁酯(dibutyl phthalate, DBP)和邻苯二甲酸二(2-乙基)己酯(di(2-ethylhexyl) phthalate, DEHP)2项塑化剂指标进行含量检测。结果 共有18批次食用植物油产品的塑化剂检测结果高于参考限值, 其中DBP超限率为11.61%, DEHP超限率为0.65%。结论 本次检测的食用植物油产品出现一定的塑化剂问题, DBP污染较为明显。污染来源可能来自塑料包装物、加工环节及环境污染, 塑化剂迁移途径和预防控制问题需要引起相关部门的重视。     

Optimisation of an analytical method and results from the inter-laboratory comparison of the migration of regulated substances from food packaging into the new mandatory European Union simulant for dry foodstuffs

This paper presents the outcome of the development, optimisation and validation at European Union level of an analytical method for using poly(2,6-diphenyl phenylene oxide – PPPO), which is stipulated in Regulation (EU) No. 10/2011, as food simulant E for testing specific migration from plastics into dry foodstuffs. Two methods for fortifying respectively PPPO and a low-density polyethylene (LDPE) film with surrogate substances that are relevant to food contact were developed. A protocol for cleaning the PPPO and an efficient analytical method were developed for the quantification of butylhydroxytoluene (BHT), benzophenone (BP), diisobutylphthalate (DiBP), bis(2-ethylhexyl) adipate (DEHA) and 1,2-cyclohexanedicarboxylic acid, diisononyl ester (DINCH) from PPPO. A protocol for a migration test from plastics using small migration cells was also developed. The method was validated by an inter-laboratory comparison (ILC) with 16 national reference laboratories for food contact materials in the European Union. This allowed for the first time data to be obtained on the precision and laboratory performance of both migration and quantification. The results showed that the validation ILC was successful even when taking into account the complexity of the exercise. The results showed that the method performance was 7–9% repeatability standard deviation (rSD) for most substances (regardless of concentration), with 12% rSD for the high level of BHT and for DiBP at very low levels. The reproducibility standard deviation results for the 16 European Union laboratories were in the range of 20–30% for the quantification from PPPO (for the three levels of concentrations of the five substances) and 15–40% from migration experiments from the fortified plastic at 60°C for 10 days and subsequent quantification. Considering the lack of data previously available in the literature, this work has demonstrated that the validation of a method is possible both for migration from a film and for quantification into a corresponding simulant for specific migration.     

超低温冷冻除脂-气相色谱串联质谱法检测食用植物油中21种邻苯二甲酸酯

建立了超低温冷冻除脂-气相色谱串联质谱(GC-MS/MS)检测食用植物油中21种邻苯二甲酸酯(PAEs)的新方法。样品用乙腈提取,经超低温(-80℃)冷冻10 min除脂,再经减压浓缩,以正己烷复溶,采用GC-MS/MS多反应监测模式进行测定。结果表明,在考察浓度范围(1~1000 ng/mL)内21种PAEs均呈现良好线性,相关系数均大于0.999,检出限为0.10~8.52 μg/kg,定量限为0.32~28.40 μg/kg,加标回收率为74.31%~116.62%,相对标准偏差为1.21%~17.82%。对市售7类19个油样的抽样检测,显示邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸(2-丁氧基)乙酯(DBEP)、邻苯二甲酸二正庚酯(DHP)、邻苯二甲酸二(2-乙基己)酯(DEHP)和邻苯二甲酸二正辛酯(DNOP)共9种PAEs被检出,其中DMP、DBP、DBEP、DHP和DEHP检出率均大于90%,含量范围为105.57~2156.76 μg/kg。该方法操作简便,成本低,可用于食用植物油中PAEs的有效测定。     

青岛市市北区居民主要邻苯二甲酸酯类物质膳食暴露水平及其风险评估

目的分析青岛市北区主要食品中邻苯二甲酸二(2-乙基己基)酯(DEHP)和邻苯二甲酸二丁酯(DBP)含量水平,计算本区居民膳食暴露水平并进行初步风险评估。方法全区采集7类样品共281份,采用气相色谱-质谱法测定食品中DEHP和DBP的含量。利用食品中DEHP和DBP的平均含量,同时结合居民平均食物消费量,计算7类食品的DEHP和DBP的膳食暴露水平,并分别与DEHP和DBP的每日可耐受摄入量(tolerable daily intake,TDI)比较,初步评估市北区居民主要食品中DEHP和DBP的暴露风险。结果 7类食品中DEHP和DBP的含量范围分别为0.00~5.90和0.00~7.20 mg/kg BW。市北区居民经7类食品中DEHP和DBP暴露量分别为0.006 927和0.005 558mg/kg BW,均未超过相应的TDI。结论市北区居民经7类食品摄入DEHP和DBP的的健康风险较低。     

Survey of plasticizers in polyvinyl chloride toys

Plasticizers in 101 samples of polyvinyl chloride (PVC) toys on the Japanese market were surveyed. No phthalates were detected in designated toys, though bis(2-ethylhexyl)phthalate, diisononyl phthalate, diisobutyl phthalate, dibutyl phthalate, diisodecyl phthalate and benzyl butyl phthalate were detected in more than half of other toys. 2,2,4-Tributyl-1,3-pentanediol diisobutylate, o-acetyl tributyl citrate, adipates and diacetyl lauroyl glycerol, which are alternative plasticizers to phthalates, were detected. The results of structural analysis confirmed the presence of di(2-ethylhexyl)terephthalate, tributyl citrate, diisononyl 1,2-cyclohexanedicarboxylate and neopentyl glycol esters; these have not previonsly been reported in Japan. There appears to be a shift in plasticizers used for designated toys from phthalates to new plasticizers, and the number of different plasticizers is increasing.