Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and hydroxylated PBDEs (OH-PBDEs) have recently been identified in fish and wildlife from the Baltic Sea. Both OH-PBDEs and MeO-PBDEs are known natural products, while OH-PBDEs also may be metabolites of PBDEs. The aim of the present study was to determine if the red macroalga Ceramium tenuicorne could be a source for MeO- and OH-PBDEs in the Baltic environment. Blue mussels (Mytilus edulis) from the same area were also investigated for their content of MeO- and OH-PBDEs. Seven OH-PBDEs and four MeO-PBDEs were present both in the red macroalga and the blue mussels. The mussels also contained a monochlorinated OH-tetraBDE. One of the compounds, 6-methoxy-2,2',3,4,4',5-hexabromodiphenyl ether, has never been reported to occur in the environment. The identification was based on comparison of relative retention times with reference standards, on two gas chromatographic columns of different polarities, together with comparisons of full-scan electron capture negative ionization (ECNI) and electron ionization (EI) mass spectra. It is shown that MeO-PBDEs and OH-PBDEs are present in algae, but at this stage it could not be confirmed if the compounds are produced by the alga itself or by its associated microflora and/or microfauna.

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).

A method for the analysis of potential endocrine-disrupting compounds, such as phenolic halogenated compounds (e.g., chlorinated and brominated phenols) and hydroxylated PCBs, in blood plasma is presented. Neutral halogenated compounds, specifically brominated diphenyl ethers and PCBs, are also included in the evaluation. An efficient denaturation and extraction step is described, and three methods for lipid removal are evaluated. The latter includes a nondestructive method based on high-resolution gel permeation chromatography (HR-GPC), a newly developed silica gel/sulfuric acid column, and lipid removal by sulfuric acid treatment. Recoveries, based on gas chromatography with an electron capture detector (GC-ECD), were between 70 and 90% for most of the studied compounds. The recoveries of phenolic compounds were generally slightly lower than those of the neutral compounds. The sulfuric acid treatment and silica gel/sulfuric acid column gave the highest yields for acid stable compounds, although a few target compounds were lost during that treatment and all compounds were recovered with the HR-GPC method.

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Levels of polybrominated dibenzo-p-dioxins (PBDDs) were measured in marine fish, mussels, and shellfish. PBDDs were nondetectable in samples from freshwater environments, and their levels were successively higher in samples from the marine environments of the Bothnian Bay and Bothnian Sea, the West Coast of Sweden, and the Baltic Proper. In Baltic Proper littoral fish the levels of PBDDs generally exceeded those of their chlorinated analogues (PCDDs). This is alarming as some Baltic fish species already are contaminated by chlorinated dioxins to such an extent that they cannot be sold on the European market. By comparing spatial trends in PBDD and PCDD distributions, and PBDD patterns in fish, mussels, and algae, we show that the PBDDs are probably produced naturally, and we propose a route for their biosynthesis. We further show that the levels of PBDDs are high (ng/g wet weight) in mussels, and that the levels increase over time. Finally, we discuss the possibility that the PBDDs have adverse biological effects, and that the levels are increasing as a result of global warming and eutrophication.