D. C. Golden

Mineralogy, composition, and alteration of Mars Pathfinder rocks and soils: Evidence from multispectral, elemental, and magnetic data on terrestrial analogue, SNC meteorite, and Pathfinder samples

Major element, multispectral, and magnetic properties data were obtained at Ares Vallis during the Mars Pathfinder mission. To understand the compositional, mineralogical, and process implications of these data, we obtained major element, mineralogical, and magnetic data for well-crystalline and nanophase ferric minerals, terrestrial analogue samples with known geologic context, and SNC meteorites. Analogue samples include unaltered, palagonitic, and sulfatetic tephra from Mauna Kea Volcano (hydrolytic and acid-sulfate alteration), steam vent material from Kilauea Volcano (hydrolytic alteration), and impactites from Meteor Crater (relithification). Salient results for Mars Pathfinder include: (1) Band depths BD530b and BD600 and the reflectivity ratio R800/R750 are consistent with the dominant ferric mineral being nanophase ferric oxide associated with an unknown amount of H2O and occurring in composite particles along with subordinate amounts of other ferric minerals. Hematite and hematite plus nanophase goethite are most consistent with the data, but maghemite, akaganeite, schwertmannite, and nanophase lepidocrocite are also possible interpretations. Ferric oxides that are consistently not favored by the data as sole alteration products are jarosites and well-crystalline goethite and lepidocrocite. (2) The strength of the ferric adsorption edge (R750/R445) implies the Fe3+/Fe2+ values for Pathfinder rock and soil are within the ranges 0.7–3 and 3–20, respectively. (3) Ferrous silicates are indicated for subsets of Pathfinder rocks and soils. One subset has a band minimum near 930 nm that can attributed to low-Ca pyroxene. Alternatively, the band could be a second manifestation of certain ferric oxides, including nanophase goethite, maghemite, akaganeite, and schwertmannite. Another subset has a negative spectral slope from ∼800 to 1005 nm which could result from the high-energy wing of a high-Ca pyroxene and/or olivine band, a mixture of bright and dark materials, and, for rocks, thin coatings of bright dust on dark rocks. (4) Chemical data on Pathfinder rocks and soils are consistent with two-component mixtures between an “andesitic” rock with low MgO and SO3 concentrations (soil-free rock) and a global, basaltic soil with high MgO and SO3 concentrations (rock-free soil). Pathfinder rock-free soil can be modeled as a chemical mixture of SNC meteorites and the Pathfinder soil-free rock. (5) Pathfinder soil cannot be obtained by chemical alteration of Pathfinder rocks by any of the hydrolytic and acid-sulfate alteration processes we studied. Presumably, global mixing has obscured and possibly erased the elemental signatures of chemical alteration. (6) The strongly magnetic phase in palagonitic and sulfatetic tephra is titanomagnetite and possibly its oxidation product titanomaghemite (Fe-Ti spinels). The saturation magnetization of the tephra samples (0.5–2.0 Am2/kg) is at or below the low end of the range inferred for Martian dust (4±2 Am2/kg), implying that lithogenic Fe-Ti spinels are a possible candidate for the Martian strongly magnetic phase. (7) The predominantly palagonitic spectral signature and magnetic nature of Martian soil and dust are consistent with glassy precursors with imbedded Fe-Ti spinel particles. Comparison with lunar glass production rates suggests that production of sufficient quantities of glassy materials on Mars by volcanic and impact processes is sufficient to account for these observations.

Identification of carbonate-rich outcrops on Mars by the Spirit rover.

