Mineral dust aerosol is one of the largest contributors to global ice nuclei, but physical and chemical processing of dust during atmospheric transport can alter its ice nucleation activity. In particular, several recent studies have noted that sulfuric and nitric acids inhibit heterogeneous ice nucleation in the regime below liquid water saturation in aluminosilicate clay minerals. We have exposed kaolinite, KGa-1b and KGa-2, and montmorillonite, STx-1b and SWy-2, to aqueous sulfuric and nitric acid to determine the physical and chemical changes that are responsible for the observed deactivation. To characterize the changes to the samples upon acid treatment, we use X-ray diffraction, transmission electron microscopy, and inductively coupled plasma-atomic emission spectroscopy. We find that the reaction of kaolinite and montmorillonite with aqueous sulfuric acid results in the formation of hydrated aluminum sulfate. In addition, sulfuric and nitric acids induce large structural changes in montmorillonite. We additionally report the supersaturation with respect to ice required for the onset of ice nucleation for these acid-treated species. On the basis of lattice spacing arguments, we explain how the chemical and physical changes observed upon acid treatment could lead to the observed reduction in ice nucleation activity.
Heterogeneous ice nucleation is an important mechanism for cloud formation in the upper troposphere. Recently, pores on atmospheric particles have been proposed to play a significant role in ice nucleation. To understand how ice nucleation occurs in idealized pores, we characterized the immersion freezing activity of various sizes of carbon nanotubes. Carbon nanotubes are used both as a model for pores and proxy for soot particles. We determined that carbon nanotubes with inner diameters between 2 and 3 nm exhibit the highest ice nucleation activity. Implications for the freezing behavior of porous materials and nucleation on soot particles will be discussed.
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