Fate of lower-brominated diphenyl ethers (LBDEs) in a red soil – Application of 14C-labelling

Abstract

Lower-brominated diphenyl ethers (LBDEs) occur ubiquitously in soil, however their fate there has not been well evaluated, mainly owing to that the unavailability of commercial radioactively labelled LBDE congeners hampers the investigation on fate of LBDEs in the environment with complex matrixes, such as soil and sediment. Here, we successfully synthesized three congeners of LBDEs, i.e., 4-bromodiphenyl ether (BDE3), 4,4′-dibromodiphenyl ether (BDE15), and 2,2′,4,4′-tetrabromodiphenyl ether (BDE47), with 14C-labelling on one aromatic ring, starting from commercially available 14C-labelled phenol in two steps with high yields and high radiochemical purities. Using the 14C-labelled congeners, we studied the fate of LBDEs in a red soil under oxic conditions, where LBDEs have been frequently detected in high levels. The major fate of the LBDE congeners in the soil was formation of NERs, followed by mineralization to CO2, while no transformation product was detected in the soil after incubation for 105 days. The mineralization strongly decreased with increasing number of the bromine atom on the congener molecule, amounting to 10.4 ± 0.3%, 2.45 ± 0.04%, and 0.51 ± 0.05% for BDE3, BDE15, and BDE47, respectively, at the end of incubation, while mineralization rate constant was independent of the molecular structure, suggesting that solubility of LBDEs is the limit factor for their persistence in soil. The mineralization was positively linearly correlated with the formation of NERs (22.5 ± 1.9%, 11.0 ± 3.6%, and 6.7 ± 2.7% for BDE3, BDE15, and BDE47, respectively), which was mainly located in humin fraction and formed also in sterilized soil, suggesting a binding of transformation intermediates to soil humic substances and a physico-chemical entrapment of LBDEs in soil. The results provide new insights into fate of LBDE congeners in soil, and suggest a need to elucidate nature of the NERs of LBDEs, especially the stability of NERs in the environment.