Emerging and historical brominated flame retardants in peregrine falcon (Falco peregrinus) eggs from Canada and Spain

Comparisons of brominated flame retardants (BFRs) in the eggs of peregrine falcons (Falco peregrinus) recently collected (2003-2007), are made between Canada (N = 12) and Spain (N = 13). Overall, concentrations of sum (Sigma) polybrominated diphenyl ethers (PBDEs; 16 di-deca-BDE congeners) exceeded Sigma hexabromocyclododecane (HBCD) and were an order of magnitude higher than 2,2'4,4',5,5'-hexabromobiphenyl (BB-1 53) > hexachlorocyclopentenyl-dibromocyclooctane (HCBDCO) > 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) > decabromodiphenylethane (DBDPE) > octabromotrimethylphenyllindane (OBIND) > hexabromobenzene (HBB) > bis(2-ethyl-1hexyl)tetrabromophthalate (BEHTBP). This is the first report of detectable HBCDCO and BEHTBP concentrations in biota, and the highest in ovo concentration of Sigma HBCD (14,617 ng/g lw; Montreal, Canada) to date. There were significantly greater egg concentrations of BB-153, Sigma HBCD, and Sigma PBDE including BDE-153, -99, -100 and -183, in Canadian than Spanish peregrines with a terrestrial diet. HBB, BTBPE, and OBIND were detected in eggs from both countries, but only Canadian peregrine eggs had detectable levels of HCDBCO (25%) and DBDPE (N = 1). The in ovo PBDE congener profile was dominated by BDE-153>BDE-99>BDE-47>BDE-183>BDE-100>BDE-209, with the isomeric HBCD pattern being alpha-HBCD > gamma-HBCD (beta-HBCD undetected). The Canadian peregrine eggs had lower enantiomeric HBCD values consistent with their higher fractions of (-) alpha-HBCD, suggesting selective enantiomeric enrichment or that the (+)alpha-isomer is more readily metabolized and so deposited in the egg through maternal transfer. Continental differences in egg burdens of peregrines are discussed relative to BFR usage patterns and exposure of peregrines on their breeding grounds. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.