Phthalates in paper and board packaging and their migration into Tenax and sugar

Packaging samples for many kinds of foodstuffs were received from manufacturers together with basic information about the materials used in their production. Half of the 29 samples studied contained phthalates in amounts exceeding 5mg/kg. Two types of paper bag intended for sugar had exceptionally high phthalate contents although they were flexo printed. The maximum contents of di-isobutylphthalate (DIBP) and dibutylphthalate (DBP) were 450 and 200 mg/kg, respectively. The phthalates found originated from adhesives used in the joints of the packaging. In other packagings manufactured at the same time, DIBP concentrations varied from 92 to 193mg/kg. Phthalates were also determined in sugar before and after packaging. Migration of phthalates ranged from 57 to 74% of the original content in the packaging after 4 months storage. Packed sugar contained DIBP 2.2-2.6mg/kg and DBP 0.5-1mg/kg. The sugar packagings were also tested using Tenax as a food stimulant. The results indicated that 69-91% of the original content of the phthalates migrated into Tenex after 10 days at 40 C. The major drawback with migration testing using Tenax is its high cost; it is not practical to fill the whole 1kg packaging with Tenax, and smaller samples of packaging must be used instead. However, the distribution of substances in the packaging might be nonuniform. In the sugar packagings studied here, the difference between phthalate concentrations in two samples taken from the same packaging was nearly 100-fold.     

Potential migration of Diisopropyl naphthalenes from recycled paperboard packaging into dry foods

The results of a study of the potential migration of diisopropyl naphthalenes (DIPN) from recycled paperboard packaging into some types of dry solid foodstuffs are reported. Paperboard diskettes containing different DIPN concentrations were prepared and put into contact with four types of dry solid foodstuffs, having high specific surface areas and different lipid contents. At regular intervals the DIPN content in the foods was determined. Two migration mechanisms have been proposed and verified. The first one relates to the direct contact existing between paperboard and foodstuff. The second one refers to the indirect contact between paperboard and food, controlled by an air space created above the paperboard into which the DIPN has diffused. Both mechanisms occurred and the migration depended on different factors: the contact time, the characteristics of the foodstuffs and the DIPN content in the cellulose-based matrix. However, only very low levels of contamination in the foodstuffs occurred in migration. As a consequence, this report also considers possible limitations which could be applied to the content of carbonless copy paper in packaging paperboard formulations.     

Safety and quality of food contact materials. Part 1: Evaluation of analytical strategies to introduce migration testing into good manufacturing practice

The results of a research project (EU AIR Research Programme CT94-1025) aimed to introduce control of migration into good manufacturing practice and into enforcement work are reported. Representative polymer classes were defined on the basis of chemical structure, technological function, migration behaviour and market share. These classes were characterized by analytical methods. Analytical techniques were investigated for identification of potential migrants. High-temperature gas chromatography was shown to be a powerful method and H-magnetic resonance provided a convenient fingerprint of plastic materials. Volatile compounds were characterized by headspace techniques, where it was shown to be essential to differentiate volatile compounds desorbed from those generated during the thermal desorption itself. For metal trace analysis, microwave mineralization followed by atomic absorption was employed. These different techniques were introduced into a systematic testing scheme that is envisaged as being suitable both for industrial control and for enforcement laboratories. Guidelines will be proposed in the second part of this paper.     

Study of diffusion through LDPE film of Di-n-butyl phthalate

The apparent diffusion coefficients (D) across a PE-LD film of Di-n-butyl phthalate (DnBP) dissolved in isooctaneand ethanol,werecalculated indifferentways and compared. DnBP, a common plasticizer of plastics and printing inks, may be a possible contaminant of flexible packaging and PE-LD is the most common food-contacting polymer. To perform diffusion measurements, small plastic sachets filled with solutions of the contaminant were used at three different temperatures. The D coefficients of the two solvents and dissolved DnBP were calculated using the lag time method, a formula taking into account the molar weight and absolute temperature,and an equation based on the initial concentration and the amounts migrated after subsequent times. The results demonstrated great solvent interference in the plasticizer diffusion across polyethylene; in particular as far as isooctane is concerned, a remarkable co-diffusion of both the plasticizer and the non-polar solvent must be assumed. Isooctane quickly penetrates PE-LD but ethanol also diffuses across PE-LD, although at a greatly reduced speed. These facts must be considered for realistic prediction of migration or effectiveness of the functional barrier.     

