Determination of epoxidized soybean oil and linseed oil in wrapping film and cap sealing

A determination method was developed for epoxidized soybean oil (ESBO) and epoxidized linseed oil (ELO), which are used as plasticizers and/or stabilizers, in wrapping film and cap sealings. The ESBO method reported by Castle et al. was improved. Samples were extracted with acetone-hexane (3: 7), transmethylated under alkaline conditions, then derivatized to the 1,3-dioxolanes and analyzed by GC/MS. The recoveries of spiked ESBO and ELO were between 92.6% and 104.4%. The determination limits were 0.01 mg/g for ESBO and 0.02 mg/g for ELO in the wrapping film, and 0.04 mg/g and 0.08 mg/g in the cap sealing. ESBO and ELO were surveyed in 10 samples each of wrapping film and cap sealings currently available on the Japanese market. ESBO was found at 34.7-82.8 mg/g in polyvinyl chloride (PVC) wrapping films and at 5.47-399 mg/g in cap sealings. ELO was detected at 8.6-11.4 mg/g in polyvinylidene chloride (PVDC) wrapping films, and at 46.4 mg/g in a PVC wrapping film.     

Determination of epoxidized soybean oil in bottled foods

A determination method for epoxidized soybean oil (ESBO) in bottled foods was developed and used to survey bottled foods on the Japanese market. The amount of sample required was decreased to 20 g and the standard addition method was adopted for the quantification, because lipid in foods interrupted the hydrolysis of ESBO. The recoveries were 87.1 and 98.9% and the determination limit was 5.0 microg/g for a 20 g sample, be cause lipid in foods interupted the hydrolysis of ESBO. The recoveries using the internal standard method varied widely, because hydrolysis of the internal standard, cis-11,14-eicosadienoic acid ethyl ester, was affected more than that of ESBO by coexisting lipid in the sample. ESBO was not detected in any of the bottled baby food samples examined (14 samples), though it had been frequently detected in previous European surveys. This difference may be related to the low fat content and low fluidity of the bottled baby foods retailed in Japan. On the other hand, ESBO was detected at levels of 25.7-494.0 microg/g in liver paste, pasta sauce, Sungan in spicy oil, and spicy oil. These foods had higher fat content and higher fluidity. However, ESBO intake from these foods appears unlikely to exceed the TDI in the EU (1 mg/kg bw/day).     

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.     

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.     

Compositional GC-FID analysis of the additives to PVC, focusing on the gaskets of lids for glass jars

A gas chromatographic (FID) method is described which aims at the quantitative compositional analysis of the additives in plasticized PVC, particularly the plastisols used as gaskets for lids of glass jars. An extract of the PVC is analysed directly as well as after transesterification to ethyl esters. Transesterification enables the analysis of epoxidized soya bean and linseed oil (ESBO and ELO) as well as polyadipates. For most other additives, the shifts in the chromatogram resulting from transesterification is used to confirm the identifications made by direct analysis. In the gaskets of 69 lids from the European market used for packaging oily foods, a broad variety of plastisol compositions was found, many or possibly all of which do not comply with legal requirements. In 62% of these lids, ESBO was the principal plasticizer, whereas in 25% a phthalate had been used.     

Epoxidized soy bean oil (ESBO) migrating from the gaskets of lids into food packed in glass jars

Epoxidized soy bean oil (ESBO) was determined in foods packed in glass jars closed by lids with a poly(vinyl chloride) (PVC) gasket. The methyl ester of a diepoxy linoleic acid isomer was measured, using transesterification directly in the homogenized food and on-line HPLC-GC-FID analysis. Infant foods from the Swiss market consisting of vegetables, potato and rice or muesli with fruits and berries contained less than 7 mg/kg ESBO, but meat (its fat?) strongly increased ESBO migration up to 86 mg/kg. Some 12% of the products exceeded 15 mg/kg. Austrian and Norwegian samples gave similar results. Edible oil strongly extracts the ESBO from the gasket in food contact within a few weeks. Since this part of the gasket on average contained 91 mg ESBO, the legal limit is likely to be far exceeded whenever the food contains free oil contacting the gasket, such as oily sauces or vegetables and fish in oil. In fact, the mean ESBO concentration in 86 samples was 166 mg/kg, with a maximum of 580 mg/kg.     

