Iron Mineralogy and Aqueous Alteration on Mars from the MER Moessbauer Spectrometers

The twin Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) used MIMOS II Moessbauer spectrometers to analyze martian surface materials in the first application of extraterrestrial Moessbauer spectroscopy. The instruments acquired spectra that identified the speciation of Fe according to oxidation state, coordination state, and mineralogical composition and provided quantitative information about the distribution of Fe among oxidation states, coordination states, and Fe-bearing phases. A total of 12 unique Fe-bearing phases were identified: Fe(2+) in olivine, pyroxene, and ilmenite; Fe(2+) and Fe(3+) in magnetite and chromite; Fe(3+) in nanophase ferric oxide (npOx), hematite, goethite, jarosite, an unassigned Fe3+ sulfate, and an unassigned Fe(3+) phase associated with jarosite; and Fe(0) in kamacite. Weakly altered basalts at Gusev crater (SO3 = 2.5 +/- 1.4 wt.% and Fe(3+)/Fe(sub T) = 0.24 +/- 0.11) are widespread on the Gusev plains and occur in less abundance on West Spur and Husband Hill in the Columbia Hills. Altered low-S rocks (SO3 = 5.2 +/- 2.0 wt.% and Fe(3+)/Fe(sub T) = 0.63 +/- 0.18) are the most common type of rock in the Columbia Hills. Ilm-bearing, weakly altered basalts were detected only in the Columbia Hills, as was the only occurrence of chromite in an altered low-S rock named Assemblee. Altered high-S rocks (SO3 > 14.2 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05) are the outcrop rocks of the ubiquitous Burns formation at Meridiani Planum. Two Fe(0)-bearing rocks at Meridiani Planum (Barberton and Heat Shield Rock) are meteorites. Laguna Class soil is weakly altered (SO3 = 6 +/- 2 wt.% and Fe(3+)/Fe(sub T) = 0.29 +/- 0.08) and widely distributed at both Gusev crater and Meridiani Planum, implying efficient global mixing processes or a global distribution of precursor rocks with comparable Fe mineralogical compositions. Paso Robles Class soil is heavily altered (SO3 approx. 31 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05), is relatively uncommon, and occurs as subsurface deposits in the Columbia Hills. Berry Class soil is also heavily altered (SO3 = 5 +/- 1 wt.% and Fe(3+)/Fe(sub T) = 0.60 +/- 0.13) and occurs at Meridiani Planum as lag deposits, at the crests of aeolian bedforms, and as isolated pockets on outcrop surfaces. Magnetite is identified as the strongly magnetic component in martian soil. Jarosite (in the Burns outcrop at Meridiani Planum) and goethite (in Clovis Class rocks at Gusev crater) are mineralogical markers for aqueous processes because they contain the hydroxide anion (OH(-)) as an essential part of their structure. Each yields approx.10 wt.% H2O upon dehydroxylation. The presence of Fe sulfates on opposite sides of Mars is evidence that aqueous processes under acid sulfate conditions are or were common. Except for Independence Class rocks in the Columbia Hills, the overall Fe mineralogical compositions and similar basaltic bulk chemical compositions (calculated with respect to S = Cl = 0) of the population of altered rocks analyzed by MER imply isochemical alteration of basaltic precursors at low water-to-rock ratios

Moessbauer Mineralogy on the Moon: The Lunar Regolith

A first-order requirement for spacecraft missions that land on solid planetary objects is instrumentation for mineralogical analyses. For purposes of providing diagnostic information about naturally-occurring materials, the element iron is particularly important because it is abundant and multivalent. Knowledge of the oxidation state of iron and its distribution among iron-bearing mineralogies tightly constrains the types of materials present and provides information about formation and modification (weathering) processes. Because Moessbauer spectroscopy is sensitive to both the valence of iron and its local chemical environment, the technique is unique in providing information about both the relative abundance of iron-bearing phases and oxidation state of the iron. The Moessbauer mineralogy of lunar regolith samples (primarily soils from the Apollo 16 and 17 missions to the Moon) were measured in the laboratory to demonstrate the strength of the technique for in situ mineralogical exploration of the Moon. The regolith samples were modeled as mixtures of five iron-bearing phases: olivine, pyroxene, glass, ilmenite, and metal. Based on differences in relative proportions of iron associated with these phases, volcanic ash regolith can be distinguished from impact-derived regolith, impact-derived soils of different geologic affinity (e.g., highlands, maria) can be distinguished on the basis of their constituent minerals, and soil maturity can be estimated. The total resonant absorption area of the Moessbauer spectrum can be used to estimate total FeO concentrations

Extraterrestrial Moessbauer Spectroscopy: More than Three Years of Mars Exploration and Developments for Future Missions

