Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have been identified as metabolites of PBDEs, and also as compounds of natural origin in the marine environment; however, there has only been very limited study of their presence in the abiotic environment. In the present study, OH-PBDEs were determined in samples of surface water and precipitation (rain and snow) collected from sites in Ontario, Canada. OH-PBDEs were detected in all the samples analyzed, although half of the observed peaks did not correspond to any of the 18 authentic standards available. Fluxes of sigmaOH-PBDEs ranged from 3.5 to 190 pg/m2 in snow and from 15 to 170 pg/m2/day in rain, and those were higher at three of the southern Ontario locations relative to a single northern remote site. Concentrations of sigmaOH-PBDEs ranged from 2.2 to 70 pg/L in water and from < 1 to 420 pg/g in particulate organic carbon (POC), and higher values were found near sewage treatment plant (STP) outfalls in Lake Ontario. Partition coefficients (log K(oc)) for OH-PBDEs ranged from 4.0 to 5.1. The results in this study suggest that OH-PBDEs are ubiquitous in the abiotic environment and most likely are produced through reaction of PBDEs with atmospheric OH radicals. As well, they may be present in surface waters near STPs due to oxidation of PBDEs and inflows from metabolism by humans and animals.

Hydroxylated PCBs (OH-PCBs) are well-known metabolites of PCBs in organisms, but there has been no direct study of their presence in the abiotic environment. In this study, OH-PCBs were determined in samples of rain, snow, and surface waters from sites in Ontario, Canada. OH-PCBs were quantified by gas chromatography with high-resolution mass spectrometry (GC-HRMS)in order to provide complete characterization of all OH-PCB homolog groups. OH-PCBs and PCBs were detected in all the samples analyzed, although half of the sigmaOH-PCBs could not be identified even with 71 individual congener standards. Total concentrations of OH-PCBs (sigmaOH-PCBs) in water ranged from 0.87 to 130 pg/L and from 230 to 990 pg/g in particulate organic matter. Total fluxes of those compounds in snow and rain were from < 1 to 100 pg/m2 and from < 1 to 44 pg/ m2/day, respectively. Higher sigmaOH-PCB fluxes in rain were found in southern Ontario than in a remote north-central Ontario site possibly reflecting greater sources of precursor PCBs near urban areas. Relatively higher sigmaOH-PCB concentrations were found in surface waters from sites near sewage treatment plant (STP) outfalls in the cities of Toronto (130 pg/L) and Hamilton (35 pg/L) than in offshore samples from Lake Ontario (1.6 pg/L). The results indicate that STPs are one of the sources of OH-PCBs for lake waters in this region. Similar homolog and congener profiles in rain and offshore surface water samples suggest that atmospheric deposition is the predominant source at offshore sites. This is the first report to detect the OH-PCBs in the abiotic environment.

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In the present study, the concentrations and fate of contaminants such as organophosphate flame retardants and plasticizers, musk compounds such as galaxolide (HHCB), tonalide (AHTN), musk ketone and musk xylene, the bactericide triclosan, as well as the metabolites HHCB-lactone and triclosan-methyl were compared in the aqueous phase of the German Bight (North Sea). The concentrations of these compounds were around 1 to 10 ng/L in nearshore areas, and the concentrations were lower in the more pristine areas. The highest concentrations were determined for tris-(2-chloro-isopropyl) phosphate in the North Sea with concentration exceeding 10 ng/L even for the offshore samples. The samples contained 1 to 20 ng/L chlorinated organophosphates, approximately 1 ng/L nonchlorinated organophosphates, and 0.3 to 3 ng/L fragrance compounds. Some samples from Lake Ontario (Canada) were analyzed in comparison. Per capita emissions were calculated for both regions. These emissions were compared and turned out to be very similar for the Canadian and German locations. For the North Sea, some observations concerning stability, dilution, and degradation, as well as sources of the respective substances, were performed. These data indicate that the chlorinated organophosphates and some musk fragrances exhibit half lives exceeding the residence times and thus can be considered to be persistent in this ecosystem. In the German Bight, the river Elbe is the dominating source for the more hydrophilic compounds, such as chlorinated organophosphate flame retardants, which are diluted only into the North Sea. However, for the more lipophilic compounds such as the musk fragrances, different input patterns as well as distribution patterns are relevant, though the river Elbe is still a major source of pollution to the German Bight of the North Sea. The data seem to indicate either relevant inputs further west of the sampling area or mobilization from the sediments.

