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In this study, we measured the concentrations of 65 flame retardants in water samples from five Lake Michigan tributaries. These flame retardants included organophosphate esters (OPEs), brominated flame retardants (BFRs), and Dechlorane-related compounds. A total of 59 samples, including both the particulate and the dissolved phases, were collected from the Grand, Kalamazoo, Saint Joseph, and Lower Fox rivers and from the Indiana Harbor and Ship Canal (IHSC) in 2015. OPEs were the most abundant among the targeted compounds with geometric mean concentrations ranging from 20 to 54 ng/L; OPE concentrations were comparable among the five tributaries. BFR concentrations were about 1 ng/L, and the most-abundant compounds were bis(2-ethylhexyl) tetrabromophthalate, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate, and decabromodiphenyl ether. The highest BFR concentrations were measured in either the IHSC or the Saint Joseph River. The dechlorane-related compounds were detected at low concentrations (<1 pg/L). The fraction of target compounds in the particulate phase relative to the dissolved phase varied by chemical and tended to increase with their octanol-water partition coefficient. The chemical loading from all the five tributaries into Lake Michigan were <10 kg/year for the BFRs and about 500 kg/year for the OPEs.
Marbon is isomeric with Dechlorane Plus (DP). Both are produced by the Diels-Alder condensation of hexachlorocyclopentadiene with cyclic dienes, and both have elemental compositions of CHCl. Dechlorane Plus is commonly found in the environment throughout the world, but Marbon has, so far, only been detected at low levels in one sediment core collected near the mouth of the Niagara River in Lake Ontario. Here we report on the concentrations of Marbon and anti-DP in 59 water samples from five Lake Michigan tributaries [the Grand, Kalamazoo, St. Joseph, and Lower Fox Rivers, and the Indiana Harbor and Ship Canal (IHSC)], 10 surface sediment samples from the IHSC, and 2 surface sediment samples from the Chicago Sanitary and Ship Canal. Three Marbon diastereomers were detected in the water and sediment samples from the IHSC, which is far from the location of its previous detection in Lake Ontario. The sum of the concentrations of the three Marbons was greater in the water from the IHSC (N = 11, median =150 pg/L) compared to those in water from the other four tributaries (N = 11-13, medians =0.9-2.0 pg/L). Marbon concentrations in sediment samples from the IHSC were up to 450 ng/g dry weight. Anti-DP was also measured for comparison. Its concentrations were not significantly different among the water samples, but its sediment concentrations in the IHSC were significantly correlated with those of Marbon. The source of Marbon contamination in the IHSC is not clear.
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