Assessment of heavy metals migrated from food contact plastic packaging: Bangladesh perspective.

Plastic-based food-contact materials are potentially threatening the environment and public health by releasing toxic heavy metals. This study aimed to identify the types of plastic commonly used in Bangladesh as food-contact materials (FCMs) and assess the migration of heavy metals from these FCMs. Plastic types were identified using attenuated total reflectance fourier transform infrared spectroscopy (ATR-FTIR), and 25 samples were selected based on the category, including Polyethylene Terephthalate (PET), Polyethylene (PE), Polypropylene (PP), Polystyrene (PS), and Polycarbonate (PC). Distilled water, 3% acetic acid, and 15% ethanol were used as food simulants to assess the overall migration of chemicals at 70 °C for 2 h. The concentrations of heavy metals (Pb, Cd, Hg, Cr, and Sb) were analyzed using an Atomic Absorption Spectrophotometer (AAS). Results revealed that the highest overall migration occurred in coffee cups measuring 3.50 ± 0.17 mg/kg (using water simulant) and in yogurt containers with a measurement of 9.17 ± 0.1 mg/kg (using 3% acetic acid). The highest concentrations of Pb, Cd, Hg, Cr, and Sb were found in PP-2 (0.45 ± 0.01 mg/kg), PP-2 (0.36 ± 0.01 mg/kg), PC-5 (0.27 ± 0.01 mg/kg), PET-2 (0.12 ± 0.01 mg/kg), and PET-1 (0.09 ± 0.01 mg/kg), respectively. The concentration of heavy metals migrated from the containers is likely to induce a health risk due to bioaccumulation from long-term ingestion of food packaged in them. The findings of this study added knowledge about harmful heavy metals leached from the FCMs in Bangladesh.

Evaluation and modeling of acrylonitrile migration from polypropylene for food packaging.

This study validated an analytical technique using headspace gas chromatography with flame ionization detection to quantify acrylonitrile monomer with a quantification limit of 0.10 ± 0.04 µg kg-1 . Subsequently, the acrylonitrile migration from polypropylene granules was evaluated in food simulants water and ethanol (50% v/v) and at two temperatures (20 ± 1°C and 44 ± 2°C) for up to 6 weeks, representing the service time of a bottle. From the experimental data obtained, pseudo-second-order kinetics were adjusted to represent the acrylonitrile migration into the simulants. For water, equilibrium concentrations of 13.58 and 16.58 µg kg-1 at 20 and 44°C, respectively, were obtained, while for 50% ethanol, 15.07 and 16.40 µg kg-1 were obtained for the same temperatures. The experimental results and the values estimated from the migration kinetics indicate that the maximum acrylonitrile concentration will not exceed the tolerable specific limit established in regulations. PRACTICAL APPLICATION: The migration of compounds such as acrylonitrile can be a drawback resulting in an undesirable reduction in the shelf life of liquid foods packaged in bottles made of materials such as polypropylene. In this paper, acrylonitrile migration kinetics and a methodology are proposed to determine whether the tolerable migration limits are ever reached, which can serve as a tool for producers of this type of packaging of food to predict shelf life.

Occurrence and migration of organophosphite and organophosphate esters into food simulants from single-use food packaging in China.

Organophosphite antioxidants (OPAs) and organophosphate esters (OPEs) are used as additives in food packaging. Because these chemicals have been found in various foods, they have caused increasing concern about potential health risks through food intake. Little information is available about the migration behaviors of OPAs and OPEs from single-use food packaging into food. In the present study, four OPAs and 23 OPEs were analyzed in paper and plastic single-use food packaging (n = 312), which are widely used for take-out food in China. The total concentrations of OPAs and OPEs in the packaging samples were 1966 and 189 ng/g, respectively. Tris (2,4-di-tert-butylphenyl) phosphite (AO168) was the dominant compound. OPAs and OPEs were present at higher concentrations in the plastic packaging than in the paper packaging. In a migration test, four OPAs and 15 OPEs were found in food simulants (4% acetic acid, 10% ethanol, and hexane). Higher levels of individual and total OPAs were found in hexane than the other food simulants, especially for AO168 migration from plastic packaging. The amounts of OPEs in the food simulants increased from the aqueous simulants (4% acetic acid and 10% ethanol) to the fatty food simulant (hexane). The migration efficiencies of the OPAs were higher than those of the OPEs. Preliminary calculations suggest that dietary exposure to OPAs and OPEs because of migration will be low for the population in China.

