Formation of polybrominated dibenzofurans (PBDFs) after heating of a salmon sample spiked with decabromodiphenyl ether (BDE-209).

Fish is a major source for the intake of polybrominated diphenyl ethers (PBDEs). However, fish is scarcely consumed without being cooked, and previous studies showed that the heating of salmon fillet contaminated with BDE-209 for longer periods of time was accompanied with the partial transformation of this brominated flame retardant. In this study, we heated salmon fillet spiked with BDE-209 and verified that this process was linked with the formation of polybrominated dibenzofurans (PBDFs) in the fish. Each minute of heating 1 g salmon fillet spiked with 200 ng BDE-209 generated about 0.5 ‰ PBDFs relative to the initial amount of the pre-dioxin BDE-209. This result of the chemical analysis by gas chromatography with mass spectrometry (GC/MS) was verified by means of an effect-directed bio-assay (DR CALUX). While unheated salmon with BDE-209 and heated salmon without BDE-209 were tested nontoxic, the bioanalytical response of fish linearly increased upon heating. We also found that PBDF formation did neither occur with BDE-47 nor when BDE-209 was heated in edible oil instead of salmon fillet. Due to the formation of PBDFs in this process, the consumption of heated, BDE-209 contaminated fish may add to the uptake of dioxin-like compounds with our diet.

Fate of polybrominated diphenyl ethers during cooking of fish in a new model cooking apparatus and a household microwave.

Fish is a major source of human exposure to polybrominated diphenyl ethers (PBDEs). Because fish is mainly consumed after cooking, this measure may alter the pattern and amounts of PBDEs that are finally consumed. To investigate this issue, we developed a model cooking apparatus consisting of a small glass bowl and a beaker glass with an exhaust fitted with a polyurethane foam filter connected to a water jet pump. In this model cooking apparatus, fish (1 g) and/or sunflower oil (0.2/0.4 g) spiked with three PBDE congeners was cooked for 30 min. Small amounts of the semi-volatile PBDEs were evaporated from the fish (BDE-47 < BDE-15), while the non-volatile BDE-209 was partly transformed. Additional experiments in a household microwave provided similar results, except that no transformation was observed for BDE-209. The model cooking apparatus proved to be well-suited to study the fate of polyhalogenated compounds in fish during cooking.

Hydrodebromination of decabromodiphenyl ether (BDE-209) in cooking experiments with salmon fillet.

Polybrominated diphenyl ethers (PBDEs) are environmental contaminants regularly detected in biota and food. Seafood has been identified as the major dietary source for human uptake. Fish is predominantly consumed after cooking, and this process may alter the actual human intake of contaminants. This study thus aimed to investigate the fate of PBDEs in this cooking process. Heating of fish fortified with 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209) at typical cooking conditions (200 °C, in plant oil) resulted in a decrease of its concentration in favor of the formation of lower brominated congeners. After 15 min, ∼25% of BDE-209 was transformed into nona- to octabrominated congeners. The major transformation route was BDE-209 → BDE-206 → BDE-196 and BDE-199. Low amounts of heptabrominated congeners as well as one hexabromodibenzofuran and a heptabromodibenzofuran isomer were also detected. However, penta- and tetrabrominated diphenyl ethers were not observed, and heating of BDE-47 did not produce new transformation products.

Heating of BDE-209 and BDE-47 in plant oil in presence of o,p'-DDT or iron(III) chloride can produce monochloro-polybromo diphenyl ethers.

Heating processes of food can alter the concentrations and composition of organohalogen compounds. In this study the fate of two polybrominated diphenyl ether (PBDE) congeners, decabromodiphenyl ether (BDE-209) and 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) was analyzed when heated in plant oil with and without additional compounds. When the PBDEs were heated in pure plant oil, no transformation was observed. Heating of decabromodiphenyl ether (BDE-209) together with ortho,para'-dichlorodiphenyltrichloroethane (o,p'-DDT) or iron(III) chloride in plant oil resulted in the formation of monochloro-nonabromodiphenyl ethers (Br(9)Cl-DEs). Almost 10% of the initial amount of BDE-209 was transferred into Br(9)Cl-DEs. Heating BDE-47 in the presence of iron(III) chloride produced two monochlorinated transformation products which were tentatively identified as 2,2',4-tribromo-4'-chlorodiphenyl ether (4'-Cl-BDE-17) and 2,4,4'-tribromo-2'-chlorodiphenyl ether (2'-Cl-BDE-28). However, the reactivity was smaller and no Br→Cl exchange was observed with o,p'-DDT. The conditions used in our experiments (200 °C; heating 30 min-3 h) indicate that such reactivity may also occur during cooking of fish, meat and other food samples.