Single sample preparation for brominated flame retardants in fish and shellfish with dual detection: GC-MS/MS (PBDEs) and LC-MS/MS (HBCDs)

An analytical method for the simultaneous determination of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in fish, shellfish and muscle of terrestrial animals was developed as an extension of a previously validated method for PBDE analysis. A single sample preparation based on QuEChERS-like extraction and a two-step clean-up, followed by a dual instrumental detection, was implemented. GC-MS/MS was used for PBDEs and LC-MS/MS for HBCDs. The method allows the quantification of fifteen PBDEs (28, 47, 49, 66, 77, 85, 99, 100, 138, 153, 154, 183, 197, 206, 209) and three HBCD isomers (α, β and γ), reaching 10 pg/g LOQs for all the analytes except BDE 206 and 209 (100 pg/g LOQ). The validated method was applied to the analysis of 12 fish and shellfish species (sole, spiny dogfish, smooth-hound, mackerel, swordfish, grey mullet, cod, anchovy, red mullet, Atlantic horse mackerel, tuna fish and mussel) collected in central Italian markets accounting for a total of 44 samples. Generally, ΣPBDEs showed higher concentration than ΣHBCDs except in the case of mussels in which ΣHBCDs > ΣPBDEs. Cod and smooth-hound are the least contaminated species among those analysed in the present study, whereas the highest brominated flame retardant (BFR) levels were found in spiny dogfish samples. The measured contamination levels were generally comparable to or lower than those already published in European studies. Literature data for HBCDs in European fish and shellfish were hard to find; therefore, PBDE and HBCD levels were also compared with European Environmental Quality Standard (EQS) in biota (Directive 2013/39/EU). EQSs for HBCDs are six orders of magnitude higher than those for PBDEs; therefore, while no exceedance was observed for the first, almost all the samples analysed for PBDEs were above EQSs. The presented preliminary data on PBDEs and HBCDs are among the first published in marine fish and shellfish commercialised in Central Italy.