The Barrier Effect of EVOH versus 1,4,7‐Triaxocyclotridecane‐8,13‐Dione,a Non‐intentionally Added Compound from Polyurethane Adhesives in Multilayer Food Packaging

The presence and migration of non‐intentionally added substances in food packaging materials are the big concerns nowadays in terms of food safety, and the identification and quantitation are an important analytical challenge. Among non‐intentionally added substances, 1,4,7‐trioxacyclotridecane‐8,13‐dione, a by‐product resulting from the interaction between ingredients in many polyurethane adhesives, has been identified and quantified. Migration tests were carried out with food simulant E (Tenax®) and 3% acetic acid (simulant B) stored at 40°C/10 days using different adhesives and with different film thickness in the presence and absence of EVOH layer. After the exposure, Tenax® was extracted and analysed by gas chromatography with mass spectrometry. For 3% acetic acid, the analyses were directly performed by the Acquity® ultra‐performance liquid chromatography system coupled to triple quadrupole mass spectrometer detector. A possible degradation of the lactone after migration tests with 3% acetic acid occurred, and total degradation after 8 days was confirmed. Two compounds were detected and identified, which were also found in the migration extracts. Partition experiments were carried out from laminates composed by polypropylene film, adhesive and non‐treated polyethylene film at 40°C for 10 days. After this, the polypropylene/adhesive and polyethylene layers were independently extracted and analysed by gas chromatography with mass spectrometry. Diffusion studies were carried out following the Moisan procedure. The results and conclusions are shown and discussed.     

Migration of alkylbenzenes from packaging into food and Tenax®

Alkylbenzenes (alkyl chain C₁₀–C₁₃) are used as solvent components in certain offset printing inks. Alkylbenzenes were identified from 10 out of 15 samples of offset‐printed food packaging made of board. Printed hamburger collars intended for hamburger restaurants had exceptionally high contents of alkylbenzenes (70–500 mg/kg). Most of the collars had varnish on both the printed surface and the non‐printed food contact surface. Migration of alkylbenzenes from the hamburger collar into a roll was 2 mg/kg. In another test, in which Tenax^® was used as simulant, the effect of a varnish layer on the food contact surface was studied. It was found that the varnish layer reduced migration by about 70%. Tests with Tenax^® as a food simulant resulted in higher migration than in tests with rolls. The European Commission has published a risk assessment report on alkylbenzenes. The report concludes that there is no need for further testing or for risk reduction measures beyond those which are currently applied. However, consumer exposure was calculated without taking into account the possibility of oral exposure to alkylbenzenes migrating from food packagings. The migration of alkylbenzenes thus merits further study. Copyright © 2001 John Wiley & Sons, Ltd.     

Effect of processing method on migration of antioxidant from HDPE packaging into a fatty food simulant in terms of crystallinity

Migration of additives from plastic packaging into food products is generally considered to be affected by polymer crystallinity. In the present work, migration of Irganox 1010 from high density polyethylene into a fatty food simulant (ethanol 95%) was studied for samples prepared with different percent crystallinities. For this purpose, 2 different processing techniques, injection and compression molding, were used, and the preparation conditions were changed to obtain high density polyethylene samples with crystallinities in the range of 50 to 70%. Migration analysis was carried out at 121°C for 2 hours, and then at 40°C for 238 hours using high performance liquid chromatography. In general, the injection molded specimens had lower crystallinity and higher overall migration than the compression molded ones. A similar trend for both injection and compression molded samples was observed indicating that the overall migration was a function of crystallinity degree. However, the specific migration rates of Irganox 1010 especially before 50 hours were found to be different for the 2 processing methods because of dissimilar morphologies. Theoretical modeling based on Fickian diffusion was applied to give more insights into the involved processes during specific migration. The interaction of the food simulant with the polymer was taken into account considering the food sorption into the polymer. By fitting the model on experimental data, it was possible to obtain the model parameters such as partition coefficients (K) and the swelling constant (B) as a function of sample crystallinity.     

