Enhanced photodegradation of dimethoxybenzene isomers in/on ice compared to in aqueous solution

Photochemical reactions of contaminants in snow and ice can be important sinks for organic and inorganic compounds deposited onto snow from the atmosphere and sources for photoproducts released from snowpacks into the atmosphere. Snow contaminants can be found in the bulk ice matrix, in internal liquid-like regions (LLRs), or in quasi-liquid layers (QLLs) at the air–ice interface, where they can readily exchange with the firn air. Some studies have reported that direct photochemical reactions occur faster in LLRs and QLLs than in aqueous solution, while others have found similar rates. Here, we measure the photodegradation rate constants for loss of the three dimethoxybenzene isomers under varying experimental conditions, including in aqueous solution, in LLRs, and at the air–ice interface of nature-identical snow. Relative to aqueous solution, we find modest photodegradation enhancements (3- and 6-fold) in LLRs for two of the isomers and larger enhancements (15- to 30-fold) at the air–ice interface for all three isomers. We use computational modeling to assess the impact of light absorbance changes on photodegradation rate enhancements at the interface. We find small (2–5 nm) bathochromic (red) absorbance shifts at the interface relative to in solution, which increases light absorption, but this factor only accounts for less than 50 % of the measured rate constant enhancements. The major factor responsible for photodegradation rate enhancements at the air–ice interface appears to be more efficient photodecay: estimated dimethoxybenzene quantum yields are 6- to 24-fold larger at the interface compared to in aqueous solution and account for the majority (51 %–96 %) of the observed enhancements. Using a hypothetical model compound with an assumed Gaussian-shaped absorbance peak, we find that a shift in the peak to higher or lower wavelengths can have a minor to substantial impact on photodecay rate constants, depending on the original location of the peak and the magnitude of the shift. Changes in other peak properties at the air–ice interface, such as peak width and height (i.e., molar absorption coefficient), can also impact rates of light absorption and direct photodecay. Our results suggest our current understanding of photodegradation processes underestimates the rate at which some compounds are broken down, as well as the release of photoproducts into the atmosphere.