Columbus crater in the Terra Sirenum region of the Martian southern highlands contains light‐toned layered deposits with interbedded sulfate and phyllosilicate minerals, a rare occurrence on Mars. ...Here we investigate in detail the morphology, thermophysical properties, mineralogy, and stratigraphy of these deposits; explore their regional context; and interpret the crater's aqueous history. Hydrated mineral‐bearing deposits occupy a discrete ring around the walls of Columbus crater and are also exposed beneath younger materials, possibly lava flows, on its floor. Widespread minerals identified in the crater include gypsum, polyhydrated and monohydrated Mg/Fe‐sulfates, and kaolinite; localized deposits consistent with montmorillonite, Fe/Mg‐phyllosilicates, jarosite, alunite, and crystalline ferric oxide or hydroxide are also detected. Thermal emission spectra suggest abundances of these minerals in the tens of percent range. Other craters in northwest Terra Sirenum also contain layered deposits and Al/Fe/Mg‐phyllosilicates, but sulfates have so far been found only in Columbus and Cross craters. The region's intercrater plains contain scattered exposures of Al‐phyllosilicates and one isolated mound with opaline silica, in addition to more common Fe/Mg‐phyllosilicates with chlorides. A Late Noachian age is estimated for the aqueous deposits in Columbus, coinciding with a period of inferred groundwater upwelling and evaporation, which (according to model results reported here) could have formed evaporites in Columbus and other craters in Terra Sirenum. Hypotheses for the origin of these deposits include groundwater cementation of crater‐filling sediments and/or direct precipitation from subaerial springs or in a deep (∼900 m) paleolake. Especially under the deep lake scenario, which we prefer, chemical gradients in Columbus crater may have created a habitable environment at this location on early Mars.
Imaging spectroscopy is a tool that can be used to spectrally identify and spatially map materials based on their specific chemical bonds. Spectroscopic analysis requires significantly more ...sophistication than has been employed in conventional broadband remote sensing analysis. We describe a new system that is effective at material identification and mapping: a set of algorithms within an expert system decision‐making framework that we call Tetracorder. The expertise in the system has been derived from scientific knowledge of spectral identification. The expert system rules are implemented in a decision tree where multiple algorithms are applied to spectral analysis, additional expert rules and algorithms can be applied based on initial results, and more decisions are made until spectral analysis is complete. Because certain spectral features are indicative of specific chemical bonds in materials, the system can accurately identify and map those materials. In this paper we describe the framework of the decision making process used for spectral identification, describe specific spectral feature analysis algorithms, and give examples of what analyses and types of maps are possible with imaging spectroscopy data. We also present the expert system rules that describe which diagnostic spectral features are used in the decision making process for a set of spectra of minerals and other common materials. We demonstrate the applications of Tetracorder to identify and map surface minerals, to detect sources of acid rock drainage, and to map vegetation species, ice, melting snow, water, and water pollution, all with one set of expert system rules. Mineral mapping can aid in geologic mapping and fault detection and can provide a better understanding of weathering, mineralization, hydrothermal alteration, and other geologic processes. Environmental site assessment, such as mapping source areas of acid mine drainage, has resulted in the acceleration of site cleanup, saving millions of dollars and years in cleanup time. Imaging spectroscopy data and Tetracorder analysis can be used to study both terrestrial and planetary science problems. Imaging spectroscopy can be used to probe planetary systems, including their atmospheres, oceans, and land surfaces.
Orbital topographic, image, and spectral data show that sulfate‐ and hematite‐bearing plains deposits similar to those explored by the MER rover Opportunity unconformably overlie the northeastern ...portion of the 160 km in diameter Miyamoto crater. Crater floor materials exhumed to the west of the contact exhibit CRISM and OMEGA NIR spectral signatures consistent with the presence of Fe/Mg‐rich smectite phyllosilicates. Based on superposition relationships, the phyllosilicate‐bearing deposits formed either in‐situ or were deposited on the floor of Miyamoto crater prior to the formation of the sulfate‐rich plains unit. These findings support the hypothesis that neutral pH aqueous conditions transitioned to a ground‐water driven acid sulfate system in the Sinus Meridiani region. The presence of both phyllosilicate and sulfate‐ and hematite‐bearing deposits within Miyamoto crater make it an attractive site for exploration by future rover missions.
