In vitro bioaccessibility of cyclodi-BADGE present in canned seafood: A new approach for the estimation of dietary exposure of the Spanish population.

Human dietary exposure to chemical compounds is a priority issue for public health authorities since it constitutes a key step in risk assessment, and food packaging could be an important source of contamination. In this study, the bioaccessibility of cyclodi-BADGE was evaluated in canned seafood samples using a standardized protocol of in vitro gastrointestinal digestion and an analytical method based on liquid chromatography coupled to tandem mass spectrometry. The impact of enzymes, different gastric pHs, and food-covering liquids on the bioaccessibility of cyclodi-BADGE was studied. The results highlighted that cyclodi-BADGE was available to be absorbed at the intestinal level (90.9-112.3%), and its bioaccessibility increased substantially in fat food samples. Finally, the estimated dietary exposure to cyclodi-BADGE in the Spanish adult population reached values of 14.26 µg/kg bw/day for tuna in tomato, exceeding the tolerable daily intake (1.5 µg/kg bw/day) recommended for chemicals with high toxicological risk.

Migration of Dihydroxy Alkylamines and Their Possible Impurities from Packaging into Foods and Food Simulants: Analysis and Safety Evaluation.

Alkyl diethanolamines are a group of compounds commonly used as antistatic agents in plastic food packaging materials. These additives and their possible impurities have the ability to transfer into the food; hence, the consumer may be exposed to these chemicals. Recently, scientific evidence of unknown adverse effects associated with these compounds was reported. N,N-bis(2-hydroxyethyl)alkyl (C8-C18) amines as well as other related compounds and their possible impurities were analyzed in different plastic packaging materials and coffee capsules using target and non-target LC-MS methods. N,N-bis(2-hydroxyethyl)alkyl amines, precisely, C12, C13, C14, C15, C16, C17 and C18, 2-(octadecylamino)ethanol and octadecylamine, among others, were identified in most of the analyzed samples. It should be emphasized that the latter compounds are not listed in the European Regulation 10/2011 and 2-(octadecylamino)ethanol was classified as high toxicity according to Cramer rules. Migration tests were carried out in foods and in the food simulants Tenax and 20% ethanol (v/v). The results showed that stearyldiethanolamine migrated into the tomato, salty biscuits, salad and Tenax. Lastly, as a crucial step in the risk assessment process, the dietary exposure to stearyldiethanolamine transferred from the food packaging into the food was determined. The estimated values ranged from 0.0005 to 0.0026 µg/kg bw/day.

Identification of potential migrants from epoxy and organosol coatings used in metal food cans.

The coatings of metal cans may release complex mixtures of migrants into the contained foods, including non-intentionally added substances (NIAS), such as reaction products. All migrating substances should be studied to demonstrate their safety. In this work, the characterisation of two epoxy and organosol coatings was performed using several techniques. Firstly, the type of coating was identified using FTIR-ATR. Screening techniques based on purge and trap (P&T) and solid-phase microextraction (SPME) coupled to GC-MS were used to investigate volatiles from coatings. For the identification of semi-volatile compounds, an appropriate extraction was performed before analysis by GC-MS. The most abundant substances were compounds with at least one benzene ring and an aldehyde or alcohol group in their structures. Furthermore, a method to quantify some of the identified volatiles was explored. Secondly, HPLC with fluorescence detection (HPLC-FLD) was used to determine non-volatile compounds such as bisphenol analogues and bisphenol A diglycidyl ethers (BADGEs), with subsequent confirmation by LC-MS/MS. Additionally, migration assays were performed by this technique to determine non-volatile compounds migrating into food simulants. Bisphenol A (BPA) and all BADGE derivatives except BADGE.HCl were detected in the migration extracts. Moreover, BADGE-solvent complexes such as BADGE.H2O.BuEtOH, BADGE.2BuEtOH, etc. were also tentatively identified using the accurate mass provided by time-of-flight mass spectrometry (TOF-MS).

Food and beverage can coatings: A review on chemical analysis, migration, and risk assessment.

