title: Multi-contaminant analysis of organophosphate and halogenated flame retardants in food matrices using ultrasonication and vacuum assisted extraction, multi-stage cleanup and gas chromatography-mass spectrometry.
abstract: A multi-residue analytical method was developed for the determination of a range of flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs), emerging halogenated FRs (EFRs) and organophosphate FRs (PFRs), in food matrices. An ultrasonication and vacuum assisted extraction (UVAE), followed by a multi-stage clean-up procedure, enabled the removal of up to 1g of lipid from 2.5 g of freeze-dried food samples and significantly reduce matrix effects. UVAE achieves a waste factor (WF) of about 10%, while the WFs of classical QuEChERS methods range usually between 50 and 90%. The low WF of UVAE leads to a dramatic improvement in the sensitivity along with saving up to 90% of spiking (internal) standards. Moreover, a two-stage clean-up on Florisil and aminopropyl silica was introduced after UVAE, for an efficient removal of pigments and residual lipids, which led to cleaner extracts than normally achieved by dispersive solid phase extraction (d-SPE). In this way, the extracts could be concentrated to low volumes, e.g. <100 μL and the equivalent matrix concentrations were up to 100g ww/mL. The final analysis of PFRs was performed on GC-EI-MS, while PBDEs and EFRs were measured by GC-ECNI-MS. Validation tests were performed with three food matrices (lean beef, whole chicken egg and salmon filet), obtaining acceptable recoveries (66-135%) with good repeatability (RSD 1-24%, mean 7%). Method LOQs ranged between 0.008 and 0.04 ng/g dw for PBDEs, between 0.08 and 0.20 ng/g dw for EFRs, and between 1.4 and 3.6 ng/g dw for PFRs. The method was further applied to eight types of food samples (including meat, eggs, fish, and seafood) with lipid contents ranging from 0.1 to 22%. Various FRs were detected above MLOQ levels, demonstrating the wide-range applicability of our method. To the best of our knowledge, this is the first method reported for simultaneous analysis of brominated and organophosphate FRs in food matrices.
authors.affiliation: Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium. Electronic address: fuchao.xu@uantwerpen.be.
authors.forename: Fuchao
authors.initials: F
authors.lastname: Xu
authors.affiliation: Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium; Department of Instrumental Analysis and Environmental Chemistry, Institute of General Organic Chemistry, CSIC, Juan de la Cierva 3, 28006-Madrid, Spain.
authors.forename: Ángel
authors.initials: Á
authors.lastname: García-Bermejo
authors.affiliation: Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium.
authors.forename: Govindan
authors.initials: G
authors.lastname: Malarvannan
authors.affiliation: Department of Instrumental Analysis and Environmental Chemistry, Institute of General Organic Chemistry, CSIC, Juan de la Cierva 3, 28006-Madrid, Spain.
authors.forename: Belén
authors.initials: B
authors.lastname: Gómara
authors.affiliation: Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium.
authors.forename: Hugo
authors.initials: H
authors.lastname: Neels
authors.affiliation: Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium. Electronic address: adrian.covaci@uantwerpen.be.
authors.forename: Adrian
authors.initials: A
authors.lastname: Covaci
mesh_terms: D000818:Animals; D004531:Eggs / Q000032:analysis; D004785:Environmental Pollutants / Q000032:analysis*; D005399:Fishes; D005411:Flame Retardants / Q000032:analysis*; D005524:Food Technology / Q000379:methods*; D008401:Gas Chromatography-Mass Spectrometry; D055768:Halogenated Diphenyl Ethers / Q000032:analysis; D054879:Halogenation; D010755:Organophosphates / Q000032:analysis; D017747:Seafood / Q000032:analysis; D052616:Solid Phase Extraction; D014618:Vacuum
chemical_list: D004785:Environmental Pollutants; D005411:Flame Retardants; D055768:Halogenated Diphenyl Ethers; D010755:Organophosphates
keywords: BFRs; Flame retardants; Food analysis; PFRs; UVAE