A Comprehensive GC-MS Approach for Monitoring Legacy and Emerging Halogenated Contaminants in Human Biomonitoring

Human exposure to persistent organic pollutants such as polychlorinated biphenyls (PCB) and brominated flame retardants (BFR), including both legacy and emerging compounds, remains a concern due to their bioaccumulative nature and potential health effects. Comprehensive analytical methods are necessary to monitor these substances in complex biological matrices, such as human serum. A gas chromatography–mass spectrometry (GC-MS) method was developed for the simultaneous determination of 44 analytes, encompassing PCB and a broad spectrum of BFR with diverse physicochemical properties. The extraction procedure and GC-MS parameters were optimized using a design of experiments approach to maximize performance while minimizing analysis time. The method demonstrated high sensitivity, precision, and accuracy, thereby meeting internationally recognized validation criteria for biomonitoring applications. To further ensure analytical reliability, compound confirmation was achieved using gas chromatography–high-resolution mass spectrometry, providing enhanced selectivity and confidence in identification, particularly for low-level analytes. Key advantages of the method include its applicability to analytes with significantly different chemical behaviors and its capacity to quantify a large number of target compounds simultaneously. This makes it a powerful tool for assessing human exposure to both regulated and emerging halogenated contaminants.