Migration of phenolic brominated flame retardants from contaminated food contact articles into food simulants and foods.

Several food contact articles (FCAs) contaminated with unapproved brominated flame retardants (BFRs) purchased in the US market were analysed and subjected to migration tests. Migration tests were performed in food simulants (water, 3% acetic acid, 10% ethanol and 50% ethanol) and food (milk, coffee and chicken bouillon soup) to evaluate the BFRs mass transfer from the contaminated FCA. The BFRs studied, 2,4,6-tribromophenol (TBP), 3,3',5,5'-tetrabromobisphenol A (TBBPA), and 1,2,5,6,9,10-hexabromocyclododecane (HBCD) were analysed by UHPLC-MS/MS. The method validation parameters were r2 ≥ 0.999, LOD ≤ 0.3 ng mL-1, and RSD ≤ 1.7 % (n = 7). HBCD was not stable under our migration conditions and was not detected in any FCA, food or food simulant, including positive controls. Phenolic BFRs (TBP and TBBPA) migrated at concentrations ranging from non-detected to 73 µg kg-1 in food simulants, and from 1 to 23 µg kg-1 in food. Phenolic BFRs migrated into 50% ethanol food simulant at higher concentrations than in more aqueous food simulants and foods.

Brominated flame retardants (BFRs) in contaminated food contact articles: identification using DART-HRMS and GC-MS.

Any food contact material (FCM) must be approved by the US FDA as being compliant with Title 21 of the Code of Federal regulations Parts 170-199, and/or obtain a non-objection letter through the Food Contact Notification Process, before being placed into the United States market. In the past years, several scientific articles identified FCM or more specifically, food contact articles (FCAs), which were contaminated with brominated flame retardants (BFRs) in the European Union. Prior research has suggested the source of BFR contamination was likely poorly recycled plastics containing waste electrical and electronic equipment (WEEE). We conducted a retail survey to evaluate the presence of BFR-contaminated reusable FCA in the US market. Using a Direct Analysis in Real Time ionisation High-Resolution Mass Spectrometry (DART-HRMS) screening technique and extraction gas chromatography-mass spectrometry (GC-MS) confirmation we were able to identify BFRs present in retail FCAs. Among non-targeted retail samples, 4 of 49 reusable FCAs contained 1-4 BFRs each. The identified BFRs, found in greatest estimated concentrations, were 2,4,6-tribromophenol (TBP), 3,3',5,5'-tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), decabromodiphenylethane (DBDPE) and decabromodiphenylether (BDE-209). A second targeted FCA sampling (n = 28) confirmed these BFRs persisted in similar articles. Combined sample sets (n = 77) estimated DART false-positive/negative incidences of 5% & 4%, respectively, for BFR screening of FCAs. Because the presence of BFRs in some contaminated FCAs has been demonstrated and since these compounds are possible migrants into food, further studies are warranted. In order to estimate the potential exposure of the identified BFRs and conduct corresponding risk assessments, the next and logical step will be to study the mass transfer of BFRs from the contaminated FCM into food simulants and food.

Assessment of the Impact of Accelerated Migration Testing for Coated Food Cans Using Food Simulants.

In this study, an accelerated migration test on food can coatings into food simulants was investigated. Food simulants covering a wide range of polarity were used to conduct migration tests at 60 °C with storage times ranging from 4 h to 30 days. Epoxy-resins, acrylic-phenolic, polyester, and vinyl coatings were exposed to water, 3% acetic acid, 50% ethanol, and Miglyol 812®. Using liquid chromatography coupled to a variety of detectors (UHPLC-Q-Orbitrap-MS, UFLC-MS/MS, and HPLC-DAD), migration of several monomers and previously identified oligomers, as well as some unidentified migrants, were determined during the experiment. The data from this study was compared to our findings from previous long-term migration studies with storage times ranging from 24 h to 540 days at 40 °C using the same can coating applications. The results illustrate that performing migration experiments for short time periods at 60 °C may mimic migration results that would be obtained at 40 °C after long-term migration tests (up to 1.5 years) from food can coatings into food simulants.

