Bisphenol A diglycidyl ether (BADGE) migrating from packaging material 'disappears' in food: reaction with food components.

Bisphenol A diglycidyl ether (BADGE) is widely used as a monomer for coatings and adhesives for food-contact applications. Previous publications indicate that, after migration from packaging into foodstuffs, BADGE undergoes various reactions with unidentified food components. In order to elucidate the fate of BADGE, losses were determined after incubation with different foodstuffs and food components. Food proteins were identified as the main reaction partner with BADGE. Adduct formation was found with nucleophilic side-chains of amino acids. In vitro, cysteine exhibited significant activity. The previously reported occurrence of methylthio-derivatives of BADGE in foodstuffs was shown to originate from the reaction of BADGE with methionine. BADGE-methylthio derivatives can, therefore, be used as marker substances in foodstuffs for protein reactions with BADGE. The reported results offer a new viewpoint on the evaluation of BADGE migration. The hydrolysis and hydrochlorination derivatives subject to European legislation make up only a fraction of the totally migrated BADGE, and a further concern is that the toxic or allergenic potential of the protein adducts are unknown.     

Bisphenol A diglycidyl ether (BADGE) migrating from packaging material ‘disappears’ in food: reaction with food components

Bisphenol A diglycidyl ether (BADGE) is widely used as a monomer for coatings and adhesives for food-contact applications. Previous publications indicate that, after migration from packaging into foodstuffs, BADGE undergoes various reactions with unidentified food components. In order to elucidate the fate of BADGE, losses were determined after incubation with different foodstuffs and food components. Food proteins were identified as the main reaction partner with BADGE. Adduct formation was found with nucleophilic side-chains of amino acids. In vitro, cysteine exhibited significant activity. The previously reported occurrence of methylthio-derivatives of BADGE in foodstuffs was shown to originate from the reaction of BADGE with methionine. BADGE-methylthio derivatives can, therefore, be used as marker substances in foodstuffs for protein reactions with BADGE. The reported results offer a new viewpoint on the evaluation of BADGE migration. The hydrolysis and hydrochlorination derivatives subject to European legislation make up only a fraction of the totally migrated BADGE, and a further concern is that the toxic or allergenic potential of the protein adducts are unknown.     

Determination of bisphenol A diglycidyl ether (BADGE) and its derivatives in food: identification and quantification by internal standard

Bisphenol A diglycidyl ether (BADGE) and its reaction products with water and hydrochloric acid have recently been subject to new regulations concerning their migration from food packaging into foodstuff. A method for the simultaneous identification and quantification of these substances and their precursor bisphenol A in food is described introducing bisphenol A di-(3-hydroxypropyl)ether as an internal standard. Analysis was carried out using RP-HPLC gradient elution with fluorescence detection. Additional information in the case of suspect samples was obtained using RP-HPLC with mass selective detection. The described method is validated for the analysis of foodstuffs as well as fatty food simulants. The limits of detection were between 10 and 30 µg/kg of food; recovery experiments gave identical behaviour for all analytes and the internal standard. The enforcement of the specific migration limit set by regulatory standards of the European Union for BADGE and its hydrolysis and hydrochlorination products is possible for producers as well as food quality surveillance institutions.     

Migration of bisphenol-A diglycidyl ether (BADGE) and its reaction products in canned foods

Bisphenol-A diglycidyl ether (BADGE) is used as an additive or starting agent in coatings for cans. The presence of hydrochloric acid in the organosol (PVC-based) lacquers results in formation of chlorohydroxy compounds of BADGE. These compounds, as well as BADGE itself, are potential migrants into the preserved food and are of toxicological concern. In the present investigation the presence of BADGE and the chlorohydroxy compounds (BADGE.HCl and BADGE.2HCl) in various kinds of canned foods from 30 brands have been determined by HPLC with fluorescence detection. BADGE was found in levels up to 5.1mg/kg in the food and only in food from cans containing BADGE.HCl and BADGE.2HCl in the lacquers. BADGE was found both in fish in oil and in fish in tomato sauce, however, the highest amounts were found in the fatty foodstuffs. BADGE.HCl and BADGE.2HCl were found in concentrations up to 2.4mg/kg and 8.3mg/kg, respectively. Unlike BADGE, BADGE.2HCl was found in similar concentrations in fish in oil and in fish in tomato sauce. In aqueous and acidic foodstuffs BADGE readily hydrolyses into mono- and dihydrolysed products (BADGE.H₂O and BADGE.2H₂O). In this study BADGE.H₂O was not found in any food sample, whereas BADGE.2H₂O was found in levels up to 2.6mg/kg. The Scientific Committee for Food (SCF) of the European Commission has proposed that a limit of restriction of 1mg/kg food shall include BADGE itself and BADGE.H₂O, BADGE.HCl, BADGE.2HCl and BADGE.HCL.H₂O. The present results indicate that the migration of BADGE.HCl and BADGE.2HCl, compounds with almost no data on toxicity, implies a greater problem than BADGE.H₂O and BADGE.2H₂O.     