European priorities for research to support legislation in the area of food contact materials and articles

A strong science base is required to underpin the planning and decision-making process involved in determining future European community legislation on materials and articles in contact with food. Significant progress has been made in the past 5 years in European funded work in this area, with many developments contributing to a much better understanding of the migration process, and better and simpler approaches to food control. In this paper this progress is reviewed against previously identified work-areas (identified in 1994) and conclusions are reached about future requirements for R&D to support legislation on food contact materials and articles over the next 5 or so years.     

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.     

Characterizing the migration of antioxidants from polypropylene into fatty food simulants

The migration (diffusion and equilibrium) processes of antioxidants (AOs) from polypropylene (PP) films of different thicknesses into n-heptane and 95% ethanol as fatty food simulants were analysed at 20, 37 and 60°C. Heptane fully extracted the AOs from the polymer while a partition equilibrium described the migration to ethanol. The kinetics of migration were also studied via the diffusion coefficients. As expected, diffusion was found to be faster when the polymer was in contact with heptane, due to polymer swelling by the solvent. The kinetics of the process in ethanol was described by different theoretical expressions which are discussed. Equations disregarding partition equilibrium failed to describe the process and the diffusion coefficient values obtained through them were much smaller than the actual ones and dependent on film thickness. The results also showed the significance of food simulant selection in the analysis of food-packaging interactions and migration variability with thickness.     

Kinetic migration studies from packaging films into meat products

One of the main concerns regarding safety of food packaging is the possible migration of chemical substances (monomers and other starting substances, additives, residues) from food contact materials into foods. To evaluate the effect of the fat content and of the temperature of storage on the migration from plastics packaging films into meat products as an important class of foodstuffs, the kinetic mass transport of a model migrant (diphenylbutadiene) from low density polyethylene (LDPE) film in contact with different meat products was investigated. From the data, the diffusion coefficients were calculated for the applied test conditions, by use of a mathematical model. The results showed that migration increased with fat content and storage temperature. Analysis of migration data corresponding to minced pork meat containing different amounts of fat, stored for 10 days at 25°C, revealed an excellent relationship between migration level and fat content. This behaviour was also found for other types of meat products (chicken and pork neck). A simplifying mathematical model was applied to derive effective diffusion coefficients in the polymer which, however, do take kinetic effects in the meat also into account. In the case of pork meat contact, the effective diffusion coefficients derived from mathematical modelling were ten times higher for storage at 25°C (1.88×10(-9)cm(2)s(-1)) than for storage at 5°C (1.2×10(-10)cm(2)s(-1)).     

Evaluation of some screening methods for the analysis of contaminants in recycled polyethylene terephthalate flakes

A range of different analytical techniques were used to test recycled polyethylene terephthalate (PET) flakes for potential chemical contaminants. The techniques used were headspace gas chromatography coupled to mass spectrometry (GC-MS), liquid extraction followed by GC-MS, supercritical-fluid extraction followed by GC-MS, and migration testing followed by elemental analysis using inductively coupled plasma mass spectroscopy (ICP-MS). The PET samples were 50 representative samples taken from 600 that had been collected throughout Europe and which had been screened for potential contaminants using a single technique of high-temperature GC-MS. Six of the 50 samples tested had been spiked with a selection of model contaminants, three samples were virgin PET flakes and two of the samples were from supercleaning processes. All samples were analysed 'blind' in this exercise. The qualitative results showed that most of the contaminants came from the first use, being flavour-aroma compounds from soft drinks. The quantitative analysis found concentrations under a few mg kg^-1 in the polymer, except for the spiked samples. Element migrations were low and only calcium, silicon and sodium had median migrations above 50 μg l^-1. This in-depth analysis of recycled PET flakes did not identify any significant contaminants that had not already been detected by the high-temperature static GC-MS screening method, thus demonstrating its utility.     

