Frost-weathering on Mars: experimental evidence for peroxide formation

A laboratory study of the interaction of H2O frost with samples of the minerals olivine (Mg,Fe)2SiO4 and pyroxene (Mg,Fe)SiO3 at -11 degrees C to -22 degrees C revealed that an acidic oxidant was produced. Exposure of the frost-treated minerals to liquie H2O produced a sudden drop in pH and resulted in the production of copious O2(g) (as much as approximately 10(20) molecules g-1). Exposure of frost-treated samples to 5 ml of 0.1M HCOONa solution resulted in the rapid oxidation of up to 43% of the formate to CO2(g). These reactions were qualitatively similar to the chemical activity observed during the active cycles of the Viking lander Gas Exchange and Labeled Release Biology experiments. Attempts to identify the oxidant by chemical indicators were inconclusive, but they tentatively suggested that chemisorbed hydrogen peroxide may have formed. The formation of chemisorbed peroxide could be explained as a byproduct of the chemical reduction of the mineral. The following model was proposed. H+ was incorporated into the mineral from surface frost. This would have left behind a residual of excess OH-(ads) (relative to surface H+). Electrons were then stripped from the surface OH-(ads) (due to the large repulsive potential between neighboring OH-(ads)) and incorporated into the crystal to restore charge balance and produce a chemical reduction of the mineral. The resultant surface hydroxyl radicals could then have combined to form the more stable chemisorbed hydrogen peroxide species. While the chemisorbed peroxide should be relatively stable at low temperatures, it should tend to decay to O(ads)+ H2O(g) at higher temperatures with an activation energy of greater than or approximately 34 kcal mole-1. This is consistent with the long-term storage and sterilization behavior of the Viking soil oxidants. It is possible that as little as 0.1--1% frost-weathered material in the martian soil could have produced the unusual chemical activity that occurred during the Viking Gas Exchange and Labeled Release experiments.