Ancient Carbonate Minerals on Mars The historical presence of liquid water on Mars together with a CO 2-rich atmosphere should have resulted in the accumulation of large deposits of carbonate minerals. Yet, evidence for the presence of carbonates on the surface of Mars has been scarce. Using data collected by the Mars Exploration Rover, Spirit, Morris et al. (p. 421, published online 3 June; see the Perspective by Harvey) now present evidence for carbonate-rich outcrops in the Comanche outcrops within the Gusev crater. The carbonate is a major outcrop component and may have formed in the Noachian era (∼4 billion years ago) by precipitation from hydrothermal solutions that passed through buried carbonate deposits. Thus, it is likely that extensive aqueous activity under neutral pH conditions did occur on Mars. Substantial carbonate concentration in martian outcrops implies extensive aqueous activity in the past. Decades of speculation about a warmer, wetter Mars climate in the planet’s first billion years postulate a denser CO2-rich atmosphere than at present. Such an atmosphere should have led to the formation of outcrops rich in carbonate minerals, for which evidence has been sparse. Using the Mars Exploration Rover Spirit, we have now identified outcrops rich in magnesium-iron carbonate (16 to 34 weight percent) in the Columbia Hills of Gusev crater. Its composition approximates the average composition of the carbonate globules in martian meteorite ALH 84001. The Gusev carbonate probably precipitated from carbonate-bearing solutions under hydrothermal conditions at near-neutral pH in association with volcanic activity during the Noachian era.

A simple inorganic process for formation of carbonates, magnetite, and sulfides in Martian meteorite ALH84001

Abstract We show experimental evidence that the zoned Mg-Fe-Ca carbonates, magnetite, and Fe sulfides in Martian meteorite ALH84001 may have formed by simple, inorganic processes. Chemically zoned carbonate globules and Fe sulfides were rapidly precipitated under low-temperature (150 °C), hydrothermal, and non-equilibrium conditions from multiple fluxes of Ca-Mg-Fe-CO2-S-H2O solutions that have different compositions. Chemically pure, single-domain, defect-free magnetite crystals were formed by subsequent decomposition of previously precipitated Fe-rich carbonates by brief heating to 470 °C. The sequence of hydrothermal precipitation of carbonates from flowing CO2-rich waters followed by a transient thermal event provides an inorganic explanation for the formation of the carbonate globules, magnetite, and Fe sulfides in ALH84001. In separate experiments, kinetically controlled 13C enrichment was observed in synthetic carbonates that is similar in magnitude to the 13C enrichment in ALH84001 carbonates.

Phyllosilicate-poor palagonitic dust from Mauna Kea Volcano (Hawaii): A mineralogical analogue for magnetic Martian dust?

The mineralogical and elemental composition of dust size fractions (<2 and <5 μm) of eight samples of phyllosilicate-poor palagonitic tephra from the upper slopes of Mauna Kea Volcano (Hawaii) were studied by X-ray diffraction (XRD), X-ray fluorescence (XRF), visible and near-IR reflectance spectroscopy, Mossbauer spectroscopy, magnetic properties methods, and transmission electron microscopy (TEM). The palagonitic dust samples are spectral analogues of Martian bright regions at visible and near-IR wavelengths. The crystalline phases in the palagonitic dust are, in variable proportions, plagioclase feldspar, Ti-containing magnetite, minor pyroxene, and trace hematite. No basal reflections resulting from crystalline phyllosilicates were detected in XRD data. Weak, broad XRD peaks corresponding to X-ray amorphous phases (allophane, nanophase ferric oxide (possibly ferrihydrite), and, for two samples, hisingerite) were detected as oxidative alteration products of the glass; residual unaltered glass was also present. Mossbauer spectroscopy showed that the iron-bearing phases are nanophase ferric oxide, magnetite/titanomagnetite, hematite, and minor glass and ferrous silicates. Direct observation by TEM showed that the crystalline and X-ray amorphous phases observed by XRD and Mossbauer are normally present together in composite particles and not normally present as discrete single-phase particles. Ti-bearing magnetite occurs predominantly as 5–150 nm particles embedded in noncrystalline matrix material and most likely formed by crystallization from silicate liquids under conditions of rapid cooling during eruption and deposition of glassy tephra and prior to palagonitization of glass. Rare spheroidal halloysite was observed in the two samples that also had XRD evidence for hisingerite. The saturation magnetization Js and low-field magnetic susceptibility for bulk dust range from 0.19 to 0.68 Am2/kg and 3.4×10−6 to 15.5×10−6 m3/kg at 293 K, respectively. Simulation of the Mars Pathfinder Magnet Array (MA) experiment was performed on Mauna Kea Volcano in areas with phyllosilicate-poor palagonitic dust and with copies of the Pathfinder MA. On the basis of the magnetic properties of dust collected by all five MA magnets and the observation that the Pathfinder MAs collected dust on the four strongest magnets, the value for the saturation magnetization of Martian dust collected in the MA experiments is revised downward from 4±2 Am2/kg to 2.5±1.5 Am2/kg. The revised value corresponds to 2.7±1.6 wt % magnetite if the magnetic mineral is magnetite (using Js = 92 Am2/kg for pure magnetite, Fe3O4) or to 5.0±3.0 to 3.4±2.0 wt % maghemite if the magnetic mineral is pure maghemite (using Js = 50 to 74 Am2/kg for pure maghemite, γ-Fe2O3). Comparison of the magnetic properties of bulk Mauna Kea palagonitic dust to those for dust collected by MA magnets shows that the MA magnets extracted (culled) a subset (25–34 wt %) of composite magnetic particles from bulk dust. The extent of culling of Martian dust is not well constrained. Because the Mauna Kea palagonitic dust satisfies the essential constraints of the Pathfinder magnetic properties experiment (composite and magnetic particles capable of being collected by five MA magnets), a working hypothesis for the strongly magnetic mineral present in Martian dust and soil is magnetite (possibly Ti-bearing) formed by rapid crystallization from silicate liquids having volcanic and/or impact origins. Subsequent palagonitization of the glass produces the nanophase ferric oxide phases that dominate the spectral properties of Martian bright regions at visible and near-IR wavelengths. Magnetic and phyllosilicate-poor palagonitic dust from Mauna Kea Volcano is thus a spectral and magnetic analogue for magnetic Martian dust.