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.     

Phthalate Esters in Foods: Sources,Occurrence, and Analytical Methods

ABSTRACT: Phthalates are a group of diesters of ortho‐phthalic acid (dialkyl or alkyl aryl esters of 1,2‐benzenedicarboxylic acid). Higher‐molecular‐weight phthalates, such as di‐2‐ethylhexyl phthalate (DEHP), are primarily used as plasticizers to soften polyvinyl chloride (PVC) products, while the lower‐molecular‐weight phthalates, such as diethyl phthalate (DEP), di‐n‐butyl phthalate (DBP), and butyl benzyl phthalate (BBzP), are widely used as solvents to hold color and scent in various consumer and personal care products. Phthalates have become ubiquitous environmental contaminants due to volatilization and leaching from their widespread applications, and thus contamination of the environment has become another important source for phthalates in foods in addition to migration from packaging materials. Human exposure to phthalates has been an increased concern due to the findings from toxicology studies in animals. DEHP, one of the important and widely used phthalates, is a rodent liver carcinogen. DEHP, DBP, BBzP, and several phthalate metabolites, such as monobutyl phthalate, monobenzyl phthalate, and mono‐(2‐ethylhexyl) phthalate, are teratogenic in animals. Since foods are the major source of exposure to phthalates, information on levels of phthalates in foods is important for human exposure assessment. The objective of this review is to identify the knowledge gaps for future investigations by reviewing levels of a wide range of phthalates in a variety of foods, such as bottled water, soft drinks, infant formula, human milk, total diet foods, and others, migration of phthalates from various food‐packaging materials, and traditional and new methodologies for the determination of phthalates in foods.     

Determination of organic compounds in bottled waters

The presence of organic compounds in bottled waters available in the Greek market and their fate when the representative samples exposed at different conditions were the main purposes of this study. The determination of the organic compounds was performed by gas chromatography–mass spectrometry techniques. Disinfection by-products compounds, such as trihalomethanes (THMs) and haloacetic acids (HAAs), were detected at low concentrations in bottled waters. As far as it concerns other organic substances, Greek bottled drinking waters did not contain volatile organic compounds (VOCs), and carbonyl compounds as well as other carcinogen and hormone disrupter phthalates were not identified, except for the plasticiser phthalate, diethylhexyl phthalate (DEHP). Moreover, samples contained other organic chemicals, whose identity has not yet been confirmed. The behavior of organic compounds was influenced by parameters such as conditions of storage, type of water. Finally, a comparison has been performed between the analysis of bottled and local tap waters.     

Investigation of the primary plasticisers present in polyvinyl chloride (PVC) products currently authorised as food contact materials

PVC is a common food contact material that is usually plasticised to increase its flexibility. Phthalates are one class of chemical compounds that are often used as plasticisers in PVC in a wide range of industries. They may be used in packaging materials for foods and can also be found in components of certain food processing equipment such as conveyor belts and tubing. Transfer of plasticisers from packaging to foods can occur. In recent years, there has been increased interest in understanding the health effects of phthalates, as well as the possible human exposure levels. However, there is limited information available about the routes of exposure to phthalates. In July 2014, the Chronic Hazard Advisory Panel (CHAP) produced a report for the U.S. Consumer Product Safety Commission detailing the potential health hazards of phthalates and phthalate alternatives. This report listed diet as one factor contributing greater than or equal to 10% of total phthalate exposure. As a result of this report, the U.S. Food and Drug Administration (FDA) is interested in determining the types of the primary plasticiser present in food packaging and processing materials as well as their concentrations. An investigation was conducted of 56 different samples of PVC food packaging and food processing materials available in the US market using a solvent extraction and GC-MS analysis. Nine different plasticisers including three phthalates, di(2-ethylhexyl) phthalate, diisononyl phthalate and diisodecyl phthalate, were identified in the products tested. The plasticiser concentrations ranged from 1 to 53% depending on the types of food contact materials and the type of plasticiser. Overall, it appears that manufacturers are switching away from phthalates as their primary plasticiser to alternate compounds such as ESBO, ATBC, DEHT, DINCH, DEHA and DINA.     