Migration Model of Toxic Metals from Ceramic Food Contact Materials into Acid Food

Migration studies of lead and cadmium from ceramic food contact materials into acid food simulants were conducted under various time–temperature conditions to investigate the kinetics of the leaching of lead and cadmium. A mathematical model based on one‐dimensional Fickian diffusion theory was derived in order to describe the migration behaviour of lead and cadmium. Moreover, diffusion coefficients of toxic metals were obtained by fitting the short‐time (24 h) migration data to the model. Comparisons of model solutions with experimental data obtained from the medium‐time tests (up to 600 h) and long‐time tests (up to 130 days) were carried out to verify the proposed model and the values of diffusion coefficients obtained from the short‐time test. Results show that the model fits the experimental data obtained under 20 and 40°C well but fails to fit the experimental data at 60°C. This indicates a change of the migration mechanisms from ion exchange to glass network dissolution as a result of higher temperature. Furthermore, results of migration experiments also reveal that the effects of temperature on the diffusion of lead and cadmium follow the Arrhenius law and that the leaching amounts of lead and cadmium decrease with pH value of the food simulant. Copyright © 2015 John Wiley & Sons, Ltd.     

Migration of Aluminum and Silicon from PET/Clay Nanocomposite Bottles into Acidic Food Simulant

Poly(ethylene terephthalate) (PET)/clay nanocomposite samples were prepared by melt blending PET and Cloisite 20A nanoparticles. A stretch blow‐moulding machine was used to produce bottles from neat PET and PET nanocomposite. Tests were performed on the migration of aluminum and silicon from PET nanocomposite bottles into acidic food simulant. The samples were stored at room temperature (about 25°C) and 45°C for time durations ranging from 7 to 90 days. A specific surface of sheets (prepared from PET/clay nanocomposite) immersed in acidic food simulant, and two‐sided migration of Al and Si was investigated. According to X‐ray diffraction analysis, the nanoclays show intercalated structure in the PET matrix. Transmission electron microscopy and atomic force microscopy micrographs displayed both intercalation and exfoliation morphology for PET/clay nanocomposites. Inductively coupled plasma was used to quantify amounts of Al and Si that had migrated into the acidic food simulant. It was observed that the migration process is dependent on storage time and temperature, and the molar ratio of aluminum and silicon in the acidic aqueous solution (Al/Si)_aq to the ratio in the solid phase of prepared nanocomposites (Al/Si)_solid was about 23% higher in the samples stored at 45°C. Copyright © 2013 John Wiley & Sons, Ltd.     

Migration of Acrylic Monomers from Methacrylate Polymers – Establishing Parameters for Migration Modelling

Acrylic acid‐based and methacrylic acid‐based monomers are widely used for the manufacture of polymers, for polymer dispersions or for other specialty resins. Some of these applications cause interactions between the polymer and contact medium such as food contact materials, eyeglasses, contact lenses or toys. More specifically, migration of monomers from the polymer into the contact medium may occur, which needs to be evaluated for safety purposes. The objective of this study was to investigate the basic diffusion properties of acrylic polymers with respect to representative monomers in order to establish a scientific basis for migration modelling simulating the mass transport of monomers from the polymers when they are in contact with foods, human skin or body fluids such as sweat and saliva. For this purpose, 11 representative acrylic polymers containing five different acrylic monomers (MA, EA, BA, MMA and nBMA) were studied in extensive kinetic migrations experiments in contact with five different contact media (simulants) at three different temperatures (20°C, 40°C and 60°C). The simulants were selected according to the applications: toys were simulated by saliva simulant and articles coming in contact with human skin by sweat simulant. For food contact applications, water (aqueous foods), Miglyol 840 (Sasol, Witten, Germany) (fatty food) and Tenax® (Sigma‐Aldrich Corporation, Munich, Germany) (an adsorbent simulating dry foods) were selected. The diffusion coefficients (D) of the monomers in the polymer as well as partition coefficients between polymer and contact media were derived. It was found that those acrylic polymer materials used for rigid plastics applications exhibit extremely low diffusion behaviour, whereas acrylic polymer resins used for coating applications showed somewhat higher diffusion behaviour but this still at very low rates in comparison with other typical polymers used for the manufacture of food packaging materials. As a result, conservative polymer‐specific constants in support of migration modelling were established, and the specifications for the model general applicability were determined and specified. The parameter related to the polymers' intrinsic mobility is applicable to model migration of any other organic chemical substances, which may be present in acrylic polymers as potential migrants when they have comparable or higher molecular weights than the studied monomers. Copyright © 2012 John Wiley & Sons, Ltd.     