Laboratory Simulated Acid-Sulfate Weathering of Basaltic Materials: Implications for Formation of Sulfates at Meridiani Planum and Gusev Crater, Mars

[1] Acid-sulfate weathering of basaltic materials is a candidate formation process for the sulfate-rich outcrops and rocks at the MER rover Opportunity and Spirit landing sites. To determine the style of acid-sulfate weathering on Mars, we weathered basaltic materials (olivine-rich glassy basaltic sand and plagioclase feldspar-rich basaltic tephra) in the laboratory under different oxidative, acid-sulfate conditions and characterized the alteration products. We investigated alteration by (1) sulfuric-acid vapor (acid fog), (2) three-step hydrothermal leaching treatment approximating an open system, and (3) single-step hydrothermal batch treatment approximating a closed system. In acid fog experiments, A1-, Fe-, and Ca-sulfates and amorphous silica formed from plagioclase-rich tephra, and Mg- and Ca-sulfates and amorphous silica formed from the olivine-rich sands. In three-step leaching experiments, only amorphous Si formed from the plagioclase-rich basaltic tephra, and jarosite, Mg-, and Ca-sulfates and amorphous silica formed from olivine-rich basaltic sand. Amorphous silica formed under single-step experiments for both starting materials. On the basis of our experiments, jarosite formation in Meridiani outcrop is potential evidence for an open system acid-sulfate weathering regime. Waters rich in sulfuric acid percolated through basaltic sediment, dissolving basaltic phases (e.g., olivine) and forming jarosite, other sulfates, and iron oxides. Aqueous alteration of outcrops and rocks on the West Spur of the Columbia Hills may have occurred when vapors rich in SO 2 from volcanic sources reacted with basaltic materials. Soluble ions from the host rock (e.g., olivine) reacted with S to form Ca-, Mg-, and other sulfates along with iron oxides and oxyhydroxides.

