Survey of bisphenol a diglycidyl ether (BADGE) in canned foods.

2,2-Bis(4-hydroxyphenyl)propane bis(2,3-epoxypropyl) ether (BADGE) is used in the manufacture of lacquers for coating the inside of food and beverage cans. In June 1996 the EC Scientific Committee for Food temporarily increased the specific migration limit applying to BADGE to 1 mg/kg pending consideration of additional toxicological data. In order to find out if there is migration of BADGE from can coatings into foods, a 'worst case' sampling exercise has been conducted to survey those canned foods where the propensity for migration of BADGE was judged to be highest. The foods surveyed include canned fish in oil, meat and milk and, altogether, BADGE was determined in 181 retail samples. Analysis for BADGE was conducted, in duplicate, by HPLC with fluorescence detection with confirmation of BADGE identity by GC/MS analysis using selected ion monitoring. BADGE was found at levels exceeding 1 mg/kg in seven of the 15 canned anchovy samples and five of the 22 sardine samples purchased during the period September 1995-July 1996. Infrared analysis of the can coatings provided strong evidence that the higher BADGE levels found were associated with use of PVC organosol lacquers, although in some cases cans coated with organosols gave low BADGE results. For canned sardine samples found to contain greater than 0.5 mg/kg BADGE in the total contents, a replicate can was opened and separate analyses performed on the drained fish and the oil. The results clearly showed that BADGE concentrations in the oil were about 20 times higher than in the drained fish. Further samples of canned sardines and anchovies were purchased in June/July 1997 and, in all cases, BADGE levels were found to be below 1 mg/kg. In the other retail canned foods, BADGE was not detectable (DL = 0.02 mg/kg) or detected at concentrations well below the temporary SML of 1 mg/kg.     

食品罐内壁涂层中双酚A-二缩水甘油醚双水合物的迁移特性的数值仿真与实验研究

对金属罐内壁涂层中的有害物质(双酚A-二缩水甘油醚双水合物,以下简称BADGE·2H2O)向食品模拟液在给定条件下的迁移特性进行了数值仿真,并与对应条件下的实验结果进行了对比、分析。结果表明:温度、初始浓度、涂层厚度对物质迁移的影响较大;对于给定的温度,温度越高,则迁移达到平衡时所需要的时间越短,迁移量越大;对于给定的初始浓度和涂层厚度,初始浓度越大,涂层厚度越厚,则迁移量越大;同时,在不同温度下,BADGE·2H2O从食品罐内壁涂层向水性模拟液迁移的数值解与实验值最大差值为0.023μg/mL。数值仿真与实验结果有较好的一致性。     

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.     

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.     

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.     

Trace contamination of foods by migration from plastics packaging—A review

Plastic packaging often contains many components in addition to the base polymer. Additives are required both for the manufacturing process to give acceptable results and for the finished product to have the desired characteristics. Furthermore, decomposition products may arise from these additives, while the base polymer itself will contain monomer and oligomers in addition to traces of constituents of the polymerisation mixture (such as catalysts) and any decomposition products arising from these. Printing inks, laminates and their adhesives further complicate the picture. Consequently, the final product can contain a multitude of components at all levels from traces to perhaps 20–30% by weight.Where these components are of low molecular weight, a potential exists for their migration into packaged foods. It is essential, therefore, that manufacturers and users of plastic packaging intended for food contact be aware of the chemical nature of the range of potential migrants expected from a given polymer/additive/food system and have some understanding of the underlying mechanisms and kinetics of migration.This paper presents an overview of current knowledge of migration. After an outline of the physical basis of migration, the concept of—and problems inherent in—measuring overall migration are described, followed by a discussion of selected specific migrants.Although information on contamination from residual monomers forms the bulk of the available literature on specific migrants, migration of other base polymer constituents and of non-volatile plastics additives and their decomposition products can be of importance and is reviewed here.     

