Migration of trimellitic acid from epoxy anhydride can coatings into foods

The migration of trimellitic acid and its esters from epoxy anhydride coatings was determined in simulants as well as in canned foods. The most appropriate simulant was a combination of EC simulants B and C: 2% acetic acid/10% ethanol in water. The average migration into food was 900 μg kg^-1. This far exceeds the 50 μg kg^-1 for which the safety of trimellitic acid and its anhydride is ensured and the Swiss legal limit (QM(T) of 5 mg kg^-1 coating). Furthermore, much trimellitic acid migrated as (unidentified) esters, i.e. toxicological testing of free trimellitic acid is inadequate for the material that in reality migrates.     

Migration of Ti from nano-TiO2-polyethylene composite packaging into food simulants

An analytical method based on ICP-MS was developed for the determination of Ti in food simulants (3% (w/v) aqueous acetic acid and 50% (v/v) aqueous ethanol). The method was used to determine the migration of Ti from nano-TiO₂-PE films used for food packaging into food simulants under different temperature and migration time conditions. The maximum migration amounts into 3% (w/v) aqueous acetic acid were 1.4 ± 0.02, 6.3 ± 0.5 and 12.1 ± 0.2 μg kg^?1 at 25, 70 and 100°C, respectively, while into 50% (v/v) aqueous ethanol, the maximum migration amounts were 0.5 ± 0.1, 0.6 ± 0.03 and 2.1 ± 0.1 μg kg^?1 at 25, 70 and 100°C, respectively. Increasing the additive content in the film promoted migration of nanoparticles. The results indicated that the migration of nanoparticles might occur via dissolution from the surface and cut edges of the solid phase (film) into the liquid phase (food simulant).     

Migration of fluorochemical paper additives from food-contact paper into foods and food simulants

Fluorochemical-treated paper was tested to determine the amount of migration that occurs into foods and food-simulating liquids and the characteristics of the migration. Migration characteristics of fluorochemicals from paper were examined in Miglyol, butter, water, vinegar, water-ethanol solutions, emulsions and pure oil containing small amounts of emulsifiers. Additionally, microwave popcorn and chocolate spread were used to investigate migration. Results indicate that fluorochemicals paper additives do migrate to food during actual package use. For example, we found that microwave popcorn contained 3.2 fluorochemical mg kg^-1 popcorn after popping and butter contained 0.1 mg kg^-1 after 40 days at 4°C. Tests also indicate that common food-simulating liquids for migration testing and package material evaluation might not provide an accurate indication of the amount of fluorochemical that actually migrates to food. Tests show that oil containing small amounts of an emulsifier can significantly enhance migration of a fluorochemical from paper.     

Migration of fluorochemical paper additives from food-contact paper into foods and food simulants

Fluorochemical-treated paper was tested to determine the amount of migration that occurs into foods and food-simulating liquids and the characteristics of the migration. Migration characteristics of fluorochemicals from paper were examined in Miglyol, butter, water, vinegar, water–ethanol solutions, emulsions and pure oil containing small amounts of emulsifiers. Additionally, microwave popcorn and chocolate spread were used to investigate migration. Results indicate that fluorochemicals paper additives do migrate to food during actual package use. For example, we found that microwave popcorn contained 3.2 fluorochemical mg kg^?1 popcorn after popping and butter contained 0.1 mg kg^?1 after 40 days at 4°C. Tests also indicate that common food-simulating liquids for migration testing and package material evaluation might not provide an accurate indication of the amount of fluorochemical that actually migrates to food. Tests show that oil containing small amounts of an emulsifier can significantly enhance migration of a fluorochemical from paper.     

