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NASA NTRS1992

Reflectivity (visible and near IR), Moessbauer, static magnetic, and X ray diffraction properties of aluminum-substituted hematites

The effect of substituting iron by aluminum in polymorphs of Fe2O3 and FeOOH on their reflectivity characteristics was investigated by comparing data on visible and NIR reflectivities and on static magnetic, XRD, and Moessbauer properties for a family of aluminum-substituted hematites alpha-(Fe,Al)2O3, with compositions where the values of the Al/(Al+Fe) ratio were up to 0.61. Samples were prepared by oxidation of magnetite, dehydroxylation of goethite, and direct precipitation. The analytical methods used for obtaining diffuse reflectivity spectra (350-2200 nm), Moessbauer spectra, and static magnetic data are those described by Morris et al. (1989).

Morris, Richard V.↗
NASA NTRS1993

Reflectance spectra of sulfate-and carbonate-bearing Fe(3+)-doped montmorillonites as Mars soil analogs

Ferric smectites and ferrihydrite may be common alteration products of igneous lithologies on Mars, and experiments involving montmorillonite enriched with Fe(3+) support the likelihood of ferric smectites on Mars. Mossbauer spectroscopy has been used to identify ferrihydrite (Fe4(O,OH,H2O)12) as the primary ferric material in Fe(3+)-doped montmorillonite. Ferrihydrite is especially interesting due to its role as a precursor in the formation of hematite and goethite. Reflectance spectroscopy in the visible and infrared regions are coupled with Mossbauer spectroscopy in this study to characterize the ferric material in montmorillonites containing Fe(3+), as well as carbonates or sulfates, in the interlayer region.

Bishop, Janice L.↗
NASA NTRS1993

Detectability of crystalline ferric and ferrous minerals on Mars

Telescopic and spacecraft spectroscopic and geochemical data have been used to constrain the surface mineralogy of Mars and to yield clues about past and present Mars surface weathering/alteration scenarios. Based primarily on their visible to near-IR reflectance properties, several terrestrial iron-bearing minerals have been either identified on Mars or proposed as Mars spectral analogs. Among these are crystalline hematite, pyroxenes, as well as poorly crystalline materials like nonophase hematite and palagonite. Other iron-bearing minerals include nontronite, magnetite, jarosite, and goethite and the have been proposed as Mars surface constituents based on Viking Lander measurements or geochemical modeling. If present on Mars, these materials likely appear as spectral mixtures at the coarse spatial resolution of remotely sensed data. The detectability of any of these components must be evaluated relative to the other components with which they occur. The primary goal of this study is to determine how much of any given mineral would have to be present for it to be detectable in remotely-sensed data. Here, the detectability of iron-bearing minerals was evaluated using detection threshold analysis (DTA), an analytical technique based on spectral mixture analysis.

Sabol, Donald E., Jr.↗
NASA NTRS1994

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).

Golden, D. C.↗
NASA NTRS1995

Mineralogic variations in fluvial sediments contaminated by mine tailings as determined from AVIRIS data, Coeur D'Alene River Valley, Idaho

The success of imaging spectrometry in mineralogic mapping of natural terrains indicates that the technology can also be used to assess the environmental impact of human activities in certain instances. Specifically, this paper describes an investigation into the use of data from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) for mapping the spread of, and assessing changes in, the mineralogic character of tailings from a major silver and base metal mining district. The area under investigation is the Coeur d'Alene River Valley in northern Idaho. Mining has been going on in and around the towns of Kellogg and Wallace, Idaho since the 1880's. In the Kellogg-Smelterville Flats area, west of Kellogg, mine tailings were piled alongside the South Fork of the Coeur d'Alene River. Until the construction of tailings ponds in 1968 much of these waste materials were washed directly into the South Fork. The Kellogg-Smelterville area was declared an Environmental Protection Agency (EPA) Superfund site in 1983 and remediation efforts are currently underway. Recent studies have demonstrated that sediments in the Coeur d'Alene River and in the northern part of Lake Coeur d'Alene, into which the river flows, are highly enriched in Ag, Cu, Pb, Zn, Cd, Hg, As, and Sb. These trace metals have become aggregated in iron oxide and oxyhydroxide minerals and/or mineraloids. Reflectance spectra of iron-rich tailing materials are shown. Also shown are spectra of hematite and goethite. The broad bandwidth and long band center (near 1 micron) of the Fe(3+) crystal-field band of the iron-rich sediment samples combined with the lack of features on the Fe(3+) -O(2-) charge transfer absorption edge indicates that the ferric oxide and/or oxyhydroxide in these sediments is poorly crystalline to amorphous in character. Similar features are seen in poorly crystalline basaltic weathering products (e.g., palagonites). The problem of mapping and analyzing the downriver occurrences of iron rich tailings in the Coeur d'Alene (CDA) River Valley using remotely sensed data is complicated by the full vegetation cover present in the area. Because exposures of rock and soil were sparse, the data processing techniques used in this study were sensitive to detecting materials at subpixel scales. The methods used included spectral mixture analysis and a constrained energy minimization technique.

