Addressing the chemical composition of secondary organic aerosol in the rural/ urban Paris area

Abstract

<p>Organic aerosol (OA) from natural or anthropogenic origin can be directly emitted into the atmosphere (primary organic aerosols, POA) or formed by secondary processes via the oxidation of volatile organic compounds (VOC). However, the formation pathways and their chemical composition of these secondary organic aerosols (SOA), which may contribute up to 90% of the OA mass, are not well understood to date, which is problematic due to the relevance of SOA on climate. To address this issue, this study uses a tracer-based approach to identify and quantify the contribution of different anthropogenic/biogenic VOCs precursors to the SOA formation. To do so, we combine experiments in a large scale atmospheric simulations chamber, CESAM (which means Multiphase Atmospheric Experimental Simulation Chamber), and field measurements during the ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) campaign conducted in the Paris area in summer 2022. This approach provides both a mechanistic study of the oxidation of targeted VOCs in simulated and controlled rural/urban atmospheres and the identification of targeted tracers in the real atmosphere, to quantify their concentrations in ambient air.</p> <p>The ACROSS dataset consists in atmospheric samples of submicron aerosols collected twice a day (day and night) in the urban area of Paris and the Rambouillet forest on the south-west of Paris, as well as samples collected onboard the Safire ATR-42 research aircraft on low-level flights targeting the  evolution and dilution of the Paris urban plume. The CESAM chamber dataset consists in samples of SOA generated by the OH oxidation of toluene/ m-xylene in various conditions.</p> <p>Filters are analyzed to provide with the chemical composition at the molecular scale by SFE-GC-MS (Supercritical Fluid Extraction Gas Chromatography- Mass Spectrometry) and UPLC-QTOF-MS (Ultra Performance Liquid Chromatography Time of Flight Mass Spectrometry). The organic mass and chemical speciation are obtained by aerosol mass spectrometry and the organic carbon (OC) concentrations by thermal-optical analysis.</p> <p>The first results of the ambient samples of Paris revealed that the OC concentration varied between 0.69 ± 0.07 and 9.48 ± 0.51 µgC/m<sup>3</sup>, which correspond to the 28% and 53% of the total mass of the submicron aerosols, for background and polluted (fire) conditions, respectively. These diverse conditions are favorable to trace the compounds identified during the simulation chamber experiments, such as benzoic acid, succinic acid, and 2-methyl-4-nitrophenol. These attempts will be presented and discussed in order to determine the contribution of specific precursors to SOA formation.</p>