Search

Ferric (Fe3+-bearing) smectites, including nontronite, constitute the majority of hydrous mineral exposures observed on Mars. These smectite exposures are commonly interpreted as weathering products of Martian basaltic crust. However, ferrous (Fe2+-dominated) smectites, not ferric, are the thermo-dynamically predicted products of weathering in anoxic conditions, as predicted for early Mars. Earth was anoxic until the Proterozoic Great Oxidation Event; Mars likely experienced an analogous oxidative evolution to its present oxidized state, but the timing of this evolution is unresolved. We hypothesize that Fe3+-smectites observed by orbital spectroscopy are not the initial products of Noachian-era chemical weathering, but are instead the oxidative products of primary Fe2+-smectites. To test this hypothesis experimentally, we synthesized ferrous smectites and exposed them to Mars-relevant oxidants.

The Mars Exploration Rover Spirit ended its mission in Gusev crater on sol 2210 after it had become stuck in a deposit of fined-grained and sulfate rich soil with dust covered solar panels unfavorably pointed toward the sun. Final analysis of remaining data from Spirit's Moessbauer spectrometer (Fe redox and mineralogy) for sols 1529 through 2071 is now complete. We focus here on chemical (APXS) and MB data for targets having high-SiO2 or high-SO3 and process link the targets through mixing and geochemical modelling to an acid-sulfate system centered at Home Plate, which is considered to be a hydrovolcanic complex.

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

Recent discoveries of highly concentrated manganese oxides in Gale Crater and on the rim of Endeavour Crater by the Mars Science Laboratory Curiosity and Mars Exploration Rover Opportunity, respectively, imply more highly oxidizing aqueous conditions than previously recognized. Manganese oxides are a significant environmental indicator about ancient aqueous conditions, provided the phases can be characterized reliably. Manganese oxides are typically fine-grained and poorly crystalline, making the mineral structures difficult to determine, and they generally have very low visible reflectance with few distinctive spectral features in the visible to near infrared, making them a challenge for interpretation from remote sensing data. Therefore, these recent discoveries motivate better characterization using methods available on Mars, particularly visible to near infrared (VNIR) spectroscopy, X-ray diffractometry (XRD), and compositional measurements. Both rovers have complementary instruments in this regard. Opportunity is equipped with its multispectral visible imager, Pancam, and an Alpha Particle X-ray Spectrometer (APXS), and Curiosity has the multispectral Mastcam, ChemCam (laser-induced breakdown spectroscopy and passive spectroscopy), and APXS for in situ characterization, and ChemMin (XRD) for collected samples.

The Mars Science Laboratory (MSL) rover Curiosity landed in Gale Crater in August 2012 and is currently roving towards the layered central mound known as Mount Sharp [1]. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) hyperspectral data indicate Mount Sharp contains an ~5 km stratigraphic sequence including Fe-Mg smectites, hematite, and hydrated sulfates in the lower layers separated by an unconformity from the overlying anhydrous strata [1,2,3]. Hematite was initially detected in CRISM data to occur in the lower sulfate layers on the north side of the mound [2]. [3] further mapped a distinct hematite detection occurring as part of a ~200 m wide ridge that extends ~6.5 km NE-SW, approximately parallel with the base of Mount Sharp. It is likely a target for in-situ analyses by Curiosity. We document here the occurrence of a stratum of hematite-bearing breccia that is exposed on the Puu Poliahu cinder cone near the summit of Mauna Kea volcano (Hawaii) (Fig.1). The stratum is more resistant to weathering than surrounding material, giving it the appearance of a ridge. The Mauna Kea hematite ridge is thus arguably a potential terrestrial mineralogical and process analog for the Gale Crater hematite ridge. We are acquiring a variety of chemical and mineralogical data on the Mauna Kea samples, with a focus on the chemical and mineralogical information already available or planned for the Gale hematite ridge.

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.

Opportunity has conducted an extensive "walk-about" and set of in-situ measurements on strata exposed on the inboard side of Cape York, a segment of the dissected rim of the Noachian-age approx.22 km wide Endeavour crater [1] (Fig. 1). The specific region for the observations (Matijevic Hill) was chosen based on along track oversampled (ATO) CRISM hyperspectral observations (processed to 5 m/pixel) that showed the presence of exposures of Fe/Mg smectite phyllosilicates. We describe the first ground-based observations of phyllosilicates on Mars and discuss implications based on the combined CRISM and Opportunity measurements.