Occurrence and migration study of chemicals from baking paper and aluminium foil.

The present work focused on the development of an analytical method suitable to study the presence and the release of organophosphate esters (OPEs) and perfluoroalkylated substances (PFASs) from food contact materials (FCMs), from baking paper and aluminium foil. Although these classes of compounds are attracting increasing attention due to their toxicity the knowledge is still insufficient. The extent of their migration from FCMs to food was estimated using different liquid simulants. Ethanol 95 % was used to simulate the contact with fatty food, whilst acetic acid 3 % to mime contact with acidic aqueous-based food and the contact mode involved the use of the ultrasound-assisted technique. Preliminary results showed the higher migration for baking paper samples in contact with aqueous simulant with contaminations in the ranges 78.30-413.21 ng/dm2 and 1.43-13.87 ng/dm2 for OPEs and PFASs respectively. These findings highlighting the need to monitor particularly OPEs in FCMs.

Determination of potential volatile compounds in polyethylene terephthalate (PET) bottles and their short- and long-term migration into food simulants and soft drink.

Head space (HS)-GC-MS was used to analyze possible migration of volatile compounds from polyethylene terephthalate (PET) bottles for soft drinks, and a total of six compounds were identified. Next, a rapid, simple, and accurate simultaneous method was established using purge-and-trap (PT)-GC-MS, to quantify their amounts in the liquid contents after short- and long-term storage in PET bottles. Starting with brand-new PET bottles, the maximum migration of 2-methyl-1,3-dioxolane into distilled water and 50 % aqueous ethanol after 2 years at 25 °C were 2.3 and 19 ng/mL, respectively. In commercially available bottled mineral water sold inside and outside Japan, we were able to detect 2-methyl-1,3-dioxolane in the same way. While nonanal was also detected in some products, 2-methyl-1,3-dioxolane was confirmed as the main volatile compound. Finally, the human exposure to 2-methyl-1,3-dioxolane was estimated based on the per capita intake of soft drinks in Japan and the migration amount in this study.

Is the use of paper food contact materials treated with per- and polyfluorinated alkyl substances safe for high-temperature applications? - Migration study in real food and food simulants.

Migration of per- and polyfluorinated alkyl substances (PFAS) from paper food contact materials (FCMs) can pose a consumer risk. However, risk assessment procedures typically do not consider PFAS contribution from FCMs. Moreover, migration studies are often limited to one subclass of PFAS or simplified by using food simulants (FS). To assess the risk comprehensively, migration of three PFAS subclasses (perfluorinated carboxylic acids/ sulfonic acids (PFCAs/PFSAs), polyfluoroalkyl phosphate esters (PAPs), and fluorotelomer alcohols (FTOHs)) from six FCMs were investigated to FS (50% and 20% ethanol) and food (oatmeal porridge, muffins, and tomato soup) under high-temperature conditions. Migration of PFCAs and FTOHs to all food samples was observed. Migration of PFCAs and FTOHs to 50% ethanol was significantly higher than migration to real food whilst FTOHs did not migrate into 20% ethanol. Estimated dietary PFAS exposure for children (1.06 - 5.67 ng/kgbw/day) exceeded EFSA's proposed safety threshold (0.63 ng/kgbw/day), risking consumer health.

Bioactive Electrospun Fibers of Poly(ε-Caprolactone) Incorporating α-Tocopherol for Food Packaging Applications.

