The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO₂, surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO₂ appears to be stronger than to biogenic MnO₂, and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe ⁺³ -rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

This paper summarizes Spirit Rover operations in the Columbia Hills, Gusev crater, from sol 1410 (start of the third winter campaign) to sol 2169 (when extrication attempts from Troy stopped to winterize the vehicle) and provides an overview of key scientific results. The third winter campaign took advantage of parking on the northern slope of Home Plate to tilt the vehicle to track the sun and thus survive the winter season. With the onset of the spring season, Spirit began circumnavigating Home Plate on the way to volcanic constructs located to the south. Silica‐rich nodular rocks were discovered in the valley to the north of Home Plate. The inoperative right front wheel drive actuator made climbing soil‐covered slopes problematical and led to high slip conditions and extensive excavation of subsurface soils. This situation led to embedding of Spirit on the side of a shallow, 8 m wide crater in Troy, located in the valley to the west of Home Plate. Examination of the materials exposed during embedding showed that Spirit broke through a thin sulfate‐rich soil crust and became embedded in an underlying mix of sulfate and basaltic sands. The nature of the crust is consistent with dissolution and precipitation in the presence of soil water within a few centimeters of the surface. The observation that sulfate‐rich deposits in Troy and elsewhere in the Columbia Hills are just beneath the surface implies that these processes have operated on a continuing basis on Mars as landforms have been shaped by erosion and deposition.