Halogenated flame retardants in sediments from the Upper Laurentian Great Lakes: Implications to long-range transport and evidence of long-term transformation

Most hydrophobic halogenated flame retardants (HFRs) are highly accumulative and persistent in aquatic sediments. The objective of this study was to reveal spatial distributions, temporal trends, and transformation of selected legacy and emerging HFRs in sediments of Lakes Superior, Michigan, and Huron. We collected Ponar grab samples at 112 locations and sediment cores at 28 sites in the three lakes, and measured concentrations of 19 brominated FRs and 12 chlorinated FRs. Based on grab samples, concentrations were higher at southeastern and sites near Sleeping Bear Dunes of Lake Michigan, and Saginaw Bay and the North Channel of Lake Huron. The annual loadings of polybrominated diphenyl either (PBDEs) and Dechlorane Plus (DPs) to sediment have leveled off or been declining since 2000, while loadings of DBDPE and Dec604 have increased since the 1960s in most cores. The concentration ratio of BB101 to BB153 increased with sediment depth, suggesting the occurrence of in situ debromination of BB153. The ratio of dechlorinated anti-Cl11DP over anti-DP increases with the increasing latitude of sampling locations, suggesting the occurrence of dechlorination of anti-DP to anti-Cl11DP during transport. This ratio also increases with increasing sediment age in most cores, implying in situ dechlorination over time.