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.
Marine ferromanganese oxides contain a large amount of trace elements, such as arsenic (As) and molybdenum (Mo). However, the host phases of tetrahedral AsO 4 3− and MoO 4 2− oxyanions therein have not been clearly identified thus far. In this work, we explored the mineralogical components of hydrogenetic (HG) ferromanganese nodules and compared the distribution behaviors of As and Mo. The X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analyses showed that the predominant manganese and iron phases were vernadite (δ-MnO 2 ) and ferrihydrite, respectively. According to the sequential extraction examination, both As and Mo were associated with the iron (oxyhydr)oxide phases. However, the XAS analyses indicated that As was retained by the ferrihydrite phase via double cornershared complexation, while Mo was preferentially adsorbed on δ-MnO 2 via edge-shared complexation. The immobilization of As and Mo by HG ferromanganese samples was attributed to specific chemical binding (ΔG chem ) rather than Coulombic interaction (ΔG coul ) as proposed in previous studies. The comparison of Mo XAS spectra before and after extraction revealed the unreliability of the sequential extraction approach to determine the host phase of trace elements as a result of the potential readsorption risk. The different distribution trends of As and Mo were due to their disparate intrinsic properties (e.g., averaged dissociation constants of conjugate acids) and the diverse properties (i.e., surface site densify, adsorption equilibrium constant, and crystalline structure) of ferrihydrite and δ-MnO 2 . These research findings would be significant for evaluating the geochemical behaviors and environmental fate of trace elements in marine systems.
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