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.     

Estimated daily intake of plasticizers in 1-week duplicate diet samples following regulation of DEHP-containing PVC gloves in Japan

Duplicate hospital diet samples obtained over 1 week in 2001 were analysed to estimate the daily intake of plasticizers and the results were compared with those obtained in 1999. The plasticizers quantified in this study were: dibutyl phthalate, butylbenzyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), di(2-ethylhexyl) adipate (DEHA), diisononyl adipate (DINA) and O-acetyl tributyl citrate (ATBC). Dipropyl, dipentyl, dihexyl and dicyclohexyl phthalate were also analysed but not detected. The analytical procedure for this follow-up study was essentially the same as in the previous one. Detection limits were 0.1-15.6 ng g^-1 for each plasticizer. One-week duplicate diet samples provided by three hospitals in three remote prefectures of Japan were analysed as individual meals. DEHP was detected at 6-675 ng g^-1 in 62 of 63 meals, significantly lower levels compared with those detected in 1999. Levels of DEHA and DINP also decreased. The mean intake of plasticizers estimated from all samples was 160 μg DEHP day^-1, 12.5 μg DEHA day^-1, 4.7 μg DINP day^-1 and 3.4 μg BBP day^-1. Levels of DINA were relatively high in meals from one hospital: in those meals, the average daily intake was 1338 μg day^-1. Those of ATBC were also higher in meals from another hospital: the average daily intake was 1228 μg day^-1. The sources of DINA and ATBC can be cling-film or sausage packaging.     

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.     

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.     

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.     

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.     

Contents of phthalate in polyvinyl chloride toys

The presence of plasticizers in PVC toys obtained in October 1998 was investigated. Diisononyl phthalate (DINP), di-2-ethylhexyl phthalate (DEHP), di-n-butyl phthalate (DBP), dinonyl phthalate (DNP), diheptyl phthalate (DHP), and di-2-ethylhexyl adipate (DEHA) were detected. The phthalates were found in all of the 68 samples. The principal phthalate found in toys was DINP, which was present in 48 of 68 samples. The DINP content ranged from 15 mg/g to 580 mg/g, and mean content was 308 mg/g. The highest content was found in a pacifier toy. DEHP was present in 20 of 68 samples and the content ranged from 2.0 mg/g to 380 mg/g. The mean content was 162 mg/g. It was found in 60% of domestic toys.     

Plasticizers in total diet samples, baby food and infant formulae

The plasticizers di-n-butylphthalate (DBP), butylbenzylphthalate (BBP), di-2-(ethylhexyl)phthalate (DEHP) and di-2-(ethylhexyl)adipate (DEHA) were analysed in 29 total diet samples, in 11 samples of baby food and in 11 samples of infant formulae. In all of the total diet samples the presence of one or more of the plasticizers was demonstrated. Maximum and minimum mean concentrations in the total diet samples were: 0.09-0.19mg DBP/kg, 0.017-0.019mg BBP/kg, 0.11-0.18mg DEHP/kg and 0.13-0.14mg DEHA/kg. One or more of the phthalates was also found in about 50% of the samples of baby food as well as in infant formulae. The calculated mean maximum intakes of the individual compounds from the total diet samples were below 10% of the restrictions proposed by the EU Scientific Committee for Food (SCF), and the spread in individual intakes was considerable. DEHP was the plasticizer determined most frequently and contributed the highest fraction of its tolerable daily intake (TDI). Hence, the maximum calculated intake of DEHP from single samples of the foodstuffs analysed could be up to one-third of the TDI. The calculated mean intake of DEHA was about 1% of the TDI with a maximum value of 13% of the TDI. Violations of the restrictions proposed by the EU Scientific Committee for Food (SCF) in the form of TDI values or specific migration limits were not found in this investigation.     

Migration of epoxidized soybean oil (ESBO) and phthalates from twist closures into food and enforcement of the overall migration limit.

Nineteen samples of food in glass jars with twist closures were collected by the national food inspectors at Danish food producers and a few importers, focusing on fatty food, such as vegetables in oil, herring in dressing or pickle, soft spreadable cheese, cream, dressings, peanut butter, sauces and infant food. The composition of the plasticizers in the gaskets was analysed by gas chromatography with flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS). Epoxidized soybean oil (ESBO) and phthalates were determined in the homogenized food samples. ESBO was the principal plasticizer in five of the gaskets; in 14 it was phthalates. ESBO was found in seven of the food samples at concentrations from 6 to 100 mg kg(-1). The highest levels (91-100 mg kg(-1)) were in oily foods such as garlic, chilli or olives in oil. Phthalates, i.e. di-iso-decylphthalate (DIDP) and di-iso-nonylphthalates (DINP), were found in seven samples at 6-173 mg kg(-1). The highest concentrations (99-173 mg kg(-1)) were in products of garlic and tomatoes in oil and in fatty food products such as sauce béarnaise and peanut butter. For five of the samples the overall migration from unused lids to the official fatty food simulant olive oil was determined and compared with the legal limit of 60 mg kg(-1). The results ranged from 76 to 519 mg kg(-1) and as a consequence the products were withdrawn from the market.     

