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.

Representaciones sociales sobre la migración haitiana en la escuela chilena / Social representations of Haitian migration in Chilean schools / Representações sociais sobre a migração haitiana na escola chilena

Resumen (analítico) Se parte de la siguiente pregunta: ¿cómo representan las y los escolares chilenos de educación básica de una escuela pública de Santiago a sus compañeras y compañeros migrantes haitianos? Se utiliza un enfoque cuantitativo que recurre a la encuesta como instrumento fundamental de estudio. Las variables examinadas son el género y el nivel escolar según la edad del estudiantado, dando como resultado, por un lado, que las estudiantes de género femenino y quienes cursan de 1º a 4º año básico tienden a representar socialmente al estudiantado haitiano de modo positivo y, por otro lado, que los estudiantes de género masculino y quienes cursan de 5º a 8º año básico tienden a generar representaciones prejuiciosas y desestimadas de las y los migrantes.

Abstract (analytical) This research begins with the following question: How do Chilean school children in a public primary school in Santiago represent their Haitian migrant classmates? A quantitative approach was with a survey selected as the main data collection tool. The variables included gender and year level. The results show that female students and those aged between 6 and 9 tend to socially represent Haitian students in an evaluative manner while male students and those aged between 10 and 15 tend to generate prejudiced and dismissive representations of migrants.

Resumo (analítico) O artigo parte da seguinte pergunta: Como os escolares chilenos do ensino básico de uma escola pública de Santiago representam seus companheiros migrantes haitianos? É utilizada uma abordagem quantitativa que utiliza a pesquisa como um instrumento de estudo fundamental. As variáveis examinadas são gênero e nível escolar de acordo com a idade do corpo discente, resultando, por um lado, que estudantes do sexo feminino e entre 6 e 9 anos tendem a representar socialmente os alunos haitianos de forma avaliativa e, por outro lado, que estudantes do sexo masculino e entre 10 e 15 anos tendem a gerar representações preconceituosas e subestimadas dos migrantes.

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.

Dietary Exposure Estimation to Chemicals Transferred from Milk and Dairy Products Packaging Materials in Spanish Child and Adolescent Population.

Packaging materials are subject to risk assessment since they can transfer their components to the food, and they may constitute a risk for the consumers' health. Therefore, estimating the exposure to chemicals migrating from packaging is required. In this study, a novel approach based on a total diet study (TDS)-like investigation to evaluate the exposure to chemicals transferred from the packaging was presented. The proposed methodology involved a non-targeted gas chromatography coupled to mass spectrometry (GC-MS) method to identify potential migrants and the determination of the migrants in composite food samples. The method was applied to evaluate the dietary exposure to chemicals from food packaging materials used for milk and dairy products in the Spanish child and adolescent populations. Several migrants identified in packaging materials were selected to determine their concentration in composite food samples. These chemicals included diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), bis(2ethylhexyl) phthalate (DEHP), benzophenone (BP), 1,3-diphenylpropane (1,3-DPP), and bis(2-ethylhexyl) terephthalate (DEHT). The method exhibited a good sensitivity (limit of detection, LOD ≤ 0.05 µg/g) and a satisfactory recovery (78.4-124%). Finally, the exposure was estimated using the Spanish national dietary survey ENALIA. Phthalates DBP and DEHP showed the highest mean exposure, ranging from 2.42 (10-17 years)-4.40 (12-35 months) and 1.35 (10-17 years)-4.07 (12-35 months) µg/kg bw/day for DBP and DEHP, respectively.

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).

Photoinitiators: a food safety review.

Ultraviolet light printing inks are considered safer than the classical inks; however, despite being on the outer surface of the packaging material, their components can migrate into foodstuffs and can give rise to contamination. Photoinitiators are a part of the formulation of printing inks, being an important class of migrant, for which there have been more than 100 incidents of contamination of packaged food with photoinitiators reported through Rapid Alert System for Food and Feed (RASFF) alerts in the European Union. In this review the process of photo-polymerisation is explained in depth to provide an insight into the complexity of the process, and the diversity of potential contaminants together with their degradation products. The critical factors affecting the migration process itself are reviewed, together with analytical methods and the current legislation in the European Union and other parts of the world.

