Determination of emerging halogenated flame retardants and polybrominated diphenyl ethers in serum by gas chromatography mass spectrometry

• Fast and sensitive chromatographic method comparable to low pressure GC/MS.
• Separation of 7 emerging flame retardants in addition to 15 PBDEs on a 15 m column.
• Emerging flame retardants detected in human serum from Norway.
• Dec602 and Dec603 are detected and quantitated for the first time in human serum.

Emerging flame retardants are used in a great variety of household goods and thus have the potential to pollute our indoor environment. Health concerns regarding exposure to these flame retardants demand new methods to survey their occurrence in humans. This work describes development and optimization of an analytical method comprising solid phase extraction and gas chromatography coupled to mass spectrometry for the determination of besides 15 polybrominated diphenyl ethers, 7 emerging halogenated flame retardants in human serum (1,2-bis[2,4,6-tribromophenoxy] ethane, decabromodiphenyl ethane, hexabromobenzene, Dechlorane Plus®, hexachlorocyclopentenyl-dibromocyclooctane, dechlorane 602 and 603). The method was thoroughly validated at three spiking levels obtaining averaged recoveries >80% with a RSD of 5% (n = 12). Accuracies ranged from 88 to 125% except for DBDPE, which averaged 66% with overall RSD of 11% (n = 12). Method limits of detection (MLD) ranged from 0.3 to 5.4 pg/mL serum, except for decabromodiphenyl ether and decabromodiphenyl ethane for which MLDs were 14 and 20 pg/mL serum, respectively. In human serum samples from Norway, we were able to detect and quantify hexabromobenzene, 1,2-bis[2,4,6-tribromophenoxy] ethane, Dechlorane Plus®, Dechlorane 602 and 603.