Application of a computer model to evaluate the ability of plastics to act as functional barriers

A simulation model computer program, which accounts for not only the diffusion process inside the polymer but also partitioning of the contaminant between the polymer and the contacting phase, was developed based on a numerical treatment, the finite element method, to quantify migration through multilayer structures. The accuracy of the model in predicting migration was demonstrated successfully by comparing simulated results to experimental data. For this study, three‐layer co‐extruded high density polyethylene (HDPE) film samples, having a symmetrical structure with a contaminated core layer and virgin outer layers as the functional barriers, were fabricated with varying thickness of the outer layers and with a known amount of selected contaminant simulant, 3,5‐di‐t‐butyl‐4‐hydroxytoluene (BHT), in the core layer. Migration of the contaminant simulant from the core layer to the liquid food simulants was determined experimentally as a function of the thickness of the outer layer at different temperatures. The computer program, developed as a total solution package for migration problems, can be applied not only to multilayer structures made with the same type of plastics but also to structures with different plastics, e.g. PP/PE/PP. This work might provide the potential for wider use of recycled plastic, especially polyolefins, which have lower barrier properties, in food packaging, and simplification of the task of convincing the FDA that adequate safety guarantees have been provided. Copyright © 2003 John Wiley & Sons, Ltd.     

微波条件下PVC食品保鲜膜中DNBP在水基模拟物中的迁移行为研究

以气相色谱-质谱联用技术为分析手段,研究了在微波条件下PVC食品保鲜膜中DNBP在3种水基食品模拟物中的迁移规律。实验结果表明,DNBP的迁移量随微波功率、加热时间和加热温度的增加而增大,并与食品模拟物的种类有关;当加热温度和加热时间相同时,微波加热条件下DNBP在3种食品模拟物中的迁移量均高于常规加热方式。     

Determination of ϵ‐caprolactam migration from polyamide plastics: a new approach

A new gas chromatography method for determination of ?‐caprolactam (CPR) migration from packaging materials such as: polyamide (PA) films, PA granulates, PA/PE (polyethylene) laminates, PA casings, etc., to food simulants has been developed. Water, 3% w/v acetic acid, 15% and 95% v/v ethanol and olive oil have been used as a food simulants. Using the 1,4‐butanediol (BUG) as an internal standard (instead of aza‐2‐cyclononanone), calibration curves were constructed. Very good separation of CPR from BUG was achieved by using a Nukol fused silica capillary column (Supelco), 25 m × 0.32 mm. The time of analysis is shorter than 12 min: 7.69 min for BUG and 11.60 min for CPR. The regression line equation for CPR migration to water is: y = 0.080x + 0.14; to olive oil: y = 0.010x. The sensitivity of the developed method is appropriate for the quantitative determination of CPR in an analyte concentration of approximately 0.2 mg/kg, when the specific migration limit (SML) for this compound, according to Directive 90/128/EEC, is 15 mg/kg food simulant. Copyright © 2001 John Wiley & Sons, Ltd.     

Degradation of Irgafos 168 and migration of its degradation products from PP‐R composite films

Food contact materials contain non‐intentionally added substances from degradation, and reaction processes could rise food safety problems. Three polypropylene random copolymer composite films were prepared by extruding the polypropylene random copolymer matrix with Irgafos 168, Irgafos 168 and nanocopper, Irgafos 168 and KH550 modified nanocooper, respectively. To evaluate the degradation behaviors of Irgafos 168, the films were treated by UV irradiation, microwave treatment, sunlight exposure, placed in different oxygen concentration conditions, suffered the extrusion process, and high temperature. Migration test was conducted at 20°C, 40°C, and 70°C with films tested in food simulant. GC‐MS was adopted to determine the concentration of Irgafos 168 and its two degradation products, 2,4‐di‐tert‐butylphenol (DP1) and tris (2,4‐di‐tert‐butylphenyl) phosphate (DP2). UV irradiation significantly accelerated the degradation of Irgafos 168 compared with other treatments; DP1 and DP2 increased to maximum value at 24 hours and decreased afterwards, simultaneously. The introduction of nanocopper notably promoted DP1 generation after extrusion whereas suppressed DP2 generation which also caused a higher degradation rate of Irgafos 168 and sharp decrease of DP1 under microwave treatment, sunlight exposure, and high temperature treatment. No significant difference between the effects of nanocopper and KH550 modified nanocopper on degradation of Irgafos 168 was found. For the migration test, the introduction of nanocopper inhibited the migration of Irgafos 168 and DP2 whereas promoted the migration of DP1. No significant difference between the introduction of nanocopper and KH550 modified nanocopper on migration of Irgafos 168 and DP1, DP2 was found.     

