Occurrence and distribution of halogenated flame retardants in an urban watershed: Comparison to polychlorinated biphenyls and organochlorine pesticides

Due to restrictions on polybrominated diphenyl ethers (PBDEs), market demand for alternative flame retardants is projected to increase, worldwide. Information regarding the environmental behavior of these compounds is limited. The present study involved field measurements of several alternative halogenated flame retardants (HFRs), along with PBDEs and legacy persistent organic pollutants (POPs) in surface water, bottom sediments and suspended particulate matter (SPM) within a highly urbanized watershed in Singapore. Several alternative HFRs were detected in water and sediments. Dechlornane Plus stereoisomers (syn- and anti-DP) were detected in all samples, exhibiting relatively high concentrations in water, sediments and SPM. The maximum syn-DP concentrations in water, sediments and SPM were 24.30 ng/L, 2.48 ng/g dry wt. and 7774 ng/g dry wt., respectively. 1,2-Bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromotoluene (PBT), hexabromobenzene (HxBBz) and tetrabromoethylcyclohexane (TBECH) were routinely detected. PBDE concentrations were relatively low and often non-detectable. Polychlorinated biphenyl (PCB) concentrations ranged from 0.017 to 8.37 ng/L in water, 9.86–27.92 ng/g dry wt. in SPM, and 6.48–212.3 ng/g dry wt. in sediments. Congener and isomer patterns suggested no recent inputs of PBDEs or dichlorodiphenyltrichloroethane (DDT). Rainfall was found to be an important factor influencing temporal and spatial patterns of DPs, BTBPE, PBDEs and some organochlorines in surface water. Land use index was found to be important for several organochlorines, but not HFRs. The observed sediment-water partitioning behavior of the studied HFRs and legacy POPs was highly dependent on chemical hydrophobicity. The data demonstrate that the studied HFRs have a relatively high affinity for SPM and bottom sediments. For example, the log KOC,OBS for TBECH, syn-DP and anti-DP and BTBPE in bottom sediments ranged between 8.1 and 9.6. The findings will aid future studies regarding fate, transport and bioaccumulation of these current-use contaminants of concern.