Rapid and simple method for determination of hexabromocyclododecanes and other LC–MS–MS-amenable brominated flame retardants in fish

Darina Lankova, Michala Kockovska, Ondrej Lacina, Kamila Kalachova, Jana Pulkrabova, Jana Hajslova

In this study, a novel analytical approach for simultaneous determination of hexabromocyclododecane isomers (HBCDs), tetrabromobisphenol A (TBBPA), three brominated phenols, and four hydroxylated derivatives of polybrominated diphenyl ethers (OH-PBDEs) was developed and validated for muscle tissue of both lean and fatty fish. The rapid, simple, and high-throughput sample-preparation procedure was based on acetonitrile extraction then purification by dispersive solid-phase extraction (d-SPE) with a combination of C18 and primary-secondary amine (PSA) sorbents. Ultra-high performance liquid chromatography (UHPLC) coupled to tandem mass spectrometry (MS-MS) was used for identification and quantification of the analytes. Method recovery for both matrices ranged from 80 to 115% with relative standard deviations (RSDs) <13% for all analytes. Limits of quantification (LOQs) were in the range 0.1-1 μg kg(-1) wet weight. The validated method was used for analysis of brominated compounds in 32 fish and five bivalve samples collected from different European markets within the monitoring survey organized in the framework of the CONffIDENCE project. Of the 12 targeted analytes, only α-HBCD, 2,4-dibromophenol (2,4-DBP), and 2,4,6-tribromophenol (2,4,6-TBP) were quantified in the samples. α-HBCD was found in six fish samples (herring and mackerel) in the range of 0.8-2.5 μg kg(-1) wet weight. 2,4-DBP and 2,4,6-TBP were found in three blue mussel samples in the range of 19.6-43.5 and 2.3-7.5 μg kg(-1) wet weight, respectively.