Antioxidant activity is an important feature for food contact materials such as packaging, aiming to preserve freshness and retard food spoilage. Common bioactive agents are highly susceptible to various forms of degradation; therefore, protection is required to maintain functionality and bioavailability. Poly(ε-caprolactone) (PCL), a biodegradable GRAS labeled polymer, was used in this study for encapsulation of α-tocopherol antioxidant, a major component of vitamin E, in the form of electrospun fibers. Rheological properties of the fiber forming solutions, which determine the electrospinning behavior, were correlated with the properties of electrospun fibers, e.g., morphology and surface properties. Interactions through hydrogen bonds were evidenced between the two components. These have strong effect on structuration of macromolecular chains, especially at low α-tocopherol amounts, decreasing viscosity and elastic modulus. Intra-molecular interactions in PCL strengthen at high α-tocopherol amounts due to decreased solvation, allowing good structural recovery after cease of mechanical stress. Morphologically homogeneous electrospun fibers were obtained, with ~6 µm average diameter. The obtained fibers were highly hydrophobic, with fast release in 95% ethanol as alternative simulant for fatty foods. This induced good in vitro antioxidant activity and significant in vivo reduction of microbial growth on cheese, as determined by respirometry. Therefore, the electrospun fibers from PCL entrapping α-tocopherol as bioactive agent showed potential use in food packaging materials.

Migration of substances from food contact plastic materials into foodstuff and their implications for human exposure.

The safety of food contact plastic materials, including PP, PE, PET, PCT, PLA, PBT and cross-linked polyester, was assessed with regard to migrated substances. The migrated concentrations of overall migrants (OMs), terephthalic acid, acetaldehyde, 1,4-butanediol and lead, were determined according to the standards and specifications for utensils, containers and packages in Korea. Food simulants of 4% acetic acid, water and n-heptane were used for the analysis of the substances. The dietary exposures of terephthalic acid, acetaldehyde and 1,4-butanediol were assessed using the dietary concentrations and the food consumption data. As a result, the dietary exposures were considered to be safe comparing to the health-based guidance values. In the case of lead, the margin of exposure (MOE) approach was applied. The MOEs calculated using the UB concentration and mean consumption data were ranged from 3 to 1000, which indicated low concern for health risk. Moreover, in this study, the dietary exposures were estimated by the Korean MFDS and U.S. FDA methods, respectively. As a result, the assessed risks were considered to be low in both cases. Based on the results of current exposure assessments, it could be considered that the food contact plastic materials are properly controlled by the regulatory authorities.

Data of the release properties of astaxanthin-loaded zein/calcium alginate composite microparticles in fatty food simulant system at 4 °C and 25 °C.

Recently, we demonstrated the characteristics and molecular interactions of Astaxanthin (Asta), extracted from shrimp (Litopenaeus vannamei) by-products to zein/calcium alginate (CA) (named as Asta-loaded zein/CA composite microparticles). The encapsulation efficiency of Asta-zein/CA composite microparticles obtained from freeze dried, 40 °C or 50 °C oven dried was across 80% [1]. In this data, we investigted the release properties of Asta-loaded zein/CA composite microparticles in simulating fatty food system (95% ethanol solution) at 4 °C and 25 °C. At different points of time, the cumulative release percentages of Asta from the tested composite microparticles were calculated. The release kinetics of Asta from the composite microparticles was investigated using Zero order, First order, Higuchi and Rigter-Peppas models. We observed all of the tested composited microparticles displayed an initial burst effect followed by subsequent attenuating release in 4 °C and 25 °C fatty food simulant system. At 4 °C fatty food system, the Asta released from 40 °C oven dried and 50 °C oven dried composite microparticles fit best with First-order and Ritger-Peppas models, respectively. At 25 °C fatty food system, all of these tested composite microparticles fit best with Higuchi model. Our results indicate the prepared composite microparticles are expected to be used as a delivery carrier for restrained release of antioxidant Asta in fatty foods, such as in natural vegetable oils or fried foods.

