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.     

Testing the influence of various conditions on the migration of epoxidised soybean oil from polyvinylchloride gaskets

Epoxidised soybean oil (ESBO) is widely used as a plasticiser and stabiliser mainly in food contact materials on the base of polyvinylchloride (PVC), especially in the gaskets of jar lids. PVC gaskets containing 10–37% of ESBO were prepared by the baking of PVC plastisols at various process temperatures (180–240°C) in the laboratory. ESBO migration into olive oil and 3% acetic acid was studied at various temperatures (4°C, 25°C, 40°C and 60°C) during a storage time up to 12 months. ESBO released into food simulants was transmethylated, derivatised and analysed by gas chromatography-mass spectrometry (GC/MS). The effect of food processing, i.e. pasteurisation (80°C and 100°C) and sterilisation (125°C) on ESBO migration was also evaluated. The results were critically assessed with respect to the test conditions of specific migration in accordance with the current European Union legislation (Regulation (EU) No. 10/2011). The levels of ESBO migration found confirmed that the test conditions (i.e. 40°C or 60°C, 10 days) representing contact in the worst foreseeable use scenario seem to be insufficient for the simulation of ESBO migration during long-term storage and thus do not provide satisfactory objective results.     

食品包装材料中双酚A迁移量的测定

建立采用高效液相色谱法对塑料食品包装材料中双酚A向食品模拟物迁移量的检测方法。使用4种食品模拟物：水、质量分数为4%乙酸溶液、体积分数30%的乙醇溶液和脂肪类模拟物(正己烷、异辛烷和橄榄油)。结果表明,双酚A在与食品塑料包装接触过程中,无论在何种情况下都会向食品模拟物中迁移,尤其向醇类模拟物中迁移最严重;在温度超过60℃时,双酚A向食品模拟物中的迁移率骤增;在微波加热条件,高火700W功率时双酚A向食品模拟物中的迁移速率最快。该方法检测限为0.3ng/mL,线性范围为0.5～100ng/mL,线性相关系数为0.9997,回收率在92.0%～102.4%之间,相对标准偏差≤2.84%(n=5)。     

Effects of lipid,PET/PE and PA/PE with high-pressure processing

The mutual effects between food components and packaging materials under high-pressure processing was investigated. Pouches made of Polyethylene terephthalate/Polyethylene and Polyamide/Polyethylene packaging olive oil and glycerol trioleate were subjected to different pressures and holding times, and then stored at 23 ± 2^oC for 40 days. The results proved that there were significant effect between lipid and packaging under high-pressure processing treatment. High pressure would be beneficial to extend food shelf life and affect the enthalpy of fusion of packaging materials, especially when making contact with olive oil which probably acted as a plasticizer to change the polymer structure.     

Release and antioxidant activity of carvacrol and thymol from polypropylene active packaging films

The migration of antioxidant (AO) agents, carvacrol and thymol, from polypropylene (PP) packaging films containing the studied compounds at 80 g/kg separately and an equimolar mixture of them into food simulants was investigated. Fast and reliable analytical procedures were developed and validated for the analysis of the studied AOs in food simulants. For aqueous food simulants, solid phase extraction followed by GC–MS analysis was performed. Fatty food simulants were directly analysed by GC–MS and HPLC-UV for isooctane and ethanol 950 mL/L, respectively. The release of AOs from the films was dependent on the type of food stimulant and AO incorporated. In particular, high levels of migration were obtained for both AOs into isooctane, showing thymol higher migration. The release kinetics of AOs from PP films showed a Fichian behaviour with diffusion coefficients ranging from 1 to 2 × 10⁻¹⁴ m²/s; except for the diffusion into isooctane where 4-6 higher values were obtained. The antioxidant activity of migration extracts was confirmed by the DPPH method, showing thymol a higher antioxidant capacity especially into isooctane with a 42.2% of inhibition. The obtained results suggest that carvacrol and thymol show a potential use as AOs for active packaging for extending the shelf-life of food products.     

Compression Heating of Selected Fatty Food Materials during High-pressure Processing

ABSTRACT: Compression heating of selected fatty and model food materials during high‐pressure processing was studied using a specially designed experimental system. Commercially available soybean oil, olive oil, beef fat, chicken fat, and salmon fish were studied at different pressures (150 to 600 MPa) and at different initial temperatures (25 to 70 °C). At an initial temperature of 25 °C, fats and oils showed higher compression heating values (up to 8.7 °C per 100 MPa) compared to 2 to 3 °C per 100 MPa for water. Though the compression heating of water depends on its initial temperature, oils have little or no effect of initial temperature.     

