Required barrier efficiency of internal bags against the migration from recycled paperboard packaging into food: a benchmark

The use of recycled paperboard and corrugated board for food packaging is in the interest of the sustainability of resources, but in most applications the food must be protected against contamination from these materials, such as by an internal bag with a functional barrier. Producers of packaging need a specification to find the most suitable and economical barrier for a given application, and the customer needs the confidence that a solution offered to him is adequate. An accurate determination of the barrier efficiency is not possible due to the large number of migrants, most of which have not been evaluated or not even identified. Hence the specification must be based on assumptions and verifiable by a simple test. The proposed benchmark presumes that the migration of all non-evaluated or even unknown substances in recycled paperboard will remain below 0.01 mg kg^–1 food, the conventional detection limit, if their transfer does not exceed 1% of the content in the paperboard. Some substances, such as mineral oil or fatty acids, will exceed the 0.01 mg kg^–1 limit, but they are known, evaluated and of no concern at the reduced migration. Since the critical substances must be assumed to be unknown, the criterion of the 1% migration is tested with three surrogate substances of similar volatility and covering a broad range of polarity. The cornerstones of the method are specified.     

Activated carbon added to recycled paperboard to prevent migration into food: approach for determining efficacy,and first results

Catcherboard MB12® from Smurfit Kappa is a recycled paperboard incorporating activated carbon to reduce the release of contaminants into food. An approach is proposed to determine the efficacy of the activated carbon. Sorption into activated carbon increases the concentration ratio paperboard/food (distribution coefficient) and reduces the migration rate, i.e. prolongs the time for equilibration. Using silicone paper as food simulant, the concentration ratio was increased by a factor of at least 1000 compared to recycled paperboard without activated carbon, which is sufficient to meet the 1% criterion proposed for barriers. Sorbents have limited capacity. A load with in total 4000 mg surrogate substances/kg paperboard (in addition to the material from the paperboard) exceeded the capacity: concentration ratios were reduced and the release of paperboard constituents increased. Capacity is consumed by constituents from the printing inks and the packed food. Total amounts of substances in dry foods of sufficient volatility to potentially migrate into the paperboard through the gas phase at ambient temperature were determined by GC-FID. For the large majority of the dry foods, these amounts were clearly below the capacity limit even under the exaggerated assumption of total transfer. Migration of mineral oil hydrocarbons into cat food over up to 1 year was not detectable at 1 mg/kg. It is concluded that recycled paperboard with activated carbon is promising for respecting the 1% criterion stipulated for functional barriers to avoid food contamination from recycled paperboard.     

Internal bags with barrier layers for foods packed in recycled paperboard: recent progress

Internal bags for packaging dry foods into boxes of recycled paperboard, collected in Dresden and Zurich in June 2013, were investigated with regard to the layer composition and the barrier efficiency against substances migrating from the recycled fibers. The layers were identified by microtome cuts and Fourier transform infrared spectroscopy, often after wet-chemical separation of the layers. The barrier efficiency was tested with five surrogate substances and classified between 1 and 5, with class 1 having no significant barrier effect, 4 being a virtually tight barrier consisting of polymeric material and 5 including an aluminum foil. Merely 17 of the 87 bags (20 %) consisted of paper or polyethylene that constituted insignificant barriers. Bags of oriented polypropylene, substantially reducing migration (class 2), were encountered in 32 % of the packs; those with more efficient, but still incomplete barriers (class 3) in 16 % and virtually tight barriers (classes 4 and 5) in 32 % of the products. This is a strong move toward efficient barriers compared to the findings in 2010. Efficient or tight barriers were found for nearly all food types, which suggests that there are no important technical obstacles against the inclusion of a barrier layer into all bags to protect the food against contamination from the recycled paper board.     

