The extent of bioaccumulation of the syn- and anti-isomers of Dechlorane Plus (DP) is assessed in archived food web samples from Lake Winnipeg and Lake Ontario. Concentrations of the isomers were determined using purified analytical solutions of individual isomers as opposed to the technical mixture. The syn-isomer was consistently detected in all samples from both lakes; the anti-isomer was detected in all Lake Ontario samples, but only 45% of the samples from Lake Winnipeg. The pattern of bioaccumulation was different for the isomers in Lake Winnipeg. The anti-isomer was dominant in higher trophic level (TL) organisms like walleye [arithmetic mean +/- 1 x standard error: 730 +/- 120 pg/g, lipid weight (1w)] and goldeye (760 +/- 170 pg/g, Iw) while the syn-isomer dominated the lower TL organisms like zooplankton (550 +/- 40 pg/g, Iw) and mussels (430 +/- 140 pg/g, Iw). In Lake Ontario, the extent of bioaccumulation of the isomers and concentrations was greatest in the lower TL benthic organism, Diporeia (syn, 1307 +/- 554; and anti, 3108 +/- 898 pg/g Iw) and also high in zooplankton (syn, 719; and anti, 1332 pg/g Iw). This suggests that the isomers are bioavailable in sediment and that, despite their molecular size, diffusion from the water column into zooplankton can occur. Differences in the mean fractional abundance of the anti-isomer (mean fanti = mean concentration of the anti-isomer divided by sum of mean syn- and anti-concentrations) were pronounced in sediments between lakes (Lake Winnipeg mean fanti = 0.610, Lake Ontario mean fanti = 0.860) and the extent of enrichment (anti-) and depletion (syn-) of the isomers were more marked in Lake Winnipeg biota. There were also differences in the biomagnification potentials, as measured bythe trophic magnification factor (TMF), between the isomers in the Lake Winnipeg food web; no statistically significant TMFs for either isomer were found for the

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.

A recently discovered chlorinated flame retardant, Dechlorane Plus (DP), was reported in air and a sediment core within the North American Great Lakes region. To further reveal the fate of DP in the Great Lakes, 40 surficial sediments from Lakes Erie and Ontario and two additional cores were analyzed using newly available analytical grade DP isomer solutions. The maximum total concentration in Lake Ontario was over 60-fold higher than Lake Erie, 586 ng/g and 8.62 ng/g, respectively. Additionally, analysis of archived suspended sediments collected from the Niagara River (1980-2002) showed a declining total DP concentration of 89 ng/g to 7.0 ng/g, suggesting a possible decrease in production orthe reduction of free DP released into the environment during manufacturing. The average syn-DP fractional abundance (f(syn)) in our study was less than the commercial DP composition indicating a stereoselective enrichment of anti-DP in the environment Mean fyn profiles were uniquely similar to both Lake Ontario and the Niagara River in comparison to Lake Erie. During the course of our analysis we noticed an increasing f(syn) value in the calibration standard which became exacerbated as the liner got dirtier and suggested the prospect of DP degradation. Followup studies indicated these compounds were dechlorinated DP species produced on the injection liner. Using a clean injection liner, these degradates were also detected in sediments from the Niagara River and Lake Ontario;tentatively identified as [-Cl+H] and [-2Cl+2H] by high resolution mass spectrometry. The observed similarity of f(syn) profiles between Lake Ontario and Niagara River and the detection of the degradates only in their locations, suggest to us that the river is a major source to Lake Ontario's DP burden. To our knowledge, this is the first report of DP degradates in the environment.

Dechlorane (Dec) 602, Dechlorane (Dec) 603, Dechlorane (Dec) 604, and Dechlorane Plus (DP) are flame retardant substitutes for mirex. Dec 602, 603, and 604 were detected in sediment and fish from the Laurentian Great Lakes. Lake Ontario surface sediments had the highest concentrations of Dec 602 and 604 at 6.0 and 4.0 ng/g dry weight, respectively. Temporal analysis of a Lake Ontario sediment core indicates that Dec 602 and 604 trends are similar to DP peaking in the early 1980s. Lake trout and whitefish from Lake Ontario also had the highest concentrations of Dec 602 and 604 at 34 and 1.2 ng/g lipid. Concentrations of Dec 602 were higher than those of DP in all fish samples, indicating that Dec 602 is likely more bioavailable and/or more readily bioaccumulates than DP. Spatial trends for Dec 602 and 604 in sediment and fish indicate that manufacturing plants along the Niagara River upstream of Lake Ontario were important sources of Dec 602 and 604 to the Great Lakes, while Dec 603 in the Great Lakes is likely from atmospheric deposition. The findings of this first report of Dec 602, 603, and 604 in the Laurentian Great Lakes basin suggests further investigation of halogenated norbornene flame retardants in the environment is merited.