The NASA Mars Exploration Rovers (MER), Spirit and Opportunity, landed on the Red Planet in January 2004. Both rovers are equipped with a miniaturized Moessbauer spectrometer MIMOS II. Designed for a three months mission, both rovers and both Moessbauer instruments are still working after more than three years of exploring the Martian surface. At the beginning of the mission, with a landed intensity of the Moessbauer source of 150 mCi, a 30 minute touch and go measurement produced scientifically valuable data while a good quality Moessbauer spectrum was obtained after approximately eight hours. Now, after about five halflives of the sources have passed, Moessbauer integrations are routinely planned to last approx.48 hours. Because of this and other age-related hardware degradations of the two rover systems, measurements now occur less frequently, but are still of outstanding quality and scientific importance. Summarizing important Moessbauer results, Spirit has traversed the plains from her landing site in Gusev crater and is now, for the greater part of the mission, investigating the stratigraphically older Columbia Hills. Olivine in rocks and soils in the plains suggests that physical rather than chemical processes are currently active

New insights into the mineralogy and weathering of the Meridiani Planum meteorite, Mars

Meridiani Planum is the first officially recognized meteorite find on the surface of Mars. It was discovered at and named after the landing site of the Mars Exploration Rover Opportunity. Based on its composition, it was classified as a IAB complex iron meteorite. Mössbauer spectra obtained by Opportunity are dominated by kamacite (a-Fe-Ni) and exhibit a small contribution of ferric oxide. Several small features in the spectra have been neglected to date. To shed more light on these features, five iron meteorite specimens were investigated as analogs to Meridiani Planum with a laboratory Mössbauer setup. Measurements were performed on (1) their metallic bulk, (2) troilite (FeS) inclusions, (3) cohenite ((Fe,Ni,Co)3C) and schreibersite ((Fe,Ni)3P), and (4) corroded rims. In addition to these room-temperature measurements, a specimen from the Mundrabilla IAB-ungrouped meteorite was measured at Mars-equivalent temperatures. Based on these measurements, the features in Meridiani Planum spectra can be explained with the presence of small amounts of schreibersite and ⁄ or cohenite and iron oxides. The iron oxides can be attributed to a previously reported coating on Meridiani Planum. Their presence indicates weathering through the interaction of the meteorite with small amounts of water

Abiotic versus biotic iron mineral transformation studied by a miniaturized backscattering Mössbauer spectrometer (MIMOS II), X-ray diffraction and Raman spectroscopy

Searching for biomarkers or signatures of microbial transformations of minerals is a critical aspect for determining how life evolved on Earth, and whether or not life may have existed in other planets, including Mars. In order to solve such questions, several missions to Mars have sought to determine the geochemistry and mineralogy on the Martian surface. This research includes the two miniaturized Mössbauer spectrometers (MIMOS II) on board the Mars Exploration Rovers Spirit and Opportunity, which have detected a variety of iron minerals on Mars, including magnetite (Fe2+Fe3+2O4) and goethite (α-FeO(OH)). On Earth, both minerals can derive from microbiological activity (e.g. through dissimilatory iron reduction of ferrihydrite by Fe(III)-reducing bacteria). Here we used a lab based MIMOS II to characterize the mineral products of biogenic transformations of ferrihydrite to magnetite by the Fe(III)-reducing bacteria Geobacter sulfurreducens. In combination with Raman spectroscopy and X-ray diffraction (XRD), we observed the formation of magnetite, goethite and siderite. We compared the material produced by biogenic transformations to abiotic samples in order to distinguish abiotic and biotic iron minerals by techniques that are or will be available onboard Martian based laboratories. The results showed the possibility to distinguish the abiotic and biotic origin of the minerals. Mossbauer was able to distinguish the biotic/abiotic magnetite with the interpretation of the geological context (Fe content mineral assemblages and accompanying minerals) and the estimation of the particle size in a non-destructive way. The Raman was able to confirm the biotic/abiotic principal peaks of the magnetite, as well as the organic principal vibration bands attributed to the bacteria. Finally, the XRD confirmed the particle size and mineralogy

Mineralogy

The power of mineralogical analysis as a descriptive or predictive technique stems from the fact that only a few thousand minerals are known to occur in nature as compared to several hundred thousand inorganic compounds. Further, all of the known minerals have specific stability ranges in pressure, temperature, an composition. A specific knowledge of the mineralogy of a planets surface or interior therefore allows one to characterize the present or past conditions under which the minerals were formed or have existed. For the purposes of this paper, a slightly broader definition of mineralogy was adopted by including not only crystalline materials found on planetary surfaces, but also ices and classes that can benefit from in situ types of analyses. Both visual examination and the various spectroscopies available for robotic probes to planetary surfaces are discussed

The MER Mossbauer Spectrometers: 40 Months of Operation on the Martian Surface

The primary MER objectives have been successfully completed. The total integration time of all MB measurements exceeds the duration of the primary 90-sols-mission for Spirit's MB spectrometer, and approaches this value for Opportunity's MB spectrometer. Both MB spectrometers continue to accumulate valuable scientific data after three years of operation (data is available for download [13]) The identification of aqueous minerals such as goethite in Gusev crater and jarosite at Meridiani Planum by the MER Mossbauer spectrometers is strong evidence for past water activity at the two landing sites

Visible and near-infrared multispectral analysis of geochemically measured rock fragments at the Opportunity landing site in Meridiani Planum

