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At least 19 records

Reflectivity and other physicochemical properties of Mn-substituted goethites and hematites

Goethite-bearing samples with values of Mn(s) (Mn/(Mn+Fe) mole fraction) up to 0.206 were synthesized by precipitation from alkaline solution. Samples with Mn(s) less than or equal 0.061 were single-phase Mn-goethites: samples with higher Mn(s) values contained another Mn-bearing phase (probably jacobsite). Mn-hematites were prepared by dehydroxylation of corresponding Mn-goethites at 500 C. Orthorhombic a and b unit cell dimensions of Mn-goethites changed in a linear manner with Mn(s), but not at rates predicted by the Vegrad law. Hexagonal unit cell dimensions of Mn-hematites did not vary with Mn(s). Moessbauer parameters isomer shift (IS), quadrupole splitting (QS), and hyperfine field (B(sub hf)) were measured at 293 and 15 K. For all single-phase Mn-goethites and Mn-hematites (Mn(s) less than or equal 0.061), magnetic splitting was observed at both temperatures. At 293 K, small but systematic decreases in B(sub hf) were observed with increasing Mn substitution; IS and QS were not dependent on Mn(s). Mn substitution strongly lowered the Morin transition temperature of hematite. At 15 K, the Morin transition was not present for Mn(s) greater than 0.020(4). The saturation magnetization of Mn-goethites and Mn-hematites (Mn(s) less than or equal 0.061) was the expected zero (within error) for antiferromagnetic goethite and for hematites obtained from dehydroxylation of goethites. Mn-geothites with Mn(s) greater than 0.061 were magnetic because of the presence of strongly magnetic jacobsite. For reflectivity spectra, bands resulting from MN(3+) were centered near 454 and 596 nm for Mn-goethites and near 545 and 700 nm for Mn-hematites. There is evidence for a approximately 700 nm band in spectral data for Martian bright regions, but association of it with Mn(3+) is not a unique interpretation. Comparison of laboratory and Martian spectral data implies that Mn(s) less than 0.032 for the Mn(3+) content of Martian hematites.

Vempati, R. K.↗

The origin and stability of lunar goethite, hematite and magnetite.

Extra-lunar contamination, fumarolic activity, and exposure to oxidizing gases from comet or carbonaceous meteorite impacts have been previously proposed as the causes of magnetite, hematite, and goethite in lunar materials. However, these minerals can occur in the stable low-temperature gas-solid equilibrium assemblages of lunar rocks. Below 600 C magnetite is in equilibrium with C-O-H gases with compositions compatible with high-temperature equilibrium with metallic iron; below 150 C hematite is stable in these same gases. Goethite is not stable in carbonaceous gases at low total pressure, and thus gases from impacting carbonaceous material cannot have produced it. Goethite is stable at low temperatures and pressures in almost pure H2-H2O gases. Its minimum stability against hematite is 2 bars total pressure at 130 C and 0.001 bars at 30 C for H2 to H2O ratios compatible with the high-temperature redox state of lunar materials. Thus the traces of magnetite, hematite, and goethite in lunar materials may be the result of normal low-temperature processes indigenous to the moon and not special processes.

Williams, R. J.↗

Synthesis and properties of Ti-substituted goethites and hematites

The objective was to synthesize Ti-substituted goethites and hematites and to characterize them using x-ray diffraction, thermogravimetric analysis, coulimetry, optical and Mossbauer spectroscopies, and magnetic data in order to determine the evidence of Ti substitution for Martian spectral data. Evidence is provided that up to 4 mole percent can be incorporated into the goethite structure during the low temperature synthesis. Because the spectral data in the visible and near-IR are not sensitive to the degree of Ti-substitution in goethites and hematites, such data cannot be used to infer the presence or absence of Ti substitution in Martian hematites and goethites.

