Composition and chemical processing of volatile organic compounds in boundary layer polluted plumes: Insights from an airborne Q-PTR-MS on-board the French ATR-42 aircraft

Over the last decade, the French ATR-42 research aircraft explored contrasting polluted plumes in the Paris megacity, the North-West Mediterranean Basin (WMB) and South West Africa (SWA) in the framework of the MEGAPOLI, ChArMEx/SAFMED and DACCIWA international projects, respectively. Major VOCs were measured by a high-sensitivity airborne Quadrupole Proton Transfer Reaction Mass Spectrometer (Q-PTR-MS), showing a robust and consistent response.Regardless of the location, the air mass composition is dominated by oxygenated VOC (OVOC: methanol, formaldehyde, acetaldehyde, acetone and isoprene oxidation products), which explain 70 % of the total VOC burden measured by the Q-PTR-MS. The distribution between OVOC, anthropogenic AVOC and biogenic BVOC is consistent between the three regions. The calculated OH loss rates (12 s-1) and ozone-forming potential (1200 OFP-relative ppb) are three times higher in the SWA plumes. These values are consistent with the calculated and measured reactivities at the ground. The reactivity of the plumes is by far dominated by biogenic BVOC.The chemical processing of VOC was examined by establishing various metrics linking Δ[O/VOC] (VOC or oxygenated VOC), plume dilution and the time processing of the plume (cumulative OH exposure Δt[OH] and the linear decay of primary AVOC and the production/decay of secondary OVOC). As expected, ∆[Ox]/∆[CO] increases with Δt[OH], with significant R2 (0.58 to 0.93). AVOC (aromatics) usually show a decay rate between -0.5 and -3.2 pptAVOC ppbCO-1 per hour, while OVOC either show an increase (secondary production) or a decrease. The production rate is by far the strongest, up to 18 pptOVOC ppbCO-1 per hour (acetaldehyde) during the eastern flight 33 in Paris. Our results set a benchmark for future photochemical studies to compare with. While the anthropogenic origin of some BVOC (terpenoids) and interferences are not excluded, it also emphasizes the importance of the VOC biogenic fraction in anthropogenically influenced environments, which is expected to increase in a warming climate.