The Effects of Aminium and Ammonium Cations on the Ice Nucleation Activity of K-Feldspar

Mineral dust is one of the most abundant types of ice nucleating particles in the atmosphere. During atmospheric transport, mineral dust particles can become coated with inorganic and organic solutes, which can impact their ice nucleation activity. Aminium cations formed from amines are one type of organic solute that can coat mineral dust particles in the atmosphere, but their effects on the ice nucleation activity of mineral dust have not been studied. We investigated the effects of primary, secondary, and tertiary aminium cations with methyl and ethyl groups, as well as ammonium cations, on the ice nucleation activity of K-feldspar, an important type of mineral dust, in the immersion freezing mode at low cation concentrations (0.2-20 mM) using a droplet-freezing apparatus. Ammonium cations substantially increased the ice nucleation activity of K-feldspar, consistent with previous studies. In contrast, primary aminium cations significantly reduced K-feldspar ice nucleation activity, and secondary and tertiary aminium cations had no significant effect (the effect was less than the uncertainty of our measurements). Our combined results are consistent with the following mechanisms: ammonium cations undergo ion exchange with K-feldspar, providing exposed N-H groups for hydrogen bonding with ice; primary aminium cations undergo ion exchange with K-feldspar, exposing a hydrophobic tail that is not effective at nucleating ice; secondary and tertiary aminium cations do not undergo ion exchange with K-feldspar due to steric effects caused by the multiple hydrophobic groups on the cation. Ice nucleating particles are particles in the atmosphere that can initiate the formation of ice in liquid clouds, impacting cloud properties, precipitation, and climate. Mineral dust is a dominant type of ice nucleating particles in the atmosphere. During atmospheric transport, aminium cations, formed from amine gases which can be abundant in the atmosphere, can coat mineral dust particles altering their ability to nucleate ice. However, the effect of aminium cations on the ice nucleation ability of mineral dust particles has not been studied. We investigated the effects of aminium and ammonium cations on the ice nucleation ability of K-feldspar, an important type of mineral dust and ice nucleating particles in the atmosphere. Our results show that secondary and tertiary aminium cations have no effect on the ice nucleating ability of K-feldspar, but primary aminium cations greatly reduce the ice nucleating ability of K-feldspar. This has possible implications for predicting cloud formation in the atmosphere. We also present a mechanism related to ion exchange that can explain our ice nucleation results. Ammonium cations significantly increased the ice nucleation activity of K-feldsparPrimary aminium cations substantially reduced the ice nucleation activity of K-feldsparSecondary and tertiary aminium had limited effects on the ice nucleation activity of K-feldspar due to their inability for ion exchange