Uptake of Hydrogen Peroxide from the Gas Phase to Grain Boundaries: A Source in Snow and Ice.

Hydrogen peroxide is a primary atmospheric oxidant significant in terminating gas-phase chemistry and sulfate formation in the condensed phase. Laboratory experiments have shown an unexpected oxidation acceleration by hydrogen peroxide in grain boundaries. While grain boundaries are frequent in natural snow and ice and are known to host impurities, it remains unclear how and to which extent hydrogen peroxide enters this reservoir. We present the first experimental evidence for the diffusive uptake of hydrogen peroxide into grain boundaries directly from the gas phase. We have machined a novel flow reactor system featuring a drilled ice flow tube that allows us to discern the effect of the ice grain boundary content on the uptake. Further, adsorption to the ice surface for temperatures from 235 to 258 K was quantified. Disentangling the contribution of these two uptake processes shows that the transfer of hydrogen peroxide from the atmosphere to snow at temperatures relevant to polar environments is considerably more pronounced than previously thought. Further, diffusive uptake to grain boundaries appears to be a novel mechanism for non-acidic trace gases to fill the highly reactive impurity reservoirs in snow's grain boundaries.

Enhanced Surface Partitioning of Nitrate Anion in Aqueous Bromide Solutions.

The proximity of nitrate anions to the air-water interface is thought to strongly influence their photodissociation quantum yield, due to a reduced solvent cage effect at the water surface. Although nitrate in aqueous solution exhibits little or no surface affinity, the release of gas phase NO2 (nitrate's primary photodissociation product) has been reported to be enhanced when halides, in particular bromide, are also present in solution. Here, we use glancing-angle Raman spectroscopy to investigate whether solutions containing both nitrate and halides show different propensities for nitrate at the air-water interface. We find that bromide enhances, and chloride has little effect on (or perhaps suppresses) the surface partitioning of nitrate anions.