Time- and temperature-dependent migration studies of Irganox 1076 from plastics into foods and food simulants

The study provides an exhaustive set of migration data for octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076) from low-density polyethylene (LDPE) in several food matrices. Irganox 1076 was used as a model migrant because it represents one of the typical substances used as an antioxidant in food packaging polymers. Kinetic (time-dependent) migration studies of Irganox 1076 were performed for selected foodstuffs chosen with different physical-chemical properties and in relation to the actual European food consumption market. The effect of fat content and of the temperature of storage on the migration from plastic packaging was evaluated. The results show that migration increased with fat content and storage temperature. All data obtained from real foods were also compared with data obtained from simulants tested in the same conditions. In all studied cases, the kinetics in simulants were higher than those in foodstuffs. The work provides data valuable for the extension of the validation of migration model developed on simulants to foodstuffs themselves.     

Time‐ and temperature‐dependent migration studies of Irganox 1076 from plastics into foods and food simulants

The study provides an exhaustive set of migration data for octadecyl 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate (Irganox 1076) from low‐density polyethylene (LDPE) in several food matrices. Irganox 1076 was used as a model migrant because it represents one of the typical substances used as an antioxidant in food packaging polymers. Kinetic (time‐dependent) migration studies of Irganox 1076 were performed for selected foodstuffs chosen with different physical–chemical properties and in relation to the actual European food consumption market. The effect of fat content and of the temperature of storage on the migration from plastic packaging was evaluated. The results show that migration increased with fat content and storage temperature. All data obtained from real foods were also compared with data obtained from simulants tested in the same conditions. In all studied cases, the kinetics in simulants were higher than those in foodstuffs. The work provides data valuable for the extension of the validation of migration model developed on simulants to foodstuffs themselves.     

Estimates of per capita exposure to substances migrating from canned foods and beverages.

A study was undertaken by European industry to estimate the consumption of canned beverages and foodstuffs. European can production data were used with adjustments for imports into and out of the EU. It was further assumed that can production, with adjustments, equalled consumption. Owing to the lack of actual consumption country-by-country or household-by-household data throughout Europe, only per capita estimates of consumption were possible. Data were compiled country-by-country for seven major can-producing EU Member States and for eight different types of canned food and two types of canned beverage (beer and soft drinks). The per capita consumption of canned foods was 1.1 cans/person/week, and consumption of canned fish was estimated as 2.2 kg/person/year. The estimate of per capita consumption of canned food was 62 g/person/day or 22.6 kg/person/year. Canned beverages account for about 60% of the consumption of canned foodstuffs. The usefulness of per capita consumption of beverages is questionable because consumption habits may vary more widely than those for canned foods. However, as the migration into beverages is insignificant, these data were added for completeness. Per capita consumption of canned beverages is 67 cans/person/year or 61 g/person/day. From the average can sizes, the surface area of the cans consumed was estimated. The per capita surface area exposure was 0.55 dm(2)/person/day for canned foods and 0.55 dm(2)/person/day for canned beverages, giving 1.1 dm(2)/person/day. Migration of a substance at 0.02 mg dm(2) gives an exposure of 0.01 mg/person/day assuming a per capita consumption, using a surface area model. Migration at 0.12 mg kg(-1) in food gives an exposure of 0.007 mg/person/day using a weight model. Both models assumed migration into all food types at the same level, which is highly unrealistic. Exposure to BADGE from canned foods has been used as a case study. The best estimate for a worst case per capita exposure to BADGE and relevant derivatives was between 6 and 10 micro g/person/day, depending upon the approach and assumptions used.     