Migration of mineral oil,photoinitiators and plasticisers from recycled paperboard into dry foods: a study under controlled conditions

Migration from recycled paperboard was monitored after 2, 4 and 9 months of storage for six test foods industrially packed in five configurations, four with internal plastic films. After 9 months, the migration of mineral oil saturated hydrocarbons into foods directly packed in the paperboard amounted to 30–52 mg/kg, which corresponded to 65%–80% of those of a volatility up to that of the n-alkane C₂₄ in the paperboard. The concentration of the migrated aromatic hydrocarbons in the foods ranged from 5.5 to 9.4 mg/kg. More than half of this migration occurred in the first 2 months. Differences between the foods amounted to mostly less than a factor of 2 and seemed to be related to porosity or permeability more than fat content. Nine photoinitiators were detected in the paperboard, of which eight migrated into the packed food at up to 24%. Several plasticisers were present in the recycled paperboard, but only butyl phthalates showed significant migration. After 9 months, up to 40% of diisobutyl phthalate and 20% of dibutyl phthalate migrated into the food with direct contact. The internal polyethylene film hardly slowed migration, but the film and the tray absorbed approximately three times more mineral oil than the food, despite constituting merely 4% of the mass of the pack. Oriented polypropylene strongly slowed migration: The highest migration of saturated hydrocarbons measured after 9 months (2.3 mg/kg) corresponded to only 3% of the content in the paperboard and included migrated polyolefin oligomeric saturated hydrocarbons. Coating of polypropylene with an acrylate further slowed the migration, but the migration from the paperboard was still detectable in four of the six samples. Polyethylene terephthalate was a tight barrier.     

Migration of perfluoroalkyl acids from food packaging to food simulants

A broad range of fluorochemicals is used to impart oil and water barrier properties to paper and paperboard food packaging. Many of the fluorochemicals are applied to paper and paperboard as complex mixtures containing reaction products and by-products and unreacted starting materials. This work primarily focussed on the determination of seven perfluorocarboxylic acids (PFCAs) in two commercially available food contact papers: a di-perfluoro-alkyloxy-amino-acid and a perfluoroalkyl phosphate surfactant. In addition, the migration of the PFCAs into five food simulants from two commercial packages was evaluated. All seven PFCAs were detected in the range of 700–2220 µg kg^?1 of paper, while three perfluoroalkyl sulphonates were under the LOD. Results from migration tests showed that migration depends on paper characteristics, time and food simulant. The percentage of migration after 10 days at 40°C ranged from 4.8% to 100% for the two papers and different food simulants.     

Identification of print-related contaminants in food packaging

Since the UV ink photoinitiator (PI) isopropylthioxanthone (ITX) was discovered in packaged milk, studies of print contamination have focused primarily on PIs but have also included amine synergists. Many other substances are used or formed during the print process, yet their identity and set-off properties have yet to be catalogued in food packaging. Three different techniques: direct analysis in real-time high-resolution mass spectrometry (DART-HRMS), gas chromatography-mass spectrometry (GC-MS) and ultra-high-pressure liquid chromatography electrospray ionisation/HRMS (UHPLC/ESI-HRMS) were used to detect and identify print-related molecules from the food-contact and print surfaces of three different packages with under-cured prints. This approach tentatively identified or confirmed 110 compounds, including 35 print-related molecules. The majority of compounds identified on food-contact surfaces were packaging monomers/byproducts, solvents/plasticisers, antioxidants/degradants or slip agents/lubricants. Of these, 28 showed evidence of set-off. The identities of 16 PIs, seven known scission products and five probable PI degradants were confirmed, most showing signs of set-off. Of the print-related molecules, at least five are novel print contaminants such as 4-morpholin-4-yl-benzaldehyde or 3-phenyl-2-benzofuran-1(3H)-one.     

