Mechanistic studies on the radiolytic decomposition of perchlorates on the Martian surface

Perchlorates—inorganic compounds carrying the perchlorate ion (${ClO}_4{}^{-}$)—were discovered at the north polar landing site of the Phoenix spacecraft and at the southern equatorial landing site of the Curiosity Rover within the Martian soil at levels of 0.4–0.6 wt%. This study explores in laboratory experiments the temperature-dependent decomposition mechanisms of hydrated perchlorates—namely magnesium perchlorate hexahydrate (Mg(ClO₄)₂·6H₂O)—and provides yields of the oxygen-bearing species formed in these processes at Mars-relevant surface temperatures from 165 to 310 K in the presence of galactic cosmic-ray particles (GCRs). Our experiments reveal that the response of the perchlorates to the energetic electrons is dictated by the destruction of the perchlorate ion (${ClO}_4{}^{-}$) and the inherent formation of chlorates (${ClO}_3{}^{-}$) plus atomic oxygen (O). Isotopic substitution experiments reveal that the oxygen is released solely from the perchlorate ion and not from the water of hydration (H₂O). As the mass spectrometer detects only molecular oxygen (O₂) and no atomic oxygen (O), atomic oxygen recombines to molecular oxygen within the perchlorates, with the overall yield of molecular oxygen increasing as the temperature drops from 260 to 160 K. Absolute destruction rates and formation yields of oxygen are provided for the planetary modeling community.