Structure and origin of the natural halogenated monoterpene MHC-1 and its concentrations in marine mammals and fish

The halogenated natural product previously named mixed-halogenated compound 1 (MHC-1) was isolated from the red seaweed Plocamium cartilagineum harvested in Helgoland, Germany. A total of 1.9 mg of pure MHC-1 was obtained from 1g air-dried seaweed. The 1H and 13C NMR data matched those reported for a natural monoterpene isolated from this species. Thus, the structure of MHC-1 was established to be (1R,2S,4R,5R,1'E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(2'-chloroethenyl)-5-methylcyclohexane. Moreover, the isolated monoterpene proved to be identical with the compound previously detected in marine mammals and fish from different locations. In addition we examined two samples of P. cartilagineum from Ireland and from the Antarctic; however MHC-1 was only present at low levels. Not only the concentrations were lower but also the pattern of polybrominated compounds differed from MHC-1. A calibrated solution of MHC-1 was used to determine correct concentrations from samples where previously only estimates existed relative to the gas chromatography-electron capture detector (GC/ECD) response of trans-chlordane, which underrated the MHC-1 concentrations by more than factor 2. The highest MHC-1 concentration determined to date in marine mammals is 0.14 mg kg(-1) blubber. Significantly higher MHC-1 concentrations were determined in farmed fish with up to 2.2 mg kg(-1) lipids. The samples with high concentrations of MHC-1 have in common that they were collected in proximity of the natural habitats of P. cartilagineum.