The internal surface of food and beverage cans is generally covered with polymeric coatings to preserve food and protect metal substrate from corrosion. Coating materials are complex formulations that contain different starting substances (e.g., monomers, prepolymers, additives, etc.) and in addition during the manufacture of the material several compounds can be formed (e.g., reaction products, degradation products, etc.). These substances have the potential to migrate into the food. Many of them have not been identified and only some have been toxicologically evaluated. This article aims to provide a comprehensive review on the analytical methods used for the identification of potential migrants in can coatings. The migration and exposure to chemicals migrating from can coatings are also reviewed and discussed so far, which is essential for risk assessment. Moreover, a brief section on the current status of the legislation on varnishes and coatings for food contact in Europe is also presented. Liquid chromatography coupled to diode array and fluorescence detectors and particularly to mass spectrometry and gas chromatography-tandem mass spectrometry seem to be the techniques of choice for the identification of potential migrants in can coatings. Some studies have reported migration levels of BPA (bisphenol A) and BADGE (bisphenol A diglycidyl ether) and derivatives exceeding the specific migration limits set in the European legislation. On the whole, low dietary exposure to migrants from can coatings has been reported. However, it is interesting to highlight that in these studies the combined exposure to multiple chemicals has not been considered.

Characterization of Polyester Coatings Intended for Food Contact by Different Analytical Techniques and Migration Testing by LC-MSn.

Polymeric coating formulations may contain different components such as cross-linking agents, resins, lubricants, and solvents, among others. If the reaction process or curing conditions are not applied in a proper way, these components may remain unreacted in the polymeric network and could be released and migrate into foods. In this study, several polyester coatings intended for food contact were investigated. Firstly, Fourier-transform infrared spectroscopy with an attenuated total reflectance (ATR-FTIR) spectrometer and confocal Raman microscopy were used to identify the type of coating. Then, different techniques, including gas chromatography coupled to mass spectrometry (GC-MS) and analysis by matrix-assisted laser desorption coupled to time-of-flight mass spectrometry (MALDI-TOF-MS), among others, were used to investigate the potential volatile and non-volatile migrants. Moreover, migration assays were carried out to evaluate the presence of monomers and to tentatively identify possible oligomers below 1000 Da. The analyses were performed by liquid chromatography coupled to ion trap mass spectrometry (LC-MSn). Using the information collected from each analytical technique, it was possible to elucidate some of the starting substances used in the formulation of the polyester coatings analyzed in this study. In migration tests, several polyester oligomers were tentatively identified for which there is not toxicological data available and, therefore, no migration limits established to date.

Identification of Volatile and Semi-Volatile Compounds in Polymeric Coatings Used in Metal Cans by GC-MS and SPME.

Polymeric coatings are used as a protective layer to preserve food or beverage quality and protect it from corrosion and avoid a metallic taste. These types of materials can contain some chemicals that are susceptible to migrate to food and constitute a risk for consumers' health. This study is focused on the identification of volatile and semi-volatile low molecular weight compounds present in polymeric coatings used for metal food and beverage cans. A method based on solid-liquid extraction followed by gas chromatography-mass spectrometry (GC-MS) was optimized for the semi-volatile compounds. Different solvents were tried with the aim of extracting compounds with different polarities. Furthermore, a method based on solid-phase microextraction (SPME) in headspace (HS) mode and gas chromatography coupled with mass spectrometry (HSSPME-GC-MS) was developed for the identification of potential volatile migrants in polymeric coatings. Some parameters such as extraction time, equilibrium temperature, or the type of fiber were optimized. Different compounds, including aldehydes such as octanal or nonanal, alcohols such as α-terpineol or 2-butoxyethanol, ethers, alkenes, or phthalic compounds, among others, were identified and confirmed with analytical standards both via SPME analysis as well after solvent extraction.

Application of chromatographic analysis for detecting components from polymeric can coatings and further determination in beverage samples.

