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.

Concentrations of Mirex, Dechlorane (Dec) Plus (DP), Dec 602, Dec 603, and Dec 604 were significantly higher in peregrine falcon (Falco peregrinus) eggs from Canada than Spain, with the former having the only measurable concentrations of the dechlorinated DP products, decachloropentacyclooctadecadiene (aCl10DP) and undecachloropentacyclooctadecadiene (aCl11DP). Large variations also occurred in the in ovo concentrations of the DP monoadduct, DPMA. This is the first study to report the accumulation and metabolism of DP by peregrines, both DP and dechloranes in European biota, as well as dechloranes in a terrestrial organism and one at the top of the food web. The geographical differences in the measured in ovo concentrations reflect local exposure of the adult peregrines on their breeding grounds, likely differences in diet of the adults, the production of DP on the Niagara River, and the greater use of Mirex and dechloranes as flame retardants in North America than Europe.

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.