Major sources of MeO/OH-BDEs in the East China Sea elucidated from their records and phytoplankton biomarkers

• The historical trends of MeO/OH-BDEs are reconstructed in the East China Sea.
• The detections of MeO/OH-BDEs are earlier than the production of artificial PBDEs.
• Phytoplankton is a potentially important source of ortho-substituted MeO/OH-BDEs.
• The patterns of MeO-BDEs are controlled by the phytoplankton community structure.

Hydroxylated (OH-) and methoxylated (MeO-) polybrominated diphenyl ethers (PBDEs) have caused much concern because of their potential toxicity and worldwide distribution. These compounds are recently suggested to originate from the natural process in the ocean. However, their source remains highly controversial. In this study, we analyzed the contents of nine MeO-BDEs, ten OH-BDEs, and phytoplankton biomarkers (PBs) in two sediment cores collected from the East China Sea (ECS). The detection of 6-MeO-BDE-47, 2′-MeO-BDE-68, and 6-OH-BDE-47 have been reported since the 1920s, prior to the production of PBDEs. Significant relations were found between MeO/OH-BDEs and indicators of marine organic matters. The similar down-core variations and significant correlations between MeO/OH-BDEs and PBs suggest the possibility that phytoplankton produced these natural compounds. Laboratory incubation further demonstrates that phytoplankton can produce MeO-BDEs. Comparisons between the content ratios of 6-MeO-BDE-47/2′-MeO-BDE-68 and brassicasterol/dinosterol indicate that the signature of MeO-BDEs is controlled by the phytoplankton community structure.