This study quantifies how surfactant-rich environments can alter the degradation kinetics of organic pollutants.

Asphalt production generates fumes classified by the IARC as possibly carcinogenic (Group 2B) containing a wide range of volatile and semi-volatile compounds, including polycyclic aromatic hydrocarbons (PAHs) and their derivatives. As the incorporation of reclaimed asphalt pavement (RAP) increases to meet circular economy goals, uncertainties remain regarding the influence of aged or potentially contaminated binders on emissions due to limited road traceability. While offline analytical methods provide detailed molecular information, they remain limited when addressing exposure-relevant aspects, highlighting the need for real-time measurements. In this study, a pilot-scale mixing system simulating asphalt production under controlled conditions was used to investigate six formulations (virgin aggregates or a mixture of virgin aggregates and RAP) at 140 °C and 160 °C. Emissions were monitored by an SMPS coupled to a PTR-ToF-MS operated either in standalone mode or coupled to a Charon inlet, enabling real-time characterization of gaseous and particulate organic species, respectively. A total of 43 compounds were assigned and quantified based on their mass spectra, providing a detailed overview of emitted VOCs, PAHs, and PAH derivatives. Increasing the temperature from 140 °C to 160 °C resulted in higher emission levels, particularly for high-molecular-weight PAHs and PAH derivatives. RAP-containing mixtures also exhibited higher emissions and a broader particle size range (100-400 nm) compared to mixtures made of virgin aggregates. This study demonstrates that both RAP and temperature significantly influence emission levels and composition, highlighting the value of online analysis for understanding asphalt emissions in future assessments of occupational exposure.

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.

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives, such as nitro-PAHs and oxygenated PAHs (oxy-PAHs), are persistent organic pollutants with significant environmental and health impacts. PAHs are primarily emitted through incomplete combustion processes and are well-recognized for their carcinogenic and mutagenic potential. While most studies have focused solely on the 16 parent PAHs classified by the US-EPA (US Environmental Protection Agency), PAH derivatives remain underexplored due to analytical difficulties, including low environmental concentrations and complex sampling matrices.For these reasons, a methodology for analyzing nitro and oxy-PAHs in atmospheric matrices was developed on an HR-MS (LC-MS Orbitrap Eclipse) using an Atmospheric Pressure Chemical Ionization (APCI) in both positive and negative modes with a resolution of 60 000. This method demonstrated excellent sensitivity, achieving a detection limit of 0,03 ng m-³ for targeted PAH derivatives with a calibration range extended from 0.3 µg L-1 to 15 µg L-1 equivalent to 0.03 ng m-3 to 1.5 ng m-3 (considering an air sample volume of 10 m³ and a sample volume of 1 mL after extraction and concentration) with excellent linearity (correlation coefficient >0.99), ensuring the accuracy and reliability of quantification across a wide concentration spectrum. The technique also incorporated rigorous validation steps, including precision, robustness, and accuracy to confirm its reliability for trace-level measurements.Finally, the methodology was applied to emissions from different asphalt formulations using a laboratory prototype that simulates road asphalt production conditions. Filters were collected, extracted, and analyzed using LC-MS Orbitrap. This enabled the detection and analysis of specific (PAHs) and their derivatives, demonstrating its capability to simultaneously identify and quantify a wide range of these compounds.