Oxychlorine species are globally widespread across the Martian surface. Despite their ubiquitous presence, the ability of oxychlorine species to serve as oxidants on Mars has largely been unexplored. While perchlorate is kinetically inert, chlorate may be a critical Fe(II) oxidant on Mars. However, the timescale over which chlorate may oxidize Fe(II) and the mineral products formed in Mars‐relevant fluids are unclear. Fe(II) oxidation by chlorate was thus investigated in magnesium chloride, sulfate, and perchlorate fluids under neutral to acidic conditions for different total Fe(II) and background salt concentrations. The results show near‐complete Fe(II) oxidation within approximately 2 to 4 weeks, accompanied by formation of the Fe(III) minerals goethite, lepidocrocite, akaganeite, and jarosite. The Fe(II) oxidation rate and the mineral products depend on Fe(II) concentration, the composition and concentration of the background salt, and the acidity of the solution. Calibration of an existing rate law to lower temperatures well reproduces the observed oxidation kinetics in all fluid compositions and allows prediction of the rate of Fe(II) oxidation by chlorate under diverse Mars‐relevant conditions. Rate comparisons demonstrates that chlorate can oxidize Fe(II) substantially faster than O2 and on similar or shorter timescales than ultraviolet light. Notably, chlorate causes rapid oxidation under acidic conditions, unlike other oxidants. Chlorate may thus represent an important abiotic Fe(II) oxidant on Mars. The expected coassociation of chlorate with perchlorate may allow for its percolation into the subsurface during brine migration, leading to oxidation in regions that are cutoff from ultraviolet radiation and atmospherically derived oxidants.

Chlorate is an important Cl-bearing species and a strong potential Fe(II) oxidant on Mars. Since the amount of oxychlorine species (perchlorate and chlorate) detected on Mars is limited (<~1 wt.%), the effectiveness of chlorate to produce iron oxides depends heavily on its oxidizing capacity. Decomposition of chlorate or intermediates produced during its reduction, before reaction with Fe(II) would decrease its effective capacity as an oxidant. We thus evaluated the capacity of chlorate to produce Fe(III) minerals in Mars-relevant fluids, via oxidation of dissolved Fe(II). Each chlorate ion can oxidize 6 Fe(II) ions under all conditions investigated. Mass balance demonstrated that 1 wt.% chlorate (as ClO3−) could produce approximately 6 to 12 wt.% Fe(III) or mixed valent mineral products, with the amount varying with the formula of the precipitating phase. The mineral products are primarily determined by the fluid type (chloride- or sulfate-rich), the solution pH, and the rate of Fe(II) oxidation. The pH at the time of initial mineral nucleation and the amount of residual dissolved Fe(II) in the system exert important additional controls on the final mineralogy. Subsequent diagenetic transformation of these phases would yield 5.7 wt.% hematite per wt.% of chlorate reacted, providing a quantitative constraint on the capacity of chlorate to generate iron oxides on Mars.

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