Development of an HPLC method for measurements of the stability of Irganox-type polymer antioxidants in fatty food simulants

 A reversed-phase high-performance liquid chromatography (RP-HPLC) method has been developed to measure the stability of four Irganox-type polymer antioxidants (Irganox 245, Irganox 1035, Irganox 1098 and Irganox 3114) in an olive oil food simulant and isooctane, which has been proposed as an alternative fatty food simulant. The tests of stability in olive oil were carried out under three different conditions, i.e. 40°C for 10 days, 100°C for 1 h and 175°C for 1 h. The exposure conditions for isooctane were 60°C for 3 h. Results showed that for all additives tested no instability phenomena in olive oil or isooctane simulants were observed under the exposure conditions applied. The analytical methodology developed could eventually be used for stability testing and migration studies of other similarly structured antioxidants in fatty food simulants. Received: 11 September 1997     

Development of an HPLC method for measurements of the stability of Irganox-type polymer antioxidants in fatty food simulants

 A reversed-phase high-performance liquid chromatography (RP-HPLC) method has been developed to measure the stability of four Irganox-type polymer antioxidants (Irganox 245, Irganox 1035, Irganox 1098 and Irganox 3114) in an olive oil food simulant and isooctane, which has been proposed as an alternative fatty food simulant. The tests of stability in olive oil were carried out under three different conditions, i.e. 40°C for 10 days, 100°C for 1 h and 175°C for 1 h. The exposure conditions for isooctane were 60°C for 3 h. Results showed that for all additives tested no instability phenomena in olive oil or isooctane simulants were observed under the exposure conditions applied. The analytical methodology developed could eventually be used for stability testing and migration studies of other similarly structured antioxidants in fatty food simulants. Received: 11 September 1997     

Migration of silver from nanosilver–polyethylene composite packaging into food simulants

An analytical method for the determination of silver in food simulants (3% (w/v) aqueous acetic acid or 95% (v/v) aqueous ethanol) was developed based on inductively coupled plasma mass spectrometry (ICP-MS). Recoveries ranged from 87% to 109% and RSDs ranged from 0.7% to 7.8%. The procedure was applied to determine the migration of silver from nanosilver–polyethylene food packaging film into food simulants at different temperatures and migration times. Results indicated that the maximum migration ratios were 1.70%, 3.00% and 5.60% for 3% (w/v) aqueous acetic acid at 20, 40 and 70°C, respectively, while for 95% (v/v) aqueous ethanol the maximum migration ratios were 0.24%, 0.23% and 0.22% at 20, 40 and 70°C.     

Assessment of the migration potential of nanosilver from nanoparticle-coated low-density polyethylene food packaging into food simulants

An experimental nanosilver-coated low-density polyethylene (LDPE) food packaging was incubated with food simulants using a conventional oven and tested for migration according to European Commission Regulation No. 10/2011. The commercial LDPE films were coated using a layer-by-layer (LbL) technique and three levels of silver (Ag) precursor concentration (0.5%, 2% and 5% silver nitrate (AgNO₃), respectively) were used to attach antimicrobial Ag. The experimental migration study conditions (time, temperature and food simulant) under conventional oven heating (10 days at 60°C, 2 h at 70°C, 2 h at 60°C or 10 days at 70°C) were chosen to simulate the worst-case storage period of over 6 months. In addition, migration was quantified under microwave heating. The total Ag migrant levels in the food simulants were quantified by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Mean migration levels obtained by ICP-AES for oven heating were in the range 0.01–1.75 mg l^?1. Migration observed for microwave heating was found to be significantly higher when compared with oven heating for similar temperatures (100°C) and identical exposure times (2 min). In each of the packaging materials and food simulants tested, the presence of nanoparticles (NPs) was confirmed by scanning electron microscopy (SEM). On inspection of the migration observed under conventional oven heating, an important finding was the significant reduction in migration resulting from the increased Ag precursor concentration used to attach Ag on the LDPE LbL-coated films. This observation merits further investigation into the LbL coating process used, as it suggests potential for process modifications to reduce migration. In turn, any reduction in NP migration below regulatory limits could greatly support the antimicrobial silver nanoparticle (AgNP)-LDPE LbL-coated films being used as a food packaging material.     