The spectral properties of anhydrous carbonates and nitrates are dominated by strong, sharp vibrational bands due to the CO32− and NO3− anions observed as absorption bands in near‐infrared spectra, ...as Reststrahlen features or absorption bands in mid‐IR spectra, depending on particle size, and as peaks in Raman spectra. These spectral features provide a reliable means to identify the occurrence of carbonates and nitrates on planetary surfaces, which in turn contribute to our understanding of the environment and chemistry of planetary bodies. Four modes occur for carbonates and nitrates due to symmetric stretching (ν1), out‐of‐plane bending (ν2), asymmetric stretching (ν3), and in‐plane bending (ν4). The vibrational absorptions of these spectral features vary with the mineral structure and the size of the cation, where the calcite‐, dolomite‐, aragonite‐, and alkali‐type structures result in different spectral features. Mid‐IR bands for carbonates and nitrates occur from 1,040 to 1,105 cm−1 for ν1, from 810 to 906 cm−1 for ν2, from 1,275 to 1,590 cm−1 for ν3, and from 670 to 756 cm−1 for ν4. In Raman spectra the carbonate and nitrate absorptions are observed near 1,050–1,080 cm−1 for ν1, near 880 cm−1 for ν2, near 1,415–1,430 cm−1 for ν3, and near 680–700 cm−1 for ν4. NIR spectra include bands due to overtones and combinations at ∼1.75, 1.9, 2.0, 2.3, 2.5, 3.4, 4.0, and 4.6 μm for carbonates and ∼1.8, 2.0, 2.2, 2.4, 2.6, 3.5, 4.1, and 4.8 μm for nitrates. This study provides data for remote determination of carbonate and nitrate chemistry and will enable better characterization of these minerals on planetary bodies including Mars, Ceres, and Bennu.
Plain Language Summary
Carbonates are widespread minerals on Earth and have been identified as well on Mars, Ceres, near Earth asteroid (101955) Bennu, and in carbonaceous meteorites. Understanding the spectral properties of carbonates enables detection and characterization of this important mineral group. Furthermore, identifying the specific type of carbonate on planetary surfaces can help us constrain the geochemical environment of these planets or bodies. The spectral properties of nitrates are presented here as well because nitrates exhibit similar spectral features to carbonates due to their similar mineral structures. Nitrates are yet to be detected on planets other than Earth, but nitrogen has been detected on bodies in our Solar System and nitrates may be detected once researchers have access to their spectral properties.
Key Points
Spectral bands are presented for remote detection of anhydrous carbonates and nitrates
Mid‐IR band center comparisons for the ν3 vibration compared to the ν2 and ν4 vibrations enable identification of carbonate chemistry
NIR band center comparisons for ∼2.3 versus 2.5 μm, ∼2.3 versus 4 μm, and ∼3.4 versus 4 μm best enable identification of carbonate chemistry
This paper presents a detailed study of the mineralogical, microscopic, thermal, and spectral characteristics of jarosite and natrojarosite minerals. Systematic mineralogic and chemical examination ...of a suite of 32 natural stoichiometric jarosite and natrojarosite samples from diverse supergene and hydrothermal environments indicates that there is only limited solid solution between Na and K at low temperatures, which suggests the presence of a solvus in the jarosite-natrojarosite system at temperatures below about 140
°C. The samples examined in this study consist of either end members or coexisting end-member pairs of jarosite and natrojarosite. Quantitative electron-probe microanalysis data for several natural hydrothermal samples show only end-member compositions for individual grains or zones, and no detectable alkali-site deficiencies, which indicates that there is no hydronium substitution within the analytical uncertainty of the method. In addition, there is no evidence of Fe deficiencies in the natural hydrothermal samples. Hydronium-bearing jarosite was detected in only one relatively young supergene sample suggesting that terrestrial hydronium-bearing jarosites generally are unstable over geologic timescales.
Unit-cell parameters of the 20 natural stoichiometric jarosites and 12 natural stoichiometric natrojarosites examined in this study have distinct and narrow ranges in the
a- and
c-cell dimensions. There is no overlap of these parameters at the 1
σ level for the two end-member compositions. Several hydrothermal samples consist of fine-scale (2–10
μm) intimate intergrowths of jarosite and natrojarosite, which could have resulted from solid-state diffusion segregation or growth zoning due to variations in the Na/K activity ratio of hydrothermal solutions.
