Depth selective Mossbauer spectroscopy: Analysis and simulation of 6.4 keV and 14.4 keV spectra obtained from rocks at Gusev Crater, Mars, and layered laboratory samples

The miniaturized Mössbauer spectrometer (MIMOS) II Mössbauer spectrometers on the Mars Exploration Rovers (MER) simultaneously obtained 6.4 keV and 14.4 keV Mössbauer spectra from rock and soil targets. Because photons with lower energy have a shallower penetration depth, 6.4 keV spectra contain more mineralogical information about the near-surface region of a sample than do 14.4 keV spectra. The influence of surface layers of varying composition and thickness on Mössbauer spectra was investigated by Monte Carlo simulation and by measurement using a copy of the MER MIMOS II instrument and samples with one or two layers of known thicknesses. Thin sections of minerals or metallic Fe foil on top of a thick mineral sample were used to produce samples with thin layers of known thickness on a thick substrate. Monte Carlo simulation of MER spectra obtained on the rock Mazatzal, which displays a coating on a basaltic substrate, and other Adirondack Class rocks results in a calculated thickness of 10 micrometer for the Mazatzal surface layer. The 6.4 keV spectra obtained on Adirondack Class rocks, on laboratory samples, and in Monte Carlo calculations show an apparent olivine enrichment which is not related to any observable surface layer

Subsurface Weathering of Rocks and Soils at Gusev Crater

Data collected by the Mars Exploration Rover (MER) Spirit at Gusev Crater suggest that enhanced weathering of rocks and soils occurs beneath the immediate surface. We suggest that this alteration occurs over geological timescales under present climatic conditions and is a result of diurnal condensation of thin-films of water on subsurface materials. Additional information is included in the original extended abstract

Application of 57Fe Mössbauer spectroscopy as a tool for mining exploration of bornite (Cu5FeS4) copper ore

Nuclear resonance methods, including Mössbauer spectroscopy, are considered as unique techniques suitable for remote on-line mineralogical analysis. The employment of these methods provides potentially significant commercial benefits for mining industry. As applied to copper sulfide ores, Mössbauer spectroscopy method is suitable for the analysis noted. Bornite (formally Cu5FeS4) is a significant part of copper ore and identification of its properties is important for economic exploitation of commercial copper ore deposits. A series of natural bornite samples was studied by 57Fe Mössbauer spectroscopy. Two aspects were considered: reexamination of 57Fe Mössbauer properties of natural bornite samples and their stability irrespective of origin and potential use of miniaturized Mössbauer spectrometers MIMOS II for in-situ bornite identification. The results obtained show a number of potential benefits of introducing the available portative Mössbauer equipment into the mining industry for express mineralogical analysis. In addition, results of some preliminary 63,65Cu nuclear quadrupole resonance (NQR) studies of bornite are reported and their merits with Mössbauer techniques for bornite detection discussed

Athena MIMOS II Mossbauer spectrometer investigation

Mössbauer spectroscopy is a powerful tool for quantitative mineralogical analysis of Fe-bearing materials. The miniature Mössbauer spectrometer MIMOS II is a component of the Athena science payload launched to Mars in 2003 on both Mars Exploration Rover missions. The instrument has two major components: (1) a rover-based electronics board that contains power supplies, a dedicated central processing unit, memory, and associated support electronics and (2) a sensor head that is mounted at the end of the instrument deployment device (IDD) for placement of the instrument in physical contact with soil and rock. The velocity transducer operates at a nominal frequency of 25 Hz and is equipped with two 57Co/Rh Mössbauer sources. The reference source (5 mCi landed intensity), reference target (alpha-Fe2O3 plus alpha-Fe0), and PIN-diode detector are configured in transmission geometry and are internal to the instrument and used for its calibration. The analysis Mössbauer source (150 mCi landed intensity) irradiates Martian surface materials with a beam diameter of 1.4 cm. The backscatter radiation is measured by four PIN-diode detectors. Physical contact with surface materials is sensed with a switch-activated contact plate. The contact plate and reference target are instrumented with temperature sensors. Assuming 18% Fe for Martian surface materials, experiment time is 6–12 hours during the night for quality spectra (i.e., good counting statistics); 1–2 hours is sufficient to identify and quantify the most abundant Fe-bearing phases. Data stored internal to the instrument for selectable return to Earth include Mössbauer and pulse-height analysis spectra (512 and 256 channels, respectively) for each of the five detectors in up to 13 temperature intervals (65 Mössbauer spectra), engineering data for the velocity transducer, and temperature measurements. The total data volume is 150 kB. The mass and power consumption are 500 g (400 g for the sensor head) and 2 W, respectively. The scientific measurement objectives of the Mössbauer investigation are to obtain for rock, soil, and dust (1) the mineralogical identification of iron-bearing phases (e.g., oxides, silicates, sulfides, sulfates, and carbonates), (2) the quantitative measurement of the distribution of iron among these iron-bearing phases (e.g., the relative proportions of iron in olivine, pyroxenes, ilmenite, and magnetite in a basalt), (3) the quantitative measurement of the distribution of iron among its oxidation states (e.g., Fe2+, Fe3+, and Fe6+), and (4) the characterization of the size distribution of magnetic particles. Special geologic targets of the Mössbauer investigation are dust collected by the Athena magnets and interior rock and soil surfaces exposed by the Athena Rock Abrasion Tool and by trenching with rover wheels

