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).

Seasonal occurrence and risk assessment of endocrine-disrupting compounds in Tagus estuary biota (NE Atlantic Ocean coast).

Estuaries are continually threatened by anthropogenic pressures, consequently, a large group of contaminants harmful to human health affects the aquatic biota; therefore, it is necessary to monitor their quality. This study deals with the determination of a large group of compounds representing different endocrine-disrupting compounds (EDCs) classes [21 pesticides, 4 polycyclic musk fragrances, 4 UV-filters, 7 bisphenols, 6 polybrominated diphenyl ethers (PBDEs) and 8 of their methoxylated (MeO-BDEs)] in several estuarine species (fish, bivalves, crustaceans, earthworm, and macroalgae) collected seasonally along one year in two distinct areas of Tagus River estuary ("contaminated" vs. "clean" areas). The most abundant compounds found were galaxolide (HHCB) (81% positive samples; 0.04-74 ng/g ww), isoamyl 4-methoxycinnamate (IMC) (64%; 1.13-251 ng/g ww), alachlor (44%; 0.08-16 ng/g ww), and BDE-47 (36%; 0.06-2.26 ng/g ww). Polycyclic musks were the most frequent contaminants in fish (seabass, barbus, mullet, and sole) and macroalgae samples, while UV-filters were predominant in bivalves and crustaceans, and bisphenols in earthworms. Seasonal variation was verified for Σpesticides and Σmusks, with significantly higher levels in summer and autumn, whereas ΣUV-filters highest levels were found in spring and summer, and for ΣPBDEs statistically higher levels were registered in cold seasons (autumn and winter). Σbisphenols were significantly lower in spring than in the other seasons. In general, considering all species analysed in both areas, no statistically significant differences (p > 0.05) were verified between the two collection areas. Based on the estimated daily intake data, consumption of fish from this estuary is unlikely to be a human health concern, since the levels of contamination were below the toxicological threshold values. Overall, the data obtained in this study will allow regulatory authorities to identify and prioritize contaminants monitoring programs in estuaries, such as the case of bisphenol A, which was found, for the first time, in earthworm and clam species.

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.

Study on the chemical behaviour of Bisphenol S during the in vitro gastrointestinal digestion and its bioaccessibility.

This study evaluated the chemical behaviour of Bisphenol S (BPS) and determined its bioaccessibility after human ingestion using a standardised in vitro gastrointestinal digestion protocol and an analytical method based on high-pressure liquid chromatography coupled with a photodiode array and tandem mass spectrometry. The effects of different factors such as gastric pH, enzymes, and food matrix on the solubility and chemical stability of BPS were studied to evaluate their contribution to its bioaccessibility. The results highlighted that BPS was available at the end of the digestion process in the range of 50-80%, and was susceptible to absorption at the intestinal level. The effect of pH was not significant as a single factor. The presence of enzymes slightly decreased the bioaccessibility of BPS in the intestinal phase with gastric pH increase. Additionally, a soy drink reduced BPS bioaccessibility by up to 5% after oral intake. Finally, a few BPS degradation products were found in non-bioaccessible fractions at different pH values.

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.

Presence of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in Food Contact Materials (FCM) and Its Migration to Food.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are synthetic chemical compounds widely used in different industry fields including food contact materials (FCM), providing resistance to fat and humidity, and non-stick properties. PFAS enter into the food chain directly from the intake of contaminated food or indirectly from the migration of the FCM into the food. This exposure published in different research highlights a public health concern. Therefore, it is necessary to perform analysis of the content of different FCM and evaluate the migration from the FCM under normal conditions of use and storage. This bibliographical review proves that different perfluoroalkyl and polyfluoroalkyl compounds are detected in fast food packaging, microwave popcorn bags, and frying pans, among others. Furthermore, it shows the conditions or factors that favor the migration of the PFAS from the FCM into the food.

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.

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.

Dialkylketones in Paperboard Food Contact Materials-Method of Analysis in Fatty Foods and Comparative Migration into Liquid Simulants Versus Foodstuffs.

Dialkyl diketene dimers are used as sizing agents in the manufacture of paper and board for food contact applications to increase wetting stability. Unbound residues can hydrolyze and decarboxylate into dialkylketones. These non-intentionally added substances (NIAS) have potential to migrate to fatty foods in contact with those packaging materials. In Germany, the Federal Institute for Risk Assessment (BfR) established a specific migration limit (SML) of 5 mg/kg for the transfer of these dialkylketones into foodstuffs. In order to investigate the differences between simulants and real foods, an analytical method was optimized for extraction and quantification of dialkylketones in edible oils and fatty foods by gas chromatography coupled with flame ionization detection (GC-FID), and additionally by gas chromatography with mass spectrometry (GC-MS), to confirm their identification and to quantify them in case of interferences. Dialkylketones are separated from the extracted fat by alkaline saponification of the triglycerides. Dialkylketones migration from paper-based food contact articles into organic solvents isooctane and dichloromethane, in olive and sunflower oils, and in fatty foods (croissants, Gouda, cheddar cheese, and salami was studied). As a result, it was found that the simulating tests, including the edible oil extraction tests, gave migration values that exceeded the SML largely, while the migration with the food samples were largely below the SML.

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.