Vempati, R. K.↗

Spectral and other physicochemical properties of submicron powders of hematite (alpha-Fe2O3), maghemite (gamma-Fe2O3), magnetite (Fe3O4), goethite (alpha-FeOOH), and lepidocrocite (gamma-FeOOH)

The spectral properties (0.35-2.20 microns) of submicron powders of hematite, maghemite, magnetite, goethite, and lepidocrocite are determined. Other physicochemical data are obtained for the powders in order to determine if deviations from stoichiometry occur due to their small particle size, to determine their state of chemical and phase purity, and to determine the physical characteristics of the individual powders. The physicochemical data obtained include mean particle diameter, discrete particle shape, chemical composition, crystallographic phase, magnetic parameters, and Moessbauer parameters. The positions of the spectral features for the hematite, maghemite, and magnetite powders are independent of temperature over the interval between about +20 and -110 C. For the goethite and lepidocrocite powders, a small shift of about 0.02 micron to shorter wavelengths is observed for some of the features after cooling to about -110 C. The spectral properties of the iron oxides and oxyhydroxides are important not only for understanding the basic physics and chemistry of the compounds but also for applications such as the remote sensing of the earth and Mars.

Morris, R. V.↗

The formation of goethite and hydrated clay minerals on Mars

Laboratory studies reported by Huguenin (1973) on the kinetics and mechanism of the photostimulated oxidation of magnetic and preliminary laboratory data on the weathering of silicates, reported herein, are applied to Mars. Basalts in the Martian dark areas are predicted to alter to hydrated Fe(2 plus or minus) depleted clay minerals, minor goethite, and minor to trace amounts of transition metal oxides such as TiO2, MnO2, and Cr2O3 at a rate of 10 to the minus 1.5 plus or minus 1.5 micron/yr. Some Ca-Mg carbonates are also expected to be formed. The clay minerals are predicted to be more silica-rich than the silicate source material, SiO2 contents of 60% or higher being expected, and strongly depleted in Fe(2+). The oxygen, OH, and H2O contents of the bulk weathering product are predicted to be significantly greater than those of the dark-area source materials, whereas the relative bulk metal abundances should be the same.

Huguenin, R. L.↗

Stability of goethite /alpha-FeOOH/ and lepidocrocite /gamma-FeOOH/ to dehydration by UV radiation - Implications for their occurrence on the Martian surface

The geochemistry of the FeOOH polymorphs is an important consideration when evaluating the likelihood of an occurrence of detectable amounts of these minerals on Mars. An investigation is conducted regarding the stability of the FeOOH polymorphs geothite and lepidocrocite to dehydration in the presence of UV radiation. A thorough characterization of the FeOOH powders used in the laboratory experiments is presented, and the irradiational facility and experimental procedures are described. The results obtained in the conducted experiments are discussed. It is found that there is as yet no basis in laboratory experiments for inferring that perceptible UV photodehydration of FeOOH polymorphs will occur naturally on the surface of Mars on a time scale of at least 10-100 years.