Evidence for exclusively inorganic formation of magnetite in Martian meteorite ALH84001

Abstract Magnetite crystals produced by terrestrial magnetotactic bacterium MV-1 are elongated on a [111] crystallographic axis, in a so-called “truncated hexa-octahedral” shape. This morphology has been proposed to constitute a biomarker (i.e., formed only in biogenic processes). A subpopulation of magnetite crystals associated with carbonate globules in Martian meteorite ALH84001 is reported to have this morphology, and the observation has been taken as evidence for biological activity on Mars. In this study, we present evidence for the exclusively inorganic origin of [111]-elongated magnetite crystals in ALH84001. We report three-dimensional (3-D) morphologies for ~1000 magnetite crystals extracted from: (1) thermal decomposition products of Fe-rich carbonate produced by inorganic hydrothermal precipitation in laboratory experiments; (2) carbonate globules in Martian meteorite ALH84001; and (3) cells of magnetotactic bacterial strain MV-1. The 3-D morphologies were derived by fitting 3-D shape models to two-dimensional bright-field transmission-electron microscope (TEM) images obtained at a series of viewing angles. The view down the {110} axes closest to the [111] elongation axis of magnetite crystals ([111]⋅{110} ≠ 0) provides a 2-D projection that uniquely discriminates among the three [111]-elongated magnetite morphologies found in these samples: [111]-elongated truncated hexaoctahedron ([111]-THO), [111]-elongated cubo-octahedron ([111]-ECO), and [111]-elongated simple octahedron ([111]-ESO). All [111]-elongated morphologies are present in the three types of sample, but in different proportions. In the ALH84001 Martian meteorite and in our inorganic laboratory products, the most common [111]-elongated magnetite crystal morphology is [111]-ECO. In contrast, the most common morphology for magnetotactic bacterial strain MV-1 is [111]-THO. These results show that: (1) the morphology of [111]-elongated magnetite crystals associated with the carbonate globules in Martian meteorite ALH84001 is replicated by an inorganic process; and (2) the most common crystal morphology for biogenic (MV-1) magnetite is distinctly different from that in both ALH84001 and our inorganic laboratory products. Therefore, [111]-elongated magnetite crystals in ALH84001 do not constitute, as previously claimed, a “robust biosignature” and, in fact, an exclusively inorganic origin for the magnetite is fully consistent with our results. Furthermore, the inorganic synthesis method, i.e., the thermal decomposition of hydrothermally precipitated Fe-rich carbonate, is a process analogue for formation of the magnetite on Mars. Namely, precipitation of carbonate globules from carbonate-rich hydrothermal solutions followed at some later time by a thermal pulse, perhaps in association with meteoritic impact or volcanic processes on the Martian surface

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR reflectivity, Mossbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to ∼15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250°C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration (Fe3+/Fetot) and ranged from ∼1000 nm (high-Ca pyroxene) to ∼850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900–920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the ∼850 and ∼1000 nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900–920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250°C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relatively high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from analyses of soil at the two Viking landing sites.

Mineralogy of three slightly palagonitized basaltic tephra samples from the summit of Mauna Kea, Hawaii

Certain palagonites from Hawaii are considered to be among the best analogs for Martian fines, based upon similar spectral properties. For this study, three distinctly colored layers were sampled from slightly palagonitized basaltic tephra just below the summit of Mauna Kea at 4145 m elevation. The mineralogy of size fractions of these samples was examined by diffuse reflectance (visible and near-IR) and far-IR spectroscopy, optical microscopy, X ray diffraction, Mossbauer spectroscopy, magnetic analysis, electron microprobe analysis (EMPA), and transmission and scanning electron microscopy. For the 20–1000 μm size fraction, sample HWMK11 (red) is essentially completely oxidized and has a hematite (Ti-hematite) pigment dispersed throughout the silicate matrix. The alteration is present throughout particle volumes, and only a trace amount of glass is present; no palagonitic rinds were detected. In addition to ferric Fe-Ti oxides, other phases detected were plagioclase feldspar and a trace of olivine. Sample HWMK12 (black) has the lowest proportion of ferric-bearing phases and is thus least weathered. It consists mostly of unaltered glass with embedded plagioclase and minor amounts of pyroxene, olivine, and Ti-magnetite. In some grains, a thin palagonitic rind is visible, indicating some surface alteration. The mineralogy for sample HWMK13 (yellow) is the same as that for HWMK12, except that it has distinct, well-developed palagonitic rinds consisting of erionite and smectite. For all samples, the amount of glass and plagioclase decreases and the amount of smectite increases with decreasing particle size for size fractions <20 μm. For HWMK11, the amount of hematite is essentially constant, and mica is present only in the coarse clay-sized fraction; smectites are low in structural Fe. For HWMK12 and HWMK13, the zeolite erionite is present along with smectites and nanophase ferric oxides (np-Ox). Erionite abundance decreases and np-Ox abundance increases with decreasing particle size. The smectite in both black and yellow samples contains some Fe3+ in octahedral layers. There were only two mineral phases containing iron in the fine clay fraction, namely, smectites and iron oxides. For HWMK11, relatively large iron oxide particles (0.1 to 0.4 μm) were dispersed on clay surfaces; for HWMK12 and HWMK13, much finer np-Ox particles were present in lesser concentrations. Formation of the zeolite erionite is consistent with the arid climate zone where these samples were collected. However, transient hydrothermal processes that occurred during the eruption of Mauna Kea volcano under its permanent ice cap during the Pleistocene may have resulted in minerals such as zeolites and smectites which may persist as relicts over a long period of time. Most of the iron released during weathering of basaltic tephra precipitated as poorly crystalline iron oxides and some of the Fe has substituted for the octahedral cations in the structure of authigenic smectites. The Ti-hematite in HWMK11, however, is the result of high-temperature oxidation of Ti-magnetite and exsolution from ironbearing silicate phases. Visible and near-IR reflectivity spectra for the <20 μm size fraction of HWMK11 is dominated by well-crystalline Ti-hematite. Corresponding spectra for HWMK12 and HWMK13, whose ferric mineralogy is dominated by np-Ox particles, are more similar to Martian bright-region spectra.