Migration of epoxidized soybean oil (ESBO) and phthalates from twist closures into food and enforcement of the overall migration limit

Nineteen samples of food in glass jars with twist closures were collected by the national food inspectors at Danish food producers and a few importers, focusing on fatty food, such as vegetables in oil, herring in dressing or pickle, soft spreadable cheese, cream, dressings, peanut butter, sauces and infant food. The composition of the plasticizers in the gaskets was analysed by gas chromatography with flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS). Epoxidized soybean oil (ESBO) and phthalates were determined in the homogenized food samples. ESBO was the principal plasticizer in five of the gaskets; in 14 it was phthalates. ESBO was found in seven of the food samples at concentrations from 6 to 100 mg kg(-1). The highest levels (91-100 mg kg(-1)) were in oily foods such as garlic, chilli or olives in oil. Phthalates, i.e. di-iso-decylphthalate (DIDP) and di-iso-nonylphthalates (DINP), were found in seven samples at 6-173 mg kg(-1). The highest concentrations (99-173 mg kg(-1)) were in products of garlic and tomatoes in oil and in fatty food products such as sauce béarnaise and peanut butter. For five of the samples the overall migration from unused lids to the official fatty food simulant olive oil was determined and compared with the legal limit of 60 mg kg(-1). The results ranged from 76 to 519 mg kg(-1) and as a consequence the products were withdrawn from the market.     

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。     

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).     

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.     

Eleven phthalate esters and di(2-ethylhexyl) adipate in oneweek duplicate diet samples obtained from hospitals and their estimated daily intake

Plasticizers in duplicate diet samples obtained over 1 week were analysed in order to estimate daily intake. The phthalate esters were as follows: diethyl, dipropyl, dibutyl, dipentyl, dihexyl, butylbenzyl, dicyclohexyl, di(2-ethylhexyl), dioctyl, diisooctyl (mixture of isomers) and diisononyl (mixture). Di(2-ethylhexyl) adipate was also determined. Homogenized samples of composite meals were extracted with acetonitrile, lipids were removed by extraction into n-hexane and the acetonitrile layer was cleaned using FlorisilR and R Bondesil PSA dual layer column. Phthalates were determined by GC/MS (SIM). Phthalate recovery from the fortified food mixture by this method was 62.5-140.8%. Quality assurance as assessed by three laboratories indicated coefficient of variance in the levels of detected phthalates in same lot samples as below 10%. Detection limits were 0.1-23ng/g for each phthalate. One-week duplicate diet samples provided by three hospitals in three remote prefectures of Japan were analysed as individual meals. In all 63 samples, DEHP was present at the highest level among all phthalates in the range 10-4400ng/g. The intake of plasticizers estimated from all samples was 519 µ g DEHP/day, 86 µ g DEHA/day, 65 µ g DINP/day, and 4.7 µ g BBP/day. Calculated DEHP in 2-day samples out of 21 days exceeded EU TDI for a person of 50kg body weight (1850 µ g per day). Disposable PVC gloves used during the preparation of meals were suspected as the source of the high DEHP content. One-day intake of the other phthalates and DEHA was below 7% of TDI in all cases. High concentrations of DEHP (5990ng/g) was found in baby food used in quality assurance work. The source of contamination was the PVC-tube used during production and was effectively reduced by replacing the tube by one made of stainless steel.     

Testing the influence of various conditions on the migration of epoxidised soybean oil from polyvinylchloride gaskets

Epoxidised soybean oil (ESBO) is widely used as a plasticiser and stabiliser mainly in food contact materials on the base of polyvinylchloride (PVC), especially in the gaskets of jar lids. PVC gaskets containing 10–37% of ESBO were prepared by the baking of PVC plastisols at various process temperatures (180–240°C) in the laboratory. ESBO migration into olive oil and 3% acetic acid was studied at various temperatures (4°C, 25°C, 40°C and 60°C) during a storage time up to 12 months. ESBO released into food simulants was transmethylated, derivatised and analysed by gas chromatography-mass spectrometry (GC/MS). The effect of food processing, i.e. pasteurisation (80°C and 100°C) and sterilisation (125°C) on ESBO migration was also evaluated. The results were critically assessed with respect to the test conditions of specific migration in accordance with the current European Union legislation (Regulation (EU) No. 10/2011). The levels of ESBO migration found confirmed that the test conditions (i.e. 40°C or 60°C, 10 days) representing contact in the worst foreseeable use scenario seem to be insufficient for the simulation of ESBO migration during long-term storage and thus do not provide satisfactory objective results.     

