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

TLDR

Atmospheric ice nucleation influences cloud properties, precipitation, and radiative balance, yet the conventional deposition nucleation model assumes a direct vapor‑to‑ice transition without an intermediate liquid phase. The authors use classical nucleation theory and molecular dynamics simulations to demonstrate that a network of closely spaced pores is required to surmount the barrier for macroscopic ice‑crystal growth from narrow cylindrical pores. The study finds that ice nucleation in porous particles proceeds via liquid water condensation in pores, a mechanism that explains the enhanced efficiency and absence of nucleation below water saturation, and that pore condensation and freezing dominates atmospheric ice nucleation below saturation, with activity governed by pore porosity and wettability, thereby enabling porous dust to influence cloud radiative forcing and climate.

Abstract

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.