Possibility of H_2O_2 decomposition in thin liquid films on Mars

摘要

In this work the pathways and possibilities of H_2O_2 decomposition on Mars in microscopic liquid interfacial water were analyzed by kinetic calculations. Thermal and photochemical driven decomposition, just like processes catalyzed by various metal oxides, is too slow compared to the annual duration while such microscopic liquid layers exist on Mars today, to produce substantial decomposition. The most effective analyzed process is catalyzed by Fe ions, which could decompose H_2O_2 under pH ＜ 4.5 with a half life of 1-2 days. This process might be important during volcanically influenced periods when sulfur release produces acidic pH, and rotational axis tilt change driven climatic changes also influence the volatile circulation and spatial occurrence just like the duration of thin liquid layer. Under current conditions, using the value of 200 K as the temperature in interfacial water (at the southern hemisphere), and applying Phoenix lander's wet chemistry laboratory results, the pH is not favorable for Fe mobility and this kind of decomposition. Despite current conditions (especially pH) being unfavorable for H_2O_2 decomposition, microscopic scale interfacial liquid water still might support the process. By the reaction called heterogeneous catalysis, without acidic pH and mobile Fe, but with minerals surfaces containing Fe decomposition of H_2O_2 with half life of 20 days can happen. This duration is still longer but not several orders than the existence of springtime interfacial liquid water on Mars today. This estimation is relevant for activation energy controlled reaction rates. The other main parameter that may influence the reaction rate is the diffusion speed. Although the available tests and theoretical calculations do not provide firm values for the diffusion speed in such a "2-dimensional" environment, using relevant estimations this parameter in the interfacial liquid layer is smaller than in bulk water. But the 20 days' duration mentioned above is still relevant, as the activation energy driven reaction rate is the main limiting factor in the decomposition and not the diffusion speed. The duration of dozen(s) days is still longer but not with orders of magnitude than the expected duration for the existence of springtime interfacial liquid water on Mars today. The results suggest such decomposition may happen today, however, because of our limited knowledge on chemical processes in thin interfacial liquid layers, this possibility waits for confirmation - and also points to the importance of conducting laboratory tests to validate the possible process. Although some tests were already realized for diffusion in an almost 2-dimensional liquid, the same is not true for activation energy, where only the value from the "normal" measurements was applied. Even if H_2O_2 decomposition is too slow today, the analysis of such a process is important, as under volcanic influence more effective decomposition might take place in thin interfacial liquids close to the climate of today if released sulfur produces pH ＜ 4.5. Large quantity and widespread occurrence of bulk liquid phase are not expected in the Amazonian period, but interfacial liquid water probably appeared regularly, and its locations, especially during volcanically active periods, might make certain sites than others more interesting for astrobiology with the lower concentration of oxidizing H_2O_2.