Volcanic ash ice nucleation activity is variably reduced by aging in water and sulfuric acid: the effects of leaching, dissolution, and precipitation.

Volcanic ash nucleates ice when immersed in supercooled water droplets, giving it the potential to influence weather and climate from local to global scales. This ice nucleation activity (INA) is likely derived from a subset of the crystalline mineral phases in the ash. The INA of other mineral-based dusts can change when exposed to various gaseous and aqueous chemical species, many of which also interact with volcanic ash in the eruption plume and atmosphere. However, the effects of aqueous chemical aging on the INA of volcanic ash have not been explored. We show that the INA of two mineralogically distinct ash samples from Fuego and Astroni volcanoes is variably reduced following immersion in water or aqueous sulfuric acid for minutes to days. Aging in water decreases the INA of both ash samples by up to two orders of magnitude, possibly due to a reduction in surface crystallinity and cation availability accompanying leaching. Aging in sulfuric acid leads to minimal loss of INA for Fuego ash, which is proposed to reflect a quasi-equilibrium between leaching that removes ice-active sites and dissolution that reveals or creates new sites on the pyroxene phases present. Conversely, exposure to sulfuric acid reduces the INA of Astroni ash by one to two orders of magnitude, potentially through selective dissolution of ice-active sites associated with surface microtextures on some K-feldspar phases. Analysis of dissolved element concentrations in the aged ash leachates shows supersaturation of certain mineral species which could have precipitated and altered the INA of the ash. These results highlight the key role that leaching, dissolution, and precipitation likely play in the aqueous aging of volcanic ash with respect to its INA. Finally, we discuss the implications for understanding the nature and reactivity of ice-active sites on volcanic ash and its role in influencing cloud properties in the atmosphere.