Analysis of melamine migration from melamine food contact articles

Migration of melamine has been determined for 41 types of retail melamine-ware products in Malaysia. This study was initiated by the Ministry of Health, Malaysia, in the midst of public anxiety on the possibility of melamine leaching into foods that come into contact with the melamine-ware. Thus, the objective of this study was to investigate the level of melamine migration in melamine utensils available on the market. Samples of melamine tableware, including cups and plates, forks and spoons, tumblers, bowls, etc., were collected from various retail outlets. Following the test guidelines for melamine migration set by the European Committee for Standardisation (CEN 2004) with some modifications, the samples were exposed to two types of food simulants (3% acetic acid and distilled water) at three test conditions (25°C (room temperature), 70 and 100°C) for 30 min. Melamine analysis was carried out using LC–MS/MS with a HILIC column and mobile phase consisting of ammonium acetate/formic acid (0.05%) in water and ammonium acetate/formic acid (0.05%) in acetonitrile (95?:?5, v/v). The limit of quantification (LOQ) was 5?ng/ml. Melamine migration was detected from all samples. For the articles tested with distilled water, melamine migration were [median (interquartile range)] 22.2 (32.6), 49.3 (50.9), 84.9 (89.9) ng/ml at room temperature (25°C), 70 and 100°C, respectively. In 3% acetic acid, melamine migration was 31.5 (35.7), 81.5 (76.2), 122.0 (126.7) ng/ml at room temperature (25°C), 70 and 100°C, respectively. This study suggests that excessive heat and acidity may directly affect melamine migration from melamine-ware products. However the results showed that melamine migration in the tested items were well below the specific migration limit (SML) of 30?mg/kg (30,000?ng/ml) set out in European Commission Directive 2002/72/EC.     

Comparison of the migration of melamine from melamine–formaldehyde plastics (‘melaware’) into various food simulants and foods themselves

A variety of melaware articles were tested for the migration of melamine into the food simulant 3% w/v acetic acid as a benchmark, and into other food simulants, beverages and foods for comparison. The results indicate that the acidity of the food simulant plays a role in promoting migration, but not by as much as might have been anticipated, since 3% acetic acid gave migration values about double those obtained using water under the same time and temperature test conditions. In contrast, migration into the fatty food simulant olive oil was not detectable and at least 20-fold lower than with the aqueous food simulants. This was expected given the solubility properties of melamine and the characteristics of the melaware plastic. Migration levels into hot acidic beverages (apple juice, tomato juice, red-fruit tea and black coffee) were rather similar to the acetic acid simulant when the same time and temperature test conditions are used, e.g. 2?h at 70°C. However, migration levels into foods that were placed hot into melaware articles and then allowed to cool on standing were much lower (6–14 times lower) than if pre-heated food was placed into the articles and then maintained (artificially) at that high temperature in the same way that a controlled time–temperature test using simulants would be conducted. This very strong influence of time and especially temperature was manifest in the effects seen of microwave heating of food or beverage in the melaware articles. Here, despite the short duration of hot contact, migration levels were similar to simulants used for longer periods, e.g. 70°C for 2?h. This is rationalized in terms of the peak temperature achieved on microwave heating, which may exceed 70°C, counterbalancing the shorter time period held hot. There was also evidence that when using melaware utensils in boiling liquids, as for stovetop use of spatulas, the boiling action of circulating food/simulant can have an additional effect in promoting surface erosion, increasing the plastic decomposition and so elevating the melamine release.     

Further insights into the mechanism of migration from the PVC gaskets of metal closures into oily foods in glass jars

Factors influencing migration from the gaskets of metal closures into oily foods were investigated. Tightening of the lid has an effect presumably through the deformation of the gasket, the amount of oil adhering to the latter, and the proportion of its surface being covered by oil. The substantial difference observed in the migration determined with the jar in an upright or a reversed position is partly related to this. The nature of the plasticizer determines the saturation in the partitioning process between the gasket and the small amount of oil in contact with the gasket as well as the adherence of oil (wettability). If saturation is rapidly reached, the frequency of exchanging the oil by shaking of the jar is an important factor. A complete exchange of the oil in contact with the gasket requires vigorous and persisting shaking, presumably because of the high viscosity and the hindered access to the angle between the gasket and the jar rim. The limited data available on long-term performance suggest that migration accelerates after roughly one year of storage. It is concluded that the extrapolation of long-term migration from short-term data presupposes a deeper investigation of the course of migration over years.     

