Novel Dechlorane Analogues and Possible Sources in Peregrine Falcon Eggs and Shark Livers from the Western North Atlantic Regions.

During the investigation of dechlorane-related chemicals in North American wildlife, two unknown polychlorinated compounds (referred to as U1 and U2) were discovered. After extensive sample cleanup, structural information on U1 and U2 was characterized by gas chromatography (GC) coupled with single quadrupole mass spectrometer (MS) or GC-quadrupole time-of-flight (QToF) MS. Mass spectral evidence suggests that both U1 and U2 are structurally related to Dechlorane 603 (Dec603; C17H8Cl12), an analogue of the chlorinated flame retardant Dechlorane Plus. From the results we suspect U1 (C17H9Cl11) to be a monohydro analogue of Dec603 (i.e., one chlorine atom in Dec603 is replaced by a hydrogen atom). U1 may be formed via the degradation of Dec603's stereoisomers or present as an impurity in commercial Dec603 products. Mass spectral characterization of U2 (C17H7OCl11) suggests it is a carbonylic derivative of Dec603, likely formed via metabolic transformation of Dec603 or its photoisomer. Semiquantitative measurement revealed that U1 and U2 were present at estimated median concentrations of 49 ng/g lipid weight (lw) and 59 ng/g lw in peregrine falcon ( Falco peregrinus) eggs, from the mid-Atlantic region of the United States, and 4.6 and 3.0 ng/g lw in shortfin mako shark ( Isurus oxyrinchus) livers from the western North Atlantic Ocean, respectively. Our results demonstrate the occurrence of these two novel Dec603-related chemicals in both terrestrial and aquatic ecosystems.

Maternal Transfer of Flame Retardants in Sharks from the Western North Atlantic Ocean.

The present work represents a comprehensive study of in utero maternal transfer of legacy and emerging flame retardants (FRs) in marine predators. We analyzed liver tissues from pregnant sharks of five viviparous species, including blacknose shark ( Carcharhinus acronotus; n = 12), blacktip shark ( Carcharhinus limbatus; n = 2), bonnethead ( Sphyrna tiburo; n = 2), Atlantic sharpnose shark ( Rhizoprionodon terraenovae; n = 2), and spinner shark ( Carcharhinus brevipinna; n = 2), as well as their embryos ( n = 84 in total from five species), collected from the western North Atlantic Ocean. Concentrations of frequently detected emerging FRs in adult female blacknose sharks were determined to be 6.1-83.3 ng/g lipid weight (lw) for dechlorane analogues, 2.5-29.8 ng/g lw for tetrabromo- o-chlorotoluene, and nondetection -32.6 ng/g lw for hexabromobenzene. These concentrations were 1-2 orders of magnitude lower than those of legacy polybrominated diphenyl ether flame retardants (85.7-398 ng/g lw). Similar contamination profiles were also found in the other four species, although FR concentrations varied in different species. A total of 21 FRs were commonly found in developing embryos of female sharks from five species, demonstrating maternal transfer in utero. The maternal transfer ratio (i.e., ratio of the mean litter concentration to their mother's concentration) determined in blacknose shark mother/embryo groups for each FR chemical was negatively associated with its octanol-water partition coefficient. Our work lays a solid foundation for future investigation of the underlying mechanisms of in utero transfer and additional physical or chemical factors that affect maternal transfer.

Legacy and emerging flame retardants in sharks from the Western North Atlantic Ocean.

Following the discontinuation of commercial polybrominated diphenyl ether (PBDE) mixtures, a variety of alternative flame retardants (FRs) have been developed and employed. To understand the contamination status of these emerging FRs in marine fish and wildlife, we investigated their bioaccumulation in four shark species, including shortfin mako shark (Isurus oxyrhinchus; n = 26), porbeagle (Lamna nasus; n = 4), sandbar shark (Carcharhinus plumbeus; n = 6), and common thresher (Alopias vulpinus; n = 4), from coastal and offshore waters of the western North Atlantic Ocean. Median concentrations of emerging FRs, including dechlorane analogues (i.e., dechlorane plus, Dec-602, -603, and - 604), tetrabromo-o-chlorotoluene (TBCT), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and hexabromobenzene (HBBZ), ranged from 1.4-7.4, 10.2-22.4, 1.0-16.7, and 4.1-17.7 ng/g lipid weight (lw), respectively. Although concentrations of emerging FRs were generally 1-2 orders of magnitude lower than those of legacy FRs (i.e., PBDEs, 312-800 ng/g lw and hexabromocyclododecane or HBCDD, 17.2-99.3 ng/g lw), they were detected in more than 80% of the shark livers. Analysis of available biological data indicated that fork length significantly correlated with the concentrations of ΣPBDEs, HBCDD, ΣDechloranes or TBCT in shortfin mako livers. This indicates that longer-term exposure likely results in elevated FR concentrations in sharks. Our findings suggest likely exposure of western North Atlantic fish and wildlife to several emerging FRs, including dechloranes, BTBPE, HBBZ, and TBCT. Additional studies are needed to better elucidate their potential risks to fish and wildlife as well as the variety of environmental and biological factors influencing these risks.