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.     

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.     

Assessment of the migration potential of nanosilver from nanoparticle-coated low-density polyethylene food packaging into food simulants

An experimental nanosilver-coated low-density polyethylene (LDPE) food packaging was incubated with food simulants using a conventional oven and tested for migration according to European Commission Regulation No. 10/2011. The commercial LDPE films were coated using a layer-by-layer (LbL) technique and three levels of silver (Ag) precursor concentration (0.5%, 2% and 5% silver nitrate (AgNO₃), respectively) were used to attach antimicrobial Ag. The experimental migration study conditions (time, temperature and food simulant) under conventional oven heating (10 days at 60°C, 2 h at 70°C, 2 h at 60°C or 10 days at 70°C) were chosen to simulate the worst-case storage period of over 6 months. In addition, migration was quantified under microwave heating. The total Ag migrant levels in the food simulants were quantified by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Mean migration levels obtained by ICP-AES for oven heating were in the range 0.01–1.75 mg l^?1. Migration observed for microwave heating was found to be significantly higher when compared with oven heating for similar temperatures (100°C) and identical exposure times (2 min). In each of the packaging materials and food simulants tested, the presence of nanoparticles (NPs) was confirmed by scanning electron microscopy (SEM). On inspection of the migration observed under conventional oven heating, an important finding was the significant reduction in migration resulting from the increased Ag precursor concentration used to attach Ag on the LDPE LbL-coated films. This observation merits further investigation into the LbL coating process used, as it suggests potential for process modifications to reduce migration. In turn, any reduction in NP migration below regulatory limits could greatly support the antimicrobial silver nanoparticle (AgNP)-LDPE LbL-coated films being used as a food packaging material.     

The effect of microwave energy on specific migration from food contact plastics.

Experiments have been carried out with (a) microwave treatment of plastics followed by migration testing using the food simulant, olive oil, and (b) microwave treatment of plastics in direct contact with an organic extractant (iso-octane). In neither of these complementary approaches was there evidence of any difference in migration from plastics that had been microwave-treated compared with plastics that had received an equivalent thermal treatment. Five plastics commonly employed in microwave applications were tested and oligomers, plasticizer, antioxidant and volatile contaminants were monitored as representatives of typical migration species.     

Migration of 4-nonylphenol from polyvinyl chloride food packaging films into food simulants and foods.

Migration of 4-nonylphenol (NP) from polyvinyl chloride (PVC) films for food packaging into food simulants and foods has been studied in domestic applications such as wrapping of food and reheating in a microwave oven. The migration of NP from the PVC films was determined by high-performance liquid chromatography with electrochemical coulometric-array detection (LC/ED). Twelve PVC films intended for commercial use and ten for domestic applications (total: 22 samples) were analysed. Some of the PVC films (two home-use and ten retail-use) contained NP at concentrations of between 500 and 3300 microg/g. Migration of NP from the films was influenced by the test conditions (n-heptane at 25 degrees C for 60 min, distilled water at 60 degrees C for 30 min and 4% acetic acid at 60 degrees C for 30 min). The amount of NP migrating from the PVC films into n-heptane (0.33-1.6 microg/cm2) was higher than the amount migrating into distilled water or 4% acetic acid (up to 9.7 ng/cm2) for the 11 films in which NP was detected. Up to 0.23% of the NP migrated into distilled water and 4% acetic acid and up to 62.5% into n-heptane. In addition, we investigated NP migration into cooked rice samples wrapped in PVC film. Using spiked samples the method gave an average recovery of 83.7% (n = 5) with a standard deviation of 2.5%. Migration of NP ranged from not detectable (< 1.0 ng/g) to 410.0 ng/g by reheating samples in a microwave oven for 1 min and from not detectable to 76.5 ng/g by keeping samples at room temperature for 30 min.     

食品包装材料中双酚A迁移量的测定

建立采用高效液相色谱法对塑料食品包装材料中双酚A向食品模拟物迁移量的检测方法。使用4种食品模拟物：水、质量分数为4%乙酸溶液、体积分数30%的乙醇溶液和脂肪类模拟物(正己烷、异辛烷和橄榄油)。结果表明,双酚A在与食品塑料包装接触过程中,无论在何种情况下都会向食品模拟物中迁移,尤其向醇类模拟物中迁移最严重;在温度超过60℃时,双酚A向食品模拟物中的迁移率骤增;在微波加热条件,高火700W功率时双酚A向食品模拟物中的迁移速率最快。该方法检测限为0.3ng/mL,线性范围为0.5～100ng/mL,线性相关系数为0.9997,回收率在92.0%～102.4%之间,相对标准偏差≤2.84%(n=5)。     