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

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

纸质食品包装材料的矿物油迁移研究进展

食品中的矿物油污染物是指石油来源的C10~C50烃类化合物, 包括烷烃矿物油(mineral oil saturated hydrocarbons, MOSH)和芳烃矿物油(mineral oil aromatic hydrocarbons, MOAH)2大类。近年来的研究表明, 食品中的矿物油污染物主要来源于食品的回收纸包装材料迁移。本文综述了国外近十年来纸质包装材料的矿物油迁移研究情况, 包括纸质包装材料迁移的矿物油分析方法——液相色谱-气相色谱联用法; 矿物油迁移至食品的2种方式: 气态扩散迁移和包装材料接触迁移; 降低矿物油迁移的技术方法, 即食品包装纸质材料的回收工艺, 向包装纸质中添加活性炭等吸附剂以及增加阻隔层以阻挡矿物油的迁移。旨在为相关企业和机构提供数据与技术参考。     

Kinetic desorption models for the release of nanosilver from an experimental nanosilver coating on polystyrene food packaging

To predict the kinetic desorption of silver from an experimental nanosilver coated polystyrene food packaging material into food simulants (0, 1, 2 and 3% acetic acid (HAc) in distilled water (dH₂O)) at 4 temperatures (10, 20, 40 and 70 °C), 5 sorption models were examined for their performance. A pseudo-second order kinetic sorption model was found to provide the best prediction of an unseen desorption validation dataset with R² = 0.90 and RMSE = 3.21. Poor predictions were witnessed for desorption at 70 °C, potentially due to re-adsorption of the silver back onto the polystyrene substrate, as shown in the kinetic migration experiments. Similarly, the temperature dependence of the desorption rate constant was satisfactorily described using the Arrhenius equation with the exception of the 70 °C scenario. The use of sorption models identified scenarios that may limit human exposure to nanosilver migrating from this experimental nanocoating, i.e. low temperature applications.Industrial relevanceThe use of antimicrobial packaging has the potential to reduce food spoilage and risk from pathogenic microorganisms while reducing food waste by extending the shelf life of food products. Coating of antimicrobial silver nanoparticles (AgNPs) to polymer surfaces is a highly advantageous technology as microbial contamination predominantly occurs on the surface of fresh and processed food products. However, uncertainty related to the potential release of nanoparticles from food packaging materials, subsequent potential human exposure and toxicology is a barrier to the uptake of these novel materials. In the European Union, where the safety assessment of these materials is stringent, mathematical models used to predict the worst case migration of nanoparticles from food packaging materials have supported the acceptance of some nanomaterials for use in food packaging. The performance of a number of desorption models was evaluated to predict the release of AgNPs from AgNP coated polystyrene. The model identified factors that influenced migration and possible industrial applications for the developed material to minimise human exposure. The study highlights the potential benefits of using predictive models to assess migration of NPs from polymers into food simulants instead of time consuming and expensive migration studies.     

Antimicrobial edible apple films inactivate antibiotic resistant and susceptible Campylobacter jejuni strains on chicken breast

Abstract: Campylobacter jejuni is the leading cause of bacterial diarrheal illness worldwide. Many strains are now becoming multidrug resistant. Apple‐based edible films containing carvacrol and cinnamaldehyde were evaluated for bactericidal activity against antibiotic resistant and susceptible C. jejuni strains on chicken. Retail chicken breast samples inoculated with D28a and H2a (resistant strains) and A24a (a sensitive strain) were wrapped in apple films containing cinnamaldehyde or carvacrol at 0.5%, 1.5%, and 3% concentrations, and then incubated at 4 or 23 °C for 72 h. Immediately after wrapping and at 72 h, samples were plated for enumeration of viable C. jejuni. The antimicrobial films exhibited dose‐ and temperature‐dependent bactericidal activity against all strains. Films with ≥1.5% cinnamaldehyde reduced populations of all strains to below detection at 23 °C at 72 h. At 4 °C with cinnamaldehyde, reductions were variable for all strains, ranging from 0.2 to 2.5 logs and 1.8 to 6.0 logs at 1.5% and 3.0%, respectively. Films with 3% carvacrol reduced populations of A24a and H2a to below detection, and D28a by 2.4 logs at 23 °C and 72 h. A 0.5‐log reduction was observed for both A24a and D28a, and 0.9 logs for H2a at 4 °C at 3% carvacrol. Reductions ranged from 1.1 to 1.9 logs and 0.4 to 1.2 logs with 1.5% and 0.5% carvacrol at 23 °C, respectively. The films with cinnamaldehyde were more effective than carvacrol films. Reductions at 23 °C were greater than those at 4 °C. Our results showed that antimicrobial apple films have the potential to reduce C. jejuni on chicken and therefore, the risk of campylobacteriosis. Possible mechanisms of antimicrobial effects are discussed. Practical Application: Apple antimicrobial films could potentially be used in retail food packaging to reduce C. jejuni commonly present on food.     

