Sediment cores were taken in 2001 and 2002 in Lake Superior at six locations away from lakeshores and segmented at 0.5-5 cm intervals. The year of sediment deposition was estimated for each segment of four cores using the 210Pb dating technique. Samples were Soxhlet-extracted and cleaned up by silica gel fractionation, and the concentrations of 10 polybrominated diphenyl ethers (PBDEs) and 19 polychlorinated biphenyls (PCBs) were measured by GC-MS in SIM mode. In contrast to recent declining or level-off trends in PCB fluxes, the sedimentary records of PBDEs generally show a significant increase in recent years. The load of total PBDEs to Lake Superior was estimated to be 2-6 metric tons, and the current loading rate was about 80-160 kg yr(-1). With the exclusion of decabromodiphenyl ether (BDE209), the surficial concentration of sumPBDE (sum of 9 congeners) ranged from 0.5 to 3 ng g(-1), and the current sumPBDEs flux was 8-31 pg cm(-2) yr(-1). The concentrations of BDE209 were about an order of magnitude higher than the sum of other congeners, comprising 83-94% of the total PBDE inventory in the sediments. Among the other nine PBDEs detected, congeners 47 and 99 were the most abundant, and congeners 100, 153, 154, and 183 were also detected in all the cores. Congener analysis demonstrated that the pattern of PBDEs in Lake Superior sediments differs from those in air and fish.

Sediment cores were taken in 2002 in Lakes Michigan and Huron at six locations. A total of 75 samples were characterized, dated using 210Pb, and analyzed for 10 congeners of polybromodiphenyl ether (PBDE) including BDE209, as well as 39 congeners of polychlorinated biphenyls (PCBs). The concentrations of nine tri- through hepta-BDE congeners (Sigma9PBDE) in the surficial sediments range from 1.7 to 4 ng g(-1) for Lake Michigan and from 1.0 to 1.9 ng g(-1) for Lake Huron, on the basis of the dry sediment weight. The Sigma9PBDEs fluxes to the sediment around the year 2002 are from 36 to 109 pg cm(-2) yr(-1) in Lake Michigan and from 30 to 73 pg cm(-2) yr(-1) in Lake Huron, with spatial variations in both lakes. The flux of BDE209 ranges from 0.64 to 2.04 ng cm(-2) yr(-1) and from 0.67 to 1.41 ng cm(-2) yr(-1) in Lake Michigan and Lake Huron, respectively. Dramatic increases in PBDE concentrations and fluxes upward toward the sediment surface and the present time are evident at all locations. The inventory of PBDEs in both lakes appears to be dependent upon latitude and the proximity to populated areas, implying that north-bound air plumes from urban areas are the major sources of PBDEs found in the lake sediments at locations away from the shores. Heavier congeners are more abundant in the sediments than in air and fish samples in the region. BDE209 is about 96% and 91% of the total PBDEs on a mass basis in Lake Michigan and Lake Huron, respectively; both are higher than the 89% found in Lake Superior, although a t test shows that the value for Lake Huron is not statistically different from that for Lake Superior at the 95% confidence level.

Sediment cores were taken in 2002 in Lakes Ontario and Erie at four locations. A total of 48 sediment samples were characterized, dated using 210Pb, and analyzed for 10 congeners of polybrominated diphenyl ethers (PBDEs) including BDE209 as well as 39 congeners of polychlorinated biphenyls (PCBs). The surficial concentrations of nine tri- through hepta-BDE congeners (sigma9PBDE) are 4.85 and 6.33 ng g(-1), at sampling sites ON40 and ON30 in Lake Ontario, and 1.83 and 1.95 ng g(-1) at ER37 and ER09 in Lake Erie, respectively, based on dry sediment weight. The surficial BDE209 concentrations are 242 and 211 ng g(-1) at ON40 and ON30 and 50 and 55 ng g(-1) at ER37 and ER09. The sigma(9-) PBDEs fluxes to the sediment around 2002 are 147 and 195 pg cm(-2) year(-1) at ON40 and ON30 and 136 and 314 pg cm(-2) year(-1) at ER37 and ER09, respectively. The fluxes of BDE209 are 6.5 and 7.3 ng cm(-2) year(-1) at ON30 and ON40 and 3.7 and 8.9 ng cm(-2) year(-1) at ER37 and ER09, respectively. Dramatic increases in PBDE concentrations and fluxes upward toward the sediment surface and the present time are evident at both locations in Lake Ontario, while PCBs concentrations peak in the middle of sediment cores around the dated time of 1970s and 1960s. For both locations of Lake Erie, the increasing trends of both PBDEs and PCBs from the bottom to the surficial segments were distorted by sediment mixing. BDE209 is the most abundant congener among PBDEs in the sediments, constituting about 96 and 91% of the total PBDEs on mass basis in Lakes Ontario and Erie, respectively.

A total of 199 sediment samples were collected from 16 locations in the five Laurentian Great Lakes, and each was analyzed for 10 congeners of polybrominated diphenyl ethers (PBDEs) as well as selected polychlorinated biphenyls (PCBs). This paper presents a comprehensive analysis on previously published results for individual lakes. The total accumulation of nine tri- to hepta-PBDE congeners (sigma9BDEs) in the sediments of all the Great Lakes was estimated to be approximately 5.2+/-1.1 tonnes, and that of decabromodiphenyl ether (BDE209) was 92+/-13 tonnes, around year 2002. The inventories of sigma9BDEs and major individual PBDE congeners show strong dependence on the latitude of sampling sites, and such dependence is believed to reflect both the influence of urbanization, which shows south-to-north gradient in the region, and the general direction of long-range transport of airborne pollutants in the northern hemisphere. From the 1970s to 2002, the increases in PBDE input flux to the sediments are exponential at all locations, with doubling times (t2) ranging from 9 to 43 years for sigma9BDEs, and from 7 to >70 year for BDE209. The longer t2 values found in sediments compared with those in human and fish in the region suggest the slower response of sediment to emissions. The correlations between the concentrations of sigma9BDEs or BDE209 in surface sediments and latitude are strengthened by normalization of the concentrations with sediment contents of the organic matter or organic carbon, but not soot carbon. Multivariate linear regression equations were developed using data obtained with sediment segments deposited after 1950. All the regressions are statistically significant; and the three independent variables-year of deposition, latitude, and organic matter content of the sediments-account for 73% and 62% of the variations in the concentrations or the fluxes of S9BDEs and BDE209, respectively, in the Great Lakes sediments.

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