Polybrominated diphenyl ethers (PBDEs) have been widely used to flame-retard products common in homes and the workplace, and subsequently, they have become widely dispersed in the environment. Detailed compositional knowledge of these complex PBDE mixtures is crucial to a fuller understanding of their toxicological potencies and environmental fate due to selective congener biomagnification, degradation, and transport. Utilizing recenttechnical enhancements and newly available commercial standards, we developed a method capable of analyzing a larger suite of mono- through deca-BDEs. We then characterized the congener composition of six common technical flame-retardant mixtures: two penta-BDE products (DE-71 and Bromkal 70-5DE) two octa-BDE products (DE-79 and Bromkal 79-8DE) and two deca-BDE products (Saytex 102E and Bromkal 82-0DE). PBDEs were analyzed by gas chromatography/mass spectrometry (GC/MS). Structural conformations based on fragmentation patterns and molecular ions were established by electron-capture negative ionization (ECNI) and electron ionization (El). Sixty-four commercially available PBDE standards were chromato-graphed on two GC columns (DB-1HT and DB-5HT) and relative retention indexes (RRI) calculated. Thirty-nine PBDEs were identified in these products, 29 at concentrations >0.02% by weight. Of these, 12 previously unreported congeners have been confirmed as commercial mixture components. Four of these congeners were detected >0.02% w/w (BDE-144, -171, -180, and -201) and three (BDE-75, -184, and -194) at <0.02%. Five other congeners (four <0.02% by weight) were tentatively identified based on their molecular ion and ECNI fragmentation in the absence of corresponding analytical standards.

Polybrominated diphenyl ethers (PBDEs) were examined in fish fillets collected from two large Virginia watersheds. Emphasis was on the tetra- to hexabrominated congeners since these exhibit the greatest bioaccumulation and toxicological potentials. These congeners are dominant constituents of Penta-, a commercial PBDE product used to flame retard polyurethane foam. In 1999, North America accounted for98% of global Penta-demand. Concentrations of total tetra- to hexabrominated congeners in fillets ranged from <5 to 47,900 microg/kg (lipid basis). BDE-47, one of the two major constituents of Penta-, was detected in 89% of samples and contributed 40-70% of the total PBDEs observed. Concentrations of BDE-99, the second major constituent of the Penta- commercial mixture, were much lower in fish. While some differences in PBDE profiles between fish species were apparent, dominant congeners were consistent with those in surficial sediments from the Virginia sites and recently published data for U.S. air samples. PCB and PBDE concentrations in fish were generally associated. These factors point to exposure from nonpoint sources. Exceptions existed, likely due to inputs from local sources. The Virginia study area has historically served as a center for furniture and textile manufacturing, although polyurethane foam production here has been limited.

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