Migration of lead and arsenic from food contact paper into a food simulant and assessment of their consumer exposure safety

ABSTRACT

Paper is one of the most commonly used food packaging materials. During the production of packaging paper, it is possible for trace amounts of heavy metals to be incorporated as contaminants. These could migrate into food when packaging paper (food contact paper) is used for cooking, storing and eating. The aim of this study was to determine the migration of lead (Pb) and arsenic (As) from food contact paper into a food simulant and then to assess human safety through the estimated daily intake (EDI) with consumption factor. Migration tests were conducted for 310 samples using 4% acetic acid as a food simulant at 25°C for 10 min and at 95°C for 30 min. Concentrations of Pb and As in a food simulant were quantified by inductively coupled plasma mass spectrometry. LODs for Pb and As were 0.002 and 0.005 µg L^?1, respectively. The migration of Pb from food contact paper ranged from not detected (ND) to 17.5 μg L^?1 at 25°C for 10 min and from 0.10 to 25.6 μg L^?1 at 95°C for 30 min while As ranged from ND to 0.44 μg L^?1 at 25°C for 10 min and from ND to 0.87 μg L^?1 at 95°C for 30 min. The migration of Pb and As determined in this study confirm that the human exposure was within safe levels based on the EDI of food contact paper compared with the provisional tolerable weekly intake for Pb of 25 μg kg^?1 bw and for As of 15 μg kg^?1 bw.     

Nano-TiO2 particles and high hydrostatic pressure treatment for improving functionality of polyvinyl alcohol and chitosan composite films and nano-TiO2 migration from film matrix in food simulants

This study investigated the impact of nano-TiO₂ and high hydrostatic pressure (HHP) treatment on microstructure, water vapor and gas barrier, antibacterial and mechanical properties of polyvinyl alcohol (PVA)–chitosan (CHI) biodegradable films and determined the migration behavior of TiO₂ nanoparticles from the films to food simulants. Apart from the effect of filler, TiO₂ nanoparticles also could improve the antibacterial activity of the films and play a role as a plasticizer in the films. HHP treatment promoted the interaction between PVA and chitosan molecules, resulting in the formation of more compacted network structures in PVA–CHI films. The migration of TiO₂ from the films was investigated in food simulants including distilled water, acetic acid, ethanol and olive oil, in which the trace amount of TiO₂ (< 4.20 × 10^− 3‰) was only detected in olive oil. HHP treatment at 200–400 MPa significantly reduced migration of TiO₂ nanoparticles from the films.Industrial relevanceResults from this study provide a new application direction of high hydrostatic pressure (HHP) in the field of food packaging materials for improving the functionality of materials. Due to the non-thermal characteristic, HHP in combination with nano-TiO₂ not only improved the mechanical and barrier properties of the biodegradable PVA–CHI composite films (polyvinyl alcohol and chitosan based materials), but also enhanced the antibacterial activity of the films. The HHP treated PVA–CHI–TiO₂ films are very stable in food simulants, such as olive oils. Therefore, the utilization of HHP and nano-TiO₂ is promising in the preparation of food packaging materials with desirable functionalities.     

Alternative fatty food simulants and diffusion kinetics of nylon 12 food packaging.