Stability of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in water-based food simulants

Varnishes used for the inner coatings of food cans are often based on epoxy resins or vinylic organosols. The epoxy resins can be produced from bisphenol A (BPA) and bisphenol F (BPF), and these also contain bisphenol A diglycidyl ether (BADGE) or bisphenol F diglycidyl ether (BFDGE) as stabilising components. These compounds may break down during storage and also by the influence of food simulants. The stability of BADGE and BFDGE were studied using reverse-phase gradient high-performance liquid chromatography (RP-HPLC) with ultraviolet detection (UV). Three experimental conditions for spiked simulants were compared: (1) the storage at 25 °C (C1), (2) the storage at 40 °C (C2) and (3) the storage at 25 °C after 15 min heating at 120 °C (C3). Distilled water, 3% acetic acid and 10% ethanol were used as food simulants. It was observed that BADGE is more stabile than BFDGE. The loss of BADGE and BFDGE were minimal in 10% ethanol (39 and 46% at 25 °C, 60 and 69% at 40 °C, respectively) and highest in 3% acetic acid (60 and 63% at 25 °C, 76 and 82% at 40 °C, respectively). At experiment (C3), the hardest conditions, significant degradation was not shown in comparison with conditions (C1) and (C2), contrariwise BADGE and BFDGE in 10% ethanol were minimal degradated at conditions (C3) from all these experiments (loss of 5 and 8%, respectively).     

Compliance work for food contact materials: feasibility of the legally required safety assessment of an epoxy/amine-based coating for domestic water pipe restoration

Options were explored for fulfilling the legally required safety assessment for a widely applied epoxy/amine coating used for restoring corroded domestic drinking water supply systems. The coating was made up of two components mixed shortly before application, the first mainly consisting of bisphenol A diglycidyl ether (BADGE), the second of various amines. The analytically identified starting substances were all authorised, but only constituted a small proportion of the low molecular mass material left after curing and potentially migrating into water. Reaction products synthesised from constituents of the starting components (expected oligomers) could not be eluted from GC even after derivatisation, indicating that standard GC-MS screening would miss most potential migrants. They were detectable by size exclusion chromatography (SEC) after acetylation. HPLC with MS or fluorescence detection was possible for constituents including a BADGE moiety, but phenalkamines could not be detected with adequate sensitivity. Possibilities for determining long-term migration relevant for chronic toxicity are discussed. Analysis in water shortly after application of the coating overestimates migration if migration decreases over time and requires detection limits far out of reach. Analysis of a solvent extract of the coating is easier and provides an upper estimate of what could migrate into the drinking water over the years. However, to satisfy the regulatory requirements, components of the complex mixture need to be identified at lower proportions than those accessible. In vitro testing of the whole mixture for genotoxicity is expected to fail because of the required sensitivity and the glycidyl functions probably wrongly resulting in positive tests. The difficulties in dealing with this situation are discussed.     

The determination of monomers and oligomers from polyester-based can coatings into foodstuffs over extended storage periods

The polymeric coating used in metal packaging such as cans for foods and beverages may contain residual amounts of monomers used in the production of the coating, as well as unreacted linear and cyclic oligomers. Traditionally, although designed for use with plastic food contact materials, food simulants have been used to determine the migration of monomers from coatings into foodstuffs. More recently, food simulants have also been used to determine oligomeric species migrating from can coatings. In the work reported here, the migration of both monomers and oligomers from polyester-based can coatings into food simulants and foodstuffs, some of which were towards the end of their shelf-life, is compared. The concentrations of monomers and selected oligomers in canned foods at the end of their shelf life were found to be significantly lower than those in food simulants, which in turn was lower than those in the extraction solvent acetonitrile.     

A LC-MS/MS method for the determination of BADGE-related and BFDGE-related compounds in canned fish food samples based on the formation of [M+NH(4)](+) aducts

A new and simple liquid chromatography tandem mass-spectrometry method for the determination of different bisphenol A (BPA) derivatives such as bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE) and their reaction products with water and hydrochloric acid in different fish food products was developed. The extraction procedure and the chromatographic conditions were optimised for complex food matrices such as fish products. Food samples were homogenised and extracted with a 1:1 solution of acetonitrile-hexane, the solvent was eliminated in a N(2) stream and the extract was reconstituted with 0.5mL of a 0.01M solution of ammonium formate. The sample solution obtained was directly measured by LC-MS/MS without any further purification under the developed conditions. The use of a mobile phase composed by ammonium formate-methanol in a binary gradient mode produced [M+NH(4)](+) aducts for the different BADGEs and BFDGEs. These aduct's fragmentations were employed for the LC-MS/MS quantification of BPA derivatives in canned fish samples. The results of the validation were appropriate: the method was linear for BADGE and its hydrolysed derivatives up to 1000μgkg(-1), for the remaining compounds linearity achieved up to 100μgkg(-1). Quantification limits were in the range 2-10μgkg(-1). RSD (intra and inter-day) was 6-12% and the recovery was comprised between 89% and 109%. Under the optimised conditions, the chromatographic separation was performed in 8min per sample. The method was applied to the determination of BADGE, BFDGE and their reaction products in different samples of canned fish from Spanish origin. Migration results obtained were in compliance with the EU regulations.     