We have used visible and near‐infrared Panoramic Camera (Pancam) spectral data acquired by the Opportunity rover to analyze 15 rock fragments at the Meridiani Planum landing site. These spectral results were then compared to geochemistry measurements made by the in situ instruments Mössbauer (MB) and Alpha Particle X‐ray Spectrometer (APXS) to determine the feasibility of mineralogic characterization from Pancam data. Our results suggest that dust and alteration rinds coat many rock fragments, which limits our ability to adequately measure the mineralogy of some rocks from Pancam spectra relative to the different field of view and penetration depths of MB and APXS. Viewing and lighting geometry, along with sampling size, also complicate the spectral characterization of the rocks. Rock fragments with the same geochemistry of sulfate‐rich outcrops have similar spectra, although the sulfate‐rich composition cannot be ascertained based upon Pancam spectra alone. FeNi meteorites have spectral characteristics, particularly ferric oxide coatings, that generally differentiate them from other rocks at the landing site. Stony meteorites and impact fragments with unknown compositions have a diverse range of spectral properties and are not well constrained nor diagnostic in Pancam data. Bounce Rock, with its unique basalt composition, is easily differentiated in the Pancam data from all other rock types at Meridiani Planum. Our Pancam analyses of small pebbles adjacent to these 15 rock fragments suggests that other rock types may exist at the landing site but have not yet been geochemically measured

Geochemical properties of rocks and soils in Gusev Crater, Mars: Results of the Alpha Particle X-Ray Spectrometer from Cumberland Ridge to Home Plate

Geochemical diversity of rocks and soils has been discovered by the Alpha Particle X-Ray Spectrometer (APXS) during Spirit’s journey over Husband Hill and down into the Inner Basin from sol 470 to 1368. The APXS continues to operate nominally with no changes in calibration or spectral degradation over the course of the mission. Germanium has been added to the Spirit APXS data set with the confirmation that it occurs at elevated levels in many rocks and soils around Home Plate. Twelve new rock classes and two new soil classes have been identified at the Spirit landing site since sol 470 on the basis of the diversity in APXS geochemistry. The new rock classes are Irvine (alkaline basalt), Independence (low Fe outcrop), Descartes (outcrop similar to Independence with higher Fe and Mn), Algonquin (mafic-ultramafic igneous sequence), Barnhill (volcaniclastic sediments enriched in Zn, Cl, and Ge), Fuzzy Smith (high Si and Ti rock), Elizabeth Mahon (high Si, Ni, and Zn outcrop and rock), Halley (hematite-rich outcrop and rock), Montalva (high K, hematite-rich rock), Everett (high Mg, magnetite-rich rock), Good Question (high Si, low Mn rock), and Torquas (high K, Zn, and Ni magnetite-rich rock). New soil classes are Gertrude Weise (very high Si soil) and Eileen Dean (high Mg, magnetite-rich soil). Aqueous processes have played a major role in the formation and alteration of rocks and soils on Husband Hill and in the Inner Basin

Discovery of Carbonate-Rich Outcrops in the Gusev Crater Columbia Hills by the MER Rover Spirit

The chemical composition, global abundance, distribution, and formation pathways of carbonates are central to understanding aqueous processes, climate, and habitability of early Mars. The Mars Exploration Rover (MER) Spirit analyzed a series of olivine-rich outcrops while descending from the summit region of Husband Hill into the Inner Basin of the Columbia Hills of Gusev Crater to the eastern edge of the El Dorado ripple field in late 2005. Reanalysis of Spirit s mineralogical data from the Moessbauer Spectrometer (MB) and the Miniature Thermal Emission Spectrometer (Mini-TES) and chemical data from the Alpha Particle X-Ray Spectrometer (APXS) in 2010, coupled with new laboratory data for carbonate-bearing samples, lead to identification of carbonate in one of the outcrops (Comanche) [Morris, R.V., et al., Science, 329, 421-424]. The carbonate is rich in magnesium and iron (Mc62Sd25Cc11Rh2, assuming all Ca and Mn is associated with the carbonate) and is a major component of the Comanche outcrops (16 to 34 wt.%). The mineralogical, chemical, and abundance data are constrained in multiple, mutually consistent ways by the MER analyses. For example, a low-Ca carbonate is required by the MB and APXS data and is consistent with Mini-TES data. Three spectral features attributable to fundamental infrared vibrational modes of low-Ca carbonate are present in the Mini-TES spectra of Comanche outcrops. The average composition of Comanche carbonate approximates the average composition of the carbonate globules in Martian meteorite ALH 84001. Analogy with ALH 84001, terrestrial, and synthetic carbonate globules suggests that Comanche carbonate precipitated from aqueous solutions under hydrothermal conditions at near neutral pH in association with volcanic activity during the Noachian era. Comanche outcrop morphology suggests they are remnants of a larger carbonate-bearing formation that evolved in ultramafic rock and then preferentially eroded by a combination of aeolian abrasion and chemical decomposition by exposure to acid-sulfate vapors/solutions. The high carbonate concentration in the Comanche outcrops supports climate models involving a CO2 greenhouse gas on a wet and warm early Mars and subsequent sequestering of at least part of that atmosphere in carbonate minerals