Farrand, W. H.↗
NASA NTRS1994

Iron alteration minerals in the visible and near-infrared spectra of low-albedo asteroids

Absorption features centered near 0.60-0.65 and 0.80-0.90 micrometers have been identified in the spectra of five low-albedo main-belt and outer-belt asteroids. These absorption features are attributed respectively to the (6)A(sub 1) goes to (4)T(sub 2)(G) and (6)A(sub 1) goes to (4)T(sub 1)(G) charge transfer transitions in minerals such as goethite, hematite, and jarosite that are products of the aqueous alteration of anhydrous silicates. A shoulder near 0.63 micrometers has also been identified in the absorption feature centered near 0.7 micrometers attributed to oxidized iron in phyllosilicates found predominantly in C- and G-class asteroids reflectance spectra. The coexistence of iron oxides with phyllosilicates in asteroids believed to have undergone aqueous alteration would be expected based upon analogy with terrestrial aqueous alteration and the observed mineralogy of carbonaceous chondrites. The number of low-albedo asteroids having only iron alteration absorption features compared to the number of low-albedo asteroids having spectral characteristics indicative of phyllosilicates is small. Either the conditions under which these asteroids formed are rare, or the iron alteration minerals could be formed in the interiors of objects where phyllosilicates dominate the surface mineralogy.

Vilas, Faith↗
NASA NTRS1995

Mid-infrared transmission spectra of crystalline and nanophase iron oxides/oxyhydroxides and implications for remote sensing of Mars

Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review exisiting data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+) - 0(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.

Bell, James F., III↗
NASA NTRS1995

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

Visible and near-IR refectivity, Moessbauer, 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 approximately 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 Fe(3+)/Fe(sub tot) and ranged from approximately 1000 nm (high-Ca pyroxene) to approximately 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 approximately 850 and approximately 1000nm 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 relativly 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 the analyses of soil at the two Viking landing sites.

Morris, Richard V.↗
NASA NTRS1995

Mid-infrared transmission spectra of crystalline and nanophase iron oxides/oxyhydroxides and implications for remote sensing of Mars

Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review existing data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestrial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+)-O(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.

Bell, James F., III↗
NASA NTRS1995

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 (Fe(3+)/Fe(sub tot)) and ranged from approx. 1000 nm (high-Ca pyroxene) to approx. 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.