Migration from the gaskets of lids into oily foods: first results on polyadipates

The migration from the gaskets of plasticized PVC in metal closures usually far exceeds the legal limits if the packed food contains some free oil. If the gaskets continue to consist of PVC, polyadipates seem to be the only acceptable plasticizers, although difficult to work with: they render the plastisol highly viscous and make it difficult to place a uniform ring into the lid. This suggests dilution with plasticizers of low viscosity. Results from simulating tests (olive oil in direct contact) confirm that the migration of polyadipates is far lower, but also that even the migration of minor portions of diluting plasticizers is critical for the overall migration. The first tests with 11 packed foods, stored and repeatedly shaken for up to 2 years, show migration of polyadipate clearly below the limits. It was lower than that determined by simulating tests, whereas the migration of ESBO was several times higher, questioning the suitability of presently applied testing.     

Di(2-ethylhexyl) adipate migration from PVC-cling film into packaged sea bream (Sparus aurata) and rainbow trout (Oncorhynchus mykiss) fillets: kinetic study and control of compliance with EU specifications

Polyvinyl chloride (PVC) film containing di(2-ethylhexyl) adipate (DEHA) plasticizer was used to wrap sea bream (Sparus aurata) and rainbow trout (Oncorhynchus mykiss) fillet samples with and without skin. After wrapping the samples were stored at 2 ± 0.5 °C and analyzed for DEHA content at time intervals between 5 and 360 h of contact (kinetic study). Determination of DEHA was performed using a direct gas chromatography (GC) method. Statistically significant differences (p < 0.05) in migration of DEHA were observed between the two fish fillet samples: the mean equilibrium migration amount of DEHA in sea bream was 2.93 mg/dm² film (91.9 mg/kg fillet) corresponding to a loss of 19.0% (w/w) DEHA from PVC film; while the mean equilibrium amount of DEHA in rainbow trout was 3.74 mg/dm² (117.6 mg/kg) corresponding to a loss of 23.9% (w/w) DEHA. The above values for DEHA in sea bream are very close to the limit of 3 mg/dm² of film surface set by the EU for DEHA while the corresponding migration values for rainbow trout exceeded this limit. Diffusion coefficients for DEHA in the PVC film during contact with both fish fillets were calculated and found significantly different between two fish samples. Furthermore, the presence of skin on the fillet decreased migration of DEHA into the fish flesh by a factor of 2.4–2.8. Based on equilibrium migration values of DEHA it is concluded that for a 60-kg adult, a daily consumption of 150 g rainbow trout or 200 g sea bream fillet packaged in PVC film would result in a daily intake of DEHA close to the tolerable daily intake (TDI) of 0.3 mg/kg body weight set by the EU.     

Contents of eleven phthalates and di(2-ethylhexyl) adipate in retail packed lunches after prohibition of DEHP-containing PVC gloves for cooking purposes

Ten samples of retail packed lunches purchased from convenience stores were determined for 11 phthalates and di(2-ethylhexyl) adipate (DEHA) in August 2000, 2 months after the prohibition of DEHP-containing PVC gloves in Japan. Each homogenized sample was extracted with acetonitrile, partitioned with n-hexane, and cleaned up using Florisil and PSA columns. Phthalates in the extract were determined by GC/MS (SIM). The limits of detection were 14.9 ng/g for di(2-ethylhexyl) phthalate (DEHP) and 18.6 ng/g for dibutyl phthalate (DBP). Levels of phthalates in packed lunch samples were 45 to 517 ng DEHP/g (198 ng/g, average), ND to 90 ng DEHA/g, and ND to 10.0 ng BBP/g. Diisononyl phthalate (DINP) was detected in one sample at 76 ng/g. Average DEHP level in ten samples was 4% of that in 1999. The contents of other phthalates were also reduced. DBP was not detected in any sample. Recovery of deuterated isomers added as surrogates was 27.9% for DNP-d4, and 40.6 to 101.5% for the other phthalates.     

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。     

Migration of plasticizers from printing inks into foods

It has been demonstrated that on storage of a tightly wound reel of polypropylene packaging film, specially printed for experimental purposes, transfer can occur of components from the ink on the outer surface of the film on to the inner food contact surface. For dicyclohexyl phthalate this transfer amounted to 6% of the total amount of plasticizer available in the printing ink system. It was subsequently shown for confectionery and snack food products wrapped in commercially printed polypropylene films that plasticizers only present in the printing ink migrated into the foods. The migration of plasticizer increased with storage time of the wrapped product; for dibutyl phthalate, for example, levels increased from 0.2 to 6.7 mg/kg over the period from 0 to 180 days storage of a chocolate-coated confectionery product. A small retail survey (47 samples) of confectionery, snack products and biscuits wrapped in printed polypropylene film showed the presence of one or more plasticizers at levels from 0.02 to 14.1 mg/kg for dibutyl phthalate, from less than 0.01 to 18.6 mg/kg for dicyclohexyl phthalate and from less than 0.01 to 1.8 mg/kg for di(2-ethylhexyl) phthalate. In all cases there was a good correlation between the plasticizers found in the printing ink from the film and those in the food. Wide variations were found, however, in the amounts and types of plasticizers used in printed packaging of the same brand of retail food product purchased from different regions of the country.