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. 2025 Aug 16;30(16):3397.
doi: 10.3390/molecules30163397.

Targeted LC-MS Orbitrap Method for the Analysis of Azaarenes, and Nitrated and Oxygenated PAHs in Road Paving Emissions

Maria Bou Saad  1 , Sylvain Ravier  1 , Amandine Durand  1 , Brice Temime-Roussel  1 , Vincent Gaudefroy  2 , Audrey Pevere  3 , Henri Wortham  1 , Pierre Doumenq  1
Affiliations

Targeted LC-MS Orbitrap Method for the Analysis of Azaarenes, and Nitrated and Oxygenated PAHs in Road Paving Emissions

Maria Bou Saad et al. Molecules. .

Abstract

Polycyclic aromatic hydrocarbon (PAH) derivatives, specifically azaarenes and nitrated and oxygenated PAHs, are emerging contaminants of concern due to their increased toxicity and persistence compared to the parent PAHs. Despite their toxicity, their simultaneous analysis in complex matrices, such as in fumes emitted from bituminous mixtures, remains challenging due to limitations of conventional analytical techniques. To address this, an advanced methodology was developed using Ultra-High-Performance Liquid Chromatography coupled with High-Resolution Mass Spectrometry (UHPLC-HRMS Orbitrap Eclipse) equipped with an APCI source for the simultaneous identification and quantification of 14 PAH derivatives. Chromatographic and ionization parameters were optimized to ensure maximum sensitivity and selectivity. Following ICH Q2(R2) guidelines, the method was validated, demonstrating excellent linearity (R2 > 0.99), high mass accuracy (≤5 ppm), strong precision (<15%), and excellent sensitivity. Limits of detection (LODs) ranged from 0.1 µg L-1 to 0.6 µg L-1 and limits of quantification (LOQs) ranged from 0.26 µg L-1 to 1.87 µg L-1. The validated method was successfully applied to emissions from asphalt pavement materials collected on quartz filters under controlled conditions, enabling the identification and quantification of all 14 targeted compounds. These results confirm the method's robustness and suitability for trace-level analysis of PAH derivatives in complex environmental matrices.

Keywords: LC-HRMS; PAH derivatives; azaarenes; nitrated PAH; oxygenated PAH; trace-level quantification.

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Conflict of interest statement

The authors declare no conflicts of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Figure 1
Figure 1
Extracted ion chromatograms (EICs) of target compounds acquired in positive ion mode. Each panel displays a comparison between a standard solution (right column) and a bitumen fume extract (left column).
Figure 2
Figure 2
Extracted ion chromatograms (EICs) of target compounds acquired in negative ion mode. Each panel displays a comparison between a standard solution (right column) and a bitumen fume extract (left column).
Figure 3
Figure 3
Concentration of the PAH derivatives identified in emissions from two different bituminous mixtures. Filter 1 corresponds to a mix design of 35/50 pen-grade bitumen and virgin aggregates. Filter 2 corresponds to a mix design with 70/100 pen-grade bitumen with a 50:50 blend of virgin and reclaimed aggregates.
See this image and copyright information in PMC

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