Estimates of spectrometer band pass, sampling interval, and signal‐to‐noise ratio required for identification of pure minerals and plants were derived using reflectance spectra convolved to AVIRIS, ...HYDICE, MIVIS, VIMS, and other imaging spectrometers. For each spectral simulation, various levels of random noise were added to the reflectance spectra after convolution, and then each was analyzed with the Tetracorder spectral identification algorithm Clark et al., 2003. The outcome of each identification attempt was tabulated to provide an estimate of the signal‐to‐noise ratio at which a given percentage of the noisy spectra were identified correctly. Results show that spectral identification is most sensitive to the signal‐to‐noise ratio at narrow sampling interval values but is more sensitive to the sampling interval itself at broad sampling interval values because of spectral aliasing, a condition when absorption features of different materials can resemble one another. The band pass is less critical to spectral identification than the sampling interval or signal‐to‐noise ratio because broadening the band pass does not induce spectral aliasing. These conclusions are empirically corroborated by analysis of mineral maps of AVIRIS data collected at Cuprite, Nevada, between 1990 and 1995, a period during which the sensor signal‐to‐noise ratio increased up to sixfold. There are values of spectrometer sampling and band pass beyond which spectral identification of materials will require an abrupt increase in sensor signal‐to‐noise ratio due to the effects of spectral aliasing. Factors that control this threshold are the uniqueness of a material's diagnostic absorptions in terms of shape and wavelength isolation, and the spectral diversity of the materials found in nature and in the spectral library used for comparison. Array spectrometers provide the best data for identification when they critically sample spectra. The sampling interval should not be broadened to increase the signal‐to‐noise ratio in a photon‐noise‐limited system when high levels of accuracy are desired. It is possible, using this simulation method, to select optimum combinations of band‐pass, sampling interval, and signal‐to‐noise ratio values for a particular application that maximize identification accuracy and minimize the volume of imaging data.
Analyses of MRO/CRISM images of the greater Mawrth Vallis region of Mars affirm the presence of two primary phyllosilicate assemblages throughout a region ∼1000 × 1000 km. These two units consist of ...an Fe/Mg‐phyllosilicate assemblage overlain by an Al‐phyllosilicate and hydrated silica assemblage. The lower unit contains Fe/Mg‐smectites, sometimes combined with one or more of these other Fe/Mg‐phyllosilicates: serpentine, chlorite, biotite, and/or vermiculite. It is more than 100 m thick and finely layered at meter scales. The upper unit includes Al‐smectite, kaolin group minerals, and hydrated silica. It is tens of meters thick and finely layered as well. A common phyllosilicate stratigraphy and morphology is observed throughout the greater region wherever erosional windows are present. This suggests that the geologic processes forming these units must have occurred on at least a regional scale. Sinuous ridges (interpreted to be inverted channels) and narrow channels cut into the upper clay‐bearing unit suggesting that aqueous processes were prevalent after, and possibly during, the deposition of the layered units. We propose that layered units may have been deposited at Mawrth Vallis and then subsequently altered to form the hydrated units. The Fe/Mg‐phyllosilicate assemblage is consistent with hydrothermal alteration or pedogenesis of mafic to ultramafic rocks. The Al‐phyllosilicate/hydrated silica unit may have formed through alteration of felsic material or via leaching of basaltic material through pedogenic alteration or a mildly acidic environment. These phyllosilicate‐bearing units are overlain by a darker, relatively unaltered, and indurated material that has probably experienced a complex geological history.
Analysis of visible to near infrared reflectance data from the MRO CRISM hyperspectral imager has revealed the presence of an ovoid-shaped landform, approximately 3 by 5
km in size, within the ...layered terrains surrounding the Mawrth Vallis outflow channel. This feature has spectral absorption features consistent with the presence of the ferric sulfate mineral jarosite, specifically a K-bearing jarosite (KFe
3(SO
4)
2(OH)
6). Terrestrial jarosite is formed through the oxidation of iron sulfides in acidic environments or from basaltic precursor minerals with the addition of sulfur. Previously identified phyllosilicates in the Mawrth Vallis layered terrains include a basal sequence of layers containing Fe–Mg smectites and an upper set of layers of hydrated silica and aluminous phyllosilicates. In terms of its fine scale morphology revealed by MRO HiRISE imagery, the jarosite-bearing unit has fracture patterns very similar to that observed in Fe–Mg smectite-bearing layers, but unlike that observed in the Al-bearing phyllosilicate unit. The ovoid-shaped landform is situated in an east–west bowl-shaped depression superposed on a north sloping surface. Spectra of the ovoid-shaped jarosite-bearing landform also display an anomalously high 600
nm shoulder, which may be consistent with the presence of goethite and a 1.92
μm absorption which could indicate the presence of ferrihydrite. Goethite, jarosite, and ferrihydrite can be co-precipitated and/or form through transformation of schwertmannite, both processes generally occurring under low pH conditions (pH 2–4). To date, this location appears to be unique in the Mawrth Vallis region and could represent precipitation of jarosite in acidic, sulfur-rich ponded water during the waning stages of drying.
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