Migration of mineral oil from party plates of recycled paperboard into foods: 1. Is recycled paperboard fit for the purpose? 2. Adequate testing procedure

Party plates made of recycled paperboard with a polyolefin film on the food contact surface (more often polypropylene than polyethylene) were tested for migration of mineral oil into various foods applying reasonable worst case conditions. The worst case was identified as a slice of fried meat placed onto the plate while hot and allowed to cool for 1?h. As it caused the acceptable daily intake (ADI) specified by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) to be exceeded, it is concluded that recycled paperboard is generally acceptable for party plates only when separated from the food by a functional barrier. Migration data obtained with oil as simulant at 70°C was compared to the migration into foods. A contact time of 30?min was found to reasonably cover the worst case determined in food.     

Simulation of the migration of mineral oil from recycled paperboard into dry foods by Tenax®?

Conventional migration testing for long-term storage at ambient temperature with Tenax^® was applied to a recycled paperboard as well as to the same paperboard with a polyethylene or polypropylene film in between. Test conditions were from the European Union plastic Regulation 10/2011, that is, 10 days at 60°C, but previous standard conditions of 10 days at 40°C were also applied. The results were compared with the migration into real packs made of the same packaging material containing six test foods and stored over 9 months. For the direct contact, simulation at 60°C overestimated the maximum migration of the saturated hydrocarbons in the real packs by 73%. Simulation reflected hardly any effect by the plastic films and resulted in an overestimation of the maximum migration into the real packs by a factor of 5.1 and 27 for the polyethylene and the polypropylene film, respectively. Analogous simulation was performed with polenta (corn semolina) instead of Tenax^®. Three main causes for this deviation were identified: (i) at 60°C, migration reached beyond n-C₃₅, whereas it ends at about n-C₂₄ in reality. (ii) Tenax^® is a far stronger adsorbent than foods, resulting in almost complete extraction. (iii) The significant barrier effect of polypropylene films at ambient temperature is lost at increased temperature. The suitability of such simulation for the prediction of long-term migration is questioned.     

Study of the migration of benzophenone from printed paperboard packages to cakes through different plastic films

Benzophenone is one of the most commonly used photoinitiators, which are mostly used in UV-cured inks for which drying times are much shorter than for conventional solvent or water-based coatings. Benzophenone levels were determined in different packaging materials used for cakes, to evaluate the safety of printed paperboard intended for food contact. For this, a simple extraction method and a rapid specific reverse-phase high performance chromatography method with UV detection were developed. Benzophenone was quantified in different samples by a rapid specific reverse-phase high performance chromatography method after extraction with acetonitrile at 70 °C for 24 h. A novel method for testing benzophenone diffusion towards plastics was also developed and different experiments were conducted in order to measure diffusion coefficients at 70 °C for 2 days and at 40 °C for 10 days. Polypropylene plastics sleeves were found not to be an effective barrier against benzophenone diffusion (3,800 μg/g of benzhophenone was found after 48 h at 70 °C in cakes protected with this film) whereas, the corresponding value in cakes wrapped with a multilayer film of PP/EVOH/PP was reduced to 1,400 μg/g, and the concentration of benzophenone in cakes wrapped with a multilayer film of PET/SiOx/PE was negligible.     

Functional barriers: Properties and evaluation

Functional barriers are multilayer structures deemed to prevent migration of some chemicals released by food-contact materials into food. In the area of plastics packaging, different migration behaviours of mono- and multilayer structures are assessed in terms of lag time and of their influence of the solubility of the migrants in food simulants. Whereas barriers to oxygen or to aromas must prevent the diffusion of these compounds under conditions of use, a functional barrier must also be efficient under processing conditions, to prevent diffusion of substances when the polymer layers are in contact at high (processing) temperatures. Diffusion in melted polymers at high temperatures is much slower for glassy polymers, than in polymers that are rubbery at ambient temperature. To evaluate the behaviour of functional barriers under conditions of use, a set of reference diffusion coefficients in the 40-60°C range were determined for 14 polymers. Conditions for accelerated migration tests are proposed based on worst-case activation energy in the 40-60°C range. For simulation of migration, numerical models are available. The rules derived from the models can be used both by industry (to optimize a material in terms of migration) or by risk assessors. Differences in migration behaviour between mono- and multilayer materials are discussed.     