Major type of internal can coating used for food and beverages is made from epoxy resins, which contain among their components bisphenol A (BPA) or bisphenol A diglycidyl ether (BADGE). These components can be released and contaminate the food or beverage. There is no specific European legislation for coatings, but there is legislation on specific substances setting migration limits. Many investigations have paid attention to BPA due to its classification as endocrine disruptor, however, few studies are available concerning to other bisphenol analogues that have been used in the manufacture of these resins. To evaluate the presence of this family of compounds, ten cans of beverages were taken as study samples. Firstly, the type of coating was verified using an attenuated total reflectance-FTIR spectrometer to check the type of coating presents in most of the samples examined. A screening method was also performed to investigate potential volatiles from polymeric can coatings of beverages using Purge and Trap (P&T) technique coupled to gas chromatography with mass spectrometry detection (GC-MS). Moreover, a selective analytical method based on high performance liquid chromatography with fluorescence detection (HPLC-FLD) for the simultaneous identification and quantification of thirteen compounds including bisphenol analogues (BPA, BPB, BPC, BPE, BPF, BPG) and BADGEs (BADGE, BADGE.H2O, BADGE.2H2O, BADGE.HCl, BADGE.2HCl, BADGE.H2O.HCl, cyclo-di-BADGE) in the polymeric can coatings and in the beverage samples was applied. In addition, a liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) method was optimized for confirmation purposes. The method showed an adequate linearity (R2 >0.9994) and low detection levels down to 5 µg/L. Cyclo-di-BADGE was detected in all extracts of polymeric coatings. The concentrations ranged from 0.004 to 0.60 mg/dm2. No detectable amounts of bisphenol related compounds were found in any of the beverage samples at levels that may pose a risk to human health, suggesting a low intake of bisphenols from beverages.

Estimation of Dietary Exposure to Contaminants Transferred from the Packaging in Fatty Dry Foods Based on Cereals.

Food packaging has received special attention from the food safety standpoint since it could be a potential source of contamination through the migration of chemical substances from the packaging material into food. The assessment of the exposure through the diet to these contaminants from food packaging is necessary. In this work, an estimation of dietary exposure of the young Spanish population (1-17 years) to target chemicals from packaging for fatty dried foods based on cereals was assessed. For this purpose, a gas chromatography coupled to mass spectrometry (GC-MS) method was developed for screening of volatile and semivolatile compounds, potential migrants from the packaging. Then, this technique was used to quantify 8 target analytes, which were previously identified in the packaging (including phthalates, acetyl tributyl citrate (ATBC), butylated hydroxytoluene (BHT) and octocrylene), in composite food samples of fatty cereals prepared according to the consumption data for different age groups. Among the phthalates, exposure to diethyl phthalate (DEP) was the highest for the three groups considered (0.0761-0.545 µg/kg body weight/day), followed by bis(2-ethylhxyl)phathalate (DEHP), while the lowest mean intake was found for di-n-octyl phathalate (DNOP; 0.00463-0.0209 µg/kg body weight/day). The estimated dietary exposures did not exceed for any of the analytes the corresponding established tolerable daily intakes.

GC-MS Screening for the Identification of Potential Migrants Present in Polymeric Coatings of Food Cans.

The coatings used in cans can release complex chemical mixtures into foodstuffs. Therefore, it is important to develop analytical methods for the identification of these potential migrant compounds in packaged food to guarantee the compliance with European food packaging legislation and ensure consumer safety. In the present work, the type of coating in a total of twelve cans collected in Santiago de Compostela (Spain) were evaluated using an ATR (attenuated total reflectance)-FTIR spectrometer. These samples were analysed after extraction with acetonitrile in order to identify potential migrants through a screening method by gas chromatography coupled to mass spectrometry (GC-MS). A total of forty-seven volatile and semi-volatile compounds were identified in these samples, including plasticizers, photoinitiators, antioxidants, lubricants, etc. Then, in a second step, a targeted analysis was carried out for the simultaneous determination of 13 compounds, including bisphenols (BPA, BPB, BPC, BPE, BPF, BPG) and BADGEs (BADGE, BADGE.H2O, BADGE.2H2O, BADGE.HCl, BADGE.2HCl, BADGE.H2O.HCl, cyclo-di-BADGE) by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) with atmospheric pressure chemical ionisation (APCI) source. Among all the bisphenols analysed, only the bisphenol A was detected in four samples; while cyclo-di-BADGE was the predominant compound detected in all the samples analysed.

Migration Studies of Two Common Components of UV-curing Inks into Food Simulants.

