Exploratory experiments on pre-activated freezing nucleation on mercuric iodide

Pre-activation of freezing nucleation was examined in laboratory experiments with mercuric iodide suspensions in water. The experiments followed the procedure designed by Edwards, Evans and Zipper (1970) but employed multiple sample drops and many repetitions of the pre-activation cycle. The results obtained confirm the basic findings of the earlier work and refine it. By also drawing on the results of Seeley and Seidler (2001), pre-activated freezing nucleation (PFN in this work) is analyzed in search of constraints that help define the process responsible for it. No firm conclusions are reached, but evidence is accumulated pointing to the role of definite structures being involved in PFN, similar to the role of sites in heterogeneous freezing nucleation in general. PFN differs from pore condensation and freezing described by Marcolli (2020) and David et al. (2020) in that it takes place in liquid water. Further exploration of this process can help understading ice nucleation at the basic level and in its practical manifestations. The results call attention to an ice nucleation pathway hitherto barely explored and which can be expected to have consequences in how ice nucleation occurs in atmospheric clouds and in other systems.

The role of contact angle and pore width on pore condensation and freezing

It has recently been shown that pore condensation and freezing (PCF) is a mechanism responsible for ice formation under cirrus cloud conditions. PCF is defined as the condensation of liquid water in narrow capillaries below water saturation due to the inverse Kelvin effect, followed by either heterogeneous or homogeneous nucleation depending on the temperature regime and presence of an ice-nucleating active site. By using sol–gel synthesized silica with well-defined pore diameters, morphology and distinct chemical surface-functionalization, the role of the water–silica contact angle and pore width on PCF is investigated. We find that for the pore diameters (2.2–9.2 nm) and water contact angles (15–78∘) covered in this study, our results reveal that the water contact angle plays an important role in predicting the humidity required for pore filling, while the pore diameter determines the ability of pore water to freeze. For T>235 K and below water saturation, pore diameters and water contact angles were not able to predict the freezing ability of the particles, suggesting an absence of active sites; thus ice nucleation did not proceed via a PCF mechanism. Rather, the ice-nucleating ability of the particles depended solely on chemical functionalization. Therefore, parameterizations for the ice-nucleating abilities of particles in cirrus conditions should differ from parameterizations at mixed-phase clouds conditions. Our results support PCF as the atmospherically relevant ice nucleation mechanism below water saturation when porous surfaces are encountered in the troposphere.

Technical note: Fundamental aspects of ice nucleation via pore condensation and freezing including Laplace pressure and growth into macroscopic ice

Pore condensation and freezing (PCF) is an ice nucleation mechanism that explains ice formation at low ice supersaturation. It assumes that liquid water condenses in pores of solid aerosol particles below water saturation, as described by the Kelvin equation, followed by homogeneous ice nucleation when temperatures are below about 235 K or immersion freezing at higher temperatures, in case the pores contain active sites that induce ice nucleation. Porewater is under tension (negative pressure) below water saturation as described by the Young–Laplace equation. This negative pressure affects the ice nucleation rates and the stability of the pore ice. Here, pressure-dependent parameterizations of classical nucleation theory are developed to quantify the increase in homogeneous ice nucleation rates as a function of tension and to assess the critical diameter of pores that is required to accommodate ice at negative pressures. Growth of ice out of the pore into a macroscopic ice crystal requires ice supersaturation. This supersaturation as a function of the pore opening width is derived, assuming that the ice phase first grows as a spherical cap on top of the pore opening before it starts to expand laterally on the particle surface into a macroscopic ice crystal.

The Role of Contact Angle and Pore Width on Pore Condensation and Freezing

It has recently been shown that pore condensation and freezing (PCF) is a mechanism responsible for ice formation under cirrus cloud conditions. PCF is defined as the condensation of liquid water in narrow capillaries below water saturation due to the Kelvin effect, followed by either heterogeneous or homogeneous nucleation depending on the temperature regime and presence of an ice nucleating active site. By using sol-gel synthesized silica with well-defined pore diameters, morphology and distinct chemical surface-functionalization, the role of the water-silica contact angle and pore width on PCF is investigated. We find that contact angle and pore width play an important role in determining the relative humidity required for capillary condensation as predicted by the Kelvin effect and subsequent ice nucleation at cirrus temperatures. For the pore diameters and contact angles covered in this study, 2.2–9.2 nm and 15–78°, respectively, our results reveal that the contact angle plays an important role in predicting the humidity required for pore filling while the pore diameter determines the ability of pore water to freeze. For T > 235 K and below water saturation, pore diameters and contact angles were not able to predict the freezing ability of the particles suggesting an absence of active sites, thus ice nucleation did not proceed via a PCF mechanism. Rather, the ice nucleating ability of the particles depended solely on chemical functionalization. Therefore, parameterizations for the ice nucleating abilities of particles at cirrus conditions should differ from parameterizations at mixed-phase clouds conditions. Our results support PCF as the atmospherically relevant ice nucleation mechanism below water saturation when porous surfaces are encountered in the troposphere.

Technical note: Fundamental aspects of ice nucleation via pore condensation and freezing including Laplace pressure and growth into macroscopic ice

Pore condensation and freezing (PCF) is an ice nucleation mechanism that explains ice formation at low ice supersaturation. It assumes that liquid water condenses in pores of solid aerosol particles below water saturation, as described by the Kelvin equation, followed by homogeneous ice nucleation when temperatures are below about 235 K or immersion freezing at higher temperatures, in case the pores contain active sites that induce ice nucleation. Pore water is under tension (negative pressure) below water saturation as described by the Young-Laplace equation. This negative pressure affects the ice nucleation rates and the stability of the pore ice. Here, pressure dependent parameterizations of classical nucleation theory are developed to quantify the increase of homogeneous ice nucleation rates as a function of tension and to assess the critical diameter of pores that is required to accommodate ice at negative pressures. For growth out of the pore into a macroscopic ice crystal, ice supersaturation is required. The required supersaturation as a function of the pore opening width is derived, assuming that the ice phase first grows as a spherical cap on top of the pore opening before it starts to expand laterally on the particle surface into a macroscopic ice crystal.

Pore condensation and freezing is responsible for ice formation below water saturation for porous particles

Ice nucleation in the atmosphere influences cloud properties, altering precipitation and the radiative balance, ultimately regulating Earth’s climate. An accepted ice nucleation pathway, known as deposition nucleation, assumes a direct transition of water from the vapor to the ice phase, without an intermediate liquid phase. However, studies have shown that nucleation occurs through a liquid phase in porous particles with narrow cracks or surface imperfections where the condensation of liquid below water saturation can occur, questioning the validity of deposition nucleation. We show that deposition nucleation cannot explain the strongly enhanced ice nucleation efficiency of porous compared with nonporous particles at temperatures below −40 °C and the absence of ice nucleation below water saturation at −35 °C. Using classical nucleation theory (CNT) and molecular dynamics simulations (MDS), we show that a network of closely spaced pores is necessary to overcome the barrier for macroscopic ice-crystal growth from narrow cylindrical pores. In the absence of pores, CNT predicts that the nucleation barrier is insurmountable, consistent with the absence of ice formation in MDS. Our results confirm that pore condensation and freezing (PCF), i.e., a mechanism of ice formation that proceeds via liquid water condensation in pores, is a dominant pathway for atmospheric ice nucleation below water saturation. We conclude that the ice nucleation activity of particles in the cirrus regime is determined by the porosity and wettability of pores. PCF represents a mechanism by which porous particles like dust could impact cloud radiative forcing and, thus, the climate via ice cloud formation.