SiO x layer as functional barrier in polyethylene terephthalate (PET) bottles against potential contaminants from post-consumer recycled PET

The barrier effect of a silicon oxide (SiO _x ) coating on the inner surface of PET bottles, in terms of the ability to reduce the migration of post-consumer compounds from the PET bottle wall into food simulants (3% acetic acid and 10% ethanol), was investigated. The barrier effect was examined by artificially introducing model substances (surrogates) into the PET bottle wall to represent a worst-case scenario. Test bottles with three different spiking levels up to ～1000 mg kg^?1 per surrogate were blown and coated on the inner surface. The SiO _x -coated bottles and the non-coated reference bottles were filled with food simulants. From the specific migration of the surrogates with different bottles wall concentrations, the maximum surrogate concentrations in the bottle wall corresponding to migration of 10 µg l^?1 were determined. It was shown that the SiO _x coating layer is an efficient barrier to post-consumer compounds. The maximum bottle wall concentrations of the surrogates corresponding to migration of 10 µg l^?1 were in the range of 200 mg kg^?1 for toluene and ～900 mg kg^?1 for benzophenone. Consequently, the SiO _x coating allows use of conventionally recycled post-consumer PET flakes (without a super-clean recycling process) for packaging aqueous and low alcoholic foodstuffs (under cold-fill conditions) and protects food from migration of unwanted contaminants from post-consumer PET.     

Analysis of Direct Contact Paper and Paperboard Food Packaging for N-nitrosomorpholine and Morpholine

Analytical methods were developed to estimate the nitrosatable morpholine and apparent N-nitrosomorpholine content of paper and paperboard direct contact food packaging. Examination of 34 different paper or paperboard food packages indicated 9 to be contaminated with detectable levels of apparent N-nitrosomorpholine. All 12 packages analyzed for nitrosatable morpholine were positive with an average level of 380 μg/kg. Migration of apparent N-nitrosomorpholine and morpholine to food was demonstrated when paper or paperboard and dry food were incubated in a closed container for 3 days at 100°C.     

Effectiveness of polypropylene film as a barrier to migration from recycled paperboard packaging to fatty and high-moisture food.

The capability of a polypropylene (PP) film barrier to prevent migration of residual contaminants from recycled paperboard into food simulants was studied. Anthracene, benzophenone, methyl stearate and pentachlorophenol were chosen as chemical surrogates to represent classes of contaminants likely to be found in recycled paper/paperboard. Each surrogate was spiked into a test specimen made of seven thin virgin paper layers at concentrations of 1-50 mg kg(-1). Test specimen were dried, stacked and sandwiched with PP films, laminated with PP film and then subjected to migration experiments using a compression cell maintained at 100 degrees C for 2 h. The concentration of the surrogates in the test specimen and in 95% ethanol, isopropanol and 10% ethanol food-simulating solvents was determined by gas chromatography with flame ionization and electron capture detection. The results show that although the concentrations of the surrogates in the food simulants decreased with an increase in PP film thickness, they were still high and generally resulted in dietary concentrations >0.5 microg kg(-1), the level that US Food and Drug Administration would equate with negligible risk for a contaminant migrating from food packaging. Only at the lowest spiking level (1 mg kg(-1) benzophenone) did migration from the paperboard through a 0.127-mm PP film result in a dietary concentration of 相似文献   

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.     

