Legacy PBDEs and NBFRs in sediments of the tidal River Thames using liquid chromatography coupled to a high resolution accurate mass Orbitrap mass spectrometer.

Surface sediment samples (n = 45) were collected along a 110 km transect of the river Thames in October 2011, starting from Teddington Lock out through the industrial area of London to the southern North Sea. Several legacy and novel brominated flame retardants (NBFRs) were analysed, including 13 polybrominated diphenyl ethers (PBDEs) (congeners 17, 28, 47, 99, 100, 153, 154, 183, 196, 197, 206, 207 and 209), hexabromocyclododecane (HBCDDs), tetrabromobisphenol A (TBBPA), hexabromobenzene (HBB), 2,4,6-tribromophenol (TBP), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB or TBB), bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP or TBPH), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), pentabromoethylbenzene (PBEB), anti/syn-dechlorane plus (a/s-DP), 2,2',4,4',5,5'-hexabromobiphenyl (BB153) and α-,ß-1,2-dibromo-4-(1,2-dibromoethyl) cyclohexane (α-,ß-DBE-DBCH or TBECH). A novel analysis method based on liquid chromatographic separation, followed by high resolution accurate mass detection using the Orbitrap platform was used for quantification. Results revealed that BDE-209 had the highest concentrations (<0.1 to 540 µg kg-1 dw) and detection frequency, accounting for 95% of all PBDE congeners measured. Indicative evidence of debromination of the PentaBDE technical mixture was observed through elevated relative abundance of BDE-28 in sediment compared to the Penta-BDE formulation. NBFRs were detected at comparable levels to PBDEs (excluding BDE-209), which indicates increasing use of the former. Spatial trend analysis showed that samples from industrial areas had significantly higher concentrations of Σ12PBDEs, ΣHBCDDs, TBBPA, BEH-TEBP, BTBPE and TBP. Three locations showed high concentrations of HBCDDs with diastereomer patterns comparable to the technical mixture, which indicate recent input sources to the sediment.

Levels and trends of PBDEs and HBCDs in the global environment: status at the end of 2012.

In this paper, we have compiled and reviewed the most recent literature, published in print or online from January 2010 to December 2012, relating to the human exposure, environmental distribution, behaviour, fate and concentration time trends of polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants, in order to establish their current trends and priorities for future study. More data are now becoming available for remote areas not previously studied, Indian Ocean islands, for example. Decreasing time trends for penta-mix PBDE congeners were seen for soils in northern Europe, sewage sludge in Sweden and the USA, carp from a US river, trout from three of the Great Lakes and in Arctic and UK marine mammals and many birds, but increasing time trends continue in polar bears and some birds at high trophic levels in northern Europe. This may be partially a result of the time delay inherent in long-range atmospheric transport processes. In general, concentrations of BDE209 (the major component of the deca-mix PBDE product) are continuing to increase. Of major concern is the possible/likely debromination of the large reservoir of BDE209 in soils and sediments worldwide, to yield lower brominated congeners which are both more mobile and more toxic, and we have compiled the most recent evidence for the occurrence of this degradation process. Numerous studies reported here reinforce the importance of this future concern. Time trends for HBCDs are mixed, with both increases and decreases evident in different matrices and locations and, notably, with increasing occurrence in birds of prey. Temporal trends for both PBDEs and HBCD in Asia are unclear currently. A knowledge gap has been noted in relation to metabolism and/or debromination of BDE209 and HBCD in birds. Further monitoring of human exposure and environmental contamination in areas of e-waste recycling, particularly in Asia and Africa, is warranted. More data on temporal trends of BDE and HBCD concentrations in a variety of matrices and locations are needed before the current status of these compounds can be fully assessed, and the impact of regulation and changing usage patterns among different flame retardants determined.

Novel brominated flame retardants: a review of their analysis, environmental fate and behaviour.

This review summarises current knowledge about production volumes, physico-chemical properties, analysis, environmental occurrence, fate and behaviour and human exposure to the "novel" brominated flame retardants (NBFRs). We define the term NBFRs as relating to BFRs which are new to the market or newly/recently observed in the environment. Restrictions and bans on the use of some polybrominated diphenyl ether (PBDE) formulations, in many jurisdictions, have created a market for the use of NBFRs. To date, most data on NBFRs have arisen as additional information generated by research designed principally to study more "traditional" BFRs, such as PBDEs. This has led to a wide variety of analytical approaches for sample extraction, extract purification and instrumental analysis of NBFRs. An overview of environmental occurrence in abiotic matrices, aquatic biota, terrestrial biota and birds is presented. Evidence concerning the metabolism and absorption of different NBFRs is reviewed. Human exposure to NBFRs via different exposure pathways is discussed, and research gaps related to analysis, environmental sources, fate, and behaviour and human exposure are identified.