Migration of di‐(2‐ethylhexyl)adipate (DEHA) and acetyl tributyl citrate (ATBC) plasticizers from PVC film into the food stimulant of isooctane

Chemical migration from food packing is influenced by several factors such as nature of chemicals, complexity of food, temperature, packing material used and properties of the migrating substances. Chemical compounds that are incorporated within polymeric packaging materials may interact with food components during processing or storage and migrate into the food by jeopardizing the food safety. This migration is higher if food remains in contact with packing material for extended time. Polyvinyl chloride (PVC) film such as di‐(2‐ethylhexyl) adipate (DEHA) and acetyl tributyl citrate (ATBC) are still widely used as a food packing material due to its flexibility, transparency and low water permeability. The present study covers the main migration phenomena of both plasticizers (di‐(2‐ethylhexyl) adipate (DEHA) and acetyl tributyl citrate (ATBC)) from PVC‐film into isooctane food stimulant using a direct gas chromatographic method. An exposure period of 48 h at 30 °C and 4 °C was used. The obtained results showed DEHA levels ranging of 7.2 mg/dm² while, no ATBC migration from PVC‐film was observed. Results are discussed in relation to EU legislation proposed upper limit for DEHA specific migration (18 mg/L or 3 mg/dm²) and overall migration limit (OM) of 10 mg/dm².     

Migration of Cyclic Monomer and Oligomers from Polyamide 6 and 66 Food Contact Materials into Food and Food Simulants: Direct Food Contact

Cyclic monomer and oligomers are the major migrating substances from polyamide (PA) food contact materials. An increase of caprolactam (+44%) and cyclic oligomer content (+27%, incl. caprolactam) in PA6 was observed by thermal treatment, here by extrusion of a PA6 film from a granulate. Migration experiments with a PA6 and a PA66 packaging film were carried out into food simulants according to directives 85/572/EEC and 82/711/EEC. Contact conditions (2 h/100°C) were chosen for a heat treatment of the food in the packaging, in this case production of scalded sausage. Aqueous and ethanolic food simulants clearly revealed to be the worst case for migration of cyclic PA6 and PA66 monomer and oligomers. Migration of cyclic oligomers into oil was one order of magnitude lower. No migration could be observed into isooctane (<8 µg dm^?2). The substitutes for oil, 95% ethanol and isooctane, were inapplicable for simulating migration of cyclic oligomers into oil. Caprolactam showed different migration behaviour compared with cyclic oligomers, migrating into oil and water to the same extent depending on contact conditions. Fifty percent of the extractable caprolactam migrated from a PA6 sausage casing into scalded sausage (4.2 mg kg^?1), residual 41% apparently were extracted by the boiling medium or during pretreatment (soaking) of the casing. Potential migration of caprolactam and cyclic oligomers from a PA6 tea bag was found to be 18% of the specific migration limit for caprolactam and 36% of the overall migration limit. Copyright © 2014 John Wiley & Sons, Ltd.     

Potential of migration of active compounds from protein‐based films with essential oils to a food and a food simulant

Migration tests at different temperatures and storage periods were performed to evaluate the release of active compounds from active whey protein films (WPFs) to a food and food simulants. Whey protein film incorporated with different levels of an optimized essential oils (EOs) blend (1%, 2%, 2.7%, and 5%, w/w) were prepared by casting. This blend contained EOs from rosemary and 2 species of cinnamon. Salami was packaged with WPF and stored during 180 days at 5°C. Temperature influenced significantly the migration of compounds (P<.1). It was observed that eucalyptol was the compound that presented the highest potential of migration into 95% ethanol (v/v). After contact of film with salami, it was observed that, in general, more than 50% of active compounds released from WPF to salami. It was observed that higher amounts of active compounds were released to salami than to fatty food simulant. Results suggested that the release of compounds depends on their affinity with the food/food simulant, temperature, their concentration in packaging, and composition of food. Active packaging may ensure the quality of food due the migration of compounds from EO with antimicrobial and antioxidant activity incorporated in the film to the foodstuff.     