Determination of toxic metal release from metallic kitchen utensils and their health risks.

The effect of simulants, repeated use, washing, and oiling on the release of toxic metals from metallic kitchen utensils was investigated. The release of As, Cd, Cr, Ni, and Pb from kitchen utensils composed of stainless steel, aluminum, copper alloy, and cast iron into food simulants was quantified using inductively coupled plasma-mass spectrometry. The results show that this release of toxic metals was highly dependent on pH. Generally, the release of toxic metals tended to decrease with repeated use, and the release of Cr and Ni from stainless steel samples was significantly higher in the first test, compared to the third test. The washing conditions affected the release of As and Cr, whose release levels were higher when washing only with water and with a steel wool pad, respectively. Furthermore, oiling cast iron cookware reduced the release of As, Cd, Cr, and Ni into acidic simulants by 66%, 83%, 71%, and 15%, respectively. The margin of exposure (MOE) was calculated for each toxic metal; the calculated MOE values indicated that it is improbable that the current level of exposure from metallic kitchen utensils would pose a health risk in Korea.

Proficiency test on the determination of polyethylene and polybutylene terephthalate cyclic oligomers in a food simulant.

The outcome of a proficiency test (PT) organised by the European Union Reference Laboratory for Food Contact Materials (EURL-FCM) is presented. The PT was set up to assess the analytical performance of National Reference Laboratories (NRLs) and Official Control Laboratories (OCLs) in the determination of mass fractions of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) cyclic dimers and trimers in the official food simulant D1 containing ethanol and water (50:50 v/v). The EURL-FCM had developed and validated an analytical method based on HPLC-UV to monitor the homogeneity and stability of the target oligomers in the PT test items and to determine the respective assigned values, as prescribed in ISO 17043, 2010ISO 17043, 2010. The standard operating procedure of the method was provided to the participants and could be used instead of their own routine methods. Laboratory results were rated using z, z' and ζ scores in accordance with ISO 13528, 2015. The standard deviation for proficiency assessment, σpt , was set to 20 % of the respective assigned value, for all the four studied oligomers, based on the perception of experts. A total of 36 participants from 26 countries have registered to the exercise. They received two test items. Solution 1 consisted of food simulant D1 fortified with a known mass fraction of the four oligomers, while Solution 2 was obtained by a migration experiment with PET bottles and food simulant D1 and further fortification of the resulting solution with the four oligomers. The majority of the participating laboratories presented satisfactory results for the four PET and PBT oligomers. For the analysis of Solution 1, 79-88 % of the participants obtained |z (or z')-scores| below 2, while the satisfactory performances ranged from 71 to 85 % for Solution 2. This PT has been organised for the first time at EU level for the analysis of polyester oligomers and confirms that most of the NRLs are able to monitor properly these oligomers in the frame of Regulation (EU) No 10/2011.

[Consideration of the Evaporation Residue Test for Plastics Intended to Contact with Oils and Fatty Foods].

The Japanese Food Sanitation Act designates the evaporation residue test as a specification for plastics that intended to contact with foods. The test conditions and migration limits for oils and fatty foods were considered on the basis of the results obtained from the evaporation residue test according to the Japanese Act and the overall migration test into olive oil according to EN1186-2. The evaporation residue test was conducted using heptane at 25℃ for 1 hour. The results of most samples were under 30 µg/mL although those of high impact polystyrene,polymethylpentene and polyvinyl chloride were found to be over 30 µg/mL. However, these results were within the acceptable range of the relaxed limits (240, 120, 150 µg/mL). Regarding the overall migration into olive oil, most plastics were under the determination limit at 60℃ for 30 min. But the results for polyethylene, polypropylene and polyvinyl chloride were over 30 µg/mL at 95 and 121℃, which were higher than their evaporation residues. In other words, the existing test conditions and limits of the evaporation residue test could be used for testing plastics that come into contact with oils and fatty foods at lower temperatures. However, they are not adequate for evaluating some plastics that come into contact with oils and fatty foods at higher temperatures.