Morris, R. V.↗

Fine-grained Goethite as a Precursor for Martian Gray Hematite

Several isolated deposits of gray, crystalline hematite on Mars were discovered using data returned from the Thermal Emission Spectrometer (TES) instrument aboard the Mars Global Surveyor spacecraft. Christensen et al. provided five testable hypotheses regarding the formation of crystalline hematite on Mars: 1) low-temperature precipitation of Fe oxides/hydroxides from standing, oxygenated, Fe-rich water, followed by subsequent alteration to gray hematite, 2) low-temperature leaching of iron-bearing silicates and other materials leaving a Fe-rich residue laterite-style weathering) which is subsequently altered to gray hematite, 3) direct precipitation of gray hematite from Fe-rich circulating fluids of hydrothermal or other origin, 4) formation of gray hematitic surface coatings during weathering, and 5) thermal oxidation of magnetite-rich lavas. Since this initial work, several authors have examined the hematite deposits to determine their formation mechanism. Lane et al. cited the absence of a 390/ cm absorption in the martian hematite spectrum as evidence for platy hematite grains. Their model for the formation of the deposits includes deposition of any of a variety of iron oxides or oxyhydroxides by aqueous or hydrothermal fluids, burial and metamorphosis to gray platy hematite grains, and exhumation in recent times. Based on a detailed geomorphic examination of the Sinus Meridiani region, Hynek et al. conclude that the most likely method of hematite formation was either emplacement by a hydrothermal fluid or oxidation of a magnetite-rich pyroclastic deposit. Similarly, Arvidson et al., favor a model involving the alteration of pyroclastic deposits by aqueous or hydrothermal fluids. Finally, based on geochemical modeling and an examination of Aram Chaos, Catling and Moore favor emplacement by hydrothermal fluids with a minimum temperature of 100 C. Comparison of the average martian hematite spectrum measured by TES to hematite emissivity spectra for a variety of naturally occurring hematites shows small but potentially important differences. In particular, band shapes, positions and relative band emissivities of hematite spectra vary over the range of samples. These differences imply that the natural variability of thermal infrared hematite spectra has not been fully characterized, especially with respect to the reaction pathway and crystal structure.

T D Glotch↗

MIMOS II on MER One Year of Mossbauer Spectroscopy on the Surface of Mars: From Jarosite at Meridiani Planum to Goethite at Gusev Crater

The miniaturized Mossbauer (MB) spectrometer MIMOS II [1] is part of the Athena payload of NASA s twin Mars Exploration Rovers "Spirit" (MER-A) and "Opportunity" (MER-B). It determines the Fe-bearing mineralogy of Martian soils and rocks at the Rovers respective landing sites, Gusev crater and Meridiani Planum. Both spectrometers performed successfully during first year of operation. Total integration time is about 49 days for MERA (79 samples) and 34 days for MER-B (85 samples). For curiosity it might be interesting to mention that the total odometry of the oscillating part of the MB drive exceeds 35 km for both rovers.

Klingelhoefer, G.↗

Inferring iron-oxide species content in atmospheric mineral dust from DSCOVR EPIC observations

The iron-oxide content of dust in the atmosphere and most notably its apportionment between hematite (α-Fe2O3) and goethite (α-FeOOH) are key determinants in quantifying dust’s light absorption, its top of atmosphere UV radiances used for dust monitoring, and ultimately shortwave dust direct radiative effects (DRE). Hematite and goethite column mass concentrations and iron-oxide mass fractions of total dust mass concentration were retrieved from the DeepSpace Climate Observatory (DSCOVR) Earth Polychromatic Imaging Camera (EPIC) measurements in the ultraviolet–visible (UV–Vis) channels. The retrievals were performed for dust-identified aerosol plumes over land using aerosol optical depth (AOD) and spectral imaginary refractive index provided by the Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm over six continental regions (North America, North Africa, West Asia, Central Asia, EastAsia, and Australia). The dust particles are represented as an internal mixture of non-absorbing host and absorbing hematite and goethite. We use the Maxwell–Garnett effective medium approximation with carefully selected complex refractive indices of hematite and goethite that produce mass fractions of iron oxides species consistent with in situ values found in the literature to derive the hematite and goethite volumetric/mass concentrations from MAIAC EPIC products. We compared the retrieved hematite and goethite concentrations with in situ dust aerosol mineralogical content measurements, as well as with published data. Our data display variations within the published range of hematite, goethite, and iron-oxide mass fractions for pure mineral dust cases. A specific analysis is presented for 15 sites over the main dust source regions. Sites in the central Sahara, Sahel, and Middle East exhibit a greater temporal variability of iron oxides relative to other sites. Niger site(13.52°N, 2.63°E) is dominated by goethite over Harmattan season with median of ~2 weight percentage (wt.%) of iron-oxide. Saudi Arabia site (27.49°N, 41.98°E) over Middle East also exhibited surge of goethite content with the beginning of Shamal season. The Sahel dust is richer in iron-oxide than Saharan and northern China dust except in Summer. The Bodélé Depression area shows a distinctively lower iron-oxide concentration (~1 wt.%) throughout the year. Finally, we show that EPIC data allow to constrain the hematite refractive index. Specifically, we select 5 out of 13 different number of hematite refractive indices widely variable in published laboratory studies by constraining the iron-oxide mass ratio to the known measured values. Provided climatology of hematite and goethite mass fractions across main dust regions of the Earth will be useful for dust shortwave DRE studies and climate modeling.