Morris, Richard V.↗
NASA NTRS1999

Origin and Reactivity of the Martian Soil: A 2003 Micromission

The role of water in the development of the martian surface remains a fundamental scientific question. Did Mars have one or more "warm and wet" climatic episodes where liquid water was stable at the surface? If so, the mineral phases present in the soils should be consistent with a history of aqueous weathering. More generally, the formation of hydrated mineral phases on Mars is a strong indicator of past habitable surface environments. The primary purpose of this investigation is to help resolve the question of whether such aqueous indicators are present on Mars by probing the upper meter for diagnostic mineral species. According to Burns [1993], the formation of the ferric oxides responsible for the visible color of Mars are the result of dissolution of Fe (+2) phases from basalts followed by aqueous oxidation and precipitation of Fe" mineral assemblages. These precipitates likely included iron oxyhydroxides such as goethite (a-FeOOH) and lepidocrocite (g-FeOOH), but convincing evidence for these phases at the surface is still absent. The stability of these minerals is enhanced beneath the surface, and thus we propose a subsurface search for hydroxylated iron species as a test for a large-scale chemical weathering process based on interactions with liquid water. It is also possible that the ferric minerals on Mars are not aqueous alteration products of the rocks. A chemical study of the Pathfinder landing site concluded that the soils are not directly derived from the surrounding rocks and are enhanced in Mg and Fe. The additional source of these elements might be from other regions of Mars and transported by winds, or alternatively, from exogenic sources. Gibson [1970] proposed that the spectral reflectivity of Mars is consistent with oxidized meteoritic material. Yen and Murray [1998] further extend Gibson's idea and show, in the laboratory, that metallic iron can be readily oxidized to maghemite and hematite under present-day martian surface conditions (in the absence of liquid water). A test for a meteoritic component of the soil can be conducted, as described below, by searching for the presence of Ni at the martian surface. The average abundance of nickel in an Fe-Ni meteorite is about 7% and, if present at measurable levels in the soil, would be indicative of an exogenic contribution. In addition, it may be possible to directly search for mineral phases common in meteorites. An understanding of the formation and evolution of the martian soil would not be complete without addressing the unusual reactivity discovered by the Viking Landers The presence of an inorganic oxidant, possibly one produced as a results of photochemical processes, is the most widely accepted explanation of the Viking results. Are these chemical species simply adsorbed on soil grains, or have they reacted with the metal oxide substrates and altered the mineral structures? Could a completely different (non-photochemical) process be responsible for the soil reactivity? The various ideas for the nature of this putative oxidant could be constrained by a measurement of the change in reactivity with depth. Different compositions will have different lifetimes and mobilities and thus will have different vertical profiles. Because the oxidizing compounds are believed to actively destroy organic molecules, determination of the reactivity gradient also has significant implications for the search for life on Mars. A DS2-based microprobe system can be instrumented for a 2003 micromission to investigate the origin and reactivity of the martian soil. These measurements would provide invaluable information regarding the climate history and exobiological potential of the planet. The NMR, X ray and chemiresistor measurement approach described embodies a highly synergistic and general set of soil interrogation methods for elements, compounds, and crystal structures and can also be applied to other geologic questions of interest. For example, if the capability for precise targeting of the probes is available, then in-situ investigations of suspected evaporite and hydrothermal deposits would be possible with the same set of instruments. Additional information is contained in the original.

Yen, Albert S.↗
NASA NTRS1998

Mineral Mapping Using AVIRIS Data at Ray Mine, AZ

Imaging Spectroscopy enables the identification and mapping of surface mineralogy over large areas. This study focused on assessing the utility of Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data for environmental impact analysis over the Environmental Protection Agency's (EPA) high priority Superfund site Ray Mine, AZ. Using the Spectral Angle Mapper (SAM) algorithm to analyze AVIRIS data makes it possible to map surface materials that are indicative of acid generating minerals. The improved performance of the AVIRIS sensor since 1996 provides data with sufficient signal to noise ratio to characterize up to 8 image endmembers. Specifically we employed SAM to map minerals associated with mine generated acid waste, namely jarositc, goethite, and hematite, in the presence of a complex mineralogical background.

McCubbin, Ian↗
NASA NTRS1999

Are Hyperion and Phoebe Linked to Iapetus?

Narrowband reflectance spectra of the Saturnian satellites S VII Hyperion and S IX Phoebe were obtained across the 0.4 - 0.8 micron spectral region. The spectrum of Phoebe is similar to the spectrum of a C-class asteroid, with an absorption feature centered near 0.43 micron superimposed on the UV/blue intervalence charge transfer transition present in the spectrum. The spectrum of Hyperion shows the strong spectral slope apparent in spectra of many outer Solar System materials and attributed to organics. We use a linear mixing model to separate the reflectance spectrum of the dark material on Hyperion from the icy material. A distinct absorption feature centered at 0.67 micron is present. A slight inflection near 0.4 - 0.6 micron and change in slope near 0.73 micron suggesting the lower wavelength edge of an absorption are also present. These absorptions are very similar to those identified in the spectrum of the dark material on the surface of Iapetus, suggesting that the dark material on these two satellites is compositionally similar and has a similar origin. These absorption features are attributed to the (6)A(sub 1) yields (4)T(sub 2)(G) and (6)A(sub 1) yields (4)T(sub 1)(G) ferric charge transfer transitions in iron alteration minerals such as goethite and hematite that are products of the aqueous alteration of anhydrous silicates.