The Rapid Alert System for Food and Feed (RASFF) has reported many cases of different UV curing inks components in foodstuffs during the last few years. These contaminants reach foodstuffs mainly by set-off, their principal migration mechanism from the package. Under this premise, this work has tried to characterize the process of migration of two common UV ink components: a photoinitiator (4-Methylbenzophenone) and a coinitiator (Ethyl-4-(dimethylamino) benzoate), from the most common plastic material used in food packaging low-density polyethylene (LDPE) into six different food simulants. The migration kinetics tests were performed at four different common storage temperatures, obtaining the key migration parameters for both molecules: the coefficients of diffusion and partition. The migration process was highly dependent on the storage conditions, the photoinitiator properties and the pH of the foodstuff.

Estimates of dietary exposure of Spanish population to packaging contaminants from cereal based foods contained in plastic materials.

Food packaging may be a potential source of contamination, through the migration of chemicals from the packaging into the food, thus food consumption is an important route of human exposure to packaging contaminants. In the present study an approach to estimate the exposure to different chemicals transferred from food packaging was designed. As a first step a GC-MS screening was conducted to identify potential contaminants in the materials. Secondly, different chemicals previously identified in the packaging materials were selected for exposure assessment. The proposed methodology was applied to cereal based foods packed with plastic packaging. A variety of chemicals including e.g. acetyl tributyl citrate (ATBC), bis (2-ethylhexyl) adipate (DEHA) and diethyl phthalate (DEP) among others were identified and analyzed in the foodstuffs. For this purpose a LC-MS/MS method was developed. The selected foodstuffs were pooled into three groups according to the population age (12-35 months, 3-9 years and 10-17 years) and based on the Spanish consumption data (Enalia). In general, ATBC mean exposure was higher than that of phthalates and DEHA for the three groups considered, with mean dietary exposure values ranging from 1.01 µg/kg bw/day (pool 12-35 months) to 2.01 µg/kg bw/day (pool 3-9 years).

Migration studies of butylated hydroxytoluene, tributyl acetylcitrate and dibutyl phthalate into food simulants.

BACKGROUND: Migration is a mass transfer process in which chemical substances with a low molecular weight are transferred from packaging into food. This phenomenon has received great attention from a food safety point of view because these chemicals could potentially represent a risk for consumers' health. The present study investigated the process of migration of two common plasticizers [tributyl acetylcitrate (ATBC) and dibutyl phthalate (DBP)] and one antioxidant [butylated hydroxytoluene (BHT)] from a common plastic material used in food packaging (low density polyethylene) into 50% ethanol (v/v), 95% ethanol (v/v) and isooctane. A mathematical model based on Fick's second law was used to determine the partition and diffusion coefficients. In addition, the effect of temperature on the diffusion was studied by applying the Arrhenius equation. RESULTS: High-performance liquid chromatography with diode-array detection and gas chromatography-mass spectrometry methods were applied to measure the amount of ATBC, DBP and BHT that migrated into the food simulants. A mathematical model based on Fick's second law of diffusion was used to estimate key migration parameters: diffusion and partition coefficients (DP and KP/F ), which were determined for each migrant and food simulant at three temperatures (10, 20 and 40 °C). The results showed that the diffusion process is significantly influenced by temperature, although the type of simulant also plays an important role in the migration process. CONCLUSION: The model investigated is shown to be appropriate for predicting the migration from food packaging into real foodstuffs at common storage temperatures. © 2018 Society of Chemical Industry.

Characterization data of chitosan-based films: Antimicrobial activity, thermal analysis, elementary composition, tensile strength and degree crystallinity.

This set of raw and analyzed data are complement to the research article that is titled "Mechanical, structural and physical aspects of chitosan-based films as antimicrobial dressings" (Escárcega-Galaz et al., 2018) [1]. The mechanical, structural and biological properties of the chitosan-based films determine their potential application in biomedicine. The films were prepared from pure chitosan and in combination with honey or glycerol. Afterwards, the characterization data related to thermal analysis, elementary composition, tensile strength and degree crystallinity was collected. The data of the antimicrobial activity of the films correspond to Klebsiella pneumoniae and Pseudomonas aeruginosa, both isolated from cutaneous ulcers. This set of data indicate that the chitosan-based films possess biological and physicochemical characteristics for their application as antimicrobial dressings for their action when are used by direct contact during the treatment of cutaneous ulcers.