Sujung Go↗

Iron Oxides of Mars: Evidence for Contemporary Weathering

Reflectance spectra of Mars were analyzed using a multiple high order derivative spectroscopy technique. Among the results of the analysis was the presence of suites of bands in each of the spectra that can be attributed to Fe(3e) phases. Several of the spectra contained bands that are very close to the band positions in the laboratory spectra of goethite, an hexagonal hydrated ferric oxide. Spectra of other areas showed absorption bands that were within 3% of the positions for hematite, and hexagonal close packed unhydrated Fe203. Remaining areas showed bands that are intermediate in position to the goethite and hematite bands, suggesting that there may be mixtures of goethite and hematite, and/or intermediate (partially dehydrated goethite) phases present in those areas. Both bright areas and dark areas showed suites of goethite bands and hematite bands, and there does not therefore appear to be a correlation with albedo. The areas that showed the goethite bands are, however, within zones of ongoing or historically frequent dust cloud activity, and the areas with the hematite bands were outside of the zones of frequent dust cloud activity. This suggests the possiblility that the more hydrated phase may occur within a mobile dust component.

Huguenin, R. L.↗

The Rio Tinto Basin, Spain: Mineralogy, Sedimentary Geobiology, and Implications for Interpretation of Outcrop Rocks at Meridiani Planum, Mars

Exploration by the NASA rover Opportunity has revealed sulfate- and hematite-rich sedimentary rocks exposed in craters and other surface features of Meridiani Planum, Mars. Modern, Holocene, and Plio-Pleistocene deposits of the Rio Tinto, southwestern Spain, provide at least a partial environmental analog to Meridiani Planum rocks, facilitating our understanding of Meridiani mineral precipitation and diagenesis, while informing considerations of martian astrobiology. Oxidation, thought to be biologically mediated, of pyritic ore bodies by groundwaters in the source area of the Rio Tinto generates headwaters enriched in sulfuric acid and ferric iron. Seasonal evaporation of river water drives precipitation of hydronium jarosite and schwertmannite, while (Mg,Al,Fe(sup 3+))-copiapite, coquimbite, gypsum, and other sulfate minerals precipitate nearby as efflorescences where locally variable source waters are brought to the surface by capillary action. During the wet season, hydrolysis of sulfate salts results in the precipitation of nanophase goethite. Holocene and Plio-Pleistocene terraces show increasing goethite crystallinity and then replacement of goethite with hematite through time. Hematite in Meridiani spherules also formed during diagenesis, although whether these replaced precursor goethite or precipitated directly from groundwaters is not known. The retention of jarosite and other soluble sulfate salts suggests that water limited the diagenesis of Meridiani rocks. Diverse prokaryotic and eukaryotic microorganisms inhabit acidic and seasonally dry Rio Tinto environments. Organic matter does not persist in Rio Tinto sediments, but biosignatures imparted to sedimentary rocks as macroscopic textures of coated microbial streamers, surface blisters formed by biogenic gas, and microfossils preserved as casts and molds in iron oxides help to shape strategies for astrobiological investigation of Meridiani outcrops.