Measurement uncertainty associated with overall migration testing

The results from a single laboratory that took part in a series of check-sample exercises for overall migration were used to calculate the measurement uncertainty for the overall migration methodology. The results span 10 years of proficiency testing and cover a range of plastic materials tested using a variety of time and temperature test conditions. Twelve sets of results for overall migration into olive oil and 10 sets of results for overall migration into volatile simulants were used. The measurement uncertainty associated with the determination of overall migration from plastics into olive oil was estimated as ± 2.6 mg dm^-2 for results between 1.2 and 15.4 mg dm^-2. The measurement uncertainty associated with the determination of overall migration into volatile simulants was estimated as ± 1.4 mg dm^-2 for results between 2.1 and 13 mg dm^-2. These estimates are within the analytical tolerances set in European Union regulations, of 3 and 2 mg dm^-2, respectively. The performance of all laboratories participating in these 22 check sample exercises was also evaluated. A very large majority (93%) of the participants used official test methods, sometimes with minor modifications as stated. For the simulant olive oil, an average of 81% of laboratories (13 rounds with an average of 21 participants in each) using official methods was within the tolerance specified in regulations. For the volatile food simulants, an average of 87% of laboratories (11 rounds with an average of 38 participants in each) using official methods was within the tolerance specified. It is concluded from this evaluation of within- and between-laboratory data that the official European Standard methods for overall migration testing are suitable for the analysis of routine samples.     

EFFECT OF MICROWAVE HEATING ON SURVIVAL OF SALMONELLA TYPHIMURIUM IN ARTIFICIALLY CONTAMINATED READY-TO-EAT FOODS

This research evaluated the destruction of Salmonella typhimurium during reheating of foods in two different types of microwave ovens: a conventional 750W oven and 700W oven with preset controls. The heating times in the conventional microwave oven were established as 50 s for baby food and 75 s for mashed potatoes as well as for the beef stroganoff samples, while for the preset oven those periods of time were determined by a built-in temperature sensor. The percentage of food samples positive for S. typhimurium in conventional microwave was 47.8% while in microwave with preset controls it was 93.3%. Our results suggest that reheating contaminated foods in microwave ovens may, therefore, not be sufficient to destroy S. thyphimurium in order to assure food safety .     

Development of an HPLC method for measurements of the stability of Irganox-type polymer antioxidants in fatty food simulants

 A reversed-phase high-performance liquid chromatography (RP-HPLC) method has been developed to measure the stability of four Irganox-type polymer antioxidants (Irganox 245, Irganox 1035, Irganox 1098 and Irganox 3114) in an olive oil food simulant and isooctane, which has been proposed as an alternative fatty food simulant. The tests of stability in olive oil were carried out under three different conditions, i.e. 40°C for 10 days, 100°C for 1 h and 175°C for 1 h. The exposure conditions for isooctane were 60°C for 3 h. Results showed that for all additives tested no instability phenomena in olive oil or isooctane simulants were observed under the exposure conditions applied. The analytical methodology developed could eventually be used for stability testing and migration studies of other similarly structured antioxidants in fatty food simulants. Received: 11 September 1997     

Development of an HPLC method for measurements of the stability of Irganox-type polymer antioxidants in fatty food simulants

 A reversed-phase high-performance liquid chromatography (RP-HPLC) method has been developed to measure the stability of four Irganox-type polymer antioxidants (Irganox 245, Irganox 1035, Irganox 1098 and Irganox 3114) in an olive oil food simulant and isooctane, which has been proposed as an alternative fatty food simulant. The tests of stability in olive oil were carried out under three different conditions, i.e. 40°C for 10 days, 100°C for 1 h and 175°C for 1 h. The exposure conditions for isooctane were 60°C for 3 h. Results showed that for all additives tested no instability phenomena in olive oil or isooctane simulants were observed under the exposure conditions applied. The analytical methodology developed could eventually be used for stability testing and migration studies of other similarly structured antioxidants in fatty food simulants. Received: 11 September 1997     

Changes in chemical composition and nutritional quality of fried sardine (Clupea pilchardus) produced by frozen storage and microwave reheating

Modifications in proximate composition, fatty acids, amino acids and –SH groups content, as well as changes in solubility and nutritional quality of protein, were studied in fillets of sardine (Clupea pilchardus) that had been successively pan-fried, frozen stored and reheated by two different means, namely conventional oven and microwave oven. Upon pan-frying in olive oil the sardine absorbed C18: 1(n-9) and C18: 2(n-6) and lost saturated (SFA) and polyunsaturated fatty acids (PUFA); this loss continued upon reheating, and as a consequence the percentage of MUFA increased compared to the just-fried sardine. A loss of water was observed during all processes. Upon frying there was a decrease of cyst(e)ine. Upon reheating by both microwave and conventional oven, methionine decreased; however, cyst(e)ine only decreased with the use of a conventional oven. A loss of –SH groups was recorded during frying and this phenomenon continued upon reheating. Biological value (BV) together with net protein utilisation (NPU) decreased upon both frying and reheating. © 1997 SCI.     

