Fresh fracture surfaces of the martian meteorite ALH84001 contain abundant polycyclic aromatic hydrocarbons (PAHs). These fresh fracture surfaces also display carbonate globules. Contamination studies suggest that the PAHs are indigenous to the meteorite. High-resolution scanning and transmission electron microscopy study of surface textures and internal structures of selected carbonate globules show that the globules contain fine-grained, secondary phases of single-domain magnetite and Fe-sulfides. The carbonate globules are similar in texture and size to some terrestrial bacterially induced carbonate precipitates. Although inorganic formation is possible, formation of the globules by biogenic processes could explain many of the observed features, including the PAHs. The PAHs, the carbonate globules, and their associated secondary mineral phases and textures could thus be fossil remains of a past martian biota.

Spectral and other physicochemical properties were determined for a suite of submicron powders of hematite (alpha-Fe2O3), maghemite (gamma-Fe2O3), magnetite (Fe3O4), goethite (alpha-FeOOH), and lepidocrocite (gamma-FeOOH). The spectral reflectivity measurements were made between 0.35 and 2.20 micrograms over the temperature interval between about -110 degrees and 20 degrees C. Other physicochemical properties determined were mean particle diameter, particle shape, chemical composition, crystallographic phase, magnetic properties, and Mossbauer properties. Only the magnetite powders have significant departures from the stoichiometric phase; they are actually cation-deficient magnetites having down to about 18.0 wt % FeO as compared with 31.0 wt % FeO for stoichiometric magnetite. A structured absorption edge due to crystal field transitions and extending from weak absorption in the near-IR to intense absorption in the near-UV is characteristic of the ferric oxides and oxyhydroxides and is responsible for their intense color. Particularly for hematite, the number and position of the spectral features are consistent with significant splitting of the degenerate cubic levels by noncubic components of the crystal field. The position of the crystal-field band at lowest energy, assigned to the envelope of the components of the split cubic 4T1 level, is near 0.86, 0.91, 0.92, and 0.98 microgram at room temperature for hematite, goethite, maghemite, and lepidocrocite, respectively. Comparison with Mossbauer data suggests covalent character increases sequentially through the aforementioned series. The positions of the spectra features are relatively independent of temperature down to about -110 degrees C. The maximum shifts observed were on the order of about 0.02 microgram shortward for the ferric oxyhydroxides. Variations in the magnitude of the reflectivity of the hematite powders as a function of mean particle diameter are consistent with scattering theory. The absorption strength of the crystal-field bands increases with increasing mean particle diameter over the range 0.1-0.8 micrometer; visually this corresponds to a change in color from orange to deep purple. The position of the split cubic 4T1 band shifts longward by about 0.02 micrometer with decreasing mean particle diameter over the same range; this trend is consistent with wavelength-dependent scattering. The cation-deficient magnetite powders are very strong absorbers throughout the near-UV, visible and near-IR; their spectral properties are independent of temperature between about -110 and 20 degrees C.

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Allan Hills (ALH) 84001 is the most recently recognized member of a suite of meteorites--the SNCs--that almost certainly originated on Mars. Several factors distinguish ALH84001 from the other SNC meteorites. Preliminary studies suggest that it may be older than other martian meteorites. Moreover, it contains abundant, zoned domains of calcium-iron-magnesium carbonate that are indigenous to the sample and thus may hold important clues regarding near-surface processes on Mars and the evolution of the martian atmosphere. We report here analyses of the carbon and oxygen stable-isotope compositions of the carbonates that place constraints on their formation conditions. Our results imply the presence of at least two chemically distinct carbonates--one Ca,Fe-rich, the other Mg-rich--that are enriched in 13C relative to terrestrial carbonates (delta 13C approximately +41/1000), consistent with martian atmospheric CO2 as the carbon source. The oxygen isotope compositions of the carbonates indicate that they precipitated from a low-temperature fluid in the martian crust. Combined with textural and bulk geochemical considerations, the isotope data suggest that carbonate deposition took place in an open-system environment in which the ambient temperature fluctuated.

Crystals of halite and sylvite within the Monahans (1998) H5 chondrite contain aqueous fluid inclusions. The fluids are dominantly sodium chloride-potassium chloride brines, but they also contain divalent cations such as iron, magnesium, or calcium. Two possible origins for the brines are indigenous fluids flowing within the asteroid and exogenous fluids delivered into the asteroid surface from a salt-containing icy object.

