Preferential Formation of Chlorate over Perchlorate on Mars Controlled by Iron Mineralogy

Perchlorate (ClO 4 − ) and possibly chlorate (ClO 3 − ) are considered to be ubiquitous on Mars 1 – 5 , and the ClO 3 − /ClO 4 − abundance ratio has critical implications for the redox conditions 6 , 7 , aqueous environments 8 , 9 and habitability on Mars 10 . However, factors that control the ClO 3 − /ClO 4 − generation ratios are not well established. Here we expose mixtures of halite salt (NaCl) with Fe sulfates, Fe (hydr)oxides and Fe 3+ montmorillonite to ultraviolet radiation or ozone in an Earth or CO 2 atmosphere and show that Fe secondary mineralogy is the dominant factor controlling the ClO 3 − /ClO 4 − generation ratio: the sulfates and montmorillonite mixtures produce much higher yields of ClO 4 − than of ClO 3 − , whereas the opposite is true for the (hydr)oxide mixtures. Consistent with previous studies 11 – 18 , our results indicate that the physical state of chloride (Cl − ) (that is, solid, liquid or gas) and the characteristics of the co-occurring minerals (for example, semiconductivity, surface area, acidity) have the greatest influence, whereas oxidation sources (ultraviolet radiation or ozone) and atmospheric composition induce only secondary effects. We conclude that, under the hyperarid climate and widespread Fe (hydr)oxide abundances prevailing on Mars since the Amazonian period 19 , Cl − oxidation should produce yields of ClO 3 − that are orders of magnitude higher than those of ClO 4 − , highlighting the importance of ClO 3 − in the surficial environments and habitability of modern Mars compared with ClO 4 − . Laboratory experiments show that the type of iron mineral is the dominant factor controlling the chlorate/perchlorate (ClO 3 − /ClO 4 − ) generation ratio on Mars over oxidation methods or atmospheric composition. Chlorate yields are found to exceed perchlorate yields by orders of magnitude in the current desiccated Martian conditions.