Jarvis, Kandy S.↗
NASA NTRS2003

Microbial Fossils Detected in Desert Varnish

Mars Global Surveyor Thermal Emission Spectrometer data indicate regions with significant levels of hematite (_Fe2O3). Fe-oxides, like hematite, can form as aqueous mineral precipitates and as such may preserve microscopic fossils or other biosignatures. Several potential terrestrial analogues to martian hematite like hydrothermal vents have preserved microfossils. Microbial fossilization in Fe-oxides is often a function of biomineralization. For example, goethite (FeO2H) encrustation of fungal mycelia from the mid-Tertiary preserved fungal morphologies such that their genera could be determined.

Flood, B. E.↗
NASA NTRS2003

Characterization of the Effects of Precursor Mineralogy on Hematite Spectra: Application to Martian Hematite Mineralization

The Thermal Emission Spectrometer (TES) instrument aboard Mars Global Surveyor discovered several isolated deposits of gray, crystalline hematite in Sinus Meridiani, Aram Chaos, and Valles Marineris. A variety of formation mechanisms has been proposed for the martian hematite deposits, including aqueous and nonaqueous processes. Comparison of the average Sinus Meridiani hematite spectrum measured by TES to laboratory emissivity spectra for a variety of naturally occurring hematites shows small but potentially important differences. In particular, the emissivity minimum at 300 and 445/cm in the Sinus Meridiani (SM) spectrum is displaced 10-25/cm to lower frequencies compared to some natural hematite samples. In addition, these bands in the TES data are narrower than the broad bands seen in many natural hematite spectra. These differences may imply that the natural variability of hematite spectra has not been fully characterized, especially with respect to the reaction pathway (precursor mineralogy and temperature of hematite formation) and crystal morphology. Here, we describe the thermal infrared spectral characteristics of several series of synthetic hematite samples derived by direct precipitation, dehydroxylation of fine-grained goethite and the oxidation of magnetite. Several natural hematite sample spectra are also presented for comparison. Transmission electron microscopy (TEM) and Mossbauer spectral analyses of selected samples were performed in order to help determine the causes of the changes seen in the infrared spectra.

Glotch, Timothy D.↗
NASA NTRS1999

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

NASA Discipline Exobiology↗
NASA NTRS2004

Evidence from massive siderite beds for a CO2-rich atmosphere before approximately 1.8 billion years ago

It is generally thought that, in order to compensate for lower solar flux and maintain liquid oceans on the early Earth, methane must have been an important greenhouse gas before approximately 2.2 billion years (Gyr) ago. This is based upon a simple thermodynamic calculation that relates the absence of siderite (FeCO3) in some pre-2.2-Gyr palaeosols to atmospheric CO2 concentrations that would have been too low to have provided the necessary greenhouse effect. Using multi-dimensional thermodynamic analyses and geological evidence, we show here that the absence of siderite in palaeosols does not constrain atmospheric CO2 concentrations. Siderite is absent in many palaeosols (both pre- and post-2.2-Gyr in age) because the O2 concentrations and pH conditions in well-aerated soils have favoured the formation of ferric (Fe3+)-rich minerals, such as goethite, rather than siderite. Siderite, however, has formed throughout geological history in subsurface environments, such as euxinic seas, where anaerobic organisms created H2-rich conditions. The abundance of large, massive siderite-rich beds in pre-1.8-Gyr sedimentary sequences and their carbon isotope ratios indicate that the atmospheric CO2 concentration was more than 100 times greater than today, causing the rain and ocean waters to be more acidic than today. We therefore conclude that CO2 alone (without a significant contribution from methane) could have provided the necessary greenhouse effect to maintain liquid oceans on the early Earth.

Greenhouse Effect↗