Migration of oligomers from PET: determination of diffusion coefficients and comparison of experimental versus modelled migration

ABSTRACT

Polyethylene terephthalate (PET) is increasingly used as food-contact material in, for example, containers for beverage such as bottles for soft drinks, mineral water, juices and beer. Mass transport of substances present in packaging materials into the packed food and beverages is monitored to verify the food law compliance of the materials. PET is known to contain or give rise to migrants that are oligomers derived from the polymeric material. Until now their actual migration potential has been investigated only poorly. A convenient way to determine their migration would be by using models. To verify existing models with experimental data, a migration kinetic study of PET oligomers was conducted. PET bottle material was submerged in 50% ethanol at 80°C for 15 h. The oligomer content in the migration solutions was determined every hour using LC-MS with the first-series cyclic PET trimer as standard. Diffusion coefficients of five PET oligomers (first-series dimer and trimer, second-series dimer and trimer, and third-series dimer) were calculated from the obtained data and compared with the calculated diffusion coefficients using the models of Welle and Piringer. This is the first study to provide diffusion characteristics of oligomers in PET other than the first-series cyclic trimer.     

Update on recycled paperboard and its compliance for food contact

The last 3 years brought much movement around the migration from recycled paperboard in general and of mineral oil in particular. It has been shown that it is unrealistic to ensure the safety of the many and variable migrants from recycled fibers. The toxicological evaluation of mineral oil remains uncertain, but the strong accumulation of certain saturated mineral hydrocarbons in human tissues might increase the concern. The draft of a German regulation on mineral oil migration from recycled paper and board struggles with the difficult analysis in food, but frequent measurement in food is avoidable if the compliance work can be based on citable systematic studies. In the discussions about potential solutions, the introduction of barriers prevails. Internal bags with barrier layers have been widely introduced. For packings without internal bags, barriers on the internal surface of the recycled paperboard have been developed, but not yet introduced into the market on broad scale. An agreed method for measuring barrier efficiency and a specification of minimum required efficiency are probably a prerequisite. Work for an industry standard on barriers is on-going in Switzerland.     

A review of dietary exposure and toxicological information on epoxidised soybean oil (ESBO) in food-contact applications

ABSTRACT

Plasticisers have a long history of use in the industrial manufacture and processing of polymers for the purpose of increasing the flexibility and strength of the material. Approximately, 80–90% of the plasticiser market is devoted to the production of PVC, a highly versatile thermoplastic used to produce both rigid and flexible articles. Many types of plasticisers, including ortho-phthalate esters (OPE), can be added to PVC to impart flexibility. Recently, alternatives to OPEs, such as epoxy esters and aliphatic adipates, are becoming more prevalent for use in PVC-based food-contact articles. Epoxidised soybean oil (ESBO) is used as a plasticiser in flexible PVC for many food-contact articles, including food packaging and food processing equipment, from which it can potentially migrate into food and become a component of an individual’s daily diet. The purpose of this review is to provide an update on the US dietary exposure and toxicological information on ESBO used in PVC-based food-contact articles. The cumulative dietary concentration (CDC) and cumulative estimated daily intake (CEDI) for ESBO from its use as a plasticiser in PVC-based food-contact articles (i.e. gaskets for glass jar lids and film wraps) was calculated to be 2.6 mg/kg (i.e. ppm) and 0.13 mg/kg bw/d, respectively, for the general population. Some regulatory agencies have reported safety levels for ESBO, and the most conservative no observed adverse effect level (NOAEL) was identified to be 100 mg/kg bw/d (i.e. 2000 ppm) based on a two-year feeding study in rats. The current CEDI is well below these levels, supporting the safe use of ESBO in food-contact applications.     

