Effect of aluminum substitution on the reflectance spectra of hematite

Hematite and aluminous hematite were synthesized and the diffuse reflectance spectra were recorded for the region between 0.35 and 1.20 microns. Results show that the near-IR based minimum for the aluminous hematite is shifted longward by about 0.02 microns and is much more shallow. Also, the aluminous specimen is considerably more reflective shortward of approximately 0.55 microns where the ferritic specimen is strongly absorbing. This is noteworthy since the visible slope and the red shoulder are often used in the construction of false color and band ratio images

Terrestrial impact melts as analogues for the hematization of Martian surface materials

Visible and near-IR reflectivity and Mossbauer data were obtained on powders of hydrothermally-altered impact melt sheets from West Clearwater Lake, Manicouagan, and Ries (Polsingen) impact structures. The data support previous interpretations that Martian bright regions spectra can be interpreted by a ferric-bearing phase that has a relatively featureless absorption edge together with some well-crystalline (bulk) hematite to account for the 860 nm hematite band. The data also show that bands at wavelengths longer than 900 nm, which are characteristic of Martian dark regions, occur when both hematite and pyroxene are present. It thus follows that hematization of Mars can be attributed, at least in part, to hydrothermal alterations of impact melt sheets. Impact heating could also form bulk-Hm from nanophase ferric oxides

Thermal and Evolved Gas Analysis of Geologic Samples Containing Organic Materials: Implications for the 2007 Mars Phoenix Scout Mission

The Thermal and Evolved Gas Analyzer (TEGA) instrument scheduled to fly onboard the 2007 Mars Phoenix Scout Mission will perform differential scanning calorimetry (DSC) and evolved gas analysis (EGA) of soil samples and ice collected from the surface and subsurface at a northern landing site on Mars. We have been developing a sample characterization data library using a laboratory DSC integrated with a quadrupole mass spectrometer to support the interpretations of TEGA data returned during the mission. The laboratory TEGA test-bed instrument has been modified to operate under conditions similar to TEGA, i.e., reduced pressure (e.g., 100 torr) and reduced carrier gas flow rates. We have previously developed a TEGA data library for a variety of volatile-bearing mineral phases, including Fe-oxyhydroxides, phyllosilicates, carbonates, and sulfates. Here we examine the thermal and evolved gas properties of samples that contain organics. One of the primary objectives of the Phoenix Scout Mission is to search for habitable zones by assessing organic or biologically interesting materials in icy soil. Nitrogen is currently the carrier gas that will be used for TEGA. In this study, we examine two possible modes of detecting organics in geologic samples; i.e., pyrolysis using N2 as the carrier gas and combustion using O2 as the carrier gas

Hematite formed from pyroxene on Mars by meteoritic impact

In earlier work, we showed using Mossbauer data that the mineralogy of iron-bearing phases in impact melt rocks from Manicouagan Crater (Quebec, Canada) is to a first approximation hematite and pyroxene. The visible and near-IR reflectivity data for these impact melt rocks show a continuous trend in band position from approximately 850 to approximately 1000 nm, which corresponds to the positions for the hematite and pyroxene endmembers, respectively. The oxidation is thought to occur shortly after the impact when oxidizing vapors and/or solutions reacted with the impact melt which was below its solidus temperature but still relatively hot. The reflectance data have important implications for Mars because band positions which occur between approximately 850 and 1000 nm bands observed for Mars can be attributed to hematite-pyroxene assemblages and not necessarily to different ferric mineralogy. Because oxidation of impact melt rocks at Manicouagan is thought to occur subsolidus, precursors for the hematite include oxides such as magnetite and ilmenite and silicates such as pyroxene and olivine. To determine if the Manicouagan impact-melt rocks are related to each other by simple thermal subsolidus oxidation, we calcined in air a relatively unoxidized Manicouagan impact-melt rock (MAN-74-608A). Previous work has shown that np-Hm (nanophase hematite) particles can be derived by calcination of iron-bearing silicates

Nanophase Magnetite and Pyrrhotite in ALH84001 Martian Meteorite: Evidence for an Abiotic Origin

The nanophase magnetite crystals in the black rims of pancake-shaped carbonate globules of the Martian meteorite ALH84001 have been studied extensively because of the claim by McKay et al.that they are biogenic in origin. A subpopulation of these magnetite crystals are reported to conform to a unique elongated shape called "truncated hexa-octahedral" or "THO" by Thomas-Keprta et al. They claim these THO magnetite crystals can only be produced by living bacteria thus forming a biomarker in the meteorite. In contrast, thermal decomposition of Fe-rich carbonate has been suggested as an alternate hypothesis for the elongated magnetite formation in ALH84001 carbonates. The experimental and observational evidence for the inorganic formation of nanophase magnetite and pyrrhotite in ALH84001 by decomposition of Fe-rich carbonate in the presence of pyrite are provided

Thermal and Evolved Gas Analysis of Calcite Under Reduced Operating Pressures: Implications for the 2011 MSL Sample Analysis at Mars (SAM) Instrument