A study on the equivalence of olive oil and the EU official substitute test media for migration testing at high temperatures

As a consequence of an increasing awareness and findings about the technical and analytical difficulties related to the employment of triglycerides as fatty food simulants in migration testing, EU Directive 82/711/ EEC on the basic rules of migration has been amended for the second time and adapted with the recent Commission Directive 97/48/EC. The major merit of this important amendment is to authorize alternative tests such as extraction tests and to allow substitute tests for the fat test with concrete indication of corresponding test conditions to be applied. As a novelty in food law compliance testing it authorizes a modified polyphenylene oxide (MPPO), well-known as Tenax®, a thermostable and highly adsorptive porous polymer, as a 'solid' matrix to substitute fat simulant D at temperatures equal to or higher than 100°C. In the study presented here, comparative migration testing overall and specific was carried out between fat simulants olive oil and ¹⁴C-labelled HB 307 and the substitute test media iso-octane, 95% ethanol and MPPO using polypropylene materials as examples at test temperatures of 100°C to 120°C and prescribed corresponding substitute test conditions. As a consequence, a number of conclusions were drawn which are relevant for overall and/or specific migration testing under the investigated test conditions. One of the major findings was that MPPO was generally more equivalent to the fat test than the other two substitute test media. The presence of volatile hydrocarbons in the test samples was found to play a crucial role with respect to the equivalence of the iso-octane-based substitute test. At high volatile concentrations in the test sample the iso-octane test underestimated the olive oil benchmark whereas low volatile concentrations led to satisfying equivalence. It is therefore recommended that the procedure is modified and GC-FID screening of the isooctane extract is carried out. As a logical consequence, the possibility of quantitative determination of the overall extract by GC-FID is recommendable and should be investigated in more depth. Concerning the overall migration test procedure in olive oil, the vacuum pre-conditioning at 60°C should be given re-consideration to avoid the possibility of loss of volatile migrants whose determination should be within the scope of the overall migration test method itself. Finally, the specific migration related equivalence between olive oil, MPPO and iso-octane needs further investigations to clarify the net effect of strongly increased diffusion rates at the regular high temperature versus the substitute test solvent accelerated extraction effect at 60°C. Stability aspects of migrants at the different test temperatures deserve further consideration.     

Contamination of dry foods with trimethyldiphenylmethanes by migration from recycled paper and board packaging

Contamination of foods with trimethyldiphenylmethanes is reported and the origin is shown to be migration from food packaging materials of which the use of recycled carbonless copy paper was found to be the major source. This chemical is one of the solvents used in the carbonless copy paper and its presence in food and the environment has not been previously identified. In this paper we have pursued previous studies on diisopropylnaphthalenes and hydrogenated terphenyls contamination from packaging and now report the identification of this new food contaminant and present evidence of its source. Solid foods such as egg pasta, barley coffee and rice were analysed by GC/MS and a mean concentration of 18 µg/kg of trimethyldiphenylmethanes was found. Extracts from carbonless copy paper were analysed by proton NMR to characterize the trimethyldiphenylmethanes. Since trimethyldiphenylmethanes are found in solid food together with diisopropylnaphthalenes, and considering their similar chemical character, they may follow the same migration pathway as one another.     

Migration of surrogate contaminants in paper and paperboard into water through polyethylene coating layer

The migration of five surrogate contaminants, anthracene, benzophenone, dimethyl phthalate, methyl stearate and pentachlorophenol, from paper and paperboard into water through a polyethylene (PE) coating layer was investigated. Virgin paper and paperboard coated with PE films of 0.012 and 0.030mm thickness were spiked evenly with standard 1-ml solutions containing 5mg of each surrogate. The spiked papers were placed in contact with the PE coating layer at 10 and 24 °C for 21 days. The resulting surrogate migration through the PE layer into 100ml water was measured by an analytical method developed here that used gas chromatography equipped with a flame ionization detector. Non-polar surrogates of anthracene and methyl stearate did not show any significant migration. In the case of the thin layer coating of 0.012mm, polar water-soluble contaminants of benzophenone, dimethyl phthalate and pentachlorophenol showed an equilibrated or maximized migration after 1 day, even at a refrigerated temperature of 10 °C. A thick PE coating of 0.030mm thickness delayed the progress of contaminant migration, which was also slower at lower temperature. Our results indicate that polyethylene coatings should not be seen as a complete barrier against possible contaminants in paper packaging materials under chilled or ambient conditions. Several variables such as coating thickness, temperature and suspected contaminants need to be considered to control the possible contamination risk from recycled or printed paper.     

