Heterogeneous Nucleation of Nitric Acid Trihydrate on Clay Minerals: Relevance to Type Ia Polar Stratospheric Clouds

Abstract

Although critical to atmospheric modeling of stratospheric ozone depletion, selective heterogeneous nuclei that promote the formation of Type Ia polar stratospheric clouds (PSCs) are largely unknown. While mineral particles are known to be good ice nuclei, it is currently not clear whether they are also good nuclei for PSCs. In the present study, a high-vacuum chamber equipped with transmission Fourier transform infrared spectroscopy and a quadrupole mass spectrometer was used to study heterogeneous nucleation of nitric acid trihydrate (NAT) on two clay minerals-Na-montmorillonite and kaolinite-as analogs of atmospheric terrestrial and extraterrestrial minerals. The minerals are first coated with a 3:1 supercooled H2O/HNO3 solution prior to the observed nucleation of crystalline NAT. At 220 K, NAT formation was observed at low SNAT values of 12 and 7 on kaolinite and montmorillonite clays, respectively. These are the lowest SNAT values reported in the literature on any substrate. However, NAT nucleation exhibited significant temperature dependence. At lower temperatures, representative of typical polar stratospheric conditions, much higher supersaturations were required before nucleation was observed. Our results suggest that NAT nucleation on mineral particles, not previously treated with sulfuric acid, may not be an important nucleation platform for Type Ia PSCs under normal polar stratospheric conditions.