Mechanical, structural and physical aspects of chitosan-based films as antimicrobial dressings.

Chitosan is a biodegradable, non-toxic, and antimicrobial polymer. Chitosan films can be used as a dressing because they promote the healing of cutaneous ulcers. In this study, the mechanical, physical, and microbiological properties films of pure chitosan and films formulated with a glycerol-honey mixture were characterized. The films were smooth, homogenous, transparent, and porous, with no fractures or cracks. Additionally, it was found that all were resistant to breaking, that the tearing force was directly related to the chitosan concentration, and that the addition of honey and glycerol improved the elongation percentage. When evaluating the antimicrobial activity of the films against Pseudomonas aeruginosa and Klebsiella pneumoniae, the films were found to have an effect only by direct contact. In the films formulated with honey, the area of contact increased to 44%. The excellent color, structural, antimicrobial, and surface morphological properties of the newly developed films make them a promising alternative for use as a dressing for the healing of skin ulcers.

Identification of intentionally and non-intentionally added substances in plastic packaging materials and their migration into food products.

Plastic materials are widely used in food packaging applications; however, there is increased concern because of the possible release of undesirable components into foodstuffs. Migration of plastic constituents not only has the potential to affect product quality but also constitutes a risk to consumer health. In order to check the safety of food contact materials, analytical methodologies to identify potential migrants are required. In the first part of this work, a GC/MS screening method was developed for the identification of components from plastic packaging materials including intentionally and "non-intentionally added substances" (NIAS) as potential migrants. In the second part of this study, the presence of seven compounds (bis (2-ethylhexyl) phthalate (DEHP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), butylated hydroxytoluene (BHT), acetyl tributyl citrate (ATBC), benzophenone (BP)) previously identified in packaging materials were investigated in food products (corn and potatoes snacks, cookies, and cakes). For this purpose, a suitable extraction method was developed and quantification was performed using GC-MS. The developed method was validated in terms of linearity, recovery, repeatability, and limits of detection and quantification. The spiked recoveries varied between 82.7 and 116.1%, and relative standard deviation (RSD) was in the range of 2.22-15.9%. The plasticizer ATBC was the most detected compound (94% samples), followed by DEP (65%), DEHP (47%), BP (44%), DBP (35%), DIBP (21%), and BHT (12%). Regarding phthalates, DEP and DEHP were the most frequently detected compounds in concentrations up to 1.44 µg g-1. In some samples, only DBP exceeded the European SML of 0.3 mg kg-1 established in Regulation 10/2011. Graphical abstract Chemical migration from plastic packaging into food.

Determination of diffusion and partition coefficients of model migrants by direct contact and vapour phase transfer from low-density polyethylene films into cake.

The aim of the present study was to determine the migration kinetics of one photoinitiator, benzophenone, and two optical brighteners, Uvitex OB and 1,4-diphenyl-1,3-butadiene (DPBD), from low-density polyethylene (LDPE) films into cake. Transfer was assessed by both direct contact and also the vapour phase. To perform the migration tests by direct contact, plastic films enriched with the additives were placed between two cake slices. To evaluate the migration through the gas phase, cake and the fortified LDPE film were placed with no direct contact in a glass container that was hermetically closed. Samples were stored at different time-temperature conditions. Target compounds were extracted from the films with ethanol (70°C, 24 h) and analysed by HPLC-DAD. Relevant parameters such as partition and diffusion coefficients between food and plastic film were calculated. The Arrhenius equation was applied to estimate the diffusion coefficient at any temperature. The data indicate that migration of benzophenone occurs in a significant extent into cake by both direct contact and through the gas phase (no direct contact). Conversely, very little migration occurred for Uvitex OB by direct contact and none through the gas phase. Results for benzophenone suggest that migration through the gas phase should be considered when evaluating migration from food packaging materials into food.

Effect of the refining process on Moringa oleifera seed oil quality.

