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Evolution of NO3 reactivity during the oxidation of isoprene

Résumé : In a series of experiments in an atmospheric simulation chamber (SAPHIR, Forschungszentrum Jülich, Germany) NO3 reactivity (kNO3) resulting from the reaction of NO3 with isoprene and stable trace gases formed as products was measured directly using a flow-tube reactor coupled to a cavity-ring-down spectrometer (FT-CRDS). The experiments were carried out in both dry and humid air with variation of the initial mixing ratios of ozone (50–100 ppbv), isoprene (3–22 ppbv) and NO2 (5–30 ppbv). kNO3 was in excellent agreement with values calculated from the isoprene mixing ratio and the rate coefficient for the reaction of NO3 with isoprene. This result serves both to confirm that the FT-CRDS returns accurate values of kNO3 even at elevated NO2 concentrations and to show that reactions of NO3 with stable reaction products like non-radical organic nitrates do not contribute significantly to NO3 reactivity during the oxidation of isoprene. A comparison of kNO3 with NO3 reactivities calculated from NO3 mixing ratios and NO3 production rates suggests that organic peroxy radicals and HO2 account for ~ 50 % of NO3 losses. This contradicts predictions based on numerical simulations using the Master Chemical Mechanism (MCM version 3.3.1) unless the rate coefficient for reaction between NO3 and isoprene-derived RO2 is roughly doubled to ≈ 5 × 10−12 cm3 molecule−1 s−1.
Abstract : In a series of experiments in an atmospheric simulation chamber (SAPHIR, 1 Forschungszentrum Jülich, Ger-many), NO 3 reactivity (k NO 3) resulting from the reaction of NO 3 with isoprene and stable trace gases formed as products was measured directly using a flow tube reactor coupled to a cavity ring-down spectrometer (FT-CRDS). The experiments were carried out in both dry and humid air with variation of the initial mixing ratios of ozone (50-100 ppbv), iso-prene (3-22 ppbv) and NO 2 (5-30 ppbv). k NO 3 was in excellent agreement with values calculated from the isoprene mixing ratio and the rate coefficient for the reaction of NO 3 with isoprene. This result serves to confirm that the FT-CRDS returns accurate values of k NO 3 even at elevated NO 2 concentrations and to show that reactions of NO 3 with stable reaction products like non-radical organic nitrates do not contribute significantly to NO 3 reactivity during the oxidation of isoprene. A comparison of k NO 3 with NO 3 reactivities calculated from NO 3 mixing ratios and NO 3 production rates suggests that organic peroxy radicals and HO 2 account for ∼ 50 % of NO 3 losses. This contradicts predictions based on numerical simulations using the Master Chemical Mechanism (MCM version 3.3.1) unless the rate coefficient for 1 Simulation of Atmospheric PHotochemistry In a large Reaction reaction between NO 3 and isoprene-derived RO 2 is roughly doubled to ∼ 5 × 10 −12 cm 3 molecule −1 s −1 .
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Patrick Dewald, Jonathan Liebmann, Nils Friedrich, Justin Shenolikar, Jan Schuladen, et al.. Evolution of NO3 reactivity during the oxidation of isoprene. Atmospheric Chemistry and Physics, European Geosciences Union, In press, 20 (17), pp.10459-10475. ⟨10.5194/acp-20-10459-2020⟩. ⟨hal-02931874⟩

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