Mineral oil migration from paper-based packaging into food,investigated by means of food simulants and model substances

ABSTRACT

Mineral oil hydrocarbons (MOH) are known to be mixtures of non-identified substances, which can migrate from, inter alia, recycled food packaging into food products. Such substances may have carcinogenic potential, which leads to a need to avoid their migration into food. In this article, we investigate the possible use of food simulants and model substances to simplify migration approaches. Tenax and Sorb-Star were chosen as simulant media. To stage the action of known components as a replacement for the migration of MOH, 16 single substances, including n-alkanes and aromatic compounds, were used. Kinetic studies were carried out at a maximum of 60°C with contact times of up to 14 days in touching contact with a medium or in gas-phase transfer to it. The results demonstrated that migration was predominantly a function of temperature, time and contact type, but it was also dependant on the molecular weight and polarity of the substances. Due to their low polarity, alkanes showed higher migration to the lipophilic food simulants than did pure aromatics without alkylation. Additionally, alkylated aromatics represent mineral oil aromatic hydrocarbons (MOAH) more realistically. In contrast to Tenax in the gas-phase transition, Tenax in touching contact may lead to overestimated values at higher temperatures. Migration values for Sorb-Star are in similar regions for both contact types. However, the values of the touching contact experiments were slightly higher than those of the gas-phase transfer. The results for Sorb-Star and Tenax with transport solely over the gas phase are also in good agreement. Sorb-Star generally represents an optimal simulant for chunky foods, whereas Tenax seems a good simulant for food types with a high contact surface. Temperatures up to 40°C are appropriate for most types of migration experiments, whereas 60°C should only be used as an option for experiments with Sorb-Star.     

Test method for measuring non-visible set-off from inks and lacquers on the food-contact surface of printed packaging materials

The main objective was to develop a technique to expose spots of invisible set-off of inks and lacquers on the food-contact surface of food-packaging materials. Set-off is the unintentional transfer of components of printing inks from the outer printed surface onto the food-contact surfaces. The target sensitivity was 20 µg cm^-2 and the technique should be capable of examining large areas of printed substrate for no more than 4% coverage by set-off. These requirements equate to an ability to detect a worst-case migration potential of less than 50 µg kg^-1. Other objectives were the industrial requirements that the equipment should be inexpensive, should be easy to use by existing personnel and should preferably be non-destructive with a clear criterion for pass or fail. The approaches investigated included chemical analysis of solvent extracts, Fourier-transform infrared spectroscopy and microbeam analytical techniques, but these were found to be cumbersome and had only limited success. The objectives were achieved using an optical approach to excite and observe luminescence from invisible set-off. In model experiments, resins were applied to different substrates (plastic, paper and cartonboard). For a given resin on a given material, the key to success was to maximize the discrimination between the luminescence from the resin and that from the substrate by selecting the optimal combination of exciting wavelength and viewing goggles with selective wavelength filters. The required level of detection (20 µg cm^-2) was achieved or exceeded for all ten resins tested on three different plastics. It was also achieved for two different papers and in all but four cases of the resins on three different cartonboards. Quantitation was achieved by the use of a calibration palette prepared using different quantities of resin spotted onto the relevant blank packaging material.     

Hyperbaric storage at and above room temperature of a highly perishable food

Hyperbaric storage at naturally variable room temperature (RT) conditions (18–21 °C) and above (30 °C) was evaluated as a possible new food preservation method, regardless of temperature. Preservation of watermelon juice (used as a case study of a highly perishable food) at RT and 5 °C at atmospheric pressure was compared to preservation under 100 MPa at RT. After 8 h of hyperbaric storage at 100 MPa, the initial microbial loads of the watermelon juice were reduced by 1 log unit for total aerobic mesophiles, and 1–2 log units for Enterobacteriaceae and yeasts and moulds, to levels of about 3 log units for the former and below the detection limit for the latter, and remained thereafter unchanged up to 60 h. Similar results were obtained at 30 °C at 100 MPa after 8 h. At atmospheric pressure at RT (24 h) and 30 °C (8 h), microbial levels were already above quantification limits and unacceptable for consumption. Furthermore, pressure attenuated the increase in titratable acidity verified at atmospheric pressure, but caused higher colour changes, especially a higher lightness and a lower browning degree. Post-hyperbaric storage at 5 °C revealed an extended shelf life, as an additional benefit of hyperbaric storage. These results show that hyperbaric storage is a very promising food preservation methodology.