Hexabromocyclododecanes in surface sediments and a sediment core from Rivers and Harbor in the northern Chinese city of Tianjin

In the present study, hexabromocyclododecanes (HBCDs) were investigated in the sediment from Haihe River (HR), Dagu Dainage Canal (DDC) and Tianjin Harbor (TH) at Bohai Bay using a total of 51 samples of surface sediments and a sediment core collected from May to September in 2010, and its diastereomer- and enantiomer-specific profiles were analyzed. The concentration of total HBCDs were generally high, with mean value and ranges of 31.0 and 1.35-634 ng g(-1)dw, respectively. The contamination followed the order of TH>DDC>HR. Higher levels (up to 634 ng g(-1)dw) occurred in the lower reach of HR and DDC located in an industrial area of Tianjin. This is the first time to report so high concentration of HBCDs in sediment in Southeast Asia. The γ-diastereomer dominated in most samples (44 out of 51), and this is in agreement with the diastereomer distribution pattern in industrial products, while α-HBCD was the dominant diastereomer in the other seven samples. However, only few samples exhibited γ-diastereomer ratio similar to that (75-89%) in technical products, indicating the inter-transformation and variable degradation of the different isomers. The high ratio of γ-diastereomer could be used as an indicator for fresh contamination input. Enantiomeric factors (EFs) of HBCD isomers in most of the samples were statistically different from technical products (p<0.05), showing a trend of more easily enrichment of the (-)-HBCD-enantiomer compared to the (+)-HBCD-enantiomer. The δ- and ε-diastereomers were frequently detected but at low level. The HBCDs in the sediment core showed several peaks, and the greatest value occurred in 2005, when a plastic manufacture plant using HBCD was set up nearby.