Headspace analysis of benzene in food contact materials and its migration into foods from plastics cookware

Concentrations of benzene of 29 and 64 mg/kg were found in two samples of thermoset polyester compounded for the manufacture of plastic cookware. In collaboration with the suppliers of the materials, it was established that the benzene originated from the use of t-butyl perbenzoate used as an initiator in the manufacture of the polymer. Samples of thermoset polyester made to the original formulations and thus contaminated with benzene showed migration levels of 1.9 and 5.6 mg/kg in olive oil after extraction for 1 hour at 175 degrees C. Migration levels into olive oil at 175 degrees C for samples produced with non-aromatic initiator were less than 0.1 mg/kg. Concentrations of benzene in thermoset polyester cookware purchased from retail outlets were 0.3 to 84.7 mg/kg. Low amounts of benzene (less than 0.01 to 0.09 mg/kg) were detected in foods when the articles were used for cooking in microwave or conventional ovens. Other plastics used for retail food packaging, such as polystyrene and PVC, which might utilise t-butyl perbenzoate catalyst, were also analysed for benzene. Levels were mostly below 0.1 mg/kg, with the highest amounts detected being from 0.2 to 1.7 mg/kg, predominantly in articles of expanded polystyrene.     

Heat treatment for the control of Bacillus cereus spores in foods

The effect of heat treatments on food products related to soybean curd contaminated with Bacillus cereus spores was investigated for the purpose of preventing food-poisoning outbreaks by B. cereus. In the case of B. cereus strains isolated from foods, heating foods inoculated with the spores for 20 min at 70 degrees C, 5 min at 75 degrees C, 2 min at 100 degrees C, or 10 sec with a microwave oven plus reheating after standing for 2 hr at 25 degrees C reduced the number of surviving cells within the foods to less than one-hundredth. In the case of a heat-resistant strain isolated from a food poisoning outbreak, heating for 20 min at 70 degrees C plus reheating after standing for 1.5-2 hr at 35 degrees C, heating for 10 min at 75 degrees C plus reheating after standing for 1.5-2 hr at 35 degrees C, or heating for 2 min at 100 degrees C plus reheating after standing for 4 hr at 25 degrees C was effective. There was not much difference between the flavor components in foods with and without heat treatment at 70 degrees C, as analyzed by gas chromatography-mass spectrometry. These results indicate that these heat treatments are available to control B. cereus spores, without affecting the sensory quality of the foods.     

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.     

Investigation of migration from paper and board into food-development of methods for rapid testing

A range of paper and board materials including carton board, corrugated board, napkins and paper towels intended for contact with food have been solvent extracted and substances present at the highest levels identified and quantified by GC/MS. Dibutyl phthalate, and diisopropylnaphthalene (DIPN) were selected to study migration to food and potential food simulants with the aim of developing a simple quick test that will give an equivalent or higher result. Tenax was found to be a suitable food simulant for dry foods and dry 'fatty foods' such as pastry and cake and was also found to be a suitable simulant for pizza base tested at higher temperatures for short contact times. The percentage migration values from corrugated and carton boards were generally in the range 15-40%, with the highest percentage being 49% for rice using conditions representing ambient storage. Quick tests were developed using Tenax under accelerated conditions of 4h at 80°C to cover room temperature storage with dry foods and fatty dry foods. These tests are suitable for compliance testing of paperboard samples if migration limits are applied in future legislation. Migration from tissues, napkins and paper towels was found to be at very low or not detectable levels, even when the levels of DIPN and DBP were significant. It is strongly suspected that this finding is due to a combination of short contact time, low grammage and the fact that the tissues absorb fat and moisture from foods, thus minimizing extraction from the paper. In all cases, the results from migration experiments into food and Tenax indicate that for the substances found at highest concentrations in the paper, currently accepted safety limits were not exceeded where they exist in EU legislation or in working documents applying to plastics.     

