Películas nanoestructuradas de PS-b-P4VP con ácido fórmico

Memoria realizada en el Departamento de Química Orgánica e Inorgánica de la Universidad de Oviedo como Trabajo Fin de Máster en Química y Desarrollo Sostenible.Este trabajo ha sido financiado con cargo al proyecto: FIS2013-45469.Peer Reviewe

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 beveragesThe study was financially supported by the Ministerio de Ciencia, Innovación y Universidades, by Fondo Europeo de Desarrollo Regional (FEDER), and by Agencia Estatal de Investigación Ref. No. PGC2018-094518-B-I00 “MIGRACOATING” (MINECO/FEDER, UE)S

Multi-analyte method for the quantification of bisphenol related compounds in canned food samples and exposure assessment of the Spanish adult population

Major types of internal can coatings used for food and beverages are made from synthetic polymers known as epoxy-based resins, mainly based on bisphenol A diglycidyl ether (BADGE). The migration of components from coatings to food is a concern for food safety. A multiresidue method was developed for the identification and quantification of six bisphenols, BADGE and its derivatives, and cyclo-di-BADGE in sixteen canned food samples based on HPLC-FLD. The method developed showed excellent validation data with an adequate linearity, low detection levels, good repeatability and acceptable recoveries. Confirmation of the obtained results was made by LC–MS/MS. The exposure of the adult population to these compounds through the consumption of canned food was assessed. In general, the results suggested a low dietary exposure to this type of compounds (0.003 to 0.985 μg/kg bw/day) with values lower than the established tolerable day intake (TDI). The highest mean concentration was observed for cyclo-di-BADGE in a sample of pickled musselsS

Characterization of the skin and gill microbiomes of the farmed seabass (Dicentrarchus labrax) and seabream (Sparus aurata)

There is substantial evidence showing that the microbiome of teleosts plays a key role in host health and wellbeing. Aquaculture practices increase the risk of dysbiosis (i.e. microbial imbalance), which is known to facilitate pathogen infections. The skin and gills are the primary defense organs against pathogens, thus, characterizing their microbiome composition in farmed fish is pivotal for detecting potential alterations that may lead to disease susceptibility. Here, we assessed the skin and gill microbiomes of two of the most important adult fish species farmed in southern Europe, the seabass and the seabream, during winter months. We coupled next-generation sequencing (MiSeq) of the 16S rRNA V4 region with the DADA2 bioinformatic pipeline to assess microbial composition and structure. Variation in microbial alpha-diversity (intra-sample) and taxa proportions were assessed using analysis of variance. Differences in beta-diversity (between-sample) were tested using permutational multivariate analysis of variance. Microbiomes of both tissues (n = 30 per species) identified 19 bacteria phyla, dominated by the phyla Proteobacteria (44–68%) and Bacteroidetes (15–37%); the families Flavobacteriaceae (11–28%), Rhodobacteraeae (4–8%) and Vibrionaceae (2–17%); and the genera Rubritalea (4–13%), Pseudomonas (4–8%) and the NS3a marine group (4–12%). Mean relative proportion of these taxa, some alpha-diversity indices and all beta-diversity distances varied significantly between tissues within and between species. ASVs belonging to the genera Polaribacter and Vibrio, which include several species that are pathogenic, were detected in the core microbiomes of seabass or seabream

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.This research was funded by the Ministerio de Ciencia, Innovación y Universidades, by Fondo Europeo de Desarrollo Regional (FEDER), and by Agencia Estatal de Investigación Ref.No. PGC2018-094518-B-I00 “MIGRACOATING” (MINECO/FEDER, UE)S

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 intakesThis research was funded by the Ministerio de Economía y Competitividad, by Fondo Europeo de Desarrollo Regional (FEDER), and by Agencia Estatal de Investigación Ref.No. AGL2015-69609-P “MIGRAEXPO” (MINECO/FEDER, UE)S

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, respectivelyThis study was financially supported by the Ministerio de Economía y Competitividad, by Fondo Europeo de Desarrollo Regional (FEDER), and by Agencia Estatal de Investigación Ref.No. AGL2015-69609-P “MIGRAEXPO” (MINECO/FEDER, UE)S

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 consideredThis study was funded by the Ministerio de Ciencia, Innovación y Universidades, Fondo Europeo de Desarrollo Regional (FEDER), and Agencia Estatal de Investigación (Ref. no. PGC2018-094518-B-I00 “MIGRACOATING” [MICIU/FEDER, UE])S

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.This research was funded by Ministerio de Economía Y Competitividad Ref. No. AGL/2011-26531 “MIGRATIN” and Fondo Europeo de Desarrollo Regional (FEDER)S

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 extractionThis research was funded by the Ministerio de Ciencia, Innovación y Universidades, by the Fondo Europeo de Desarrollo Regional (FEDER), and by the Agencia Estatal de Investigación Ref. No. PGC2018-094518-B-I00 “MIGRACOATING” (MICIU/FEDER, UE). The authors are grateful to the Ministerio de Ciencia, Innovación y Universidades for the predoctoral fellowship (ref. PRE2019-088195) awarded to P.V.-L.; A.L.-C. is grateful for her grant Programa de axudas á etapa predoutoral da Xunta de Galicia (Consellería de Cultura, Educación e Ordenación Universitaria)S