Safety assessment of paper and board food packaging: Chemical analysis and genotoxicity of possible contaminants in packaging

In order to identify potential genotoxicant(s) in recycled paperboard, samples were fractionated using multiple liquid/liquid extraction, and gel permeation chromatography, and analysed by gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry. The rec-assay was used as an indicator of genotoxicity. Genotoxicants in the recycled paperboard were identified as dehydroabietic acid (DHA) and abietic acid (AA). DHA and AA were detected in two out of five virgin products, and in all seven recycled products for food-contact use. Total amounts of DHA and AA were 240 and 990 µg/g in the virgin products and 200-990 µg/g in the recycled products. A good correlation was observed in the total amount of DHA and AA content determined in paper products and DNA-damaging activity. Moreover, genotoxic effects in paper products showed a good match with standard compounds, indicating that the genotoxic effects of these paper products was mostly attributable to DHA and AA.     

Migration of bisphenol A and benzophenones from paper and paperboard products used in contact with food

Migration of bisphenol A (BPA) and benzophenones, i.e., benzophenone (BZ), 4-(dimethylamino)benzophenone (DMAB), Michler's ketone (MK) and 4,4'-bis(diethylamino)benzophenone (DEAB), from 21 paper and paperboard products (15 recycled paperboard boxes and 6 virgin paper products) used in contact with food was examined. Migration levels of compounds from recycled paperboard were compared under various food-simulating conditions. BPA showed the highest migration into 20% ethanol and benzophenones into 95% ethanol. No compounds migrated from virgin paper products, but compounds did migrate into food simulants from recycled paperboard food boxes. BPA migrated into 20% ethanol from all recycled paperboard food boxes between 1.0 and 18.7 ng/mL. Into 95% ethanol, migration of BZ was observed in 8 samples (1.0-18.9 ng/mL), DMAB in 12 samples (1.2-3.7 ng/mL), MK in 13 samples (1.9-9.0 ng/mL), and DEAB in 13 samples (1.0-10.6 ng/mL). The highest migration level was 27.2 ng/mL and most of the migration levels were below 10 ng/mL. These values are sufficiently low compared with the TDI and NOAEL levels. Moreover, the amount of food in daily meals that comes into contact with paperboard products is relatively small. Consequently, it was concluded that there was no safety concern regarding the tested compounds in recycled paperboard food boxes.     

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   

Cell transformation activities of abietic acid and dehydroabietic acid: safety assessment of possible contaminants in paper and paperboard for food contact use

Abietic acid (AA) and dehydroabietic acid (DHA) have been detected in virgin paper products and recycled paper products used for food packaging. In order to evaluate the cell transformation activities of AA and DHA, the Bhas 42 cell-transformation assay for initiation and promotion was carried out. Tested in the initiation stage, AA and DHA did not significantly increase transformation frequencies. On the other hand, both chemicals induced transformed foci dose dependently at the promotion stage. The highest transformed foci density induced by AA was about 13 foci/well at 60 nmol ml^?1, and that of DHA was about 16 foci/well at 40 nmol ml^?1 (solvent control = 2.3 ± 1.4 foci/well). The present results suggest that AA and DHA may have tumour-promoting potential.     

Dietary exposure assessment of infants to bisphenol A from the use of polycarbonate baby milk bottles

The residual bisphenol A (BPA) levels in 28 different brands of polycarbonate (PC) baby milk bottles available in the Singapore market were measured. With a detection limit of 3 mg/kg, BPA residues were detected in 19 out of the 28 PC baby milk bottles at levels between 4.01 and 141 mg/kg, with a mean of 28.1 ± 31.4 mg/kg and a median of 17.2 mg/kg. The potential migration of BPA from each of the 28 PC milk bottles was also measured using food-simulating solvents and time conditions recommended by the US Food and Drug Administration (US FDA), but using temperatures more severe than actual use. The highest upper-bound mean BPA migration levels of 0.64 ± 0.48 µg/in² in 10% ethanol at 70°C and 0.43 ± 1.25 µg/in² in corn oil at 100°C were observed after incubating cut portions of the milk bottles for 240 h. With this migration data and using US FDA's procedure for estimation of dietary exposure, the worst-case dietary exposure assessment for the intake of BPA by infants between birth and three months of age was below the oral Reference Dose of 0.05 mg/kg bw/day established by the US Environmental Protection Agency. This study showed that the dietary exposure to BPA from actual uses of PC milk bottles is unlikely to pose a health risk in infants.     

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.     

