R. Sendón

Migration and diffusion of diphenylbutadiene from packages into foods.

Monitoring of exposure to chemicals from food contact materials is a subject of increasing importance. The concentration of the chemicals and their migration levels, as well as food consumption and packaging usage data, are required to enable calculation of the degree of such exposure. The present study investigated the migration kinetics of diphenylbutadiene (DPBD) from packages into flour, rice, honey, milk powder and toast. Migration was not always negligible, except in honey and skimmed milk powder. Experiments carried out with starch alone enabled us to conclude that diffusion of migrants occurred through starch and fat. Key diffusion parameters were determined (diffusion coefficient and partition coefficient) based on Ficks second equation. The following diffusion coefficients were obtained at 25 degrees C: 2.7 x 10(-10), 3.4 x 10(-11), 3.2 x 10(-10), 8.4 x 10(-11), 8.1 x 10(-11) cm(2) s(-1), for wheat flour, rice, milk powder and toast, with 4 and 21% fat, respectively. A very good fit between experimental and predicted data was achieved. The data obtained in the present study confirm the validity of the mathematical model for predicting migration from Food Contact Materials (FCM) into foods.

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.

Ultra-high pressure LC for astaxanthin determination in shrimp by-products and active food packaging

Nowadays, there is increasing interest in natural antioxidants from food by-products. Astaxanthin is a potent antioxidant and one of the major carotenoids in crustaceans and salmonids. An ultra-high pressure liquid chromatographic method was developed and validated for the determination of astaxanthin in shrimp by-products, and its migration from new packaging materials to food simulants was also studied. The method uses an UPLC® BEH guard-column (2.1 × 5 mm, 1.7 µm particle size) and an UPLC® BEH analytical column (2.1 × 50 mm, 1.7 µm particle size). Chromatographic separation was achieved using a programmed gradient mobile phase consisting of (A) acetonitrile-methanol (containing 0.05 m ammonium acetate)-dichloromethane (75:20:5, v/v/v) and (B) ultrapure water. This method was evaluated with respect to validation parameters such as linearity, precision, limit of detection, limit of quantification and recovery. Low-density polyethylene films were prepared with different amounts of the lipid fraction of fermented shrimp waste by extrusion, and migration was evaluated into food simulants (isooctane and ethanol 95%, v/v). Migration was not detected under the tested conditions.

Ultra‐high pressure LC determination of glucosamine in shrimp by‐products and migration tests of chitosan films

Chitosan, a multiple applications molecule, was isolated from shrimp by-products by fermentation. The amount of chitosan in the solid fraction of the fermented extract was measured after its conversion in the respective glucosamine units. The procedure includes an acid hydrolysis (110 °C, 4 h with HCl 8 M) and a derivatization with 9-fluorenylmethyl chloroformate (Fmoc-Cl). Ultra-high-pressure liquid chromatography method was developed and optimized. Excellent peaks resolution was achieved in just 10 min. The method was evaluated in what concerns to validation parameters such as linearity, repeatability, quantification limit, and recovery. Migration tests of films prepared with chitosan were carried out in two simulants: ultrapure water and ethanol 95% (v/v).

Determination of key diffusion and partition parameters and their use in migration modelling of benzophenone from low-density polyethylene (LDPE) into different foodstuffs

ABSTRACT The mass transport process (migration) of a model substance, benzophenone (BZP), from LDPE into selected foodstuffs at three temperatures was studied. A mathematical model based on Fick’s Second Law of Diffusion was used to simulate the migration process and a good correlation between experimental and predicted values was found. The acquired results contribute to a better understanding of this phenomenon and the parameters so-derived were incorporated into the migration module of the recently launched FACET tool (Flavourings, Additives and Food Contact Materials Exposure Tool). The migration tests were carried out at different time–temperature conditions, and BZP was extracted from LDPE and analysed by HPLC-DAD. With all data, the parameters for migration modelling (diffusion and partition coefficients) were calculated. Results showed that the diffusion coefficients (within both the polymer and the foodstuff) are greatly affected by the temperature and food’s physical state, whereas the partition coefficient was affected significantly only by food characteristics, particularly fat content.

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 Ficks 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.

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.