Migration kinetics of four photo-initiators from paper food packaging to solid food simulants

ABSTRACT

The migration behaviour of four photo-initiators (BP, EHA, MBP and Irgacure 907) was studied by ‘printing’ onto four different food-packaging materials (Kraft paper, white cardboard, Polyethylene (PE)-coated paper and composite paper) and tracking movement into the food simulant: Tenax-TA (porous polymer 2,6-diphenyl furan resin). The results indicated that the migration of the photo-initiators was related to the molecular weight and log K_o/w of each photo-initiator. At different temperatures, the migration rates of the photo-initiators were different in papers with different thicknesses. The amount of each photo-initiator found in the food was closely related to the food matrix. The Weibull model was used to predict the migration load into the food simulants by calculating the parameters τ and β and determining the relationship of the two parameters with temperature and paper thickness. The established Weibull model was then used to predict the migration of each photo-initiator with respect to different foods. A two-parameter Weibull model fitted the actual situation, with some deviation from the actual migration amount.     

陶瓷食品包装材料中铅、镉向真实食品的迁移研究

陶瓷食品包装容器中的有害重金属铅、镉向食品的迁移会造成食品污染进而危害消费者身体健康。本文通过制备含有铅、镉这两种重金属元素的陶瓷样品,使之分别在20℃和40℃的条件下与白酒、黄酒、醋和酸豆角汁这四种真实食品接触一定时间来研究这两种重金属的迁移行为。结果表明:铅、镉迁移量随着温度的升高而增加,并且迁移速率也与温度成正比;铅、镉的迁移量受食品的pH影响,pH越低,迁移量越高;铅的迁移量还与酒精度成反比,酒精度越高,铅的迁移量越少。      

有机涂层食品接触材料中甲醛在食品模拟物中迁移规律的研究

目的 研究了有机涂层食品接触材料中毒害物质甲醛在食品模拟物中的迁移规律。方法 根据产品的实际使用条件,以食品模拟物对样品进行模拟浸泡,以乙酰丙酮分光光度法对食品模拟物中甲醛迁移量进行测定。结果 在相同的使用条件下,酸性模拟物中甲醛的迁移量最大;在接触同种食品模拟物时,甲醛的迁移量随着高压灭菌时间的延长和灭菌温度的升高而增加;货架存放时间对甲醛的迁移量无明显影响。结论 通过对甲醛迁移规律的考察,得出了有机涂层食品接触中甲醛的迁移风险。     

Migration of antimony from PET trays into food simulant and food: determination of Arrhenius parameters and comparison of predicted and measured migration data

Migration experiments with small sheets cut out from ovenable PET trays were performed in two-sided contact with 3% acetic acid as food simulant at various temperatures. The fraction of diffusible antimony (Sb) was estimated to be 62% in the PET sample under study. Apparent diffusion coefficients of Sb in PET trays were determined experimentally. Measurement of migration between 20 and 150°C yielded a linear Arrhenius plot over a wide temperature range from which the activation energy (E _a) of 188?±?36?kJ?mol^?1 and the pre-exponential factor (D ₀) of 3.6?×?10¹⁴?cm²?s^?1 were determined for diffusing Sb species. E _a was similar to previously reported values for PET bottles obtained with a different experimental approach. E _a and D ₀ were applied as model parameters in migration modelling software for predicting the Sb transfer in real food. Ready meals intended for preparation in a baking oven were heated in the PET trays under study and the actual Sb migration into the food phase was measured by isotope dilution ICP-MS. It was shown that the predictive modelling reproduces correctly experimental data.     