Modelling of simultaneous two-sided migration into water and olive oil from nylon food packaging

Nylon 6 and nylon 12 food packaging materials used as sausage casings are typically exposed to fatty food on one side and boiling water on the other during the cooking process. To simulate the migration behaviour under these conditions, a special migration cell was constructed and filled with olive oil on one side of the polymer and water on the other to find out what amounts of the migrants will transfer to either side and phase at 100 °C. Results show that when a nylon 6 film is exposed to the conditions as described above, total mass transfer of the monomer—caprolactam—into the water phase occurs after 2 h at 100 °C. Nylon 12 sausage casings release similar amounts of their monomer—laurolactam—into both the aqueous and oil phase. An existing computer migration model was adapted to simulate the situation of simultaneous two-sided migration applying previously determined diffusion and partitioning coefficients. The suitability of the model was confirmed by experimental data.     

The specific diffusion behaviour in paper and migration modelling from recycled board into dry foodstuffs

Recycled board plays an important role in food packaging, but the great variety of organic impurities must be considered as potential food contaminants. The diffusion behaviour of the impurities is significantly different from that in plastic materials. The two-layer concept for paper and board introduced recently is now treated in more detail. In the rate-determining surface region the diffusion coefficients of the n-alkanes in the homologous series with 15–35 carbon atoms decrease proportionally as their vapour pressures. This leads to a different equation of the diffusion coefficients in comparison with that for the core layer. Different polarities of the migrants have additional influences on the diffusion due to their interactions with the fibre matrix. A new analytical method for the quantification of aromatic impurities has previously been developed. Based on this method and on the described diffusion behaviour, a migration model for specific and global mass transfer of impurities from recycled board into dry food and food simulants is given.     

The migration from the internal coatings of food cans; summary of the findings and call for more effective regulation of polymers in contact with foods: a review

The analysis of migrates from the internal coatings of food cans showed that the present regulation is not sufficient to ensure safety of food contact polymers. The migrates often consist of complex mixtures of reaction products and impurities, and their harmlessness cannot be deduced from the use of non-toxic starting substances compiled in positive lists. The regulation proposed herein asks producers to analyse the composition of the migrates. It includes an upper limit for the molecular weight (e.g. 1000Da) and thresholds defining concentrations in the foods down to which components must be identified and evaluated. Primarily considering feasibility at reasonable costs, thresholds of 30 mu g/kg for individual components and 300 mu g/kg for the sum of the unidentified materials are proposed. Producers must be able to demonstrate that the individual components or mixtures exceeding this limit, including reaction products with food components, have no toxic effect.     

Development and validation of analytical methods for monomeric and oligomeric migrants from nylon 12 packaging materials

Analytical methods for the determination of laurolactam--the monomer of nylon 12--as well as the cyclic dimer and trimer were established. High performance liquid chromatography using ultraviolet (HPLC-UV) and mass spectrometric detection (HPLC-MS) were both found suitable to identify and quantify monomer, cyclic dimer and trimer well below the specific migration limit (SML) of laurolactam, being 5 mg/kg of food (simulant). Gas chromatography with flame ionisation detection (GC-FID) showed to be an appropriate method for the detection of only laurolactam in aqueous and fatty food simulants. Food simulants could be analysed directly by all three methods, or after a change of solvents. For olive oil, a method for sample clean-up by size-exclusion chromatography (SEC) was established.     