Bioassay Guided Analysis of Migrants from Can Coatings

Migrants from can coatings consist of a complex mixture of a variety of substances that mostly are not toxicologically evaluated. 95% ethanolic migrates from a polyester and an epoxy coating were screened in different bioassays on mutagenicity (Ames II-Test), on aquatic toxicity (Fish Embryo Assay) and on cytotoxicity (BrdU-ELISA, WST-1-Assay, Neutral Red Assay (NRA), RNA-Synthesis-Inhibition). No mutagenic effect was detected in the Ames II-Test and no lethal effects were induced in the fish embryo test up to a concentration of 60 dm²/l. Strongly varying cytotoxicity effects have been determined depending on the type of the assay, the cell line in use (Hela-S3, Caco-2, HT-29, Hep-G2) as well as the incubation conditions. The NRA was validated for the investigation of the coating migrates. Legally regulated substances known to migrate from epoxy coatings, BPA, BADGE, BADGE*2H₂O, BADGE*HCl*H₂O and BADGE*2HCl were investigated in the NRA with two different cell lines, a human colon adenocarcinoma cell line (HT-29) and a human hepatocellar carcinoma cell line (Hep-G2). The IC_{50, Hep-G2}-values of the regulated epoxy based substances ranged from 7 mg/l for BADGE to 83 mg/l for BADGE*2H₂O. The 95% ethanolic migrate of the epoxy coating revealed a significant effect in the NRA (IC_{50, Hep-G2} =  6.6 ±  0.8 dm²/l) while the polyester coating induced no effect (IC_{50, Hep-G2}  >  30 dm²/l). The amount of the legally regulated substances (BPA, BADGE, BADGE*2H₂O) in the migrate of the epoxy coating was analysed and their part on the cytotoxic effect of the migrate was estimated. Only about 0.5% of the effect of the migrate in the NRA could be traced back to these substances.     

Optimizing the traditional processing of beef into Kilishi

Kilishi, a meat-based traditional product of Sahelian Africa, is a sun-dried, coated and grilled beef. The effect of moisture content of the dried meat before coating and sauce ingredients, on coating quality and product yield of kilishi were determined. Analysis of the losses after the coating and grilling stages highlighted the mechanisms that determine coating quality. To improve sauce adhesion to the dried meat, wheatflour was added to the traditional sauce (a mixture of groundnut paste, water, and spices). The amounts of water and wheat flour required to ensure that the sauce adhered to the meat well were also determined. This has optimized the kilishi processing to improve product yield.     

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.     

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).     

运用胶体特性探讨纸用涂料胶粘剂迁移

涂料是由颜料、胶粘剂、添加剂及水组成的胶体系统,涂料胶体体系特性影响胶粘剂迁移。颜料对涂料胶体特性的作用体现在涂料脱水速率过程中,颜料的润湿能力、颜料与胶粘剂的相互作用及颜料对液相的吸附能力等对脱水过程有影响。水溶性胶粘剂和增稠剂是另一个决定涂料胶体特性的成份,体现在颜料颗粒吸附这些高聚物,使胶体体系变得更加稳定,这种体系只有在一定外部压力作用下才会产生胶粒与吸附物的分离。胶乳也是胶体体系的主要成分,实际上胶乳本身也是一种胶体体系,当胶乳粒子因絮凝效应失稳时会弱聚结。涂料中胶乳粒子可以看成是分散在颜料胶体体系的网络中。文中重点举例介绍了多种涂料体系的胶体特性及改善胶粘剂迁移的研究结果。     

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...     

In vitro stability of triclosan in dentifrice under simulated use condition

Triclosan has been formulated into a dentifrice at a 0.3% level to enhance the antibacterial function of the dentifrice, to improve oral health and to decrease the daily malodor inside the mouth cavity. The hypothesis that chloroform may be generated from triclosan when contacted with chlorinated drinking water has challenged our guarantee of safe use of triclosan in oral care products, especially in Colgate Total toothpaste. Currently, there was no available analytical method to detect chloroform levels under the use conditions expected during daily tooth brushing. To fill this gap and to continue guaranteeing that our customers can safely use Colgate Total toothpaste products, a gas chromatography-single ion monitoring-mass spectrometry method for detecting chloroform in artificial saliva media has been developed. The limit of detection (LOD) and limit of quantitation are about 41 and 130 ppb, respectively. This LOD level is lower than the current Environmental Protection Agency trihalomethanes contamination limit, which is required for our daily drink water. Our in vitro study indicated that Colgate Total does not form detectable chloroform levels (41 ppb) over the range of expected consumer-brushing times while using normal chlorinated drinking water.     

Bisphenol A (BPA) and its source in foods in Japanese markets

The determination of bisphenol A (BPA) and/or bisphenol A diglycidyl ether (BADGE) in foods sold in Japanese markets and in water leached from six epoxy resin cans with similar diameters was carried out using high-performance liquid chromatography (HPLC) with electrochemical detection (LC/ECD), LC-mass spectrometric detection (LC/MS) and LC-tandem mass spectrometric detection (LC/MS/MS). BPA concentrations were 0-842 ng g^-1 for 48 canned foods, 0-14 ng g^-1 for 23 foods in plastic containers, and 0-1 ng g^-1 for 16 foods in paper containers. No BADGE was detected in three canned foods. There was no difference in leaching concentrations of BPA into glycine buffers at pHs 8 and 11, and water. The amounts of BPA leached into water from six epoxy resin cans held at 121°C for 20 min were almost the same as the cans' contents and were much higher than the amounts leached from cans held at or below 80°C for 60 min. The amount leached depended on the type of can, but not on the amount of BADGE leached from the cans. Considerably more BPA than BADGE leached to water from six cans. Two cans whose contents had high concentrations of BPA showed no BADGE leaching even at 121°C, suggesting the different kinds of epoxy resin can linings from others. The results imply that the main source of human exposure to BPA is food from cans with linings that contain high percentages of BPA as an additive or an unforeseen contaminant.     