Decontamination efficiency of a new post-consumer poly(ethylene terephthalate) (PET) recycling concept

The aim of the study was to investigate and evaluate the cleaning efficiency of a new recycling concept for post-consumer poly(ethylene terephthalate) (PET). The so-called Flake To Resin (FTR®) recycling process produces PET pellets or preforms from conventionally recycled PET flakes for the application in new PET packaging in direct food contact. The investigated process can be considered as 'super-clean' recycling process and was developed to introduce conventional recycled post-consumer (PCR) PET flakes up to an amount of 50% into the pellet and preform production. Within the study the cleaning efficiency of the investigated FTR process was determined by a challenge test. The experimental results obtained from three challenge tests with different input concentrations of the surrogates and different amounts of post-consumer PET flakes show that all applied surrogates are very efficiently removed by the investigated recycling process. The cleaning efficiencies for all surrogates are above 99.9%. In the final product of the process no surrogates could be determined above the detection limits (0.5 mg kg^-1) even if the initial concentrations were in the percentage range. From a migrational point the final product, which are either PET pellets or preforms, was similar to virgin PET. Only the PET typical substances acetaldehyde and ethylene glycol had slightly higher concentrations than found in a conventional PET virgin sample used as reference. The generally accepted migration limit of 10 µg kg^-1 for the surrogates in the final products of the challenge tests is established for all kinds of foodstuffs.     

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.     

Migration of monomers from liquid crystalline poly(p-hydroxybenzoic acid-co-2-hydroxy-6-naphthoic acid)

Liquid-crystalline co-polyesters (e.g. a random copolyester based on p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA) known as Vectra A950) offer good barrier properties, but for food-contact use require overall and specific migration testing. For Vectra A950 films, the highest overall migration level obtained was 2.3 mg kg^-1 in olive oil (10 days at 40°C) well below the EC limit of 60 mg kg^-1. The highest specific migration for p-hydroxybenzoic acid was 15.2 μg dm^-2 in olive oil (2h at 175°C). For 2-hydroxy-6-naphthoic acid, the highest value obtained was 4.3 μg dm^-2 in 10% ethanol (4h at 100°C), although it was not on the EC positive and cannot yet be used for food-contact materials. At conditions considered as severe, the estimated daily intake for p-hydroxybenzoic acid was calculated as 11.9 μg/person day^-1 and for 2-hydroxy-6-naphthoic acid it was 5.3 μg/person day^-1. The results exceed the threshold of regulation of 1.5 μg/person day^-1.     

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 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.     

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.     

Determination of acrylamide in coffee and coffee products by GC-MS using an improved SPE clean-up

An improved gas chromatography-mass spectrometry (GC-MS) method to determine acrylamide (AA) in coffee and coffee products was developed. The method was based on two main purification steps: the first with ethanol and Carrez solutions in order to precipitate polysaccharides and proteins, respectively; and the second with a layered solid-phase extraction (SPE) column which proved to be efficient in the elimination of the main chromatographic interferences. The method is applicable to a wide range of coffee products. Twenty-six samples of different coffee products were analysed. The levels of AA were in the range 11.4-36.2 µg l^-1 for 'espresso coffee' and 200.8-229.4 µg l^-1 for coffee blends with cereals. The results indicate that the presence of cereals significantly increased the levels of AA.     

快餐包装纸中矿物油向固体食品模拟物的迁移

研究从市场上收集到的24 种快餐包装纸中的矿物油向固体食品模拟物Tenax的迁移规律。在多个不同的迁移条件（40 ℃/0.5、1、2、3 h,40 ℃/10 d和70 ℃/2 h）,探究矿物油的迁移行为及其影响因素,以评价其安全性。选择正己烷-乙醇（1∶1,V/V）混合溶液对Tenax进行过夜萃取,采用质量分数0.3%硝酸银固相萃取柱对饱和烃矿物油（mineral oil saturated hydrocarbons,MOSH）和芳香烃矿物油（mineral oil aromatic hydrocarbons,MOAH）进行分离纯化,最后用气相色谱-氢火焰离子化检测法和气相色谱-质谱法分别进行定量和定性分析。结果表明：随着温度的升高,多种快餐包装纸中矿物油向Tenax的迁移量也随之增加。涂蜡纸中MOSH迁移量均有所检出,其数值为110.49～615.40 mg/kg,而MOAH部分均未检出,这可能是因为涂蜡纸表面涂覆的石蜡层属于MOSH类,导致其MOSH部分的迁移量较高。网购餐盘纸和常规餐盘纸中MOSH迁移量约为其特定限量值（0.6 mg/kg）的10～400 倍,MOAH的迁移量约为其特定限量值（0.5 mg/kg）的10～70 倍,而使用优质胶印油墨的原生纤维餐盘纸均未超过其限量值。最后,通过对印有胶印油墨的原生纤维餐盘纸中矿物油进行溯源分析,发现经过迁移的矿物油一部分可能来源于其所用油墨,其他来源可能来自于回收纤维、黏合剂、添加剂和加工助剂等。     