Application of 57Fe Mössbauer spectroscopy as a tool for mining exploration of bornite (Cu5FeS4) copper ore

Nuclear resonance methods, including Mössbauer spectroscopy,are considered as unique techniques suitable for remote on-line mineralogical analysis. The employment of these methods provides potentially significant commercial benefits for mining industry. As applied to copper sulfide ores, Mössbauer spectroscopy method is suitable for the analysis noted. Bornite (formally Cu5FeS4) is a significant part of copper ore and identification of its properties is important for economic exploitation of commercial copper ore deposits. A series of natural bornite samples was studied by 57Fe Mössbauer spectroscopy. Two aspects were considered: reexamination of 57Fe Mössbauer properties of natural bornite samples and their stability irrespective of origin and potential use of miniaturized Mössbauer spectrometers MIMOS II for in-situ bornite identification. The results obtained show a number of potential benefits of introducing the available portative Mössbauer equipment into the mining industry for express mineralogical analysis. In addition, results of some preliminary 63,65Cu nuclear quadrupole resonance (NQR) studies of bornite are reported and their merits with Mössbauer techniques for bornite detection discussed. © 2013 Springer Science+Business Media Dordrecht

Mineralogy and chemistry of cobbles at Meridiani Planum, Mars, investigated by the Mars Exploration Rover Opportunity

Numerous loose rocks with dimensions of a few centimeters to tens of centimeters and with no obvious physical relationship to outcrop rocks have been observed along the traverse of the Mars Exploration Rover Opportunity. To date, about a dozen of these rocks have been analyzed with Opportunity’s contact instruments, providing information about elemental chemistry (Alpha Particle X‐ray Spectrometer), iron mineralogy and oxidation states (Mössbauer Spectrometer) and texture (Microscopic Imager). These “cobbles” appear to be impact related, and three distinct groups can be identified on the basis of chemistry and mineralogy. The first group comprises bright fragments of the sulfate‐rich bedrock that are compositionally and texturally indistinguishable from outcrop rocks. All other cobbles are dark and are divided into two groups, referred to as the “Barberton group” and the “Arkansas group,” after the first specimen of each that was encountered by Opportunity. Barberton group cobbles are interpreted as meteorites with an overall chemistry and mineralogy consistent with a mesosiderite silicate clast composition. Arkansas group cobbles appear to be related to Meridiani outcrop and contain an additional basaltic component. They have brecciated textures, pointing to an impact‐related origin during which local bedrock and basaltic material were mixed

In-Situ and Experimental Evidence for Acidic Weathering of Rocks and Soils on Mars

Experimental data for alteration of synthetic Martian basalts at pH=0-1 indicate that chemical fractionations at low pH are vastly different from those observed during terrestrial weathering. Rock analyses from Gusev crater are well described by the relationships apparent from low pH experimental alteration data. A model for rock surface alteration is developed which indicates that a leached alteration zone is present on rock surfaces at Gusev. This zone is not chemically fractionated to a large degree from the underlying rock interior, indicating that the rock surface alteration process has occurred at low fluid-to-rock ratio. The geochemistry of natural rock surfaces analyzed by APXS is consistent with a mixture between adhering soil/dust and the leached alteration zone. The chemistry of rock surfaces analyzed after brushing with the RAT is largely representative of the leached alteration zone. The chemistry of rock surfaces analyzed after grinding with the RAT is largely representative of the interior of the rock, relatively unaffected by the alteration process occurring at the rock surface. Elemental measurements from the Spirit, Opportunity, Pathfinder and Viking 1 landing sites indicate that soil chemistry from widely separated locations is consistent with the low-pH, low fluid to rock ratio alteration relationships developed for Gusev rocks. Soils are affected principally by mobility of FeO and MgO, consistent with alteration of olivine-bearing basalt and subsequent precipitation of FeO and MgO bearing secondary minerals as the primary control on soil geochemistry

