Significance: Phase transitions of ice are a major source of a diverse set of natural phenomena on Earth. In particular, quasi-liquid layers (QLLs) resulting from surface melting are recognized to be key players involved in various natural phenomena spanning from making snowballs to electrification of thunderclouds. With the aid of in situ observations with our advanced optical microscopy combined with two-beam interferometry, we elucidate a thermodynamic origin of the formation of QLLs and their unique wetting behavior (pseudo-partial wetting and wetting transitions) on ice surfaces. We show that QLLs are a metastable transient state formed through vapor growth and sublimation of ice that are absent at equilibrium.

Surfaces of ice are covered with thin liquid water layers, called quasi-liquid layers (QLLs), even below their melting point (0 °C), which govern a wide variety of phenomena in nature. We recently found that two types of QLL phases appear that exhibit different morphologies (droplets and thin layers) [Sazaki G. et al. (2012) Proc Natl Acad Sci USA 109(4):1052−1055]. However, revealing the thermodynamic stabilities of QLLs remains a longstanding elusive problem. Here we show that both types of QLLs are metastable phases that appear only if the water vapor pressure is higher than a certain critical supersaturation. We directly visualized the QLLs on ice crystal surfaces by advanced optical microscopy, which can detect 0.37-nm-thick elementary steps on ice crystal surfaces. At a certain fixed temperature, as the water vapor pressure decreased, thin-layer QLLs first disappeared, and then droplet QLLs vanished next, although elementary steps of ice crystals were still growing. These results clearly demonstrate that both types of QLLs are kinetically formed, not by the melting of ice surfaces, but by the deposition of supersaturated water vapor on ice surfaces. To our knowledge, this is the first experimental evidence that supersaturation of water vapor plays a crucially important role in the formation of QLLs.

Ice-binding proteins (IBPs) affect ice crystal growth by attaching to crystal faces. We present the effects on the growth of an ice single crystal caused by an ice-binding protein from the sea ice microalga Fragilariopsis cylindrus (fcIBP) that is characterized by the widespread domain of unknown function 3494 (DUF3494) and known to cause a moderate freezing point depression (below 1 °C). By the application of interferometry, bright-field microscopy, and fluorescence microscopy, we observed that the fcIBP attaches to the basal faces of ice crystals, thereby inhibiting their growth in the c direction and resulting in an increase in the effective supercooling with increasing fcIBP concentration. In addition, we observed that the fcIBP attaches to prism faces and inhibits their growth. In the event that the effective supercooling is small and crystals are faceted, this process causes an emergence of prism faces and suppresses crystal growth in the a direction. When the effective supercooling is large and ice crystals have developed into a dendritic shape, the suppression of prism face growth results in thinner dendrite branches, and growth in the a direction is accelerated due to enhanced latent heat dissipation. Our observations clearly indicate that the fcIBP occupies a separate position in the classification of IBPs due to the fact that it suppresses the growth of basal faces, despite its moderate freezing point depression. Significance Ice-binding proteins (IBPs) can be considered a prominent example of macromolecules affecting ice growth kinetics. Until now, two groups of IBPs have been described based on their activity as ice growth inhibitors: moderate and hyperactive IBPs. The mechanism underlying these activity differences has not been clarified yet. Although it is commonly believed that hyperactivity is related to growth inhibition of the basal faces of ice crystals, we show that a moderate IBP can also attach to the basal faces and inhibit their growth. Our observations clearly indicate that this moderate IBP occupies a separate position in the classification of IBPs and contribute to our understanding of interaction between macromolecules and ice and more generally, between macromolecules and inorganic crystals.