Spatial and Temporal Trends (2004–2016) of Selected Alternative Flame Retardants in Fish of the Laurentian Great Lakes

Abstract

Following the phase-out of polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCDD) flame retardants (FRs) from North American markets, the use of alternative FRs has increased. In this study the occurrence and spatiotemporal distributions of 18 dechlorane analogues (collectively referred to as DECs) and 20 alternative brominated FRs (referred to as ABFRs, i.e., brominated FRs other than PBDEs and HBCDD) were investigated in top predator fish megacomposites (i.e., a composite of all 50 fish) collected yearly from each of the Great Lakes from 2004 to 2016. Frequently detected substances include dechlorane 602, 603, 604 Component B, anti-and syn-dechlorane plus, and chlordene plus, as well as several brominated benzene FRs (i.e., hexabromobenzene, pentabromotoluene, and tetrabromo-o-chlorotoluene). Concentrations of ΣDECs and ΣABFRs ranged from 0.33−31.9 ng/g lipid weight (lw) (0.01−8.3 ng/g wet weight or ww) and 0.91−54.7 ng/g lw (0.09−7.1 ng/g ww), respectively. Flame retardant contamination exhibited chemical-specific spatial variations across the five lakes. Concentrations of ΣABFRs in Lake Erie fish were generally lower than those from other lakes. By contrast, fish ΣDEC concentrations were highest in Lake Ontario and the composition of dechlorane analogues differed significantly between Lake Ontario and the other lakes, indicating likely point-source influences. Temporal analyses revealed declining trends of ΣDECs and ΣABFRs in most lakes except Lake Erie, with age corrected trend slopes of −13.5% to −8.8% and −20.1% to −7.0% per year, respectively.

Legacy and alternative halogenated flame retardants in Lake Geneva fish

“…Fish above the third quartile (0.552 ng g -1 ww when both species are considered together) were sampled in areas B, C and D, and were partitioned evenly between the two species. These findings contrast with a recent study on Northern American Great Lake fish, where PBBs and dechloranes were predominant while DBDPE remained below the limit of detection and was considered as practically non-bioavailable (Wu et al 2019). DBDPE was not detected in Lake Maggiore zooplankton and fish, despite concentrations as high as 30 ng g -1 dry weight (dw) in sediments (Poma et al 2014).…”

Spatiotemporal Trends of Legacy and Alternative Flame Retardants in Harbor Seals from the Coasts of California, the Gulf of Maine, and Sweden

“…In fish of the Laurentian Great Lakes, declining trends of ΣDECs were observed in most lakes except Lake Erie. 28 In terms of the individual DEC compounds, DEC 602 was the major compound with high detection rates in all the three populations (>90%, Tables S8 and S9), for which we did not observe any significant trends (Figure S6). DP has been studied more intensively than other DECs; however, it has been suggested that DEC 602 has greater bioaccumulation potential than DP in aquatic ecosystems, 46 which likely explained its high detection rates in harbor seals in the present study.…”

“…The decreasing HBBZ and constant PBEB observed here in seals from Sweden are in line with a previous study in the blubber of belugas (Delphinapterus leucas) in the St. Lawrence Estuary, which found that the concentrations of PBEB did not vary from 1997 to 2013, whereas HBBZ showed a significant decreasing trend. 36 HBBZ also declined significantly in fish from several Great Lakes, 28 which could respond to the fact that HBBZ production in the vicinity of the Great Lakes Basin was shut down during the 1980s. 43 The production history of HBBZ in Europe is not clear, but a European study also reported a drastic decline of HBBZ levels in striped dolphin (Stenella coeruleoalba) from the Mediterranean Sea.…”

“…A total of 44 legacy and alternative FRs were quantitatively determined, including 21 tri-through deca-BDEs (i.e., BDE 17,28,47,49,66,85,99,100,138,153,154,183,196,197,201,202,203,206,207,208,and 209), 1 polybrominated biphenyl (PBB; BB 101), 13 aBFRs (i.e., ATE, BEH-TBP, BTBPE, EH-TBB, HBBZ, HCDBCO, PBBA, PBBZ, PBEB, PBT, TBB, TBCT, and TBPX), and 9 DECs (i.e., DEC 601, DEC 602, DEC 603, DEC 604, DEC 604CB, Cplus, Cl 11 -DP, syn-DP, and anti-DP) (full names are given in Table S1). Instrumental analysis was performed using an Agilent 7890B gas chromatograph equipped with a DB-5ht column (15 m × 0.25 mm × 0.1 μm; Agilent Technologies, USA), which was interfaced to an Agilent 5977A mass spectrometer (Agilent Technologies, Palo Alto, USA) operated in the electron capture negative ionization mode.…”

Insights into the Occurrence, Fate, and Impacts of Halogenated Flame Retardants in Municipal Wastewater Treatment Plants

“…The extensive usage of HFRs has led to contamination in various natural environmental matrices (e.g., air, surface water, and soil), − wildlife (e.g., fishes and snakes), , and human populations . A certain fraction of HFRs can escape from consumer products during production, use, disposal, and recycling as most HFRs are not chemically bound to consumer products.…”