Formation of Hydroxyl Radical from the Photolysis of Frozen Hydrogen Peroxide

Hydrogen peroxide (HOOH) in ice and snow is an important chemical tracer for the oxidative capacities of past atmospheres. However, photolysis in ice and snow will destroy HOOH and form the hydroxyl radical (^•OH), which can react with snowpack trace species. Reactions of ^•OH in snow and ice will affect the composition of both the overlying atmosphere (e.g., by the release of volatile species such as formaldehyde to the boundary layer) and the snow and ice (e.g., by the ^•OH-mediated destruction of trace organics). To help understand these impacts, we have measured the quantum yield of ^•OH from the photolysis of HOOH on ice. Our measured quantum yields (Φ(HOOH → ^•OH)) are independent of ionic strength, pH, and wavelength, but are dependent upon temperature. This temperature dependence for both solution and ice data is best described by the relationship ln(Φ(HOOH → ^•OH)) = −(684 ± 17)(1/T) + (2.27 ± 0.064) (where errors represent 1 standard error). The corresponding activation energy (E_a) for HOOH (5.7 kJ mol^-1) is much smaller than that for nitrate photolysis, indicating that the photochemistry of HOOH is less affected by changes in temperature. Using our measured quantum yields, we calculate that the photolytic lifetimes of HOOH in surface snow grains under midday, summer solstice sunlight are approximately 140 h at representative sites on the Greenland and Antarctic ice sheets. In addition, our calculations reveal that the majority of ^•OH radicals formed on polar snow grains are from HOOH photolysis, while nitrate photolysis is only a minor contributor. Similarly, HOOH appears to be much more important than nitrate as a photochemical source of ^•OH on cirrus ice clouds, where reactions of the photochemically formed hydroxyl radical could lead to the release of oxygenated volatile organic compounds to the upper troposphere.