The martian meteorite ALH84001 contains small, disk-shaped concretions of carbonate with concentric chemical and mineralogical zonation. Oxygen isotope compositions of these concretions, measured by ion microprobe, range from delta18O = +9.5 to +20.5 per thousand. Most of the core of one concretion is homogeneous (16.7 +/- 1.2 per thousand) and over 5 per thousand higher in delta18O than a second concretion. Orthopyroxene that hosts the secondary carbonates is isotopically homogeneous (delta18O = 4.6 +/- 1.2 per thousand). Secondary SiO2 has delta18O = 20.4 per thousand. Carbon isotope ratios measured from the core of one concretion average delta13C = 46 +/- 8 per thousand, consistent with formation on Mars. The isotopic variations and mineral compositions offer no evidence for high temperature (>650 degrees C) carbonate precipitation and suggest non-equilibrium processes at low temperatures (< approximately 300 degrees C).

The Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks. These carbonate disks are believed to have precipitated 3.9 Ga ago at beginning of the Noachian epoch on Mars during which both the oldest extant Martian surfaces were formed, and perhaps the earliest global oceans. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe 3 O 4 ) with unusual chemical and physical properties, whose origins have become the source of considerable debate. One group of hypotheses argues that these magnetites are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of magnetite and carbonate may be unrelated; that is, from the perspective of the carbonate the magnetite is allochthonous. For example, the magnetites might have already been present in the aqueous fluids from which the carbonates were believed to have been deposited. We have sought to resolve between these hypotheses through the detailed characterization of the compositional and structural relationships of the carbonate disks and associated magnetites with the orthopyroxene matrix in which they are embedded. Extensive use of focused ion beam milling techniques has been utilized for sample preparation. We then compared our observations with those from experimental thermal decomposition studies of sideritic carbonates under a range of plausible geological heating scenarios. We conclude that the vast majority of the nanocrystal magnetites present in the carbonate disks could not have formed by any of the currently proposed thermal decomposition scenarios. Instead, we find there is considerable evidence in support of an alternative allochthonous origin for the magnetite unrelated to any shock or thermal processing of the carbonates.

McKay et al. [(1996)Science 273, 924 -930] suggested that carbonate globules in the meteorite ALH84001 contained the fossil remains of Martian microbes. We have characterized a subpopulation of magnetite (Fe3O4) crystals present in abundance within the Fe-rich rims of these carbonate globules. We find these Martian magnetites to be both chemically and physically identical to terrestrial, biogenically precipitated, intracellular magnetites produced by magnetotactic bacteria strain MV-1. Specifically, both magnetite populations are single-domain and chemically pure, and exhibit a unique crystal habit we describe as truncated hexaoctahedral. There are no known reports of inorganic processes to explain the observation of truncated hexa-octahedral magnetites in a terrestrial sample. In bacteria strain MV-1 their presence is therefore likely a product of Natural Selection. Unless there is an unknown and unexplained inorganic process on Mars that is conspicuously absent on the Earth and forms truncated hexaoctahedral magnetites, we suggest that these magnetite crystals in the Martian meteorite ALH84001 were likely produced by a biogenic process. As such, these crystals are interpreted as Martian magnetofossils and constitute evidence of the oldest life yet found. W e report here the presence of single-domain, chemically pure, truncated hexa-octahedral magnetite crystals in terrestrial samples and Martian meteorite ALH84001. We suggest that the truncated hexa-octahedral magnetite crystals in the Martian meteorite ALH84001 were likely formed by a biogenic process. These magnetite crystals are embedded in Ϸ3.91 (Ϯ0.05)-Ga-old carbonate globules (1) that fill cracks and pore space in the 4.5-Ga-old Martian meteorite ALH84001. These truncated hexa-octahedral magnetite crystals are identical to those produced intracellularly by the marine magnetotactic bacterium strain MV-1 (2-7); natural selection has optimized the magnetic moment of MV-1 magnetite particles (2,(8)(9)(10)(11)(12). There is no known natural terrestrial inorganic mechanism that can explain the observation of truncated hexa-octahedral magnetite crystals associated with MV-1. Therefore, unless there is an unknown inorganic process on Mars, which seems to be absent on the Earth, we suggest that ALH84001 truncated hexaoctahedral magnetites formed by a similar mechanism to their terrestrial biogenic counterparts. As such, these crystals are interpreted as Martian magnetofossils and they constitute evidence of the oldest life yet found. In support of this, we note that early Mars likely had free-standing bodies of liquid water (13,14), and both organic (15) and inorganic carbon and energy (e.g., atmospheric CO 2 13 ) sources. Furthermore, early Mars also likely possessed a substantial planetary magnetic field (16), which would have been sufficient to support the evolution and growth of magnetotactic bacteria. Characteristics of Biogenic MagnetiteMagnetotactic bacteria produce well ordered membranebounded intracellular crystals of magnetite (Fe 3 O 4 ) and͞or greigi...