Heterogeneous processes can control atmospheric composition. Snow and ice present important, but poorly understood, reaction media that can greatly alter the composition of air in the cryosphere in polar and temperate regions. Atmospheric scientists struggle to reconcile model predictions with field observations in snow-covered regions due to experimental challenges associated with monitoring reactions at air-ice interfaces, and debate regarding reaction kinetics and mechanisms has persisted for over a decade. In this work, we use wavelength-resolved fluorescence microscopy to determine the distribution and chemical speciation of the pollutant anthracene at the surfaces of environmentally relevant frozen surfaces. We show that anthracene adsorbs to frozen surfaces in monomeric form, but that following lateral diffusion, molecules ultimately reside within brine channels at saltwater ice surfaces, and in micron-sized clusters at freshwater ice surfaces; emission profiles indicate extensive self-association. We also measure anthracene photodegradation kinetics in aqueous solution and artificial snow prepared from frozen freshwater and saltwater solutions and use the micro-spectroscopic observations to explain the rate constants measured in different environments. These results resolve long-standing debates and will improve predictions of pollutant fate in the cryosphere. The techniques used can be applied to numerous surfaces within and beyond the atmospheric sciences.
Supplementary information for Direct Observation of Anthracene Clusters at Ice Surfaces