Identification of Hydroxylated and Methoxylated Polybrominated Diphenyl Ethers in Baltic Sea Salmon (Salmo salar) Blood

Abstract

Methoxylated and hydroxylated polybrominated diphenyl ethers (MeO-PBDEs and OH-PBDEs) have recently been reported to be present in wildlife from Northern Europe. The structures of a majority of these compounds have however been unknown. In the present study, nine OH-PBDEs and six MeO-PBDEs were identified in Baltic Sea salmon (Salmo salar) blood. All OH- and MeO-PBDEs identified were substituted with four or five bromines, and five of these had one chlorine substituent. Fourteen of the OH- and MeO-PBDEs have the methoxy or hydroxy group substituted in the ortho position to the diphenyl ether bond. Identification was done by comparison of relative retention times of authentic reference standards with compounds present in salmon plasma on two gas chromatographic columns of different polarities. The identification was supported by comparisons of full-scan mass spectrometric data: electron ionization (EI) and electron capture negative ionization (ECNI). Nine of the 15 OH- and MeO-PBDEs identified have not previously been reported to occur in the environment. The structures of several identified OH- and MeO-PBDEs support natural origin. However, at least one of the OH-PBDEs may be a hydroxylated metabolite of anthropogenic polybrominated diphenyl ether (PBDE).

Levels and distribution of methoxylated and hydroxylated polybrominated diphenyl ethers in plant and soil samples surrounding a seafood processing factory and a seafood market

“…Concentration of SPBDEs was 725.7 pg/g in hairtail. Besides, a small amount of 5-MeO-BDE-47 (43.5 pg/g), 6 0 -MeO-BDE-99 (63.3 pg/g) and 2 0 -OH-BDE-68 (57.8 pg/g) which were usually found in marine organisms (Kelly et al, 2008;Marsh et al, 2004;Routti et al, 2009) was also identified in these fish. The results showed that MeO-and OH-PBDEs in the soil and plant samples may come from the marine products that processed in the factory.…”

Developmental neurotoxicity of polybrominated diphenyl ether (PBDE) flame retardants

“…PBDEs distribute to several tissues including the brain, and highest and more persistent concentrations are found in adipose tissue (Hakk and Letcher, 2003), however, this is not the case for BDE-209 (Morck et al 2003). Tetra-and pentaBDEs are metabolized by mixed function oxidases to mono-and di-hydroxylated metabolites (Hakk et al 2002;Hakk and Letcher, 2003;Malmberg et al 2005;Marsh et al 2004), while decaBDE is metabolized to lower brominated congeners (nona-and octaBDE) (Morck et al 2003;Huwe and Smith, 2007). There appears to be a species difference in the rate of excretion, with a higher urinary excretion in mice (Orn and Klasson-Wehler, 1998).…”

“…Additionally, humans can also be directly exposed to hydroxylated BDEs, which are known to be a product of PBDE metabolism (Malmberg et al 2005;Marsh et al 2006). Hydroxylated PBDEs are found, for example, in fish such as salmon (Marsh et al 2004), and some may also have a natural origin. As said earlier, hydroxylated-PBDEs have a much greater affinity for TTR than PBDEs (Meerts et al 2000).…”

Hydroxylated PBDEs and brominated phenolic compounds in particulate matters emitted during recycling of waste printed circuit boards in a typical e-waste workshop of South China

“…Several compounds, assigned to be mono-OH-PBDEs and di-OH-PBDEs were also detected, however, their structures could not be identified in the present study because of an absence of authentic standards. It is suggested that meta-methoxysubstituted PBDEs does not contain fragment ions of [MÀCH 3 (Malmberg et al, 2005;Marsh et al, 2004). Therefore, position of the hydroxylated group in the unidentified monohydroxylated PBDE congeners was suggested based on the characteristic fragmentation pattern of their EI mass spectra.…”

“…Hydroxylated PBDEs (OH-PBDEs), which are a relatively new group of phenolic compounds, have been detected in biological samples including fish (Marsh et al, 2004;Valters et al, 2005), algae (Malmvarn et al, 2005(Malmvarn et al, , 2008, birds (Verreault et al, 2005), rats and mice (Malmberg et al, 2005;Qiu et al, 2007), as well as human blood Qiu et al, 2009;Yu et al, 2010). It has been shown that OH-PBDEs can be naturally formed in marine algae or by their associated microorganisms (Malmvarn et al, 2005(Malmvarn et al, , 2008Unson et al, 1994).…”