¹Keisuke Fukushi,^1,2Yasuhito Sekine,³Elizabeth B.Rampe
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2022.02.005]
¹Institute of Nature and Environmental Technology, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192 Japan
²Earth-Life Science Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 Japan
³Astromaterials Research and Exploration Science Division, NASA Johnson Space Center, Houston, TX77058, USA
Copyright Elsevier

Mars once possessed liquid water on its surface. In investigations of aqueous conditions on early Mars, the Mars Science Laboratory rover Curiosity has provided mineralogical and geochemical data from lacustrine sediments of Gale Crater, site of a former lake. Recently, the top-down method for quantitative reconstruction of the chemical parameters of ancient pore water, based on exchangeable cation compositions in smectite and secondary minerals, was developed and applied to the Yellowknife Bay sediments in Gale Crater. Here we report the application of this method to lacustrine sediment from the Quela drill site in Gale Crater, in the Karasburg member of the Murray formation. The results show that the final pore water to interact with the sediments had the following chemistry: pH = 3.6–5.6, Eh > 0.22 V, molality of Na ({Na}) = 0.14–2.2 mol/kg, {K} = 0.0080–0.31 mol/kg, {Ca} = 0.021–0.21 mol/kg, {Mg} < 0.14 mol/kg, {Fe(II)} < 0.063 mol/kg, {Cl} = 0.096–2.6 mol/kg and {SO4} = 0.048–0.33 mol/kg. At two adjacent drill sites (Marimba and Sebina), the comparable mineral assemblages and smectite interlayer compositions imply that they have water chemistry similar to that of the Quela sediment. The inferred pore water was undersaturated with respect to halite by an order of magnitude, although the sediment contains halite. This suggests that the final water in the Quela sediment disappeared by freezing and sublimation rather than evaporation. One interpretation of the high Na and Cl concentrations of the final pore water at Quela is that the sediment was deposited in an arid climate at around 3.5 Ga. The high salinity of the final pore water at Quela relative to that at Yellowknife Bay suggests that climate may have shifted from semi-arid when the Yellowknife Bay formation was deposited to arid when the Karasburg member was deposited. Alternatively, the high salinity at Quela suggests that the post-depositional fluids at 2–3 Ga was enriched in Na. In contrast to low Na in the post-depositional fluids in the underlying Yellowknife Bay, the high salinity of the post-depositional fluids of the Quela suggests different origin and/or timing of the re-wetting events between these two sites. The acidic pH and high Eh suggest that the Quela sediment was intensively affected by oxidizing and acidic post-depositional fluids. The pH of the final pore water would not have allowed the preservation of Ca and Mg carbonates under attainable CO2 partial pressures, which is consistent with the scenario of carbonate dissolution by acidic post-depositional fluids on Mars.

¹Bidong Zhang,²Nancy L.Chabot,^1,3Alan E.Rubin⁴Munir Humayun,⁵Joseph S.Boesenberg,⁶Deonvan Niekerk
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2022.02.004]
¹Department of Earth, Planetary & Space Sciences, University of California, Los Angeles, CA 90095-1567, USA
²Johns Hopkins University Applied Physics Laboratory, Laurel, MD 20723, USA
³Maine Mineral & Gem Museum, 99 Main Street, P.O. Box 500, Bethel, ME 04217, USA
⁴National High Magnetic Field Laboratory and Department of Earth, Ocean & Atmospheric Science, Florida State University, Tallahassee, FL 32310, USA
⁵Earth, Environmental and Planetary Sciences, Brown University, Providence, RI 02912, USA
⁶Department of Geology, Rhodes University, Makhanda 6140, South Africa
Copyright Elsevier

Group IIIF was established as a magmatic iron-meteorite group based on similar Ga and Ge abundances, unusually high Ga/Ge ratios, and the IIIAB-like interelement trends in its members; recent Mo and Ru isotopic data indicate that three of its members exhibit the isotopic signature of carbonaceous-chondrite (CC) irons. Here we report the elemental chemistry of this group and model its crystallization history. Included are new elemental data for IIIF irons acquired by both instrumental neutron activation analysis (INAA) and laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS). A fractional-crystallization model was used to evaluate the IIIF compositional trends for 19 elements and was unable to explain the observed fractionation trends for several key elements (Co, Ga, Ge). In particular, the inability of this model to match Co in the IIIF irons is striking because (1) group IIIF has the widest Co variation among all magmatic iron groups and (2) none of the tested initial S contents (0−20 wt.%) explains both the wide Co variation and steep Co-As slope. Attempts to fit subsets of the IIIF irons were also unsuccessful. In addition, group IIIF has the greatest variety of structural classes and kamacite bandwidths among all established magmatic iron groups. If the IIIF irons constitute a coherent group, they were derived from a parent body that experienced more complex processes than simple fractional crystallization of the core.

The Zinder and Northwest Africa (NWA) 1911 pyroxene-bearing pallasites were recently suggested to be related to group IIIF based on their Ga and Ge contents, and we completed a petrographic study of the pallasite silicates and LA-ICP-MS analyses of their metal fractions. The two pallasites are related to one another: they have nearly identical mineralogical, elemental and O-isotopic compositions in their silicates and metals. Their metallic compositions resemble those of the IIIF irons Moonbi, St. Genevieve County, and Cerro del Inca, but their O-isotopic compositions resemble those of non-carbonaceous (NC) achondrites. Additional isotopic measurements are needed to test the potential genetic relationship to group IIIF.