Polybrominated diphenylethers and methoxylated tetrabromodiphenylethers in cetaceans from the Mediterranean Sea

Eight tetrabrominated to hexabrominated diphenylethers were present at ppb levels in liver from cetaceans found stranded on the beaches of the Mediterranean Sea, Italy. The highest concentration was found in striped dolphin (sum polybrominated diphenyl ethers [PBDE] 8133 ng/g l.w.) and the lowest concentration in bottlenose dolphin (sum PBDE 66 ng/g lipid weight [l.w.]). The predominant congener in all samples was 2,2',4,4'-tetraBDE (PBDE # 47) followed by, in decreasing order, the pentaPBDE # 99 and 100 and the hexaPBDE # 154 and 153. In 12 of the 14 analyzed samples, 3 different methoxylated PBDEs (MeO-PBDE # 1, 2, and 3) were detected at semiquantitatively calculated concentration ranges of 2 to 14 ng/g l.w.; 5 to 167 ng/g l.w.; and 7 to 628 ng/g l.w., respectively. In addition, several unidentified bromine compounds were seen when screening the samples in negative-chemical ionization (NCI) mode monitoring m/z 79 and 81, which illustrates the importance of running both electron-impact ionization and NCI when analyzing environmental samples. Electron-impact ionization is more specific for monitoring the molecular ion compared with NCI, which might overestimate the concentration of certain PBDE congeners.