Analysis of Brominated Flame Retardants and Their Derivatives by Atmospheric Pressure Chemical Ionization Using Gas Chromatography Coupled to Tandem Quadrupole Mass Spectrometry

A validated method using an atmospheric pressure chemical ionization source for coupling gas chromatography (GC-APCI) to tandem quadrupole mass spectrometry (MS/MS) for the determination of brominated flame retardants (BFRs) is presented. Polybrominated diphenyl ethers (PBDEs), their methoxylated derivatives (MeO-PBDEs) and other emerging BFRs were included in this study. The method showed good linearity and repeatability. The relative standard deviation (RSD) of the relative response factors (RRFs) of all compounds was below 16%. Repeatability for BFRs was tested on one or two concentration levels of calibration standards with RSDs for RRFs below 16%. The lowest calibration standards (0.075-0.1pg/µL for emerging BFRs, BDE 209 and MeO-PBDEs mixtures, 0.625-6.25pg/µL for Br PBDEs mixtures) were used as instrument detection limits (IDL). The method was applied on biotic samples, including fish, osprey, and seal. In general, BDE 209 and decabromodiphenyl ethane (DBDPE) were detected in 50% of the seal samples. A 100% detection rate was achieved for 6-MeO-BDE 47 in all the samples (72-580pg/g ww in osprey samples, 24,000-96,000pg/g ww in seal samples and 78-99pg/g ww in fish samples). All Br PBDEs (BDE 28, 47, 99, 100, 153, 154) were detected in all the samples (ranging from 12 to 20,000pg/g ww), while BDE 183 was detected in 60% of the osprey eggs, 20% of the seal samples and below MDL in all fish samples. The results presented indicate the capability of the GC-APCI-MS/MS system for the detection and quantification of BFRs.