Occurrence of polybrominated diphenyl ethers and emerging halogenated flame retardants in food items

Brominated flame retardants (BFRs) are chemicals used in a wide range of commercial and household products in order to reduce their flammability. Because most BFRs are not chemically bonded to the products which they are added to, they can easily leach into the environment. The main exposure of the population to BFRs is via the diet, inhalation of indoor air and ingestion of indoor dust. In particular, the lack of data on the occurrence of BFRs in food prevents an accurate estimation of the human intake. The main aim of this Project was to follow the EU Commission Recommendation 2014/118/EU on the monitoring of BFRs in various food items from the Belgian market and to provide data on their occurrence and levels in the main food categories.The presence of polybrominated diphenyl ethers (PBDEs), novel BFRs (hexabromobenzene (HBB), bis(tribromophenoxy)ethane (BTBPE), tetrabromobenzoate (TBB), tetrabromophthalate (TBPH)), tribromoanisole (TBA), and dechlorane plus (syn-DP and anti-DP) in various food items was assessed using an analytical method developed and validated in the frame of the this Project. This novel method uses low sample amounts and solvent volumes, and involves a two-step clean-up, including Florisil and acid silica. The determination of BFRs was performed using gas chromatography-mass spectrometry operated in electron-capture negative ionization mode (GC-ECNI/MS). The validated procedure was first used for the determination of BFRs in 20 individual food items purchased from Antwerp supermarkets (including fish, meat, eggs, milk, grains, and vegetable oil), and, in a second stage, has been used for the analysis of more than 200 food samples in the frame of the Belgian food monitoring Project. A high extraction performance was obtained, which, combined with an efficient two-step clean-up procedure, enabled the accurate determination and quantification of the target compound residues in a wide variety of food matrices, with very different characteristics and lipid content. In all considered food categories, PBDEs were the most frequently detected BFRs, and the fish/sea-food categories were the most PBDE contaminated food. Among the other FRs, TBA was detected only in fish/sea-food, indicating its primary natural origin from the marine environment, rather than its transfer from plastic used for packaging. For the other compounds, the results showed a generally low contamination of all analyzed food samples, with values generally below LOQ.</p

Brominated flame retardants in Belgian foodstuffs - recent evaluation by a novel UPLC-MS/MS method

The study was undertaken as consequence of the Commission Recommendation 2014/118/EU on the Europe-wide monitoring of brominated flame retardants (BFRs) in food. BFRs are anthropogenic chemicals that are added to a wide variety of consumer products in order to improve their fire resistance. BFRs may leach from the products into the environment. Due to their persistence and potential to bioaccumulate in the food chain, BFRs may cause toxic effects in humans and animals. There is a lack of information on the occurrence of BFRs in foodstuffs, which has hampered accurate completion of intake assessments. The main objective of this work was to evaluate the presence and to measure the levels of BFRs, namely brominated phenols (BPs), hexabromocyclododecanes (HBCDs), tetrabromobisphenol A (TBBPA) and its derivatives in foodstuffs consumed by the Belgian population.Quantitative measurements were performed using ultra-high performance - tandem mass spectrometry (UPLC-MS/MS) on an ACQUITY UPLC system coupled to a Xevo-TQ-S mass spectrometer. Sample preparation protocol consisted of a QuEChERS-based extraction followed by two parallel clean-up procedures. Column chromatography with acidified silica gel and dispersive solid-phase extraction with C18 and carbon sorbents were used to eliminate lipids, pigments and eventually other matrix components from the extract. The method is applicable to a wide variety of food matrices and was in-house validated. Representative portions of food samples belonging to different categories, such as fish and seafood, meat and meat products, chicken eggs, oils and fats, milk and dairy products, were collected from Belgian (super)markets in 2015. The samples were pooled per food category according to the consumption data of the Belgian Food Consumption Survey, after which they were lyophilized and subjected to the multi-analyte LC-MS/MS analysis. In this work, data on the occurrence and levels of BFRs in different food commodities consumed in Belgium will be presented. The results will be discussed with regards to the frequency of occurrence and highest detected concentrations of the BFRs, and compared to existent data for other (European) countries. This data will be decisive in the subsequent calculation of intake levels.</p