聚氯乙烯密封圈中环氧大豆油向食品中的迁移及其风险评估

目的研究带聚氯乙烯(polyvinyl chloride,PVC)密封圈的玻璃罐装食品中的环氧大豆油(epoxidized soybean oil,ESBO)的迁移规律,并对其进行风险评估。方法对112种带聚氯乙烯密封圈的玻璃罐装食品中的ESBO进行定量检测,计算其估计摄入量(estimated intake,ETI),同时对ESBO进行Cramer分类,并用毒理学关注阈值(threshold of toxicological concern,TTC)对其进行风险评估。结果调味酱中ESBO的含量最高,平均含量为4.58~263.50 mg/kg,其中14.63%超过了EU 10/2011限量要求;腌制果蔬中为5.04~13.78 mg/kg;油浸鱼中为0.05~15.31 mg/kg;而果酱、果汁等水基食品、咖啡等仅含有极少量的ESBO;ESBO的迁移受到脂肪含量、食品接触形式、储放时间等多种因素的影响。所测食品中ESBO的EDI有5.36%超过日耐受量(tolerable dailyintake,TDI)值;ESBO在Cramer分类中为ClassⅢ,其对应的阈值为0.09 mg/d,有74.11%的样品超过对应的阈值。结论相对于欧盟的限量要求,TTC法对ESBO的评估更加严格,ESBO存在较大的风险,需要进行更详细的安全评估。     

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.     

PVC plasticizers/additives migrating from the gaskets of metal closures into oily food: Swiss market survey June 2005

Foods with at least a few percent of free oil packed in glass jars with metal closures were analyzed for migration of additives, primarily plasticizers, from the gasket of the lid. One hundred and fifty-eight samples were collected in June 2005, i.e., some 10 months after the problem of excessive migration into oily food was communicated to the industry. In a first step, the composition of the additives in the gaskets was determined. Then the compounds found in the lid were measured in the jar content. Sixty-four percent of the gaskets contained epoxidized soy bean oil (ESBO) as principal plasticizer, 22% a phthalate, and 6% substantial amounts of di(2-ethylhexyl) adipate (DEHA). Concentrations in the food reached 1,170 mg/kg for ESBO, 270 mg/kg for diisononyl phthalate (DINP), 740 mg/kg for diisodecyl phthalate (DIDP), 825 mg/kg for di(2-ethylhexyl) phthalate (DEHP), and 180 mg/kg for DEHA. Further, elevated concentrations of plasticizers not authorized by the EU were found: diisononyl-cyclohexane-1,2-dicarboxylate (DINCH), 2-ethylhexyl palmitate and stearate, as well as epoxidized linseed oil (ELO). The few samples complying with the European rules contained little or well emulsified oil; some others were probably of very recent production (beginning of shelf life). It is concluded that there was still no lid reliably complying with the European rules (EU and national legislation).     

Migration of plasticizers phthalates, 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 13130-1. 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.     

Analysis of formaldehyde, acetaldehyde and oligomers in recycled polyethylene terephthalate

Formaldehyde (FA), acetaldehyde (AA) and oligomers in recycled polyethylene terephthalate (PET) were analyzed by HPLC. All of the physically recycled PET contained detectable levels of FA, AA and oligomers, and the levels were almost the same as in used bottles. Most superclean-like and chemically recycled PET contained lower levels than new pellets. These compounds showed no decrease upon physical recycling, but showed a marked decrease upon superclean-like recycling. In PET sheets made using physically recycled PET, FA was decreased, though AA was increased by the sheeting process as same as new one. FA, AA and oligomers originated from PET resin and their levels in recycled products were almost equivalent to those in new products. It was concluded that there is no particular safety concern about their presence in recycled PET.     