Review of the toxicology, human exposure and safety assessment for bisphenol A diglycidylether (BADGE).

BADGE (whose chemical names are bisphenol A diglycidylether and 2,2-bis(4-(2,3-epoxypropyl)phenyl)propane) is the lowest molecular weight oligomer in commercial epoxy resins and the major component in commercial liquid epoxy resins. The major application areas for epoxy resins are protective coatings and civil engineering. Additional applications include printed circuit boards, composites, adhesives and tooling, while a relatively small amount of epoxy resins (< 10%) finds use in protective coatings inside food and drink cans. The use of BADGE in food-contact applications was first regulated through EC Directive 2002/16/EC and amended in EC Directive 2004/13/EC with migration levels in food-contact applications being generally well below the regulatory thresholds. The paper discusses the commercial use of BADGE focusing on the current knowledge of human exposure from canned food applications. To assess the safety of this application, the exposure data are compared with no adverse effect levels (NOAEL) from various toxicological investigations with BADGE including reproductive and developmental assays, endocrine toxicity investigations, and sub-chronic and chronic assays. Consumer exposure to BADGE is almost exclusively from migration of BADGE from can coatings into food. Using a worst-case scenario that assumes BADGE migrates at the same level into all types of food, the estimated per capita daily intake for a 60-kg individual is approximately 0.16 microg kg(-1) body weight day(-1). A review of one- and two-generation reproduction studies and developmental investigations found no evidence of reproductive or endocrine toxicity, the upper ranges of dosing being determined by maternal toxicity. The lack of endocrine toxicity in the reproductive and developmental toxicological tests is supported by negative results from both in vivo and in vitro assays designed specifically to detect oestrogenic and androgenic properties of BADGE. An examination of data from sub-chronic and chronic toxicological studies support a NOAEL of 50 mg kg(-1) body weight day(-1) from the 90-day study, and a NOAEL of 15 mg kg(-1) body weight day(-1) (male rats) from the 2-year carcinogenicity study. Both NOAELS are considered appropriate for risk assessment. Comparing the estimated daily human intake of 0.16 microg kg(-1) body weight day(-1) with the NOAELS of 50 and 15 mg kg(-1) body weight day(-1) shows human exposure to BADGE from can coatings is between 250,000 and 100,000-fold lower than the NOAELs from the most sensitive toxicology tests. These large margins of safety together with lack of reproductive, developmental, endocrine and carcinogenic effects supports the continued use of BADGE for use in articles intended to come into contact with foodstuffs.     

Food and beverage can coatings: A review on chemical analysis,migration, and risk assessment

The internal surface of food and beverage cans is generally covered with polymeric coatings to preserve food and protect metal substrate from corrosion. Coating materials are complex formulations that contain different starting substances (e.g., monomers, prepolymers, additives, etc.) and in addition during the manufacture of the material several compounds can be formed (e.g., reaction products, degradation products, etc.). These substances have the potential to migrate into the food. Many of them have not been identified and only some have been toxicologically evaluated. This article aims to provide a comprehensive review on the analytical methods used for the identification of potential migrants in can coatings. The migration and exposure to chemicals migrating from can coatings are also reviewed and discussed so far, which is essential for risk assessment. Moreover, a brief section on the current status of the legislation on varnishes and coatings for food contact in Europe is also presented. Liquid chromatography coupled to diode array and fluorescence detectors and particularly to mass spectrometry and gas chromatography–tandem mass spectrometry seem to be the techniques of choice for the identification of potential migrants in can coatings. Some studies have reported migration levels of BPA (bisphenol A) and BADGE (bisphenol A diglycidyl ether) and derivatives exceeding the specific migration limits set in the European legislation. On the whole, low dietary exposure to migrants from can coatings has been reported. However, it is interesting to highlight that in these studies the combined exposure to multiple chemicals has not been considered.     

Alternative fatty food simulants for migration testing of polymeric food contact materials.

The amounts of substances migrating from plastics into foodstuffs with high fat contents are in most cases higher than in foodstuffs with water contents. This increase in migration commonly is due to the higher solubility of the migrating organic compounds in fat compared to water. The increase in migration is not necessarily due to an increase in the substance's diffusion coefficient due to interactions between the fat and the plastic as is often assumed. Ethanol is a good simulant for fatty foods because it has little interaction with many plastics, e.g. polyolefins, migrants are readily soluble in it, and because it is easy to work with analytically. The utilizable limits of ethanol and ethanol/water mixtures as food simulants are developed from the physical background of diffusion. The use of ethanol and ethanol/water mixtures is supported by published experimental migration results.     