Evaluating the potential of nanoparticles for controlling zinc stearate release from low‐density polyethylene into food simulants

The present study addressed the effect of polymer nanocomposites with different loading contents of fume silica (nanospheres) and nanoclay (nanosheet) on migration of zinc stearate from packaging materials into food simulants. Specific migration levels of zinc stearate from neat low‐density polyethylene (LDPE) and LDPE/nanocomposites into two food simulants stored at 40°C for 10 days were determined by gas chromatography coupled with flame ionization detector. Differential scanning calorimetry (DSC) analysis showed that incorporation of nanoparticles, especially at 1 wt% loading level of nano silica, noticeably increased degree of crystallinity, which significantly reduced water vapour permeability. Nanocomposites had a lower migration of zinc stearate in comparison with neat polymer. Additionally, results of this study revealed that physical properties of the food simulant had dominant effect on migration of zinc stearate.     

Mass transport studies of different additives in polyamide and exfoliated nanocomposite polyamide films for food industry

The development of new food packaging films through the incorporation of nanoparticles, and the effect of the nanoparticles on the process of migration of the substances used in manufacturing the new films is expected to lead to an improvement in the shelf life of food and thus, consumer safety and health. In recent years, attention has focused on nanocomposites because these compounds often exhibit unexpected hybrid properties derived from synergistic reactions between nanoparticles and the polymeric matrix. The exfoliation of nanoclays in polyamide film provides a film with better barrier properties than that obtained through the intercalation of nanoclays. Migration of chemicals from food packaging into food may produce potential adverse health effects because of exposure to toxic compounds. The present study addressed the migration of caprolactam, 5‐Chloro‐2‐(2,4‐dichlorophenoxy)phenol (triclosan) and trans,trans‐1,4‐diphenyl‐1,3‐butadiene (DPBD) from polyamide and polyamide‐nanoclays to different types of food simulants. The values for limit of detection (LOD) obtained for caprolactam, triclosan and DPBD was 0.5 mg/L, 0.02 mg/L and 0.01 mg/L, respectively. Furthermore, instrumental precision was evaluated through repeatability injections, resulting in relative standard deviations lower than 3.08%. Diffusion coefficients were calculated according to a mathematical model based on Fick's Second Law, and the results were discussed in terms of the parameters that may have the greatest effect on migration. The presence of polymer nanoparticles was found to slow down the rate of migration of substances from the matrix polymer into the food up to six times. Copyright © 2009 John Wiley & Sons, Ltd.     

化学物在食品和包装系统中分配系数的一种近似处理

对化学物在食品和包装系统中的分配系数进行了研究.应用一种近似方法得到分配系数对化学物迁移过程的影响.以BHT向模拟食品(酒精)的迁移为例,验证了该近似方法的准确性.该方法为分配系数应用于化学物迁移过程提供了简洁有效的途径.     

Effect of high‐pressure food processing on the mass transfer properties of selected packaging materials

The effect of high‐pressure processing (HPP) on the total migration into distilled water and olive oil and on the barrier properties of four complex packaging materials were evaluated. The films were polyethylene/ethylene‐vinyl‐alcohol/polyethylene (PE/EVOH/PE), metallized polyester/polyethylene, polyester/polyethylene (PET/PE), and polypropylene‐SiOx (PPSiOx). Pouches made from these films were filled with food simulants, sealed and then processed at a pressure of 400 MPa for 30 min, at 20 or 60°C. Pouches kept at atmospheric pressure were used as controls. Prior to and after treatment, all films were evaluated for their barrier properties (oxygen transmission rate and water vapour transmission rate) and ‘Total’ migration into the two food simulants. In the case of water as the food stimulant, a low ‘Total’ migration was observed and even a lower one after the HPP treatment. In the case of oil as the food simulant, a higher ‘Total’ migration was found compared to the control as a result of damage to the structures during the HPP treatment. The gas permeability of the films increased after the HPP, compared to the control, due to damages in the structure caused during the treatment. The PET/PE film presented minimum changes in properties after HPP. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of high‐pressure processing on selected polymeric materials and on the migration of a pressure‐transmitting fluid