Poly (α-Dodecyl γ-Glutamate) (PAAG-12) and Polylactic Acid Films Charged with α-Tocopherol and Their Antioxidant Capacity in Food Models.

Poly (α-dodecyl γ-glutamate) (PAAG-12) was successfully synthesized from poly(γ-glutamic acid) (PGGA) according to Nuclear Magnetic Resonance (NMR) analyses. PAAG-12 films were prepared and enriched with 5% α-tocopherol, with the aim of using them as novel antioxidant active packaging for food applications. Thermogravimetric Analysis (TGA) characterization determined that α-tocopherol improved thermal stability of films, which is beneficial for industrial processing. Polylactic Acid (PLA) films prepared with the same amount of α-tocopherol were used to set a comparative frame and both types of films were applied to two different food models to assess their protective action against oxidation. Water, 50% ethanol (EtOH) and 95% EtOH were used as food simulants and HPLC analyses were performed to determine diffusion and partition coefficients in PLA and the novel polymer, the latter exhibiting slower release rates. Primary oxidation was measured with peroxide value, which revealed that PAAG-12 films with α-tocopherol protected oil-in-water (O/W) emulsions up to 29 days, complying with the Codex Alimentarius.

HS-GC/MS method development and exposure assessment of volatile organic compounds from food packaging into food simulants.

A simultaneous headspace-gas chromatography/mass spectrometry (HS-GC/MS) method was developed and validated to determine the migration of 12 volatile organic compounds (methanol, acetone, methylethylketone, ethylacetate, isopropylalcohol, benzene, toluene, ethylbenzene, xylene, cumene, propylbenzene, and styrene) from food contact materials into food simulants (water, 4% acetic acid, 50% ethanol, and n-heptane). The limits of detection and quantification were 0.007-0.201 mg L-1 and 0.023-0.668 mg L-1, respectively. The method was applied to 205 samples of paper/paperboard, polyethylene, polypropylene, polystyrene, and polyethylene terephthalate. The estimated daily intake (EDI) was calculated using the migration results. Exposure assessments were carried out to compare the EDI to the tolerable daily intake (TDI); the results indicated that the EDI of styrene represented only a small percentage (8.0%) of the TDI. This analytical method will be a useful tool to examine levels of various volatile compounds migrating from food packaging to food simulants using HS-GC/MS method.

Influence of Food with High Moisture Content on Oxygen Barrier Property of Polyvinyl Alcohol (PVA)/Vermiculite Nanocomposite Coated Multilayer Packaging Film.

This study investigates the potential complications in applying nanoclay-based waterborne coating to packaging films for food with high moisture content. Multilayer packaging films were prepared by dry laminating commercially available polyvinyl alcohol (PVA)/vermiculite nanocomposite coating films and linear low-density polyethylene film, and the changes in oxygen barrier properties were investigated according to different relative humidity using 3 types of food simulants. When the relative humidity was above 60%, the oxygen permeability increased sharply, but this was reversible. Deionized water and 3% acetic acid did not cause any large structural change in the PVA/vermiculite nanocomposite but caused a reversible deterioration of the oxygen barrier properties. In contrast, 50% ethanol, a simulant for the semifatty food, induced irreversible structural changes with deterioration of the oxygen barrier property. These changes are due to the characteristics of PVA rather than vermiculite. PRACTICAL APPLICATION: We believe this manuscript would be of interest to the wide group of researchers, organizations, and companies in the field of developing nanoclay-based gas barrier packaging for foods with high moisture content. Hence, we wish to diffuse our knowledge to the scientific community.

Potential silver nanoparticles migration from commercially available polymeric baby products into food simulants.

