Soot-PCF: Pore condensation and freezing framework for sootaggregates

Abstract. How ice crystals form in the troposphere strongly affects cirrus cloud properties. Atmospheric ice formation is often initiated by aerosol particles that act as ice nucleating particles. The aerosol-cloud interactions of soot and associated feedbacks remain uncertain, in part because a coherent understanding of the ice nucleation mechanism and activity of soot has not yet emerged. Here, we provide a new framework that predicts ice formation on soot particles via pore condensation and freezing (PCF) that, unlike previous approaches, considers soot particle properties capturing their vastly different pore properties compared to other aerosol species such as mineral dust. During PCF, water is taken up below water saturation into pores on soot aggregates by capillary condensation. At cirrus temperatures, pore water can freeze homogeneously and subsequently grow into a macroscopic ice crystal. In the soot-PCF framework presented here, the relative humidity conditions required for these steps are derived for different pore types as a function of temperature. The pore types considered here evolve from idealized stacking of equally sized primary particles, either in tetrahedral or cubic packing arrangements. Specifically, we encompass n-membered ring pores that form between n individual spheres within the same layer of primary particles as well as pores in the form of inner cavities that form between two layers of primary particles. We treat soot primary particles as perfect spheres and use the contact angle between soot and water (θsw), the primary particle diameter (Dpp) and the degree of primary particle overlap (overlap coefficient, Cov) to characterize soot pore properties. We find that n-membered ring pores are the dominant pore structures for soot-PCF, as they are common features of soot aggregates and have a suitable geometry for both, filling with water and growing ice below water saturation. We focus our analysis on three-membered and four-membered ring pores as they are of the right size for PCF assuming primary particle sizes typical for atmospheric soot particles. For these pore types, we derive equations that describe the conditions for all three steps of soot-PCF, namely capillary condensation, ice nucleation, and ice growth. Since at typical cirrus conditions homogeneous ice nucleation can be considered immediate as soon as the water volume within the pore is large enough to host a critical ice embryo, soot-PCF becomes either limited by capillary condensation or ice crystal growth. For instance, our results show that at typical cirrus temperatures of T = 220 K, three-membered ring pores formed between primary particles with θsw = 60°, Dpp = 20 nm, and Cov = 0.05 are ice growth limited, as the ice requires a relative humidity with respect to ice of RHi = 137 % to grow out of the pore, while a sufficient volume of pore water for ice nucleation has condensed already at RHi = 86 %. Conversely, four-membered ring pores with the same primary particle size and an overlap coefficient of Cov = 0.1 are capillary condensation limited as they require RHi = 129 % to gather enough water for ice nucleation, compared with only 124 % RHi, required for ice growth. We use the soot-PCF framework to derive a new equation to parameterize of ice formation on soot particles via PCF. This equation is based on soot properties that are routinely measured, including the primary particle size and overlap, and the fractal dimension. These properties, along with the number of primary particles making up an aggregate and the contact angle between water and soot, constrain the parameterization. Applying the new parameterization to previously reported laboratory data of ice formation on soot particles provides direct evidence that ice nucleation on soot aggregates takes place via PCF. We conclude that this new framework clarifies the ice formation mechanism on soot particles at cirrus conditions and provides a new perspective to represent ice formation on soot in climate models.

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