Critical review of analytical methods for the determination of flame retardants in human matrices
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Date
2022
Authors
Hajeb, Parvaneh
Castaño, Argelia
Cequier Manciñeiras, Enrique
Covaci, Adrian
Esteban López, Marta
Gonzalez Antuña, Ana
Småstuen Haug, Line
Henríquez-Hernández, Luis Alberto
Melymuk, Lisa
Pérez Luzardo, Octavio Luis
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Abstract
Human biomonitoring is a powerful approach in assessing exposure to environmental pollutants. Flame
retardants (FRs) are of particular concern due to their wide distribution in the environment and adverse
health effects. This article reviews studies published in 2009e2020 on the chemical analysis of FRs in a
variety of human samples and discusses the characteristics of the analytical methods applied to different
FR biomarkers of exposure, including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane
(HBCD), novel halogenated flame retardants (NHFRs), bromophenols, incl. tetrabromobisphenol
A (TBBPA), and organophosphorous flame retardants (PFRs). Among the extraction
techniques, liquid-liquid extraction (LLE) and solid phase extraction (SPE) were used most frequently due
to the good efficiencies in the isolation of the majority of the FR biomarkers, but with challenges for
highly lipophilic FRs. Gas chromatography-mass spectrometry (GC-MS) is mainly applied in the instrumental
analysis of PBDEs and most NHFRs, with recent inclusions of GC-MS/MS and high resolution MS
techniques. Liquid chromatography-MS/MS is mainly applied to HBCD, bromophenols, incl. TBBPA, and
PFRs (including metabolites), however, GC-based analysis following derivatization has also been used for phenolic compounds and PFR metabolites. Developments are noticed towards more universal analytical
methods, which enable widening method scopes in the human biomonitoring of FRs. Challenges exist
with regard to sensitivity required for the low concentrations of FRs in the general population and
limited sample material for some human matrices. A strong focus on quality assurance/quality control
(QA/QC) measures is required in the analysis of FR biomarkers in human samples, related to their variety
of physical-chemical properties, low levels in most human samples and the risk of contamination.
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Analytica Chimica Acta, 2022, vol. 1193, art. 338828.