This study investigated the migration of 1,2‐propanediol (PG) through selected food packaging films exposed to high‐pressure processing (HPP). Pouches made from these materials were filled with 95% ethanol as a food‐simulating liquid. These packages were then processed using a pilot‐scale high‐pressure food processor at 400, 600 and 827 MPa and 30, 50 and 75°C for 10 min. Controls were processed at similar temperatures and times, but at atmospheric pressure. To investigate any structural changes to these films during HPP, water was used as the food simulant at temperatures of 30, 75, 85, 90 and 95°C and at pressures of 200, 400, 690 and 827 MPa. No detectable PG migration into the polyester/nylon/aluminium (Al) polypropylene (PP) meal‐ready‐to eat (MRE)‐type pouches was observed. PG migration into the nylon/ethylene vinyl alcohol (EVOH)/PE (EVOH) pouches was similar at 30, 50 and 75°C after 10 min under atmospheric pressure. However, PG migration into the EVOH pouches significantly decreased when treated with high pressure at 30, 50 and 75°C. At 75 and 50°C, the PG migration was significantly higher than the amounts detected at 30°C. Visible signs of delamination between the polypropylene (PP) and aluminum (Al) layers were observed in the MRE pouches processed at ≥200 MPa and 90°C for 10 min. This delamination appeared to occur between the PP and Al layers. The differential scanning calorimetric analyses and Fourier transform infrared (FTIR) spectra were similar for the high‐pressure treated pouches when compared to their respective controls. This indicated that there were no HPP‐induced molecular changes to the treated pouches. Results from this study should be useful to HPP users for predicting PG migration trends and in deciding the selection of appropriate packaging materials for use under similar processing conditions. Copyright © 2002 John Wiley & Sons, Ltd.     

Electrospray Ionization‐Mass Spectrometry Analysis Reveals Migration of Cyclic Lactide Oligomers from Polylactide Packaging in Contact with Ethanolic Food Simulant

Electrospray ionization‐mass spectrometry analysis revealed rapid migration of cyclic oligomers from polylactide (PLA) packaging when stored in contact with 96% ethanol. The mass losses in contact with water, 3% acetic acid, 10% ethanol and isooctane were 3 to 5 times smaller and no migration of cyclic oligomers was observed. The presence of cyclic oligomers in the original PLA films and their solubility in ethanol, thus, explains the rapid mass loss for PLA in contact with ethanolic food simulant. On prolonged ageing no further mass loss was observed in 96% ethanol, whereas mass loss in aqueous food simulants increased because of hydrolysis of PLA matrix or the cyclic oligomers to water‐soluble linear products. The mass losses were generally somewhat smaller for the stereocomplex material compared with the poly‐l ‐lactide materials. Similar trend was observed for solvent uptakes, which is easily explained by the higher degree of crystallinity and stronger secondary interactions in the stereocomplex material. The use of ethanol as a fatty food simulant for PLA materials could, thus, lead to overestimation of the overall migration values. Copyright © 2012 John Wiley & Sons, Ltd.     

Suitability of alternative fatty food simulants to study the effect of thermal and microwave heating on overall migration of plastic packaging

The suitability of alternative fatty food simulants on overall migration determination under thermal treatment and microwave heating were analysed for different plastic materials commonly used for packs subjected to thermal treatment or microwave heating. Elevated temperature and microwave heating increased overall migration. The results demonstrated that polymer–simulant affinity plays a large role in determining the suitability of the alternative simulant. For PA/PE, ethanol 95% represented the best alternative fatty food simulant to reproduce overall migration with olive oil. PVC presented a high overall migration. Microwave heating increased migration up to 45 mg/dm². For PVC, isopropanol was able to reproduce olive oil even after microwave heating. For PP, none of the alternative fatty food simulants were able to reproduce overall migration with olive oil. PP presented high inert behaviour. Microwave heating did not produce a significant increase in overall migration; meanwhile, the time of exposure produced a more significant migration. Copyright © 2004 John Wiley & Sons, Ltd.