Fate of 4-bromodiphenyl ether (BDE3) in soil and the effects of co-existed copper

The quantitative fate of polybrominated diphenyl ethers (PBDEs) in soil is unknown. Furthermore, the effects of co-contamination by toxic copper on the behavior of PBDEs have not been investigated. Using a ¹⁴C-tracer, we studied mineralization, metabolism, and formation of non-extractable residues (NERs) of one PBDE congener, i.e., the 4-bromodiphenyl ether (BDE3) in oxic soil for 50 days, without and with amendment of Cu (400 mg kg^-1 soil dw). BDE3 rapidly dissipated with a half-life of 5.5 days and large amounts of CO₂ (38.8 ± 0.3% of initial applied amount at the end of incubation) and NERs (42.5 ± 0.4%) were rapidly produced. One hydroxylated metabolite (4'-HO-BDE3) was formed (8.1 ± 0.6%) at the beginning of the incubation, but then decreased to 2.2 ± 0.4%. Only BDE3 occurred in physico-chemically entrapped NERs, amounting to 9.2 ± 0.7%, while only 4'-HO-BDE3 in ester-linked NERs (10.9 ± 0.7%). The addition of Cu strongly reduced the kinetics constants of the transformations (including dissipation, mineralization, and NER-formation), the predicted maximal amounts of mineralization, as well as covalent binding of 4'-HO-BDE3 to soil. The results provide first quantitative insights into the fate of low-brominated congeners of PBDEs in soil and indicate that co-contamination by Cu may increase the environmental risks of biodegradable PBDEs in soil by increasing their persistence.