Overall migration from commercial coextruded food packaging multilayer films and plastics containers into official EU food simulants

The overall migration from a wide range of commercial five-layer coextruded packaging films into aqueous food simulants (distilled water, 3% aqueous acetic acid) and alternative fatty food simulant (iso-octane) was studied. The overall migration from commercial plastics cups (PS, HIPS, and PP) used for ice-cream or yogurt packaging into distilled water and 3% aqueous acetic acid was also studied. Test conditions for packaging material/food simulant contact and method of overall migration analysis were according to the EU directives and CEN-standards. The results showed that for all tested five-layer films and plastics (PS, HIPS, and PP) cups values of overall migration into aqueous simulants (0.11-0.79 mg/dm², 2.3-15.9 mg/l) and (<0.10-0.41 mg/dm², <0.80-3.1 mg/l) were significantly lower than the upper limit (10 mg/dm²) for overall migration from plastic packaging materials and articles into food and food simulants set by the EU Directive 90/128/EEC and their revisions. The overall migration values from five-layer materials into iso-octane were significantly higher (0.94-8.23 mg/dm², 18.8-164.7 mg/l) than the above values but are still lower than the upper limit for overall migration. Global migration values of five-layer films into aqueous food simulants seems to be independent of material thickness. In contrast, overall migration into iso-octane increases with film thickness.     

Migration study of carvacrol as a natural antioxidant in high-density polyethylene for active packaging

The migration behaviour of low molecular weight compounds from food packaging materials is one of the key issues in assessing the possibility of use in such applications. The aim of this work was to study the migration of carvacrol (1% and 2% w/w) when added to high-density polyethylene. All materials were exposed to the food simulants olive oil and distilled water separately at 40°C and 25°C. Three significant variables influencing the migration process were considered: incubation temperatures, the initial concentration of antioxidant, and the type of simulant (oil and aqueous). The amount of carvacrol migrating to olive oil was significantly higher than in water because of the higher solubility of this antioxidant in oil. Experimental results agreed reasonably well with those obtained by the application of a simple model derived from Fick's Second Law. Carvacrol could therefore be used in active packaging formulations as its release from the polymer matrix can be controlled.     

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.     

Effect of microwave heating on the migration of dioctyladipate and acetyltributylcitrate plasticizers from food-grade PVC and PVDC/PVC films into olive oil and water

Migration of dioctyladipate (DOA) and acetyltributylcitrate (ATBC) plasticizers from plasticized Polyvinylchloride (PVC) and polyvinylidene chloride (PVDC/PVC (Saran) films into both olive oil and distilled water during microwave heating has been studied. The plasticizer migrating into olive oil and water was determined using an indirect GC method after saponification of the ester-type plasticizer (DOA or ATBC) and subsequent collection of the alcohol component of the ester, namely: 2-ethyl-1-hexanol and 1-butanol, respectively. Migration was dependent on heating time, microwave power setting, the nature of the food simulant and the initial concentration of the plasticizer in the film. Migration of DOA into olive oil reached equilibrium after heating for 10 min at full power (604.6 mg DOA/1). Migration into distilled water was 74.1 mg/1 after 8 min of microwave cooking at full power. The amount of ATBC migrating into olive oil reached equilibrium after heating for 10 min at full power (73.9 mg ATBC/1). Migration into distilled water was 4.1 mg/1 after heating at full power for 8 min. Control samples containing olive oil gave DOA migration values which were significantly higher than the upper limit for global migration (60 mg/1) set by the European Community. It is proposed that PVC should not be used in direct contact with food in the microwave oven, while Saran may be used with caution in microwave heating and reheating applications, avoiding its direct contact with high fat foodstuffs.     

Survey of the migration of melamine and formaldehyde from melamine food contact articles available on the UK market

The migration of melamine and formaldehyde, monomers used in the production of melamine-ware food contact articles, has been determined from 50 retail articles purchased in the UK. The food simulant 3% aqueous acetic acid was used as this is the most aggressive simulant towards melamine plastics. The test conditions used were repeated exposure to the simulant for 2 hours at 70°C, since the articles were all intended for general use including contact with hot foods and beverages. Melamine migrated from 43 of the 50 samples tested and formaldehyde migrated from all 50 samples. Directive 2002/72/EC specifies migration limits for both of these monomers in foods and food simulants. Melamine is restricted by a specific migration limit (SML) of 30 mg/kg (equivalent to 5 mg/dm²) and formaldehyde, along with hexamethylenetetramine expressed as formaldehyde, is restricted by a total (T) SML(T) of 15 mg/kg (equivalent to 2.5 mg/dm²). In all cases the migration of melamine was much lower than the SML for this monomer. The migration of formaldehyde exceeded the SML(T) for 5 of the 50 samples tested. The failure to comply with the SML(T) was accompanied by a number of visible surface effects including discolouration and/or pitting of the simulant contact surface and cracking of the articles. Similar surface effects were observed when one of the samples was exposed to fruit juice which confirmed the suitability of the exposure conditions and 3% acetic acid as a simulant for the articles tested. The ratio of specific migration to overall migration was consistent with, but did not prove, the hypothesis that high formaldehyde migration could be due to the use of excessive hexamethylenetetramine in the polymer formulation. All illegal products were voluntarily removed from the market by the product suppliers.