Heterogeneous freezing of water droplets containing kaolinite particles

Abstract. Clouds composed of both ice particles and supercooled liquid water droplets exist at temperatures above ~236 K. These mixed phase clouds, which strongly impact climate, are very sensitive to the presence of solid particles that can catalyse freezing. In this paper we describe experiments to determine the conditions at which the clay mineral kaolinite nucleates ice when immersed within water droplets. These are the first immersion mode experiments in which the ice nucleating ability of kaolinite has been determined as a function of clay surface area, cooling rate and also at constant temperatures. Water droplets containing a known amount of clay mineral were supported on a hydrophobic surface and cooled at rates of between 0.8 and 10 K min⁻¹ or held at constant sub-zero temperatures. The time and temperature at which individual 10–50 μm diameter droplets froze were determined by optical microscopy. For a cooling rate of 10 K min⁻¹, the median nucleation temperature of 10–40 μm diameter droplets increased from close to the homogeneous nucleation limit (236 K) to 240.8 ± 0.6 K as the concentration of kaolinite in the droplets was increased from 0.005 wt% to 1 wt%. This data shows that the probability of freezing scales with surface area of the kaolinite inclusions. We also show that at a constant temperature the number of liquid droplets decreases exponentially as they freeze over time. The constant cooling rate experiments are consistent with the stochastic, singular and modified singular descriptions of heterogeneous nucleation; however, freezing during cooling and at constant temperature can be reconciled best with the stochastic approach. We report temperature dependent nucleation rate coefficients (nucleation events per unit time per unit area) for kaolinite and present a general parameterisation for immersion nucleation which may be suitable for cloud modelling once nucleation by other important ice nucleating species is quantified in the future.