We evaluated the physicochemical properties and oxidative stability of the oil extracted from the seeds of Moringa oleifera during its refining process. Refining is accomplished in three stages: neutralization, degumming, and bleaching. Four samples were analyzed, corresponding to each step of the processed and crude oil. Increases in the density, viscosity, saponification value and oxidation of the oil were detected during the refining, while the peroxide value and carotenoid content diminished. Moreover, the refractive index and iodine content were stable throughout the refining. Nine fatty acids were detected in all four samples, and there were no significant differences in their composition. Oleic acid was found in the largest amount, followed by palmitic acid and behenic acid. The crude, neutralized, and degummed oils showed high primary oxidation stability, while the bleached oil had a low incidence of secondary oxidation.

Active food packaging based on molecularly imprinted polymers: study of the release kinetics of ferulic acid.

A novel active packaging based on molecularly imprinted polymer (MIP) was developed for the controlled release of ferulic acid. The release kinetics of ferulic acid from the active system to food simulants (10, 20, and 50% ethanol (v/v), 3% acetic acid (w/v), and vegetable oil), substitutes (95% ethanol (v/v) and isooctane), and real food samples at different temperatures were studied. The key parameters of the diffusion process were calculated by using a mathematical modeling based on Fick's second law. The ferulic acid release was affected by the temperature as well as the percentage of ethanol of the simulant. The fastest release occurred in 95% ethanol (v/v) at 20 °C. The diffusion coefficients (D) obtained ranged between 1.8 × 10(-11) and 4.2 × 10(-9) cm(2)/s. A very good correlation between experimental and estimated data was obtained, and consequently the model could be used to predict the release of ferulic acid into food simulants and real food samples.

Development of new active packaging films coated with natural phenolic compounds to improve the oxidative stability of beef.

The aim is to develop active packaging films containing natural antioxidants and to evaluate their capacity to enhance the oxidative stability of beef during refrigeration. The antioxidant activity of a natural extract obtained from a brewery residual waste was evaluated and compared with that of a commercial rosemary extract and two synthetic antioxidants (BHT and propyl gallate). Different concentrations of each antioxidant were also added directly to beef samples, resulting in a reduction in lipid oxidation of up to 70-80% relative to the control. Active antioxidant films coated with PVPP-WS extract reduced lipid oxidation by up to 80%, relative to the control, during cold storage. The use of active packaging films containing natural extracts could improve the oxidative stability of meat products and should therefore be of great interest in the food industry.

Correlation of foodstuffs with ethanol-water mixtures with regard to the solubility of migrants from food contact materials.

Today most foods are available in a packed form. During storage, the migration of chemical substances from food packaging materials into food may occur and may therefore be a potential source of consumer exposure. To protect the consumer, standard migration tests are laid down in Regulation (EU) No. 10/2011. When using those migration tests and applying additional conservative conventions, estimated exposure is linked with large uncertainties including a certain margin of safety. Thus the research project FACET was initiated within the 7th Framework Programme of the European Commission with the aim of developing a probabilistic migration modelling framework which allows one (1) to calculate migration into foods under real conditions of use; and (2) to deliver realistic concentration estimates for consumer exposure modelling for complex packaging materials (including multi-material multilayer structures). The aim was to carry out within the framework of the FACET project a comprehensive systematic study on the solubility behaviour of foodstuffs for potentially migrating organic chemicals. Therefore a rapid and convenient method was established to obtain partition coefficients between polymer and food, KP/F. With this method approximately 700 time-dependent kinetic experiments from spiked polyethylene films were performed using model migrants, foods and ethanol-water mixtures. The partition coefficients of migrants between polymer and food (KP/F) were compared with those obtained using ethanol-water mixtures (KP/F's) to investigate whether an allocation of food groups with common migration behaviour to certain ethanol-water mixtures could be made. These studies have confirmed that the solubility of a migrant is mainly dependent on the fat content in the food and on the ethanol concentration of ethanol-water mixtures. Therefore dissolution properties of generic food groups for migrants can be assigned to those of ethanol-water mixtures. All foodstuffs (including dry foods) when allocated to FACET model food group codes can be classified into a reduced number of food categories each represented by a corresponding ethanol-water equivalency.