Formation of mixed-phase particles during the freezing of polar stratospheric ice clouds.

Polar stratospheric clouds (PSCs) are extremely efficient at catalysing the transformation of photostable chlorine reservoirs into photolabile species, which are actively involved in springtime ozone-depletion events. Why PSCs are such efficient catalysts, however, is not well understood. Here, we investigate the freezing behaviour of ternary HNO₃-H₂SO₄-H₂O droplets of micrometric size, which form type II PSC ice particles. We show that on freezing, a phase separation into pure ice and a residual solution coating occurs; this coating does not freeze but transforms into glass below ∼150 K. We find that the coating, which is thicker around young ice crystals, can still be approximately 30 nm around older ice crystals of diameter about 10 µm. These results affect our understanding of PSC microphysics and chemistry and suggest that chlorine-activation reactions are better studied on supercooled HNO₃-H₂SO₄-H₂O solutions rather than on a pure ice surface.