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Whole-body polychlorinated biphenyls (ΣPCBs) and plasma hydroxylated PCBs (OH-PCBs) concentrations were determined in brown bullhead (Ameiurus nebulosus) from Wheatley Harbour, Ontario, Canada. Elevated ΣPCBs in Wheatley Harbour are suspected to have originated from industrial waste disposal and/or discharges from nearby fish processing through discarding of fish remains. Mean ΣPCB concentrations in brown bullhead from Wheatley Harbour were approximately 250 ng/g wet weight compared with approximately 40 ng/g wet weight for brown bullhead from the reference sites, Hillman Marsh and Turkey Creek (both in Ontario, Canada). A significant relationship was found between the concentrations of non-ortho and mono-ortho PCB concentrations (toxic equivalents) and liver mixed-function oxygenase in brown bullhead (r = 0.74, p < 0.001). Plasma OH-PCB concentrations were greater in Wheatley Harbour brown bullhead than in those from Hillman Marsh (3.6 vs 1.5 ng/g wet wt, p < 0.01), and were detected infrequently in those from Turkey Creek (0.1 ng/g wet wt, n = 2). The OH-PCB congeners most frequently detected were 4'-OH-CB172, 3'-OH-CB180, 4-OH-CB187, 4-OH-CB146, 3-OH-CB138, and 4-OH-CB130, which are structurally similar to the thyroid hormones. To test the hypothesis of fish waste as the cause of the observed PCB contamination of Wheatley Harbour brown bullhead, a principal component analysis (PCA) was used to compare the brown bullhead PCB congener data with equivalent data for Lake Erie walleye, Lake Erie sediment, and industrial Aroclor mixtures. The relative proportions of each Aroclor mixture were estimated using the conjugated gradient method. The high similarity between the congener signatures for Lake Erie walleye and Wheatley Harbour brown bullhead supports the hypothesis of contamination from the fish processing industry.

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Polybrominated diphenyl ethers (PBDEs) and hydroxylated PBDEs (OH-PBDEs) were determined in plasma of free-ranging bottlenose dolphins (Tursiops truncatus) from Charleston (CHS), South Carolina, and the Indian River Lagoon (IRL), Florida, U.S.A. Significantly lower sums (sigma) of PBDE concentrations (sum of 12 congeners) were found in animals from the IRL (arithmetic mean, 5.45 +/- 4.63 ng/g wet wt) compared with those from CHS (30 +/- 40 ng/g wet wt). Brominated diphenyl ether (BDE)-47 was the predominant PBDE in dolphins from the IRL (50% of the sigma PBDEs) and CHS (58%). The sigma PBDE concentrations in plasma of dolphins were negatively correlated with age at both locations. Fifteen and sixteen individual OH-PBDE congeners could be quantified in plasma of dolphins from IRL and CHS, respectively. Similar to sigma PBDE, mean sigma OH-PBDE concentrations were significantly higher in plasma of dolphins at CHS (1150 +/- 708 pg/g wet wt) compared with those at IRL (624 +/- 393 pg/g wet wt). The predominant congener at both locations was 6-OH-PBDE-47 (IRL, 384 +/- 319 pg/g wet wt; CHS, 541 +/- 344 pg/g wet wt), representing 61.5% of total sigma OH-PBDE at IRL and 47.0% at CHS. Concentrations of sigma OH-PBDEs were weakly negatively correlated with age in dolphins from both locations (p < 0.05; IRL, r2 = 0.048; CHS, r2 = 0.021). In addition to the OH-PBDE congeners identified with technical standards, eight and four unidentified OH-PBDEs were detected and quantified, respectively, in animals from CHS (sum of unidentified OH-PBDEs = 1.35 +/- 0.90 pg/g wet wt) and IRL (0.73 +/- 0.40 pg/g wet wt). Results of the present study suggest that, unlike OH-PCBs, OH-PBDEs in bottlenose dolphins are minor products in plasma relative to sigma PBDEs and a significant proportion may be a consequence of the dietary uptake of naturally produced methoxylated- and OH-PBDEs.