Aerosol climate effects are intimately tied to interactions with water. Here we combine hygroscopicity measurements with direct observations about the phase of secondary organic aerosol (SOA) particles to show that water uptake by slightly oxygenated SOA is an adsorption‐dominated process under subsaturated conditions, where low solubility inhibits water uptake until the humidity is high enough for dissolution to occur. This reconciles reported discrepancies in previous hygroscopicity closure studies. We demonstrate that the difference in SOA hygroscopic behavior in subsaturated and supersaturated conditions can lead to an effect up to about 30% in the direct aerosol forcing—highlighting the need to implement correct descriptions of these processes in atmospheric models. Obtaining closure across the water saturation point is therefore a critical issue for accurate climate modeling.

Bulk‐surface partitioning of surface active species affects both cloud droplet activation by aerosol particles and heterogeneous atmospheric chemistry. Various approaches are given in the literature to capture this effect in atmospheric models. Here we present a simple, yet physically self‐contained, monolayer model for prediction of both composition and thickness of the surface layer of an aqueous droplet. The monolayer surface model is based on assuming a finite surface layer and mass balance of all species within the droplet. Model predictions are presented for binary and ternary aqueous surfactant model systems and compared to both experimental and model data from the literature and predictions using a common Gibbsian model approach. Deviations from Gibbsian surface thermodynamics due to volume constraints imposed by the finite monolayer lead to stronger predicted surface tension reduction at smaller droplet sizes with the monolayer model. Process dynamics of the presented monolayer model are also contrasted to other recently proposed approaches to treating surface partitioning in droplets, with different underlying assumptions.

Surface tension influences the fraction of atmospheric particles that become cloud droplets. Although surfactants are an important component of aerosol mass, the surface tension of activating aerosol particles is still unresolved, with most climate models assuming activating particles have a surface tension equal to that of water. By studying picoliter droplet coalescence, we demonstrate that surfactants can significantly reduce the surface tension of finite-sized droplets below the value for water, consistent with recent field measurements. Significantly, this surface tension reduction is droplet size-dependent and does not correspond exactly to the macroscopic solution value. A fully independent monolayer partitioning model confirms the observed finite-size-dependent surface tension arises from the high surface-to-volume ratio in finite-sized droplets and enables predictions of aerosol hygroscopic growth. This model, constrained by the laboratory measurements, is consistent with a reduction in critical supersaturation for activation, potentially substantially increasing cloud droplet number concentration and modifying radiative cooling relative to current estimates assuming a water surface tension. The results highlight the need for improved constraints on the identities, properties, and concentrations of atmospheric aerosol surfactants in multiple environments and are broadly applicable to any discipline where finite volume effects are operative, such as studies of the competition between reaction rates within the bulk and at the surface of confined volumes and explorations of the influence of surfactants on dried particle morphology from spray driers.

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A new monolayer model predicts the bulk-surface partitioning, surface composition, and thickness of droplets comprising chemically unresolved, atmospherically relevant organic aerosols.