Fractionation of plant material. III.—Two schemes for chemical fractionation of fresh leaves,having special applicability for isolation of the bulk protein

Nearly all the protein of broad-bean leaves other than cell-wall protein was readily extracted into phenol-acetic acid-water mixtures, and further purified by free-solution eletrophoresis therein, using the continuous apparatus of Hannig. Under these conditions RNA migrated cationically in association with the protein. Adding salt did not greatly improve the separation, but it reversed the relative cationic migration rates of phaeophytin a and protein. Liquid-liquid partition between phenol and aqueous buffer phases gave good separation of the protein from RNA. Scheme I involved successive extraction of the leaves with 5% (w/v) aqueous trichloroacetic acid, ethanol and phenol-acetic acid-water; the bulk of the protein went into this last solvent mixture and did not require further electrophoretic treatment. In Scheme II, components of low molecular weight were washed out from the plasmolysed leaves with water. Extraction was then carried out with phenol-acetic acid-water, and this extract was further fractionated by electrophoresis. The non-migrating fraction should be valuable starting material for studies of a variety of leaf constituents. The extraction residues are promising starting material for studies of the leaf polysaccharides and other cell-wall components. The protein preparations contained little phosphorus or carbohydrate but were brown and had high C/N ratios and higher ultra-violet absorption than corresponded to the aromatic amino acids present. This was decreased, but not abolished, by keeping the work under nitrogen. Model experiments showed good electrophoretic separation of protein from polyphenols and tannic acid under the same conditions. The extraneous aromatic material is therefore presumed to be bound covalently to the protein. Coupling of oxidatively polymerising quinones to side-chains of amino acid residues, especially lysine, seems probable. The occurrence of such reactions in leaves has implications for the nutritive value of their proteins. Such products may also contribute directly to the ‘humic acid’ fraction of soil.     

Improved sample extraction and clean-up for the GC-MS determination of BADGE and BFDGE in vegetable oil.

A straightforward method was established for the determination of migration contaminants in olive oil with a special focus on the two can-coating migration compounds bisphenol A diglycidyl ether (BADGE) and bisphenol F diglycidyl ether (BFDGE). The preferred sample preparation was a single liquid-liquid extraction of compounds from the oil into 20% (v/v) methanol in acetonitrile, followed by clean-up with solid-phase extraction on aminopropyl bonded to silica. This purification procedure selectively removed all free fatty acids from the extracts without removing phenolic compounds of interest. The solid-phase extraction columns were used many times by implementing a procedure of washing out the strongly retained fatty acids with 2% acetic acid in methanol. Gas chromatography coupled with full scan (m/z 33-700) electron ionization mass spectrometry was used for the determination of several model compounds in olive oil samples. BADGE and BFDGE could be determined in the 0.05-2 mg kg(-1) range in oil samples with a relative SD of <6% (six replicates). The method was used in an enforcement campaign for the Norwegian Food Control Authority to analyse vegetable oil samples from canned fish-in-oil.     

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。     

Ultrasonically induced degradation and detoxification of microcystin-LR (cyanobacterial toxin)

Cyanobacterial toxins (CBTs), produced by glue-green algae, are one of the most common naturally occurring toxins found in potable waters. The microcystin family of CBTs present in drinking water sources poses a considerable threat to human health. In this study, we have demonstrated that ultrasonic irradiation at 640 kHz leads to rapid degradation of microcystin-LR (MC-LR). Degradation of MC-LR present in the crude cyanobacterial extracts containing cell constituents has been studied with ultrasound under a variety of conditions. The degradation of MC-LR was demonstrated over a concentration range from 0.03 to 3.0 microM. Hydroxyl radical scavenger experiments indicate that hydroxyl radical is responsible for a significant fraction of the observed degradation, but other processes (hydrolysis/ pyrolysis) are also important. Analysis of the protein phosphatase inhibition activity of the reaction products indicates that the products from ultrasonic degradation of MC-LR do not exhibit any measurable biological activity. The results demonstrate that ultrasonic irradiation maybe an effective and practical method for the detoxification of microcystins from drinking water.