Migration from can coatings: Part 2. Identification and quantification of migrating cyclic oligoesters below 1000 Da

Metal cans for food use can be coated with lacquers based on polyester resins. Recent research has focussed on the identification and quantification of migrants released by coatings that are potentially absorbable (below 1000 Da). The presented method describes a procedure that was optimized to hydrolyse the polyester migrants into their monomers, polyvalent acids and polyols. The polyols were identified by gas chromatography with flame ionization detection GC-FID and the acids by high-performance liquid chromatography (HPLC) coupled with an ultraviolet and an electrospray ionization-mass selective detector (HPLC-ESI-MSD/UVD), respectively. With the knowledge of the polyester monomers, it was possible — at least tentatively — to identify the main components in the migrate as cyclic oligoesters by HPLC-ESI-MSD/UVD. A cyclic oligomer, CYCLO [3IPA (isophthalic acid) 3EG (ethylene glycol)] was synthesized and characterized by infrared, nuclear magnetic resonance and mass spectrometry as well as by elementary analysis for further confirmation. To determine the amount of migrating cyclic oligoesters, the response of the migrating substances was compared using different detectors, UVD, MSD and evaporative light scattering detector (ELSD). The response of the ELSD was dependent on the molecular weight of the analytes that reduced the accuracy of this detection type. The wavelength with the same absorption coefficient for IPA and terephthalic acid (TPA) was obtained at 232 nm. The UV_232nm response of an oligoester is proportional to the number of its IPA/TPA moieties, which was verified for several TPA/IPA esters. The amount of the migrating oligoesters was determined using an UV_232nm calibration of a commercially available TPA ester and the number of IPA/TPA moieties molecules gained from the ESI-MSD spectra. According to this method, the amount of migrating oligoesters below 1000 Da in the 95% ethanol migrate varied from 0.1 to 0.6 mg dm^-2 (0.6-3.6 mg kg^-1 food) in the examined coatings. The determined amounts account for about 50% of the total migrate below 1000 Da.     

Migration of polyolefin oligomeric saturated hydrocarbons (POSH) into food

POSH are polyolefin oligomeric saturated hydrocarbons, such as oligomers from polyethylene or polypropylene. POSH that have migrated into foods are easily mistaken for mineral oil-saturated hydrocarbons (MOSH). In fact, both POSH and MOSH largely consist of highly isomerised branched and possibly cyclic hydrocarbons, both forming humps of unresolved components in gas chromatography. Chromatograms are reported to show typical elution patterns of POSH and help analysts distinguishing POSH from MOSH as far as possible. Since the structures of the POSH are not fundamentally different from those of the MOSH, it would be prudent to apply the evaluation of the MOSH. However, the migration is frequently beyond that for which safety has been demonstrated. This is shown for a few examples, particularly for powdered formula for babies.     

Survey of furan in foods and coffees from five European Union countries

Canned and jarred baby foods (74), canned and jarred adult foods (63) and 70 coffees sold in Belgium, Italy, Portugal, Spain and The Netherlands were analysed for their furan content using a validated automated headspace GC–MS procedure. Seven balsamic vinegars from Italy and Spain were also analysed. All 74 baby food samples contained detectable furan, with an average level of 37 ng/g. A total of 54 of 63 canned and jarred foods contained detectable furan with an average level of 24 ng/g. Levels of furan in coffee as consumed were very variable and reflected different preparation methods and coffee strengths. Over 50% of Italian samples contained more than 200 ng/g, whereas over 20% of Belgian coffees contained less than 21 ng/g furan. Some brews made from fine grained coffee contained much more furan than did brews made from normal or coarse grained coffee. Although furan was low in most instant coffees, two Italian products “instant espresso” and “instant mocha” contained about 150 ng/g furan. Balsamic vinegars from Spain contained 159–662 ng/g of furan; however, other samples from Spain and Italy contained only 6–25 ng/g.     

