A direct immersion-solid-phase microextraction method for the automated determination of 3- to 6-ring polycyclic aromatic hydrocarbons in saliva by gas-chromatography-tandem mass spectrometry

• Published in: Journal of Chromatography A 2024-11, Vol.1736, p.465404, Article 465404
• Main Authors: Naccarato, Attilio, Elliani, Rosangela, Tagarelli, Antonio
• Format: Article
• Language: English
• Subjects: Experimental design, exposomics tools; Human biomonitoring; Microextraction techniques; Polycyclic aromatic hydrocarbons; Saliva
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2024.465404

•An easy method for polyclyclic aromatic hydrocarbons (PAHs) quantitation in human saliva is presented.•PDMS/DVB/PDMS fiber was used in direct immersion for extraction of thirteen PAHs including low-volatile analytes such as benzo[a]pyrene and dibenzo[a,h]anthracene.•The evaluation of the robustness of fiber coating over time revealed highly satisfactory extraction performance, with no significant drop in signal.•The target compounds were quantified with LLOQs at 100 and 500 ng/L.•The “green” character of the procedure was evaluated by greenness metrics. This work presents a novel method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in saliva samples using solid phase microextraction (SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The protocol utilizes the latest commercially available overcoated fiber (PDMS/DVB/PDMS) for direct immersion extraction of the target analytes, enabling the determination of thirteen PAHs, including low-volatile compounds. The SPME extraction method was optimized using a central composite design (CCD). The evaluation of the fiber coating's robustness over time demonstrated excellent extraction performance with no significant degradation. The validation procedure confirmed good performance for all parameters, with LOQ values (100 ng/L for ten analytes and 500 ng/L for three analytes) comparable to other chromatographic methods. The environmental impact of the protocol was objectively assessed using two recently proposed metrics: the Green Analytical Procedure Index (GAPI) and the Analytical Greenness metric for sample preparation (AGREEprep). Both metrics indicated good overall environmental friendliness, with AGREEprep providing a satisfactory comprehensive score despite the use of highly impactful instrumentation. These characteristics make the developed method suitable for routine analysis in environmental and epidemiological monitoring.