The Curiosity and Opportunity rovers have found depositions of manganese (Mn) (hydr)oxides within the veins of the sedimentary rocks at Gale and Endeavour craters. Since Mn is a redox sensitive element, revealing the chemical form of the Mn (hydr)oxide provides unique information on the redox state of the near‐surface/groundwater at the time of deposition. Here we report results of laboratory experiments that investigated scavenging patterns of trace metals (zinc, nickel, and chromium) on different Mn (hydr)oxides in order to constrain the chemical form of the Mn precipitates found on Mars. Our results show manganese dioxide (MnO2) scavenges zinc and nickel effectively but not for chromium. The agreement of this scavenging pattern with the observations strongly suggests that the Mn (hydr)oxides found on Mars are highly likely to be MnO2. To form MnO2, oxidizing aqueous environments are required (e.g., Eh > 0.5 V at pH ~ 8). The candidates of the oxidant include molecular oxygen, ozone, nitrates, and perchlorate acids; all of which are considered to be produced by photochemical processes. The presence of MnO2 veins in sediments suggests that such atmospheric high‐Eh oxidants may have been supplied to the subsurface, possibly through hydrological cycles activated by transient warming.

Ferrous saponite is a secondary mineral that can be used to reveal the redox state of past aqueous environments on Mars. In mineralogical analyses for ferrous saponite formed in laboratory simulations or contained in future returned samples from Mars, its oxidation by the Earth’s air could be problematic due to the high redox sensitivity. Here, we performed micro X-ray diffraction and scanning transmission X-ray microscopy analyses for a single particle of synthesized ferrous saponite without any exposure to air. The sample was reanalyzed after air exposure for 10–18 h to assess the adequacy of our anoxic preparation/measurement methods and the impacts of air on the sample. We found that the crystal structures agreed with ferrous saponite, both before and after air exposure; however, ferrous iron in saponite was partially oxidized, at least until 0.1–1 μm from the surface, after air exposure at the submicron scale, forming micro-vein-like Fe(III)-rich features. Together with our results of infrared spectroscopy of ferrous saponite, we showed that oxidation of octahedral iron occurred rapidly and heterogeneously, even in a short time of air exposure without any structural rearrangement. Since ferrous saponite is expected to exist on carbonaceous asteroids and icy dwarf planets, our methodology is also applicable to mineralogical studies of samples returned from these bodies.