Mossbauer mineralogy of rock, soil, and dust at Meridiani Planum, Mars: Opportunity's journey across sulfate-rich outcrop, basaltic sand and dust, and hematite lag deposits

The Mössbauer (MB) spectrometer on Opportunity measured the Fe oxidation state, identified Fe-bearing phases, and measured relative abundances of Fe among those phases at Meridiani Planum, Mars. Eight Fe-bearing phases were identified: jarosite (K,Na,H3O)(Fe,Al)(OH)6(SO4)2, hematite, olivine, pyroxene, magnetite, nanophase ferric oxides (npOx), an unassigned ferric phase, and metallic Fe (kamacite). Burns Formation outcrop rocks consist of hematite-rich spherules dispersed throughout S-rich rock that has nearly constant proportions of Fe3+ from jarosite, hematite, and npOx (29%, 36%, and 20% of total Fe). The high oxidation state of the S-rich rock (Fe3+/FeT ~ 0.9) implies that S is present as the sulfate anion. Jarosite is mineralogical evidence for aqueous processes under acid-sulfate conditions because it has structural hydroxide and sulfate and it forms at low pH. Hematite-rich spherules, eroded from the outcrop, and their fragments are concentrated as hematite-rich soils (lag deposits) on ripple crests (up to 68% of total Fe from hematite). Olivine, pyroxene, and magnetite are primarily associated with basaltic soils and are present as thin and locally discontinuous cover over outcrop rocks, commonly forming aeolian bedforms. Basaltic soils are more reduced (Fe3+/FeT ~ 0.2–0.4), with the fine-grained and bright aeolian deposits being the most oxidized. Average proportions of total Fe from olivine, pyroxene, npOx, magnetite, and hematite are 33%, 38%, 18%, 6%, and 4%, respectively. TheMB parameters of outcrop npOx and basaltic-soil npOx are different, but it is not possible to infer mineralogical information beyond octahedrally coordinated Fe3+. Basaltic soils at Meridiani Planum and Gusev crater have similar Fe-mineralogical compositions.Additonal co-authors: P Gütlich, E Kankeleit, T McCoy, DW Mittlefehldt, F Renz, ME Schmidt, B Zubkov, SW Squyres, RE Arvidso

Geochemical and mineralogical indicators for aqueous processes in the Columbia Hills of Gusev crater, Mars

Water played a major role in the formation and alteration of rocks and soils in the Columbia Hills. The extent of alteration ranges from moderate to extensive. Five distinct rock compositional classes were identified; the order for degree of alteration is Watchtower = Clovis >Wishstone = Peace > Backstay. The rover’s wheels uncovered one unusual soil (Paso Robles) that is the most S-rich material encountered. Clovis class rocks have compositions similar to Gusev plains soil but with higher Mg, Cl, and Br and lower Ca and Zn; Watchtower and Wishstone classes have high Al, Ti, and P and low Cr and Ni; Peace has high Mg and S and low Al, Na, and K; Backstay basalts have high Na and K compared to plains Adirondack basalts; and Paso Robles soil has high S and P. Some rocks are corundum-normative, indicating that their primary compositions were changed by loss and/or gain of rock-forming elements. Clovis materials consist of magnetite, nanophase ferric-oxides (npOx), hematite, goethite, Ca-phosphates, Ca- and Mg-sulfates, pyroxene, and secondary aluminosilicates. Wishstone and Watchtower rocks consist of Fe-oxides/oxyhydroxides, ilmenite, Ca-phosphate, pyroxene, feldspar, Mg-sulfates, and secondary aluminosilicates. Peace consists of magnetite, npOx, Mg- and Ca-sulfates, pyroxene, olivine, feldspar, apatite, halides, and secondary aluminosilicates. Paso Robles consists of Fe3+-, Mg-, Ca-, and other sulfates, Ca-phosphates, hematite, halite, allophane, and amorphous silica. Columbia Hills outcrops and rocks may have formed by the aqueous alteration of basaltic rocks, volcaniclastic materials, and/or impact ejecta by solutions that were rich in acid-volatile elements