Migration of bisphenol A from can coatings—effects of damage, storage conditions and heating

Bisphenol A (BPA) is an important monomer used in the manufacture of epoxy resins for internal food can linings. Experiments were conducted to investigate the effects of different storage conditions and can damage on the migration of BPA to foods. These experiments were conducted in a systematic fashion by filling empty epoxyphenolic coated cans with four foods: soup, minced beef, evaporated milk and carrots and a food simulant (10% ethanol). Filled cans of each food type or simulant were then sealed and processed using appropriate conditions, before storage at three different temperatures: 5°C, 20°C and 40°C. For each of the storage regimes, 50% of the cans were dented to establish if this would lead to increased BPA migration. Cans were removed from these stocks at intervals of 1, 3 and 9 months storage at 5°C and 20°C or 10 days, 1 and 3 months at 40°C. Some initial problems of heterogeneity between samples was overcome by determining the amount of BPA in food as well as in the can lining. It was found that 80-100% of the total BPA present in the coating had migrated to foods directly after can processing by pilot plant filling with food or simulant, sealing and sterilization. This level was not changed by extended storage (up to 9 months) or can damage, indicating most migration was occurring during the can processing step. There was no noticeable difference, in this respect, between the different foods or the food simulant. Analysis of control samples (foods fortified with ∼0.1 mg kg^-1 BPA and contained in Schott bottles) showed that BPA was stable under both processing and storage. Experiments were also conducted to investigate the potential effects, on the migration of BPA from can coatings, of cooking or heating foods in the can prior to consumption. Food cans were purchased and the food either cooked or heated in the can. BPA was analysed prior to and after the heating/cooking process. It was concluded from the results that there were no appreciable differences in the BPA level before and after cooking or heating.     

Survey of counterfeit melamine tableware available on the market in Thailand,and its migration

A simple measurement of sample density by adopting the principles of buoyancy could help screen counterfeit melamine ware if the density was below 1.50?g?cm^?3. However, samples with a density exceeding 1.50?g?cm^?3 were not necessarily made from melamine formaldehyde. FTIR analysis showed that all counterfeit products were made of urea formaldehyde and coated on the food-contact side with melamine formaldehyde, a tactic probably intended to cover up the true product features. The overall migration of real and counterfeit melamine samples complied with both European Union and Thai regulations, as the exposure layers in both cases were melamine formaldehyde. Formaldehyde migration failed to comply with Thai standards, but this was not the case for European Union standards. However, the results showed a significant inconsistency between individual items of the same brand and between individual exposures of the same test specimen. This indicated the inherent inhomogeneity between individual items, which mainly resulted from the manufacturing process: for instance, insufficient temperature and time to obtain complete polycondensation of monomers. Therefore, it is recommended that constant surveillance be conducted on melamine articles available in the marketplace in terms of quality and safety.     

食品罐内涂层中双酚A及其环氧衍生物的迁移及检测研究进展

食品罐内涂层中的双酚A及其环氧衍生物会向食品内容物迁移,对人体健康造成危害。本文综述了近年来国内外食品罐内涂层中双酚A及其环氧衍生物的迁移规律、与食品的反应及提取与分析方法等方面的最新研究进展,并在分析目前不足之处的基础上展望了未来研究的方向。      

高温下白卡纸中二苯甲酮和1-羟基环己基苯基甲酮向食品模拟物质的迁移

研究了在70℃和90℃下,采用直接浸泡法使白卡纸中的固化剂二苯甲酮（BP）和1-羟基环己基苯基甲酮（HCH）向水、3%乙酸、15%乙醇、50%乙醇、95%乙醇等食品模拟物质迁移,采用高效液相色谱仪（HPLC）分别检测迁移后模拟物质中的迁移量。结果表明两种固化剂在0.64⁴0mg/L的质量浓度范围内呈良好线性,相关系数不小于0.9995。温度越高,迁移时间越长,迁移量也越大;随着乙醇浓度的增高,BP、HCH的迁移量也增加;对于3%乙酸,BP和HCH迁移率最小。      

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.