The Mars Science Laboratory (MSL) is scheduled for launch in 2011. The science objectives for MSL are to assess the past or present biological potential, to characterize the geology, and to investigate other planetary processes that influence habitability at the landing site. The Sample Analysis at Mars (SAM) is a key instrument on the MSL payload that will explore the potential habitability at the landing site [1]. In addition to searching for organic compounds, SAM will have the capability to characterized evolved gases as a function of increasing temperature and provide information on the mineralogy of volatile-bearing phases such as carbonates, sulfates, phyllosilicates, and Fe-oxyhydroxides. The operating conditions in SAM ovens will be maintained at 30 mb pressure with a He carrier gas flowing at 1 sccm. We have previously characterized the thermal and evolved gas behaviors of volatile-bearing species under reduced pressure conditions that simulated operating conditions of the Thermal and Evolved Gas Analyzer (TEGA) that was onboard the 2007 Mars Phoenix Scout Mission [e.g., 2-8]. TEGA ovens operated at 12 mb pressure with a N2 carrier gas flowing at 0.04 sccm. Another key difference between SAM and TEGA is that TEGA was able to perform differential scanning calorimetry whereas SAM only has a pyrolysis oven. The operating conditions for TEGA and SAM have several key parameter differences including operating pressure (12 vs 30 mb), carrier gas (N2 vs. He), and carrier gas flow rate (0.04 vs 1 sccm). The objectives of this study are to characterize the thermal and evolved gas analysis of calcite under SAM operating conditions and then compare it to calcite thermal and evolved gas analysis under TEGA operating conditions

Lepidocrocite to Maghemite to Hematite: A way to have Magnetic and Hematitic Martian Soil

We examined decomposition products of lepidocrocite, which were produced by heating the phase in air at temperatures up to 525 C for 3 and 300 hr, by XRD, TEM, magnetic methods, and reflectance spectroscopy (visible and near-IR). Single-crystal lepidocrocite particles dehydroxilated to polycrystalline particles of disordered maghemite which subsequently transformed to polycrystalline particles of hematite. Essentially pure maghemite was obtained at 265 and 223 C for the 3 and 300 hr heating experiments, respectively. Its saturation magnetization (J(sub s)) and mass specific susceptibility are approximately 50 A(sq m)/kg and approximately 40 cubic micrometers/kg, respectively. Because hematite is spectrally dominant, spectrally-hematitic samples (i.e., characterized bv a minimum near 860 nm and a maximum near 750 nm) could also be strongly magnetic (J(sub s) up to approximately 30 A(sq m)/kg) from the masked maghemite component. TEM analyses showed that individual particles are polycrystalline with respect to both maghemite and hematite. The spectrally-hematitic and magnetic Mh+Hm particles can satisfy the spectral and magnetic constraints for Martian surface materials over a wide range of values of Mh/(Mh+Hm) and as either pure oxide powders or (within limits) as components of multiphase particles. These experiments are consistent with lepidocrocite as the precursor of Mh+Hm assemblages on Mars, but other phases (e.g., magnetite) that decompose to Mh and Hm are also possible precursors. Simulations done with a copy of the Mars Pathfinder Magnet Array showed that spectrally hematitic Mh+Hm powders having J(sub s) equal to 20.6 A(sq m)/kg adhered to all five magnets

High Resolution Transmission Electron Microscopy (HRTEM) of nanophase ferric oxides

Iron oxide minerals are the prime candidates for Fe(III) signatures in remotely sensed Martian surface spectra. Magnetic, Mossbauer, and reflectance spectroscopy have been carried out in the laboratory in order to understand the mineralogical nature of Martian analog ferric oxide minerals of submicron or nanometer size range. Out of the iron oxide minerals studied, nanometer sized ferric oxides are promising candidates for possible Martian spectral analogs. 'Nanophase ferric oxide (np-Ox)' is a generic term for ferric oxide/oxihydroxide particles having nanoscale (less than 10 nm) particle dimensions. Ferrihydrite, superparamagnetic particles of hematite, maghemite and goethite, and nanometer sized particles of inherently paramagnetic lepidocrocite are all examples of nanophase ferric oxides. np-Ox particles in general do not give X-ray diffraction (XRD) patterns with well defined peaks and would often be classified as X-ray amorphous. Therefore, different np-Oxs preparations should be characterized using a more sensitive technique e.g., high resolution transmission electron microscopy (HRTEM). The purpose of this study is to report the particle size, morphology and crystalline order, of five np-Ox samples by HRTEM imaging and electron diffraction (ED)

Formation of "Chemically Pure" Magnetite from Mg-Fe-Carbonates Implications for the Exclusively Inorganic Origin of Magnetite and Sulfides in Martian Meteorite ALH84001

Magnetite and sulfides in the black rims of carbonate globules in Martian meteorite ALH84001 have been studied extensively because of the claim by McKay et al. that they are biogenic in origin. However, exclusively inorganic (abiotic) processes are able to account for the occurrence of carbonate-sulfide-magnetite assemblages in the meteorite. We have previously precipitated chemically zoned and sulfide-bearing carbonate globules analogous to those in ALH84001 (at less than or equal to 150 C) from multiple fluxes of variable-composition Ca-Mg-Fe-CO2-S-H2O solutions. Brief heating of precipitated globules to approx. 470 C produced magnetite and pyrrhotite within the globules by thermal decomposition of siderite and pyrite, respectively. We have also shown that morphology of magnetite formed by inorganic thermal decomposition of Fe-rich carbonate is similar to the morphology of so-called biogenic magnetite in the carbonate globules of ALH84001. Magnetite crystals in the rims of carbonate globules in ALH84001 are chemically pure [Note: "Chemically pure" is defined here as magnetite with Mg at levels comparable or lower than Mg detected by [8] in ALH84001 magnetite]. A debate continues on whether or not chemically pure magnetite can form by the thermal decomposition of mixed Mg-Fe-carbonates that have formed under abiotic conditions. Thomas-Keprta et al. argue that it is not possible to form Mg-free magnetite from Mg-Fe-carbonate based on thermodynamic data. We previously suggested that chemically pure magnetite could form by the thermal decomposition of relatively pure siderite in the outer rims of the globules. Mg-Fe-carbonates may also thermally decompose under conditions conducive for formation of chemically pure magnetite. In this paper we show through laboratory experiments that chemically pure magnetite can form by an inorganic process from mixed Mg-Fe-carbonates