Fernandez-Remolar, David C.↗

Moessbauer Mineralogy of Rock, Soil, and Dust at Gusev Crater, Mars: Spirit's Journey through Weakly Altered Olivine Basalt on the Plains and Pervasively Altered Basalt in the Columbia Hills

The Moessbauer spectrometer on Spirit measured the oxidation state of Fe, identified Fe-bearing phases, and measured relative abundances of Fe among those phases for surface materials on the plains and in the Columbia Hills of Gusev crater. Eight Fe-bearing phases were identified: olivine, pyroxene, ilmenite, magnetite, nanophase ferric oxide (npOx), hematite, goethite, and a Fe(3+)-sulfate. Adirondack basaltic rocks on the plains are nearly unaltered (Fe(3+)/Fe(sub T)<0.2) with Fe from olivine, pyroxene (Ol>Px), and minor npOx and magnetite. Columbia Hills basaltic rocks are nearly unaltered (Peace and Backstay), moderately altered (WoolyPatch, Wishstone, and Keystone), and pervasively altered (e.g., Clovis, Uchben, Watchtower, Keel, and Paros with Fe(3+)/Fe(sub T) approx.0.6-0.9). Fe from pyroxene is greater than Fe from olivine (Ol sometimes absent), and Fe(2+) from Ol+Px is 40-49% and 9-24% for moderately and pervasively altered materials, respectively. Ilmenite (Fe from Ilm approx.3-6%) is present in Backstay, Wishstone, Keystone, and related rocks along with magnetite (Fe from Mt approx. 10-15%). Remaining Fe is present as npOx, hematite, and goethite in variable proportions. Clovis has the highest goethite content (Fe from Gt=40%). Goethite (alpha-FeOOH) is mineralogical evidence for aqueous processes because it has structural hydroxide and is formed under aqueous conditions. Relatively unaltered basaltic soils (Fe(3+)/Fe(sub T) approx. 0.3) occur throughout Gusev crater (approx. 60-80% Fe from Ol+Px, approx. 10-30% from npOx, and approx. 10% from Mt). PasoRobles soil in the Columbia Hills has a unique occurrence of high concentrations of Fe(3+)-sulfate (approx. 65% of Fe). Magnetite is identified as a strongly magnetic phase in Martian soil and dust.

Morris, R. V.↗

Formation of Fe(III) (hydr)oxides from Fe(II) sulfides: Implications for akaganeite detection on Mars

Akaganeite (β-FeO(OH,Cl)) is a Fe(III) (hydr)oxide with a tunnel structure typically occupied by chloride. This mineral was first proposed to be present in Meridiani Planum and Gusev crater on Mars and akaganeite was subsequently detected by X-ray diffraction in Yellowknife Bay and Vera Rubin Ridge locations in Gale crater. Akaganeite in Gale crater has been proposed to form from Fe(II) sulfides but formation conditions remain unconstrained. We investigated akageneite formation by oxidative alteration of natural Fe(II) sulfide pyrrhotite exposed to HCl and oxidation-hydrolysis of Fe(II) HCl-leached from pyrrhotite at initial pH0 1.5, 2, 3, and 4. X-ray diffraction and Mössbauer analyses revealed formation of poorly-crystallized akageneite in oxidative alteration experiments. Air-exposure of the HCl-reacted dry pyrrhotite led to an increase in akageneite formation and precipitation of Fe(II) hydrated sulfates, goethite, and hydronium jarosite. Iron(II) oxidation-hydrolysis was sensitive to Si dissolved from phyllosilicates in one pyrrhotite sample. Akaganeite and goethite formed at pH0 1.5 and 2 with akageneite more abundant at dissolved Si/Fe ratio of 0.08 and goethite more abundant at Si/Fe of 0.01. Akaganeite formed together with hematite, ferrihydrite, and goethite at pH0 3, and formation was suppressed at pH0 4. Well-crystallized akageneite precipitated at pH0 1.5 while akaganeite of poorer crystallinity formed at pH0 2 and 3. Akageneite in Gale crater could form from sulfides by both mechanisms: oxidative alteration of sulfide minerals and oxidation-hydrolysis of leached Fe(II). The processes likely occurred during late diagenetic events triggered by interactions of acidic Cl-bearing groundwater with Fe(II) sulfides. Akaganeite in Yellowknife Bay, Gale crater could have formed by Fe(II) oxidation-hydrolysis either as a sole Fe(III) (hydr)oxide at pH<2 or along with ferrihydrite and hematite at 2<pH<4 in Si-enriched conditions. Akaganeite formation at Vera Rubin Ridge, Gale crater could have occurred through oxidative alteration of sulfides in Cl-bearing pH 1.2-1.5 solutions. The presence of well-crystalline akageneite in Vera Rubin Ridge indicates that Fe(II) oxidation-hydrolysis contributed to akageneite formation.