No abstract

Our previous research on atmospheric samples suggested that Lake Ontario might receive significant amounts of Dechlorane Plus (DP), a highly chlorinated flame retardant, from the atmosphere and from inputs from DP's manufacturing facility in Niagara Falls, New York. To confirm this suspicion, a sediment core from the central basin of Lake Ontario was analyzed for the two isomers of DP, for polybrominated diphenyl ethers (PBDEs), and for 1,2-bis-(2,4,6-tribromophenoxy)ethane (TBE). The results showed that the concentration of DP in sediment increased rapidly starting in the mid-1970s and reached its peak concentration (310 ng g(-1) dry weight) in the mid-1990s. The peak flux and total inventory of DP were estimated to be 9.3 ng cm(-2) yr(-1) and 120 ng cm(-2), respectively. These values suggest that the total burden of DP in Lake Ontario is approximately 20 tons and that the maximum load rate was approximately 2 tons per year. The highest concentrations of PBDEs and TBE were found in the surficial sediment, with average concentrations of 2.8, 14, and 6.7 ng g(-1) d.w. for PBDE(3-7) (tri-through hepta-BDEs), BDE-209, and TBE, respectively. The surface fluxes were 0.08, 0.43, and 0.20 ng cm(-2) yr(-1), and the inventories were 0.87, 3.9, and 1.8 ng cm(-2) for PBDE3-7, BDE-209, and TBE, respectively. The concentration of DP in Lake Ontario sediment exceeds that of the brominated flame retardants combined.

The extent of bioaccumulation of hexabromocyclododecane (HBCD) isomers (alpha, beta, and gamma) was determined in the Lake Ontario pelagic food web using liquid chromatography tandem mass spectrometry (LC/MS/MS). Concentrations of the alpha-isomer were consistently higher than that of the gamma-isomer. The beta-isomer was below method detection limits in all samples. Whole body concentrations (ng/g, wet wt) of alpha- and gamma-HBCD were highest in the top predator lake trout samples ranging from 0.4 to 3.8 ng/g for the alpha-isomer and 0.1 to 0.8 ng/g for the gamma-isomer. For the prey fish species, the trends in alpha- and gamma-HBCD levels were slimy sculpin > smelt > alewife. Mean concentrations of total (sigma) HBCD (sum of alpha- and gamma-isomers) in the macrozooplankter Mysis relicta (0.14 +/- 0.02 ng/g wet wt) and in the benthic invertebrate Diporeia hoyi (0.16 +/- 0.02 ng/g, wet wt) were similar and approximately twice as high as in plankton (0.06 +/- 0.02 ng/g, wet wt). A strong positive linear relationship was found between sigmaHBCD concentrations (wet wt) and trophic level based on delta15N suggesting that HBCD biomagnifies in the Lake Ontario food web. The trophic magnification factor (TMF = 6.3) derived from the slope of the sigmaHBCD - trophic level relationship was slightly higher than TMFs for p,p'-DDE (6.1) and sigmaPCBs (5.7) found previously. Biomagnification factors (BMF, calculated as the ratio of lipid corrected concentration in predator/lipid corrected concentration in prey) were variable between feeding relationships and ranged from 0.4 to 10.8 for the alpha-isomer and from 0.2 to 10 for gamma-isomers.

The extent of trophic transfer of the three diastereoisomers of hexabromocyclododecane (HBCD) and seven brominated diphenyl ether (BDE) congeners was examined in components of an Arctic marine food web from eastern Canada. Alpha and gamma-HBCD diastereoisomers were detected in all species and total (sigma) HBCD concentrations ranged from 0.6 +/- 0.2 pg/g (geometric mean +/- 1 x standard error (SE), lipid weight (lw)) in arctic cod to 3.9 +/- 0.9 ng/g (lw) in narwhal. beta-HBCD was below method detection limits in all the samples. Mean sigmaBDE (sum of seven congeners) concentrations ranged from 0.4 +/- 0.2 ng/g (lw) in walrus to 73 +/- 10 ng/g (lw) in zooplankton. The relative trophic status of biota was determined by nitrogen stable isotopes (delta15N), and results indicated clear differences in HBCD isomer and BDE congener profiles with trophic level (TL). Trophic magnification was observed for the alpha-diastereoisomer and BDE-47 as concentrations increased with increasing TL in the food web, whereas there was trophic dilution of gamma-HBCD and BDE-209 through the food web. Only the (-)alpha-enantiomer showed a strong positive relationship between concentration and TL (p < 0.01) with a trophic magnification factor (TMF) value of 2.2. A small but significant increase in the enantiomeric fraction value of the alpha-enantiomers with TL was also observed (r2 = 0.22, p < 0.005), implying that there is an overall preferential enrichment of the (-)alpha-enantiomer relative to the (+)alpha-enantiomer likely due to the greater bioaccumulation potential of the (-)alpha-enantiomer and/or to the greater susceptibility of the (+)alpha-enantiomer to metabolism.