Has the phase-out of PBDEs affected their atmospheric levels? Trends of PBDEs and their replacements in the Great Lakes atmosphere.

Air and precipitation samples were collected every 12 days at five sites near the North American Great Lakes from 2005 to 2011 (inclusive) by the Integrated Atmospheric Deposition Network (IADN). The concentrations of polybrominated diphenyl ethers (PBDEs) and selected alternative brominated flame retardants [pentabromoethyl benzene (PBEB), hexabromobenzene (HBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (TBE or BTBPE), decabromodiphenylethane (DBDPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), and bis(2-ethylhexyl)-tetrabromo-phthalate (TBPH)] were measured in these samples. The concentrations of almost all of these flame retardants were related to the number of people within a 25 km radius of the sampling site, except for HBB, the concentrations of which were relatively high at Sturgeon Point, and PBEB, the concentrations of which were relatively high at Eagle Harbor. The temporal trends of all of these concentrations were variable. For example, BDE-47 vapor phase concentrations were increasing with doubling times of 5-10 years at Sturgeon Point, Sleeping Bear Dunes, and Eagle Harbor, but these concentrations were slowly decreasing in all phases at Chicago. The most consistent trend was for TBE, which showed concentrations that were unchanging or decreasing in all phases at all sites. TBPH concentrations in particles and HBB concentrations in precipitation were rapidly increasing at most sites with doubling times of ~2 years. The concentrations of DBDPE and BDE-209 were strongly and positively correlated, and the concentrations of TBB and TBPH were also strongly and positively correlated. The concentrations of TBB plus TBPH (representing Firemaster 550) and BDE-47, 85, 99, 100, 153, plus 154 (representing the withdrawn penta-BDE commercial mixture) were also strongly and positively correlated. These positive relationships indicate that the replacement of the deca-BDE commercial product by DBDPE and the penta-BDE product by Firemaster 550 have not yet become evident in the Great Lakes' atmospheric environment.