Methodological approach for a simultaneous determination of persistent and non-persistent organic pollutants in human blood (serum/plasma) using gas chromatography and mass spectrometry techniques

Human biomonitoring of persistent organic pollutants (POPs) remains essential for tracking long-term exposure, evaluating health risks, and assessing the effectiveness of regulatory bans. For this purpose, an experimental and analytical methodology has been optimized allowing the determination of 47 POPs, encompassing chlorinated cyclodienes, chlorobenzenes, cyclohexanes, polychlorodiphenyl derivatives, several congeners of polychlorobiphenyls (PCBs) and polybromodiphenyl ethers (PBDEs, including the deca-BDE), as well as three non-persistent chemicals (namely quintozene, tecnazene and vinclozolin). The method uses a single liquid-liquid extraction procedure with 500 µL of serum/plasma. Instrumental analysis involves gas chromatography (GC) with electron capture detection (ECD) for the analysis of organochlorines, and a subsequent injection into a GC coupled to mass spectrometry in negative chemical ionization mode (MS-NCI) for the determination of PBDEs. The analytical procedure has been successfully validated, demonstrating high sensitivity (limits of detection: 0.0016-0.012 ng/mL; limits of quantification: 0.0029-0.021 ng/mL), acceptable linearity (R² > 0.9962), good precision (coefficients of variation <25%, except for BDE-209), satisfactory accuracy (recoveries within 70-130% for 41 out of 47 compounds) and minimal matrix effects. Proficiency Testing Materials from the AMAP Ring Test for POPs in human serum confirmed the method's reliability with results within the accepted reference range. This method represents an efficient and practical approach for human biomonitoring studies, with a simplified workflow suitable for routine application.