Supplementary material to "Extension of the AIOMFAC model by iodine and carbonate species: applications for aerosol acidity and cloud droplet activation"

Abstract. Aerosol particles strongly influence global climate by modifying the properties of clouds. An accurate assessment of the aerosol impact on climate requires knowledge of the concentration of cloud condensation nuclei (CCN), a subset of aerosol particles that can activate and form cloud droplets in the atmosphere. Atmospheric particles typically consist of a myriad of organic species, which frequently dominate the particle composition. As a result, CCN concentration is often a strong function of the hygroscopicity of organics in the particles. Earlier studies showed organic hygroscopicity increases nearly linearly with oxidation level. Such increase of hygroscopicity is conventionally attributed to higher water solubility for more oxidized organics. By systematically varying the water content of activating droplets, we show that for the majority of secondary organic aerosols (SOA), essentially all organics are dissolved at the point of droplet activation. Therefore, the organic hygroscopicity is not limited by solubility, but is dictated mainly by the molecular weight of organic species. Instead of increased water solubility as previously thought, the increase of the organic hygroscopicity with oxidation level is largely because (1) SOA formed from smaller precursor molecules tend to be more oxidized and have lower average molecular weight and (2) during oxidation, fragmentation reactions reduce average organic molecule weight, leading to increased hygroscopicity. A simple model of organic hygroscopicity based on molecular weight, oxidation level, and volatility is developed, and it successfully reproduces the variation of SOA hygroscopicity with oxidation level observed in the laboratory and field studies.

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Modeling CCN activity of chemically unresolved model HULIS, including surface tension, non-ideality, and surface partitioning

10.5194/acp-2018-789 ◽

2018 ◽

Cited By ~ 3

Author(s):

Nonne L. Prisle ◽

Bjarke Molgaard

Keyword(s):

Surface Tension ◽

Water Activity ◽

Cloud Droplet ◽

Tension Reduction ◽

Surface Tension Reduction ◽

Surface Partitioning ◽

Critical Supersaturation ◽

Surface Active ◽

Droplet Activation ◽

Ccn Activity

Abstract. Cloud condensation nuclei (CCN) activity of aerosol particles comprising surface active Nordic Aquatic Fulvic Acid (NAFA) and NaCl was modeled with four different approaches to account for NAFA bulk-to-surface partitioning and the combined influence of NAFA and NaCl on surface tension and water activity of activating droplets. Calculations were made for particles with dry diameters of 30–230 nm and compositions covering the full range of relative NAFA and NaCl mixing ratios. Continuous ternary parametrizations of aqueous surface tension and water activity with respect to independently varying NAFA and NaCl mass concentrations were developed from previous measurements on macroscopic bulk solutions and implemented to a Köhler model framework. This enabled comprehensive thermodynamic predictions of cloud droplet activation, including equilibrium surface partitioning, for particles comprising chemically unresolved organic NAFA mixtures. NAFA here serves as a model for surface active atmospheric humic-like substances (HULIS) and for chemically complex organic aerosol in general. Surfactant effects are gauged via predictions of a suite of properties for activating droplets, including critical supersaturation and droplet size, bulk phase composition, surface tension, Kelvin effect, and water activity. Assuming macroscopic solution properties for activating droplets leads to gross overestimations of reported experimental CCN activation, mainly by overestimating surface tension reduction from NAFA solute in droplets. Failing to account for bulk-to-surface partitioning of NAFA introduces severe biases in evaluated droplet bulk and surface composition and critical size, which here specifically affect cloud activation thermodynamics, but more generally could also impact heterogeneous chemistry on droplet surfaces. Model frameworks based on either including surface partitioning and/or neglecting surface tension reduction give similar results for both critical supersaturation and droplet properties and reproduce reported experimental CCN activity well. These perhaps counterintuitive results reflect how the bulk phase is nearly depleted in surface active organic from surface partitioning in submicron droplets with large surface area for a given bulk volume. As a result, NAFA has very little impact on surface tension and water activity at the point of droplet activation. In other words, the predicted surfactant strength of NAFA is significantly lower in sub-micron activating droplets than in macroscopic aqueous solutions of the same overall composition. These results show similar effects of chemically complex surfactants as have previously been seen only for simple surfactants with well-defined molecular properties and add to the growing appreciation of the complex role of surface activity in cloud droplet activation.

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An investigation into the performance of four cloud droplet activation parameterisations

Geoscientific Model Development ◽

10.5194/gmd-7-1535-2014 ◽

2014 ◽

Vol 7 (4) ◽

pp. 1535-1542 ◽

Cited By ~ 18

Author(s):

E. Simpson ◽

P. Connolly ◽

G. McFiggans

Keyword(s):

Aerosol Particle ◽

Large Scale ◽

Aerosol Particles ◽

Cloud Droplet ◽

Particle Growth ◽

Systematic Evaluation ◽

Climate Modelling ◽

Median Diameter ◽

Droplet Activation ◽

Simulation Time

Abstract. Cloud droplet number concentration prediction is central to large-scale weather and climate modelling. The benchmark cloud parcel model calculation of aerosol particle growth and activation, by diffusion of vapour to aerosol particles in a rising parcel of air experiencing adiabatic expansion, is too computationally expensive for use in large-scale global models. Therefore the process of activation of aerosol particles into cloud droplets is parameterised with an aim to strike the optimum balance between numerical expense and accuracy. We present a detailed systematic evaluation of three cloud droplet activation parameterisations that are widely used in large-scale models and one recent update. In all cases, it is found that there is a tendency to overestimate the fraction of activated aerosol particles when the aerosol particle "median diameter" is large (between 250 and 2000 nm) in a single lognormal mode simulation. This is due to an infinite "effective simulation time" of the parameterisations compared to a prescribed simulation time in the parcel model. This problem arises in the parameterisations because it is assumed that a parcel of air rises to the altitude where maximum supersaturation occurs, regardless of whether this altitude is above the cloud top. Such behaviour is problematic because, in some cases, large aerosol can completely suppress the activation of drops. In some cases when the "median diameter" is small (between 5 and 250 nm) in a single lognormal mode the fraction of activated drops is underestimated by the parameterisations. Secondly, it is found that in dual-mode cases there is a systematic tendency towards underestimation of the fraction of activated drops, which is due to the methods used by the parameterisations to approximate the sink of water vapour.

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