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Multiphase oxidative aging is a ubiquitous process for atmospheric organic aerosols (OA). But its kinetics was often found to be slow in previous laboratory studies where high hydroxyl radical concentrations ([•OH]) were used. In this study, we performed heterogeneous oxidation experiments of several model OA systems under varied aging timescales and gas-phase [•OH]. Our results suggest that OA heterogeneous oxidation may be 2–3 orders of magnitude faster when [•OH] is decreased from typical laboratory flow tube conditions to atmospheric levels. Direct laboratory mass spectrometry measurements coupled with kinetic simulations suggest that an intermolecular autoxidation mechanism mediated by particle-phase peroxy radicals greatly accelerates OA oxidation, with enhanced formation of organic hydroperoxides, alcohols, and fragmentation products. With autoxidation, we estimate that the OA oxidation timescale in the atmosphere may be from less than a day to several days. Thus, OA oxidative aging can have greater atmospheric impacts than previously expected. Furthermore, our findings reveal the nature of heterogeneous aerosol oxidation chemistry in the atmosphere and help improve the understanding and prediction of atmospheric OA aging and composition evolution.

Inorganic species always coexist with organic materials in atmospheric particles and may influence the heterogeneous oxidation of organic aerosols. However, very limited studies have explored the role of the inorganics in the chemical evolution of organic species in mixed aerosols. This study examines the heterogeneous oxidation of glutaric acid–ammonium sulfate and 1,2,6-hexanetriol–ammonium sulfate aerosols by hydroxyl radicals (OH) under varied organic mass fractions (forg) and relative humidity in a flow tube reactor. Coupling the oxidation kinetics and product measurements with kinetic model simulations, we found that under both low relative humidity (RH, 30–35%) and high RH conditions (85%), the decreased forgfrom 0.7 to 0.2 accelerates the oxidation of the organic materials by a factor of up to 11. We suggest that the faster oxidation kinetics under low-RH conditions is due to full or partial phase separation, with the organics greatly enriched at the particle outer region, while enhanced “salting-out” of the organics and OH adsorption caused by higher inorganics could explain the observations under high-RH conditions. Analysis of the oxidation products reveals that the dilution of organics by the inorganic salts and corresponding water uptake under high-RH conditions will favor alkoxy radical fragmentation by a factor of 3–4 and inhibit its secondary chain propagation chemistry. Our results suggest that atmospheric organic aerosol oxidation lifetime and composition are strongly impacted by the coexistent inorganic salts.

Water vapor supersaturation, as one of the most important environmental parameters during the formation of clouds or fogs, cannot be directly measured, and few studies have been carried out to estimate it in the ambient activation process. In this study, a new method to estimate the water vapor supersaturation based on the inverse application of κ‐Köhler theory is proposed. Aerosol hygroscopic parameter κ, dry particle size distributions, and wet droplet size distributions were employed and a comparison of predicted droplet number concentration with the measurement results was made to obtain the effective supersaturation during the activation process. Using this method, we acquired the supersaturations varying from 0.01% to 0.05% in a fog episode observed in the North China Plain. In this fog episode, both hydrated unactivated droplets and activated droplets play a part in the total detected droplet number concentrations with the unactivated droplets' ratio decreasing with size. The sensitivity study was also made to evaluate the effects of droplet and aerosol hygroscopic measurement errors on the supersaturation ratio estimation. Water vapor supersaturation obtained with this method can be regarded as an effective value and can be further applied to cloud analysis in the future. This method is only based on conventional measurements of aerosol and droplets and does not rely on any other data, which makes it flexible and easy to perform. Calculated supersaturations and critical diameters can also deepen the understanding of ambient activation process and corresponding interactions between aerosol and droplet characteristics. Ambient water vapor supersaturation can be calculated using aerosol and cloud measurementsLow supersaturations less than 0.05% were found for a dense radiation fog in the North China PlainSignificant contribution of unactivated haze particles to the total fog droplets was found in the heavily polluted fog episode