Guaiacol photodegradation rate constants in solution, liquid-like regions in ice (frozen solutions), and at the air–ice interface (vapor-deposited to snow).

Some organic pollutants in snowpacks undergo faster photodegradation than in solution. One possible explanation for such effect is that their UV−visible absorption spectra are shifted toward lower energy when the molecules are adsorbed at the air− ice interface. However, such bathochromic shift is difficult to measure experimentally. Here, we employ a multiscale/multimodel approach that combines classical and first-principles molecular dynamics, quantum chemical methods, and statistical learning to compute the light absorption spectra of two phenolic molecules in different solvation environments at the relevant thermodynamic conditions. Our calculations provide an accurate estimate of the bathochromic shift of the lowest-energy UV−visible absorption band when these molecules are adsorbed at the air−ice interface, and they shed light into its molecular origin.

Abstract. Many important chemical reactions occur in polar snow, where solutes may be present in several reservoirs, including at the air–ice interface and in liquid-like regions within the ice matrix. Some recent laboratory studies suggest chemical reaction rates may differ in these two reservoirs. While investigations have examined where solutes are found in natural snow and ice, few studies have examined either solute locations in laboratory samples or the possible factors controlling solute segregation. To address this, we used micro-computed tomography (microCT) to examine solute locations in ice samples prepared from either aqueous cesium chloride (CsCl) or rose bengal solutions that were frozen using several different methods. Samples frozen in a laboratory freezer had the largest liquid-like inclusions and air bubbles, while samples frozen in a custom freeze chamber had somewhat smaller air bubbles and inclusions; in contrast, samples frozen in liquid nitrogen showed much smaller concentrated inclusions and air bubbles, only slightly larger than the resolution limit of our images (∼ 2 µm). Freezing solutions in plastic vs. glass vials had significant impacts on the sample structure, perhaps because the poor heat conductivity of plastic vials changes how heat is removed from the sample as it cools. Similarly, the choice of solute had a significant impact on sample structure, with rose bengal solutions yielding smaller inclusions and air bubbles compared to CsCl solutions frozen using the same method. Additional experiments using higher-resolution imaging of an ice sample show that CsCl moves in a thermal gradient, supporting the idea that the solutes in ice are present in mobile liquid-like regions. Our work shows that the structure of laboratory ice samples, including the location of solutes, is sensitive to the freezing method, sample container, and solute characteristics, requiring careful experimental design and interpretation of results.

Snowpacks contain a variety of chemicals, including organic pollutants such as toxic polycyclic aromatic hydrocarbons (PAHs). While PAHs undergo photodegradation in snow and ice, the rates of these reactions remain in debate. Some studies report that photochemical reactions in snow proceed at rates similar to those expected in a supercooled aqueous solution, but other studies report faster reaction rates, particularly at the air−ice interface (i.e., the quasi-liquid layer, or QLL). In addition, one study reported a surprising nonlinear dependence on photon flux. Here we examine the photodegradation of two common PAHs, anthracene and pyrene, in/on ice and in solution. For a given PAH, rate constants are similar in aqueous solution, in internal liquid-like regions of ice, and at the air−ice interface. In addition, we find the expected linear relationship between reaction rate constant and photon flux. Our results indicate that rate constants for the photochemical loss of PAHs in, and on, snow and ice are very similar to those in aqueous solution, with no enhancement at the air−ice interface.