In recent years, silver nanoparticles (AgNPs) have been extensively employed in food packaging systems as a potential antibacterial agent. Although proven to be highly effective, the increased number of AgNP-containing products raises concerns among consumers regarding the migration of AgNPs from the packaging material into foods, which may exert toxic effects. To address this, five baby products were chosen (baby bottle A, baby bottle B, pacifier A, pacifier B and breastmilk storage bag) to investigate AgNPs migration into three food simulants (deionised water, 4% acetic acid (w/v) and 50% ethanol (v/v)) using inductively coupled plasma mass spectrometry (ICP-MS). As a result, the highest level of migrated Ag was observed for 4% acetic acid in the case of baby bottle B, pacifier A, pacifier B and the breastmilk storage bag, with the detection amount ranging from 1.05-2.25 ng/mL. On the other hand, baby bottle A showed the maximum migration for 50% ethanol due to the polymer nature. Finally, a centrifugal ultrafiltration experiment was conducted to determine the fraction of dissolved Ag in acidic simulant and it was found that migrated Ag was predominantly in Ag+ form, with a small fraction of non-ionic AgNPs. Thus, it has been found that the amount of migrated Ag in baby products was low; however, the migration was dependent on the type of food simulant and polymer nature.

Effect of sterilisation and storage conditions on the migration of bisphenol A from tinplate cans of the Lebanese market.

The use of bisphenol A (BPA) in lacquer coating of food cans has been restricted by different authorities in many countries, such as in Europe. However, such regulation does not exist in many other countries including Lebanon. Due to the lack of data on the quality of Lebanese can production; this study investigates the migration of BPA from two types of tinplate cans manufactured in Lebanon, before and after sterilisation. Cans were analysed under different storage conditions (time and temperature) and filled with an aqueous simulant. The determination of BPA was carried out using UPLC with fluorescence detection, and further confirmed by MS detection. After sterilisation BPA levels drastically increased from an average of 0.15 to 109 µg/kg, giving a BPA migration around 10.5 µg/dm2 for both types of cans. Storage temperature and time had no significant influence on BPA levels in sterilised cans (p-value > 0.05); however, these factors significantly affected BPA levels in non-sterilised cans.

How Stress Treatments Influence the Performance of Biodegradable Poly(Butylene Succinate)-Based Copolymers with Thioether Linkages for Food Packaging Applications.

Biodegradable poly(butylene succinate) (PBS)-based random copolymers containing thioether linkages (P(BSxTDGSy)) of various compositions have been investigated and characterized from the gas barrier, thermal, and mechanical point of view, after food contact simulants or thermal and photoaging processes. Each stress treatment was performed on thin films and the results obtained have been compared to the same untreated film, used as a standard. Barrier properties with different gases (O2 and CO2) were evaluated, showing that the polymer chemical composition strongly influenced the permeability behavior. The relationships between the diffusion coefficients (D) and solubility (S) with polymer composition were also investigated. The results highlighted a correlation between polymer chemical structure and treatment. Gas transmission rate (GTR) mainly depending on the performed treatment, as GTR increased with the increase of TDGS co-unit amount. Thermal and mechanical tests allowed for the recording of variations in the degree of crystallinity and in the tensile properties. An increase in the crystallinity degree was recorded after contact with simulant liquids and aging treatments, together with a molecular weight decrease, a slight enhancement of the elastic modulus and a decrement of the elongation at break, proportional to the TDGS co-unit content.

Use of Tenax® films to demonstrate the migration of chemical contaminants from cardboard into dry food.

Contaminants in food packaging are a challenge of our time since the packaging material itself has been found to represent a source of food contamination through the migration of substances from it. Before first use, packaging materials destined for the packaging of dry foods can be evaluated by performing migration experiments with the simulant for dry foods, Tenax®. This simulant is commercially available as a powder that is more difficult to handle during the migration experiments. This paper reports the development of a Tenax film. The film can be applied to the cardboard surface to conduct the migration test. After the migration is completed, the film can be easily extracted to determine the concentration of the contaminants in the film. Finally, the performance of the Tenax film was compared with the conventional Tenax powder for the evaluation of 15 model migrants.

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

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.