Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE Technical Flame-retardant Mixtures

Abstract

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.

Aerosol-Mediated Transport and Deposition of Brominated Diphenyl Ethers to Antarctica

“…24,25 The source of the elevated airborne particulate BDE209 to the Marguerite Bay region in 23 The local source of BDE 209 was reflected in the lack of a significant correlation (p ≥ 0.14) between it and the other BDE congeners associated with aerosol particles. In contrast, BDEs -47, -99, and -100, the primary components of the commercial pentaBDE formulations 27 were significantly correlated ( Figure 3) and provide insights into the sources and fate of BDEs during atmospheric transport to Antarctica. The average ratio of BDE47/100 (± standard error) in the Antarctic aerosol samples (3.6(±0.3); Figure 3) falls in between ratios measured in the commercial pentaBDE formulations (DE-71 = 2.92; Bromkal 70-5DE = 5.47), 27 whereas the average ratio of BDE99/100 (2.45(±0.41); Figure 3) falls below ratios measured in the commercial pentaBDE formulations (DE-71 = 3.71; Bromkal 70-5DE = 5.37).…”

“…In contrast, BDEs -47, -99, and -100, the primary components of the commercial pentaBDE formulations 27 were significantly correlated ( Figure 3) and provide insights into the sources and fate of BDEs during atmospheric transport to Antarctica. The average ratio of BDE47/100 (± standard error) in the Antarctic aerosol samples (3.6(±0.3); Figure 3) falls in between ratios measured in the commercial pentaBDE formulations (DE-71 = 2.92; Bromkal 70-5DE = 5.47), 27 whereas the average ratio of BDE99/100 (2.45(±0.41); Figure 3) falls below ratios measured in the commercial pentaBDE formulations (DE-71 = 3.71; Bromkal 70-5DE = 5.37). 27 The photodegradation half-lives for the pentaBDE components decrease as follows: BDE100 > BDE47 > BDE99 indicating that BDE99 is the most photolabile of these three BDE congeners.…”

Particle-bound Dechlorane Plus and polybrominated diphenyl ethers in ambient air around Shanghai, China

“…The three commercial PBDE products, penta-, octa-and deca-BDEs, are all mixtures of many congeners, of which congener composition ratios were analyzed by La Guardia et al (2006). Similar to the principle component analysis, multiple linear regression analysis is also used to investigate the most important contributor in several known factors with the formula of…”

“…We assumed the congener composition in the different districts of Shanghai as the dependent variable (y) and those of the three common technical mixtures of PBDE as three independent variables (x 1 , x 2 , x 3 ), which were measured by La Guardia et al (2006). The averaged values were selected as the final results.…”

PBDE levels in franciscana dolphin (Pontoporia blainvillei): Temporal trend and geographical comparison

“…This profile suggests sources originating from the use of the penta-BDE mixture. However, the technical penta-BDE mixture has a higher proportion of BDE 99 than BDE 47 (La Guardia et al, 2006). Thus, the lower proportion of BDE 99 in comparison to BDE 47 suggests the preferential elimination or metabolic degradation of BDE 99.…”