The extent of bioaccumulation and trophic transfer of brominated diphenyl ether (BDE) congeners, hexabromocyclododecane (HBCD) diastereoisomers (alpha, beta, and gamma), decabromodiphenylethane (DBDPE), and bis(2,4,6-tribromophenoxy)ethane (BTBPE) was examined in a Lake Winnipeg (Canada) food web. Six species of fish, zooplankton, mussels, sediment, and water from the south basin of the lake were selected for study. Significant positive correlations were found between concentrations of total (sigma) polybrominated diphenylethers (PBDEs; p < 0.005), sigmaHBCDs (p < 0.0001), BTBPE (p < 0.0001), and lipid content in fish. Strong positive linear relationships also were observed from individual plots of BDE 47, BDE 209, and DBDPE concentrations (lipid wt) and trophic level (based on delta15N), suggesting that these compounds biomagnify in the Lake Winnipeg food web. Biomagnification factors varied for the chemicals studied. Plots of log bioaccumulation factors for mussel and zooplankton versus log octanol-water partition coefficient (Kow) were similar and suggest that neither mussels nor zooplankton are in equilibrium with the water. Fifteen BDE congeners were consistently detected in water (dissolved phase, n = 3), with BDE 47 having the greatest concentration (17 pg/L). The rank order of compounds in water (arithmetic mean +/- standard error) were sigmaPBDEs (49 +/- 12 pg/ L) > alpha-HBCD (11 +/- 2 pg/L) > BTBPE (1.9 +/- 0.6 pg/L). Concentrations of DPDPE, BDE 209, and beta- and -gamma-HBCD isomers were below their respective method detection limits (MDLs) in water. Total PBDE concentrations in sediment (n = 4) were greater than any other brominated flame retardant examined in the present study and ranged from 1,160 to 1,610 ng/g (dry wt), with BDE 209 contributing roughly 50% of the total. The gamma-HBCD isomer was detected at concentrations of 50 +/- 20 pg/g (dry wt) in sediment, whereas BTBPE and DBDPE were consistently below their respective MDLs in sediment.
Juvenile rainbow trout (Oncorhynchus mykiss) were exposed to three diastereoisomers (alpha, beta, gamma) of hexabromocyclododecane (C12H18Br6) via their diet for 56 d followed by 112 d of untreated food to examine bioaccumulation parameters and test the hypothesis of in vivo bioisomerization. Four groups of 70 fish were used in the study. Three groups were exposed to food fortified with known concentrations of an individual diastereoisomer, while a fourth group were fed unfortified food. Bioaccumulation of the gamma-diastereoisomer was linear during the uptake phase, while the alpha- and beta-diastereoisomers were found to increase exponentially with respective doubling times of 8.2 and 17.1 d. Both the beta- and the gamma-diastereoisomers followed a first-order depuration kinetics with calculated half-lives of 157 +/- 71 and 144 +/- 60 d (+/-1 x standard error), respectively. The biomagnification factor (BMF) for the alpha-diastereoisomer (BMF = 9.2) was two times greater than the beta-diastereoisomer (BMF = 4.3); the large BMF for the beta-diastereoisomer is consistent with this diastereoisomer dominating higher-trophic-level organisms. Although the BMF of the beta-diastereoisomer suggests that it will biomagnify, it is rarely detected in environmental samples because it is present in small quantities in commercial mixtures. Results from these studies also provide evidence of bioisomerization of the beta- and gamma-diastereoisomers. Most importantly, the alpha-diastereoisomer that was recalcitrant to bioisomerization by juvenile rainbow trout in this study and known to be the dominant diastereosiomer in fish was bioformed from both the beta- and the gamma-diastereoisomers. To our knowledge, this is the first report of bioisomerization of a halogenated organic pollutant in biota.
The emergence of hexabromocyclododecane (HBCD) as a bromine-based flame retardant of concern is partly attributable to recent measurements on the environmental occurrence of the individual diastereoisomers (alpha, beta and gamma). These measurements were fuelled by a newly developed liquid chromatography/tandem mass spectrometric (LC/MS/MS)-based analytical method. However, in the course of our recent studies on the environmental fate and behaviour of the diastereoisomers of HBCD, some interesting features of the LC/MS/MS method became apparent. For example, the ion signal of the native ions was found to be dependent on the final extract volume. This was true for both biotic and sediment samples and was found to arise from the suppression of the ion signal due to endogenous material in the extracts that escape clean-up. We have also found differences in the stability of the diastereoisomers in different solvents. If left unaccounted for, both factors can compromise analytical measurement data. By way of a series of controlled experiments conducted at our two laboratories [Department of Fisheries & Oceans Canada (DFO) and Environment Canada (EC)], we illustrate these features and demonstrate that use of newly synthesized labelled HBCD isomers [(13-carbon (13C) and deuterium (d18)] can minimize and often circumvent matrix-related effects.
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