Study of amount of evaporation residue in extracts from plastic kitchen utensils into four food-simulating solvents

The amount of evaporation residue was investigated as an index of total amount of non-volatile substances that migrated from plastic kitchen utensils into four food-simulating solvents (water, 4% acetic acid, 20% ethanol and heptane). The samples were 71 products made of 12 types of plastics for food contact use. The amount was determined in accordance with the Japanese testing method. The quantitation limit was 5 μg/mL. In the cases of polyethylene, polypropylene, polystyrene, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, polyvinyl chloride, polyvinylidene chloride, polymethylpentene, polymethylmethacrylate and polyethylene terephthalate samples, the amount was highest for heptane and very low for the other solvents. On the other hand, in the cases of melamine resin and polyamide samples, the amount was highest for 4% acetic acid or 20% ethanol and lowest for heptane. These results enabled the selection of the most suitable solvent, and the rapid and efficient determination of evaporation residue.     

Contaminants in organically and conventionally produced winter wheat (Triticum aestivum) in Belgium

A database has been compiled with the levels of important contaminants (mycotoxins, heavy metals and pesticides) measured from 2002 to 2005 in winter wheat (Triticum aestivum) grown in Belgium according to the organic and conventional farming systems. Assuming no further change in contaminant levels during cereal processing and during the preparation of foodstuffs, conservative intakes are estimated for the consumers of cereal-based products such as flour, bread, breakfast cereals, dough and pastry. The results show that for the consumer of organic foodstuffs, estimated daily intakes are 0.56 µg deoxynivalenol (DON), 0.03 µg zearalenone (ZEA), 0.19 µg Cd, 0.28 µg Pb and 0.0006 µg Hg kg^-1 body weight, taking into account the average contaminant levels in unprocessed grains and the average cereal products consumptions in Belgium. For the consumers of conventional foodstuffs, the corresponding estimated daily intakes are 0.99 µg DON, 0.06 µg ZEA, 0.17 µg Cd, 0.12 µg Pb and 0.0007 µg Hg kg^-1 body weight. In addition, it appears that for the consumers of conventional products, intakes of some post-harvest insecticides have to be taken into account (0.11 µg chlorpyriphos-methyl, 0.2 µg dichlorvos and 0.24 µg pirimiphos-methyl kg^-1 bw). When expressed as a percentage of the tolerable/acceptable daily intake (TDI/ADI), it seems that the corresponding estimated (conservative) intakes are the highest for DON (56% for organic and 99% for conventional cereal products), ZEA (16% for organic and 32% for conventional cereal products), and Cd (19% for organic and 17% for conventional cereal products), all other estimated intakes of contaminants (including pesticides) being lower than 10% of the TDI/ADI.     

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.     

Migration of model contaminants from PET bottles: influence of temperature, food simulant and functional barrier

To simulate post-consumer recycled plastics, selected model contaminants were incorporated into PET bottles using a time saving method. Migration into 3% acetic acid, a cola-type beverage and 95% ethanol was followed during 1 year of storage at 20 and 40°C. Aroma compounds previously found in post-consumer PET material were used as model contaminants. Benzaldehyde was found to migrate to the highest extent. Storage at 40°C affected the bottle material and this might be one reason for the high migration values of these bottles. Migration into ethanol was up to 20 times higher than into 3% acetic acid or a cola-type beverage. Bottles with a functional barrier resisted migration into food simulants even when filled with 95% ethanol and stored for 1 year at 40°C. Differential scanning calorimetry measurements showed that ethanol was interacting with the plastic material. This resulted in a lower glass transition temperature of bottles stored with ethanol compared with bottles stored empty or with other food simulants.     

Migration of a UV stabilizer from polyethylene terephthalate (PET) into food simulants

The migration characteristics of the UV stabilizer Tinuvin 234 (2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl)phenol) into food simulants has been measured from polyethylene terephthalate (PET) using HPLC with UV detection. Ethanol/water, isooctane and a fractionated coconut oil simulant (Miglyol®) were used as food simulating solvents. The migration characteristics were measured at temperatures in the range of 40-70°C. Diffusion coefficients were determined to be in the range of 1 × 10^-14 cm² s^-1 to 1 × 10^-18 cm² s^-1. At 40°C, the amount of migration into 95% ethanol after 10 days was 2 μg dm^-2. Isooctane is determined to be a good fatty food simulant that provides similar results for PET to those of fatty foods.     

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.