Juana Bustos

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.

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.

Migration of bisphenol A from polycarbonate baby bottles purchased in the Spanish market by liquid chromatography and fluorescence detection.

During the last decade the safety of bisphenol A (BPA) monomer in polycarbonate baby bottles has drawn the attention of both the public and the scientific community. This paper presents the results of BPA migration from polycarbonate baby bottles bought in the Spanish market, into simulant B (3% acetic acid), 50% ethanol and into real food (reconstituted infant formula). Furthermore, it was also the objective of this study to assess the suitability of 50% ethanol as a simulant for infant formula. BPA was analysed by a multi-analyte liquid chromatography method with fluorescence detection and mass spectrometry confirmation. The method was in-house validated and accredited by the national accreditation body. The validation results for this analyte in the previous mentioned matrices were: LOD = 0.004–0.007 mg kg–1; LOQ (validated) = 0.03 mg kg–1; RSD% = 3.4–5.8; and recovery = 106.6–118.2%. A collection of 72 different baby bottle samples from 12 different brands were analysed. Baby bottle material was identified by FTIR. The migration test conditions used were those recommended for baby bottles in the Guidelines on testing conditions for articles in contact with foodstuffs (with a focus on kitchenware), prepared by the European network of laboratories for food-contact materials. In most of the migration assays the results were below the LOD. In four of the commercial brands there was detectable migration into the simulant 50% ethanol and BPA was detected in only two samples of infant formula (0.01 mg kg–1). Migration results obtained were in compliance with European Union regulations.

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 µg kg−1). Global internal reproducibility was in the range 5.6–21.4% (RSDR) 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.

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.

Instability of an aromatic amine in fatty food and fatty food simulant: characterisation of reaction products and prediction of their toxicity

It is a well-known fact that amines are not stable in food of a fatty nature. In this study the synthesis and characterisation of the products obtained as a result of the reaction of amines in a fatty medium are reported. Based on the well-known reactions among amines and acid and esters groups, two novel compounds were synthesised using m-xylylenediamine (mXDA), a primary diamine widely used as monomer in the manufacture of food contact materials and two fatty acids, oleic acid and palmitic acid, which occur in most fats. The resulting compounds were two molecules belonging to the family of fatty acid amides, dioleamide and dipalmitamide. A complete characterisation of both products was carried out employing several techniques such as infrared spectroscopy, 1H- and 13C-NMR spectroscopy, electron ionisation mass spectrometry, LC-MS/MS and UV spectrometry. The results obtained by the different techniques were well correlated. In the second part of the work, the formation of these compounds in real samples was evaluated. For this purpose a certain volume of olive oil was spiked with a known amount of mXDA. Olive oil was selected as a fatty medium since it is a widely consumed food and additionally is used as a fatty food simulant in migration studies of food contact materials. A method was developed to extract the fatty acid amides from the fatty matrix, which were then identified by LC-MS/MS. The toxicity of the synthesised compounds was predicted using a toxicity estimation software tool. Graphical Abstract