Determination of diffusion and partition coefficients of model migrants by direct contact and vapour phase transfer from low-density polyethylene films into cake.

The aim of the present study was to determine the migration kinetics of one photoinitiator, benzophenone, and two optical brighteners, Uvitex OB and 1,4-diphenyl-1,3-butadiene (DPBD), from low-density polyethylene (LDPE) films into cake. Transfer was assessed by both direct contact and also the vapour phase. To perform the migration tests by direct contact, plastic films enriched with the additives were placed between two cake slices. To evaluate the migration through the gas phase, cake and the fortified LDPE film were placed with no direct contact in a glass container that was hermetically closed. Samples were stored at different time-temperature conditions. Target compounds were extracted from the films with ethanol (70°C, 24 h) and analysed by HPLC-DAD. Relevant parameters such as partition and diffusion coefficients between food and plastic film were calculated. The Arrhenius equation was applied to estimate the diffusion coefficient at any temperature. The data indicate that migration of benzophenone occurs in a significant extent into cake by both direct contact and through the gas phase (no direct contact). Conversely, very little migration occurred for Uvitex OB by direct contact and none through the gas phase. Results for benzophenone suggest that migration through the gas phase should be considered when evaluating migration from food packaging materials into food.

Evaluation of Short-Term and Long-Term Migration Testing from Can Coatings into Food Simulants: Epoxy and Acrylic-Phenolic Coatings.

Traditionally, migration testing during 10 days at 40 °C has been considered sufficient and appropriate for simulating the potential migration of substances from food-contact materials into foods. However, some packages, such as food cans, may be stored holding food for extended time periods (years). This study attempts to verify whether common testing conditions accurately estimate long-term migration. Two types of can coatings, epoxy and acrylic-phenolic, were subjected to short-term and long-term migration testing (1 day-1.5 years) using food simulants (water, 3% acetic acid, 50% ethanol, and isooctane) at 40 °C. Using HPLC-DAD/CAD, HPLC-MS, UHPLC-HRMS (where HRMS is accurate mass, mass spectrometry), and DART-HRMS, we identified potential migrants before starting the experiment: BPA, BADGE, BADGE derivatives, benzoguanamine, and other relevant marker compounds. During the experiment using a water-based food simulant, migrants remained stable. Most of the cans in contact with 3% acetic acid did not survive the experimental conditions. Tracked migrants were not detected in isooctane. In the presence of 50% ethanol, the traditional migration test during 10 days at 40 °C did not predict migration during long-term storage. These results suggest that migration protocols should be modified to account for long-term storage.

Identification of unknown compounds from polyester cans coatings that may potentially migrate into food or food simulants.

Cross-linked polyester resins are being introduced into the market as alternatives to epoxy resins as coatings for metal food cans. Identification of potential migrants, from these coatings into food, is a significant analytical challenge due to the diversity of substances employed in the manufacture of the coatings. However, such identification is required to assess migration from the can coating into the food and quantify dietary exposure. Polyester can coatings were extracted with acetonitrile at 40°C for 24h and the extracts were analyzed by a variety of analytical techniques, including GC-MS, HPLC-DAD/MS, HPLC-DAD/CAD and UHPL C-HRMS. Twenty nine non-volatile oligomers were tentatively identified using retention times, UV spectra, and accurate mass measurements. Identified oligomers suggest the coating in use for food cans is a polyester coating and is mainly based on the monomers isophthalic acid, terephthalic acid and nadic acid. To give confidence in the identification, one of the tentatively identified oligomer was synthetized and analyzed by (13)C and (1)H NMR and UHPL C-HRMS. The NMR and HRMS results, confirmed the presence of this compound in the can extracts. Finally, to determine if rapid, direct detection of the oligomers was practical, the coatings were analyzed by DART-HRMS. Twenty three out of the 29 oligomers were identified in the coating by direct measurement with DART-HRMS in few minutes.

Study of the partition coefficients Kp/f of seven model migrants from LDPE polymer in contact with food simulants.

