Pre-activation of aeosol particles by pore condensation and freezing
Authors: Marcolli Claudia 
Published: September 2016

Abstract. Pre-activation denotes the capability of particles or materials to nucleate ice at lower relative humidities or higher temperatures compared to their intrinsic ice nucleation efficiency after having experienced an ice nucleation event or low temperature before. This review presumes a pore condensation and freezing (PCF) mechanism to analyze studies on pre-activation. Idealized trajectories of air parcels are used to discuss the pore characteristics needed for ice to persist in pores and to induce macroscopic ice-growth out of the pores. The pore width needed to keep pores filled with water decreases with decreasing relative humidity as described by the inverse Kelvin equation. Thus, narrow pores remain filled with ice well below ice saturation. However, the smaller the pore width, the larger the melting and freezing point depressions within the pores. Therefore, pre-activation by PCF is constrained by the melting of ice in narrow pores and the sublimation of ice from wide pores imposing severe restrictions on the temperature and relative humidity range of pre-activation for cylindrical pores. Ice is better protected in ink-bottle-shaped pores with a narrow opening leading to a large cavity. However, whether pre-activation is efficient also depends on the capability of ice to grow macroscopically, i.e. out of the pore. A strong effect of pre-activation is expected for swelling pores, because at low relative humidity (RH) their openings narrow and protect the ice within them against sublimation. At high relative humidities, they open up and the ice can grow to macrosopical size and form an ice crystal. Similarly, ice protected in pockets are perfectly sheltered against sublimation but needs the dissolution of the surrounding matrix to be effective. Pores partially filled with condensable material may also show pre-activation. In this case, complete filling occurs at lower RH than for empty pores and freezing shifts to lower temperatures. Pre-activation experiments confirm that materials susceptible to pre-activation are indeed porous. Pre-activation was observed for clay minerals like illite, kaolinite and montmorillonite with inherent porosity. The largest effect was observed for the swelling clay mineral montmorillonite. Some materials may acquire porosity depending on the formation and processing conditions. Particles of CaCO3, meteoritic material, and volcanic ash showed pre-activation for some samples or in some studies but not in other ones. Quartz and silver iodide were not susceptible to pre-activation. Atmospheric relevance of pre-activation by a PCF mechanism may not be generally given but depend on the atmospheric scenario. Lower-level cloud seeding by pre-activated particles released from high-level clouds crucially depends on the ability of pores to retain ice at the relative humidities and temperatures of the air masses they pass through. Porous particles that are recycled in wave clouds may show pre-activation with subsequent ice growth as soon as ice saturation is exceeded after having passed a first cloud event. Volcanic ash particles and meteoritic material likely influence ice cloud formation by pre-activation. Therefore, pre-activation needs to be considered when ice crystal number densities in clouds exceed the number of ice-nucleating particles measured at the cloud forming temperature.