Hydrothermal synthesis of hematite spherules and jarosite: Implications for diagenesis and hematite spherule formation in sulfate outcrops at Meridiani Planum, Mars

Abstract We synthesized hematite spherules whose mineralogic, chemical, and crystallographic properties are strikingly similar to those for the hematite-rich spherules in lag deposits on the surface and embedded in outcrops at Meridiani Planum, Mars. The spherules were synthesized in the laboratory along with hydronium jarosite and minor hydronium alunite from Fe-Al-Mg-S-Cl acid-sulfate solutions under hydrothermal conditions. The reaction sequence was (1) precipitation of hydronium jarosite; (2) jarosite dissolution and precipitation of hematite spherules; and (3) precipitation of hydronium alunite upon depletion of hydronium jarosite. The spherules exhibit a radial growth texture with the crystallographic c axis aligned along the radial direction, so that thermal emission spectra have no hematite emissivity minimum at ~390 cm-1. Our experiments show that hydrothermal, acid-sulfate solutions are a pathway for formation of jarosite and the hematite spherules at Meridiani Planum, Mars.

Thermal and Evolved Gas Analyzer: Part of the Mars Volatile and Climate Surveyor integrated payload

The Thermal and Evolved Gas Analyzer (TEGA) on the Mars Polar Lander spacecraft is composed of two separate components which are closely coupled: a Differential Scanning Calorimeter (DSC) and an Evolved Gas Analyzer (EGA). TEGA has the capability of performing differential scanning calorimetry on eight small (0.038 mL) soil samples selected in the vicinity of the lander. The samples will be heated in ovens to temperatures up to 950°C, and the volatile compounds water and carbon dioxide, which are released during the heating, will be analyzed in the EGA. The power required by the sample oven is continuously monitored during the heating and compared to that required to heat simultaneously a similar, but empty, oven. The power difference is the output of the DSC. Both endothermic and exothermic phase transitions can be detected, and the data can be used in the identification of the phases present. By correlating the gas release with the calorimetry, the abundance of the volatile compounds associated with the different phases can be determined. The EGA may also be able to detect the release of oxygen associated with any superoxide that may be on the surface of the soil grains. The instrument can detect the melting of ice in the DSC down to abundances on the order of 0.2% of the sample, and it can detect the decomposition of calcite, CaCO3, down to abundances of 0.5%. Using the EGA, TEGA can detect small amounts of water, down to 8 ppm in the sample, and it can detect the associated release of CO2 down to the equivalent abundances of 0.03%. The EGA also has the ability to determine the 13C/12C ratio in the evolved CO2, but it is not clear if the accuracy of this ratio will be sufficient to address the scientific issues.