Detection of migration of phthalates from agglomerated cork stoppers using HPLC-MS/MS.

Agglomerated stoppers are manufactured from natural cork granules and adhesives. Esters, such as phthalates and adipates, are commonly used in adhesives at concentrations of typically 2-5%. Because of this, and regarding consumer safety, it is necessary to ensure that these compounds do not migrate into the beverage where the cork stopper is used. A reversed-phase high performance liquid chromatography method with tandem mass spectrometry detection is developed for the separation of nine phthalates into 12% ethanol, used as simulant of alcoholic beverages. The chromatographic separation was carried out with a Luna C18 (2) HSTcolumn (50 × 3.0 mm, 2.5 µm) with a gradient elution of water/methanol with 0.1% acetic acid at 300 µL min(-1). The method was validated for four selected phthalates: di-butylphthalate, di-isononylphthalate, di-isodecylphthalate, and butyl-benzyl phthalate, with recoveries ranging between 95% and 112% and intralaboratory precision (RSD) between 5 and 14%, depending on the phthalate. The lowest quantification limit, 0.15 mg kg(-1), was achieved for di-butylphthalate. Nevertheless, in all cases, the limits obtained guarantee the method utility if restriction limits set in Commission Regulation No 10/2011 for plastic materials are taken into account.

Analytical method for the simultaneous determination of polyfunctional amines used as monomers in the manufacture of food packaging materials.

This paper describes the development of a multi-analyte method for the determination of polyfunctional amines commonly used as monomers in the manufacture of food contact materials. Amines were analyzed by high-performance-liquid chromatography with diode-array detection (HPLC-DAD) after derivatization with dansyl chloride. The chromatographic analysis and the derivatization conditions were optimized. The proposed method was validated in terms of linearity, limits of detection and repeatabilities. The method showed an excellent sensitivity (LOD≤0.05 µg/mL) and appropriate repeatabilites (RSD (n=7)≤5%)). LC-MS/MS was used as a confirmatory technique. The stability of the amines in five food simulants (distilled water, 3% acetic acid, 10% ethanol, 50% ethanol and olive oil) under the most common testing conditions (10 days at 40 °C) was also studied. Results showed that amines had an acceptable stability in aqueous simulants but in the olive oil a loss of 100% was observed for all analytes.

Chromatographic Methods for the Determination of Polyfunctional Amines and Related Compounds Used as Monomers and Additives in Food Packaging Materials: A State-of-the-Art Review.

Polyfunctional amines are a group of substances commonly used as additives or monomers in food-contact materials. These substances can migrate into foodstuffs and, consequently, may be potentially dangerous for human health. Due to their different chemical structures and physicochemical properties there does not exist a standard method to analyze polyfunctional amines. This review aims to provide an update on the chromatographic methods used for the determination of polyfunctional amines that are commonly used in the manufacture of food packaging materials. Detailed information regarding chromatographic conditions (mobile phases, chromatographic columns, detection systems, and so on) is provided. Moreover, chemical structures and physicochemical properties of the substances studied are also presented.

Validation of a liquid chromatography-mass spectrometry method for determining the migration of primary aromatic amines from cooking utensils and its application to actual samples.

Many cooking utensils are made of nylon, a material that may incorporate azodyes and where primary aromatic amines (PAAs) are the starting substances. Moreover, aromatic amines may also be present as technical impurities. Another source of PAAs could be aromatic isocyanates used as monomers in the production of polyurethanes. The aim of this work was to validate a simple LC-MS/MS method for the determination of eight primary aromatic amines (m-phenylenediamine, 2,6- and 2,4-toluenediamine, 1,5-diaminonaphthalene, aniline, 4,4'-diaminonaphenylether, 4,4'-methylenedianiline and 3,3'-dimethylbenzidine) in the aqueous food simulant 3% acetic acid (w/v). The detection limits calculated were adequate with respect to present legislation. The method was validated at four concentration levels (2, 5 10 and 20 microg kg(-1)). Global internal reproducibility was in the range 5.6-21.4% (RSD(R)) depending on the compound and concentration. Mean recoveries for all levels varied between 89 and 100%, depending on the amine. A total of 39 samples of cooking utensils were analyzed using the described method and the results obtained after the third migration test were not compliant in approximately half of the samples.