This study evaluated the influence of parameters such as temperature and type of low-density polyethylene (LDPE) film on the log Kp/f values of seven model migrants in food simulants. Two different types of LDPE films contaminated by extrusion and immersion were placed in contact with three food simulants including 20% ethanol, 50% ethanol and olive oil under several time-temperature conditions. Results suggest that most log Kp/f values are little affected by these parameters in this study. In addition, the relation between log Kp/f and log Po/w was established for each food simulant and regression lines, as well as correlation coefficients, were calculated. Correlations were compared with data from real foodstuffs. Data presented in this study could be valuable in assigning certain foods to particular food simulants as well as predicting the mass transfer of potential migrants into different types of food or food simulants, avoiding tedious and expensive laboratory analysis. The results could be especially useful for regulatory agencies as well as for the food industry.

Evaluation of Long-Term Migration Testing from Can Coatings into Food Simulants: Polyester Coatings.

FDA guidance for food contact substances recommends that for food packaging intended for use at sterilized, high temperature processed, or retorted conditions, a migration test with a retort step at 121 °C for 2 h followed by a 10 day migration test at 40 °C should be performed. These conditions are in intended to simulate processing and long-term storage. However, can coatings may be in contact with food for years, and there are very few data evaluating if this short-term testing accurately simulates migration over extended time periods. A long-term migration test at 40 °C with retorted and non-retorted polyester cans using several food simulants (water, 3% acetic acid, 10% ethanol, 50% ethanol, and isooctane) was conducted to verify whether traditional migration testing protocols accurately predict migration from food contact materials used for extended time periods. Time points were from 1 day to 515 days. HPLC-MS/MS was used to analyze polyester monomers, and oligomer migration was monitored using HPLC-DAD/CAD and HPLC-MS. Concentrations of monomers and oligomers increased during the migration experiments, especially in ethanol food simulants. The data suggest that current FDA migration protocols may need to be modified to address changes in migrants as a result of long-term storage conditions.

Target and non-target analysis of migrants from PVC-coated cans using UHPLC-Q-Orbitrap MS: evaluation of long-term migration testing.

A simple, rapid and sensitive method for analyzing multi-target and non-target additives in polyvinyl chloride (PVC) food can coatings using ultra-high-performance liquid chromatography coupled to quadrupole-orbital ion-trap mass spectrometry was developed. This procedure was used to study the behaviour of a cross-linking agent, benzoguanamine (BGA), two slip agents, oleamide and erucamide, and 18 other commonly used plasticisers including phthalates, adipates, sebacates, acetyl tributyl citrate and epoxidised soybean or linseed oils. This optimised method was used to detect these analytes in food simulants (water and 3% acetic acid) in a long-term migration test of PVC-coated food cans for a period ranging from 1 day to 1.5 years at 40°C. Although very low detection limits (5 ng ml(-1)) were obtained for the majority of compounds, none of the monitored plasticisers and slip agents was detected in simulants extracted from cans over the period of the test. However, the presence of BGA in both aqueous food simulants was confirmed based on high-resolution mass spectrometry, product ion spectra and analysis of a reference standard. The BGA concentration in both simulants continued to increase with storage time: after 1.5 years storage in aqueous food simulants at 40°C, BGA was detected at concentrations up to 84 µg dm(-2). We believe this is the first study describing the long-term migration capacity of BGA from any vinyl coating material intended for use in PVC-coated food cans. Our results may have implications for migration test protocols for food cans that will be stored for extended time periods.

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.

Migration of photoinitiators by gas phase into dry foods.

Photoinitiators are components widely used in UV-cured inks for printing food packaging. In the present study, the migration of seven photoinitiators through the vapor phase was investigated. To perform the migration test, an additive enriched polyethylene wax was used as a source to release photoinitiators. The method was applied to evaluate the migration of the photoinitiators into five selected dry foods (cake, bread, cereals, rice and pasta). The highest level of migration was found in the cake. Parameters affecting the migration process were evaluated, and high migration level was found to correlate with both the porosity and the fat content. In addition, the kinetics of migration of the photoinitiators from the additive enriched wax into the cake were studied under accelerated conditions.