Mars gale crater akaganeite↗

Spectral Anomalies in the 11 and 12 micron Region From the Mariner Mars 7 Infrared Spectrometer

Two hundred-forty infrared spectra acquired by the 1969 Mariner Mars 7 Infrared Spectrometer (IRS), spanning the wavelength region 1.8-14.4 micron (5550-690/cm), have recently been recovered and calibrated in both wavelength and intensity. An examination of these IRS spectra has revealed absorptions at 11.25 and 12.5 micron that have not previously been reported for Mars. A search of the literature and spectral data bases shows that materials that exhibit a doublet at 11.25 and 12.5 micron are rare. In this paper we examine potential causes for these features and include a detailed discussion of carbonates, goethite, CO2 ice, and water ice. CO2 ice and water ice measured in transmission do not exhibit bands that match those recorded at 11.25 and 12.5 micron for Mars, which indicates that CO2 or water ice clouds are not the source of these features. Since these bands show no clear correlation with atmospheric path length, they are most likely caused by a surface material. In the IRS database they appear to be exceptionally intense in the western part of the Hellas basin. Goethite exhibits bands that are a good spectral match, but confirming whether goethite causes the features will require additional studies of the 20-50 micron region. These studies will require laboratory measurements of weathering coatings and an examination of spectra recorded of Mars by the 1971 Mariner Mars Infrared Interferometer Spectrometer (IRIS; 5-50 micron 2000200/cm) and the 1996 Thermal Emission Spectrometer (TES; 6-50 micron 1667-200/cm).

Kirkland, Laurel E.↗

Possible Evidence for Iron Sulfates, Iron Sulfides, and Elemental Sulfur at Gusev Crater, Mars, from Mer, Crism, and Analog Data

The Mossbauer (MB) spectrometers on the Mars Exploration Rovers (MER) Spirit (Gusev crater) and Opportunity (Meridiani Planum) have detected 14 Fe-bearing phases, and mineralogical assignments have been made for all except 3. Identified Fe2+-bearing phases are olivine, pyroxene, ilmenite, and troilite. Magnetite and chromite are present as mixed Fe(2+) and Fe(3+) phases. Identified Fe(3+) phase are jarosite, hematite, goethite, and nanophase ferric oxide (npOx). Fe(sup 0) (iron metal) is present as kamacite. Nanophase ferric oxide (npOx) is a generic name for octahedrally coordinated Fe(3+) alteration products that cannot be otherwise mineralogically assigned on the basis of MER data. On the Earth, npOx would include ferrihydrite, iddingsite, schwertmannite, akaganeite, and superparamagnetic hematite and goethite. The Mars Reconnaissance Orbiter CRISM instrument, a visible, near-IR hyperspectral imager (approximately 0.35 to 4 micron) enables mineralogical examination of Mars with a tool that is sensitive to H2O and to M-OH (M = Al, Si, Fe, Mg, etc.) at spatial resolution of about 20 m/pixel. We examined a CRISM image of the MER region of Gusev crater (Columbia Hills and plains to the west), looking for spectral evidence of the aqueous process apparent from the MER analyses. We also searched for spectral constraints for the mineralogical composition of our unidentified Fe-bearing phases and the forms of npOx present on Mars. We also consider evidence from analogue samples that the precursor for the goethite detected by MB in Clovis Class rocks is an iron sulfide. We suggest that there is some indirect evidence that elemental sulfur might be present to different extents in Clovis Class rocks, the Fe3Sulfate-rich soils, and perhaps even typical (Laguna Class) surface soils.

Morris, R. V.↗