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.     

Survey of phthalate levels in Italian oily foods contained in glass jars with PVC gaskets

A method based on gas chromatography/tandem mass spectrometry was used to assess levels of twelve phthalates in 50 samples of oily foods packed in glass jars with metal closure obtained from a retail market. The amounts of di-methyl phthalate, di-ethyl phthalate, di-propyl phthalate, di-butyl phthalate, di-pentyl phthalate, benzyl butyl phthalate, di-cyclohexyl phthalate, di-n-octyl phthalate, di-isononyl phthalate and di-isodecyl phthalate in all samples analysed were less than the limit of quantification (LOQ). Di-(2-ethylhexyl) phthalate was detected in 20 samples in the range from 0.1 to 6 mg kg^?1 with an average of 1.0 mg kg^?1, and it exceeded the specific migration limit (SML) of 1.5 mg kg^?1 in five cases with an average of 3.0 mg kg^?1. Di-isobutyl phthalate was found in four samples at 0.1–0.4 mg kg^?1. The PVC gaskets used for the lids were negative for all tested phthalates, suggesting that the contamination of the foods originated from other sources, e.g. olive oil.     

瓶装碳酸饮料的“爆瓶”和“射盖”

探讨了瓶装碳酸饮料可能发生的“爆瓶”和“射盖”现象的内因和防止措施，瓶装碳酸饮料瓶内的弹射能和射盖速度与瓶内的压力和温度呈线性正比关系，弹射能和射盖速度还与瓶内顶隙体积的大小呈正比。采取降低温度和减少顶隙等措施，可防止或减少由于瓶装碳酸饮料发生爆瓶和射盖所致的人身伤害。     

Migration of di(2-ethylhexyl) phthalate from polyvinyl chloride tubes used in preparation of foods

Three samples of polyvinyl chloride products for food use were examined for di(2-ethylhexyl) phthalate (DEHP) migration levels under the conditions described in the Japanese Food Sanitation Law. These samples were two kinds of tubes and one stretched film, containing 12 to 41% DEHP by weight. DEHP migration levels from them were very low, all below 0.1 ppm, into 3 kinds of food simulant; water, 4% acetic acid and 20% ethanol. However, high levels of DEHP migrated into n-heptane, 12 ppm from the stretched film sample and more than 800 ppm from the tube samples. Migration from the 2 tubes was higher than 150 ppm, the limit of residues after evaporation in containers and wraps. Though the limit of residues after evaporation is not set for equipment used in the preparation of foods, the tested tubes were considered to be unsuitable for uses in which they come into direct contact with oils, fats or oily foods.     

Migration of epoxidised soybean oil from PVC gaskets of commercial lids: simulation of migration under various conditions and screening of food products from Czech markets

Previous studies have shown that a large number of polyvinylchloride (PVC) lid gaskets exceed the existing migration limits for epoxidised soybean oil (ESBO) and correct prediction of ESBO release into food therefore appears to be a difficult issue. ESBO migration from PVC gaskets of metal closures into food simulants and food products from the Czech market is evaluated during a survey in 2009 and subsequently one in 2012 to assess progress in lid manufacturing and official testing conditions. ESBO migration from lids into various food simulants was studied at various temperatures (25, 40 and 60°C) during storage times up to 12 months. ESBO released into food simulants or food products was transmethylated, derivatised and analysed by GC-MS. The levels of ESBO migration in foodstuffs in 2012 exceeded the specific migration limit (SML) in fewer products in comparison with the previous survey. However, most of the products were analysed at a time far from the expiry date and exceedance of the SML at the end of the product shelf life is not therefore excluded. More severe test conditions (60°C for 10 days) for specific migration given by the current European Union legislation (Regulation (EU) No. 10/2011) still seem to be insufficient for the simulation of ESBO migration during long-term storage.