Photoinitiators: a food safety review

Ultraviolet light printing inks are considered safer than the classical inks; however, despite being on the outer surface of the packaging material, their components can migrate into foodstuffs and can give rise to contamination. Photoinitiators are a part of the formulation of printing inks, being an important class of migrant, for which there have been more than 100 incidents of contamination of packaged food with photoinitiators reported through Rapid Alert System for Food and Feed (RASFF) alerts in the European Union. In this review the process of photo-polymerisation is explained in depth to provide an insight into the complexity of the process, and the diversity of potential contaminants together with their degradation products. The critical factors affecting the migration process itself are reviewed, together with analytical methods and the current legislation in the European Union and other parts of the world.     

食品金属罐中14种双酚类物质迁移量的同时测定及杀菌过程对其迁移的影响

为了调查国内食品金属罐中双酚类物质的迁移水平,本文建立了同时测定食品金属罐中14种双酚类物质迁移量的高效液相色谱法,并研究了杀菌过程对双酚类物质迁移的影响及食品金属罐中双酚类物质的迁移规律.结果表明,14种双酚类物质在4种食品模拟物(4％体积乙酸、10％体积乙醇、50％体积乙醇和异辛烷)中线性关系良好,加标回收率为83...     

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.     

A study on the migration of organic pollutants from recycled paperboard packaging materials to solid food matrices

Paper and board are widely used as food packaging materials, mainly for disposable products. As public interest in conservation of natural resources has accelerated in the past several years, the use of recycled paper and board has increased. Recycled fiber materials can be used in certain limits as food contact materials. The safety of recycled fiber-based materials for food contact applications is largely dictated by the ability of post-consumer contaminants to be absorbed into recycled materials and later released by the packaging material and trapped on the food. The present work was undertaken with the aim of investigating the physicochemical behavior of selected model contaminants on paper and board, in contact with foodstuffs thus producing a fundamental set of data about their mobility from recycled paper and board into foods. More specifically, the kinetics of migration of selected model contaminants (surrogates) from contaminated recycled paper packaging samples into dry foodstuffs with different fat content was studied using a method based on solvent extraction and GC-FID quantification. Results showed the ability of selected contaminants of various types and various volatilities to potentially transfer to dry foods. The proportion of substances migrated to food was strongly dependent on the nature of the paper samples, fat content of the food, chemical nature and volatility of the migrant. The highest level of migration of organic pollutants was observed for the substrate with the highest fat content. Furthermore, it is shown that contact time and temperature have a significant effect on migration of model contaminants into foods.     

Effect of protein glycation in the presence or absence of wheat proteins on detection of soybean proteins by commercial ELISA

Soybean (Glycine max) is the world's primary provider of protein and oil and is widely used in foodstuffs. However, the use of soybean in foodstuffs might pose a serious threat to allergic consumers since some proteins can cause allergic reactions. To date mostly ELISA methods are used for testing contamination of foodstuffs with soybean. In view of the complexity regarding allergen detection in foodstuffs and appropriate food product labelling, the aim of this study was to investigate the impact of the Maillard reaction on the detectability of soybean proteins using commercial ELISA kits. Accumulation of protein-bound carbonyls, modification of reactive lysine residues and severe aggregation as a result of incubation with glucose, in the presence or absence of soluble wheat proteins, were recorded. Moreover, detection of soybean proteins by means of three commercial ELISA kits was strongly altered and was highly dependent on the type of kit used.     

肉类罐头食品中双酚A二缩水甘油醚及其衍生物的迁移

本实验应用高效液相色谱-电喷雾串联质谱法分析检测肉类罐头食品中双酚A二缩水甘油醚(BADGE)及其衍生物的残留,重点研究了肉类罐头中的内容物、存储时间(6个月、9个月、12个月)以及存储温度(4、20、100℃)对双酚A二缩水甘油醚(BADGE)及其衍生物的迁移量的影响,单因素方差分析(One-way ANOVA)检验实验结果表明,不同内容物罐头中从内壁涂层迁移至样品的BADGE及其衍生物存在显著性差异(p<0.05),Student-Newman-Keuls法检验表明存储12个月后目标化合物的迁移量与6个月、9个月存在显著性差异,存储温度为4、20℃时化合物迁移量没有显著差异,但是罐头加热到100℃后目标化合物迁移量是最大的。