食品包装塑料制品中掺杂回收塑料的分析及 检测方法研究现状

随着高分子材料工业的飞速发展,塑料制品已广泛应用于食品包装行业,同时食品包装塑料制品中掺杂回收塑料的问题也日益严重。本文综述了食品包装塑料制品中掺杂回收塑料的分析及检测方法研究现状,重点讨论了红外光谱法、热分析法、分子量及其分布法、气相色谱-质谱联用法、机械性能法等分析方法的应用现状及可行性。同时对该领域的发展趋势进行了展望。     

Polymer additive migration to foods-a direct comparison of experimental data and values calculated from migration models for polypropylene

To reduce the amount of compliance testing for food contact polymers the use of migration modelling is under discussion and being evaluated by an EU Commission funded project (Evaluation of Migration Models No. SMT4-CT98-7513). The work reported in this paper was exclusively funded by industry to provide data for the independent evaluation of a diffusion based model using eight different samples of polypropylene (PP) covering the range of polymers specification and five commonly used plastics additives. One hundred and fifty experimental migration data have been obtained in triplicate and used to evaluate a Fickian-based migration model in the prediction of specific migration of five additives into olive oil. All tests were conducted using olive oil, representing the most severe case for fatty foods, with test conditions of 2h at 121 ° C, 2h at 70 ° C and 10 days at 40 ° C, representing short term exposures at high temperatures and room temperature storage. Predicted migration values were calculated using the Piringer 'Migratest Lite' model by entering the measured initial concentration of additive in the polymers(C_p,0) in to the equations together with known variables such as additive molecular weight, temperature and exposure time. Where necessary the data generated in this study have been used to update the model. The results indicate the Piringer migration model, using the 'exact' calculations of the Migratest Lite program, predicted migration values into olive oil close to, or in excess of, the experimental results for > 97% of the migration values generated in this study. For all measurements, the predicted migration from the Migratest Lite program was greater than 70% of the observed value. This study has identified the possibility that random co-polymers of propylene and ethylene give higher migration than other grades of polypropylenes and could be treated as a separate case. However, further work on more samples of random co-polymers is required to confirm this finding.     

Model studies of migration from paper and board into fruit and vegetables and into Tenax™ as a food simulant

Four samples of paper and board (P/B) of a type used for packaging dry foods were subjected to migration tests using mushrooms, apples, potatoes and bananas, and using the polymeric powder Tenax? as a food simulant. The P/B samples contained only low levels of diisopropylnaphthalene (DiPN) and diisobutyl phthalate (DiBP) and so the experiments were conducted after impregnating the P/B with added model substances. These were o-xylene, acetophenone, dodecane, benzophenone, DiPN and DiBP. Migration levels depended strongly on the nature of the substance and on the nature of the food and much less on the characteristics of the P/B, except insofar as they affected the contact area – flexible papers giving more extensive contact with the food than thick rigid board. Migration into Tenax? was at least a factor of 10 higher than migration into the fresh fruit and vegetables. The food samples were placed in contact with the P/B and then overwrapped loosely with aluminium foil and so this correction factor will tend to be conservative compared with a more open storage of the packed foods. Washing, peeling or cooking the fruits and vegetables after contact with the P/B had a surprisingly small effect on contaminant levels in general, and no one processing step was effective in giving a significant reduction of all the types of chemicals studied. This was because either they had penetrated into the food (so resisting peeling), or were not freely water-soluble (so resisting washing) or were not particularly volatile (so resisting loss by evaporation during cooking).     

快速检测羟自由基的试纸开发

目的 开发用试纸条检测羟自由基(·OH)的方法,并用该方法检测具有抗氧化活性能力的抗氧化物质。方法 利用Fenton反应的原理,优化了羟基萘酚蓝(Hydroxynaphthol blue, HNB )、浓度、显色剂的浓度、pH、金属离子和H2O2等条件,并测定产生的羟自由基产生量。检测H2O2,观察试纸的颜色变化。结果最佳试纸条件为： Mn2+的浓度是2×10-6 mol/L、pH 10.5的(NaOH-KHCO3缓冲溶液)、HNB浓度为5×10-3 mol/L、H2O2溶液浓度是0.15 mol/L,以硫尿、甘露醇为对照,以优化试纸条件检测H2O2,验证其可以检测具有抗氧化活性能力的抗氧化物质。 结论 所建立的试纸检测方法简单、方便、快速,可用于现场抗氧化物质清除率羟自由基(·OH)活性的快速检测方法。