Formation of environmentally relevant brominated dioxins from 2,4,6,-tribromophenol via bromoperoxidase-catalyzed dimerization.

Polybrominated dibenzo-p-dioxins (PBDD) are emerging environmental pollutants with structural similarities to the highly characterized toxicants polychlorinated dibenzo-p-dioxins. The geographical and temporal variations of PBDD in biota samples from the Baltic Sea do not display features that are normally related to anthropogenic sources such as incineration, and therefore the natural formation of PBDDs has been suggested. This study of the bromoperoxidase mediated oxidative coupling of 2,4,6-tribromophenol (an abundant substance that is naturally formed in marine systems) identified the formation of ppb-level yields of 1,3,6,8-tetrabromodibenzo-p-dioxin (1,3,6,8-TeBDD) through direct condensation. Additional TeBDDs (1,3,7,9-TeBDD, 1,2,4,7-TeBDD, and/or 1,2,4,8-TeBDD) and tri-BDDs (1,3,7-TrBDD and 1,3,8-TrBDD) were frequently formed but at lower yields. The formation of these TeBDDs probably proceeds via bromine shifts or Smiles rearrangements, whereas the TrBDDs may result from subsequent debromination processes. Because all of the congeners formed by oxidative coupling and subsequent reactions are also found in Baltic Sea biota, the results support the theory that PBDDs are formed from natural precursors.