The migration of laurolactam and cyclic di- and trimer of nylon 12 was assessed using three different films and five food simulants (olive oil, isooctane, 95% ethanol, 50% ethanol, water). Substitute test conditions for migration into olive oil according to European Union Directive EC/97/48 were applied using 95% ethanol and isooctane. Results showed that 95% ethanol overestimated while isooctane underestimated the respective migration into olive oil. Water was the best olive oil substitute, as migration of laurolactam into water and olive oil using the same temperature gave similar results. Additionally, diffusion kinetics of laurolactam were investigated by migration kinetic studies using isooctane and olive oil. Diffusion coefficients determined with isooctane were significantly higher than those found using olive oil. It was proved that isooctane had an interaction and olive oil was inert to the polymer. The diffusion conductance parameter, A(p), for nylon 12 determined using olive oil ranged from 0.3 to 0.6.     

采用ICP-MS研究聚酯类食品包装材料中锑向食品模拟物的迁移规律

目的 建立聚酯(PET)和4种食品模拟物中锑的电感耦合等离子体质谱(ICP-MS)测定方法.用该方法研究PET中的锑向水、10％(V/V)乙醇溶液、3％(W/V)乙酸水溶液和精炼橄榄油4种食品模拟物迁移的行为与浸泡时间、温度、食品模拟物属性、锑初始含量等参数的关系.方法 在不同的温度下,将不同的PET浸泡于食品模拟物中,于一定的时间点吸取少量浸泡液,用ICP-MS测定其含量.结果 ICP-MS方法回收率在94.3％ ～96.1％之间,相对标准偏差在1.38％ ～3.31％之间.结论 锑迁出量随温度升高而增加;随着时间的延长,锑迁出量逐渐增加,一定时间后达到迁移平衡;大部分PET材料本底含量越高迁出量越高;PET中锑易于在酸性食品模拟物中迁出,应少食用PET包装的酸性食品.     

Active Banana Flour Nanocomposite Films Incorporated with Garlic Essential Oil as Multifunctional Packaging Material for Food Application

Active plasticized banana flour nanocomposite film (APBNF) incorporated with a different garlic essential oil (GO) content was formed using a solution casting to determine the film properties prior to the investigation of its effectiveness to preserve the roasted peanut quality. The GO concentration was positively correlated with the ultraviolet (UV) light barrier property and antioxidant activity indicating the ability to protect the packed food product from lipid oxidation. Additionally, incorporation of 1 mg/mL GO into APBNF showed the highest antioxidant activity and completely inhibited the growth of Aspergillus flavus. Fourier-transform infrared spectroscopy confirmed the functional group interactions between the film matrix and GO which act as an antioxidant and antimicrobial agent. Thus, APBNF incorporated with 1 mg/mL GO as an active packaging to preserve the quality of roasted peanuts was investigated comparing with a commercial plastic packaging of polyethylene terephthalate/low-density polyethylene (PET/LDPE; PET). The shelf life estimation of roasted peanuts packed in both packaging materials (APBNF and PET) based on the peroxide value (PV) was similar at high storage temperature (45 °C). Therefore, APBNF shows a multifunctional primary food packaging to maintain the quality of roasted peanuts or oily food products.     

Properties of polyethylene films with incorporated benzoic anhydride and/or ethyl and propyl esters of 4-hydroxybenzoic acid and their suitability for food packaging

Benzoic anhydride and ethyl and propyl esters of 4-hydroxybenzoic acid (ETP and PRP, respectively, also termed parabens) incorporated into low density polyethylene (LDPE) film were studied with regard to migration into food and food simulants at 6°C and 25°C, and changes in selected properties of the film were investigated. Antimicrobials were incorporated into polymer film in concentrations of 5g/kg and 10g/kg. The addition of parabens into the polymer was more difficult than benzoic anhydride due to their volatility. For benzoic anhydride, 30-40% and 10-20% of the added amount was found to leach from the film into aqueous and olive oil food simulants, respectively. The migration into both water and olive oil followed a very similar course in the case of parabens. Migration levels over 90% and in the range of 70% to 80%, relative to the amount of agent in the film, were determined for ETP and PRP respectively. The incorporation of antimicrobials into the film significantly changed the functional characteristics of the packaging material, i.e. permeability of oxygen, carbon dioxide and water vapour, tensile strength, coefficient of friction, sealing strength and transparency. Shelf life tests with packaged cheese and toasted bread demonstrated the efficiency of the film containing 10g/kg of BA against mould growth on the food surface during storage at 6°C.