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Mineralogical Trends Over the Clay-Sulfate Transition in Gale Crater from the Mars Science Laboratory CheMin Instrument

The Mars Science Laboratory Curiosity rover landed in Gale crater in 2012 to explore a sedimentary sequence in lower Aeolis Mons (informally known as Mount Sharp)that shows changes in mineralogy from orbital visible/near-infrared reflectance spectroscopy[1]. Sedimentary layers with spectral signatures of hydrated Mg sulfate overly layers with signatures of Fe/Mg smectite, a mineralogical stratigraphy that is seen in other ancient sedimentary rocks across Mars[e.g., 2-4]. Curiosity recently completed its campaign in a valley with a strong orbital signature of smectite, named Glen Torridon. Mineralogical measurements by the CheMin X-ray diffractometer(XRD), complemented by evolved gas analyses by the Sample Analysis at Mars (SAM) instrument suite, allowed the identification of abundant Fe3+-bearing dioctahedral smectite (i.e., nontronite) in Glen Torridon [5-6]. Curiosity left Glen Torridon in February 2021 and began traversing through a “clay-sulfate transition” zone on the way to the pediment and the sulfate unit[e.g., 7]. This clay-sulfate transition is defined in orbital reflectance spectroscopy as having a weak signature of hydrated Mg sulfate. Curiosity has drilled five outcrops over the traverse through the clay-sulfate transition and delivered the rock powders to CheMin for mineralogical analysis. Here, we report on the mineral assemblages of those five targets derived from CheMin XRD patterns and discuss mineralogical trends as the rover approaches the sulfate unit.

Mars↗
NASA NTRS1984

Magnetic cristobalite (?) - A possible new magnetic phase produced by the thermal decomposition of nontronite

The effect of heat treatment for 1 h or more at 900-1000 C on the magnetic properties of nontronite, an iron-rich smectite clay thought to be an important component of Martian regolith, is investigated experimentally, extending the findings of Moskowitz and Hargraves (1982). The results are presented in graphs and tables and discussed. A phase with Curie temperature 200-220 C, remanent coercivity greater than 800 mT, and a type-2 room-temperature-coercivity response to thermomagnetic cycling is observed and attributed to an iron-substituted cristobalite which may form by topotactic growth from a smectite precursor.

Moskowitz, B. M.↗
NASA NTRS1988

Analysis of chondritic interplanetary dust thin-sections

Chondritic interplanetary dust particles (IDPs) are heterogeneous aggregates of predominantly submicron mineral grains and carbonaceous material, whose bulk compositions agree within a factor of two with type CI/CM carbonaceous chondrites. The mineralogy and petrography of 25 such particles were studied by analytical electron microscopic examination of ultramicrotomed thin sections (500-1000 A thick). Four classes of chondritic IDPs were recognized, referred to as pyroxene, olivine, smectite, and serpentine, and their relative abundances were 9:4:10:2, respectively. Quantitative thin-film analyses indicate that pyroxene particles most closely resemble material emitted from comet Halley. Smectite particles may have formed from pyroxene particles by aqueous alteration of glass and enstatite crystals. Serpentine particles are the only class that are similar to the matrices of carbonaceous chondrites, but these are the least abundant chondritic IDPs. Collectively, chondritic particles are a mineralogically diverse group of extraterrestrial materials.

Bradley, John P.↗
NASA NTRS1990

The spectroscopic, chemical, and photophysical properties of Martian soils and their analogs (MERC, phase 2)

A series of variably proportioned iron/calcium smectite clays and iron loaded smectite clays containing iron up to the level found in the Martian soil were prepared from a typical montomorillonite clay using the Banin method. Evidence was obtained which supports the premise that these materials provide a unique and appropriate model soil system for the Martian surface in that they are consistent with the constraints imposed by the Viking surface elemental analysis, the reflectance data obtained by various spacecraft instruments and ground based telescopes, and the chemical reactivity measured by one of the Viking biology experiments, the Labeled Release (LR) experiment.

Banin, Amos↗
NASA NTRS1992

The fate of iron on Mars: Mechanism of oxidation of basaltic minerals to ferric-bearing assemblages

Perhaps the most conspicuous indication that chemical weathering has occurred on the surface of Mars is the overall color of the red planet and the spectroscopic features that identify ferric-bearing assemblages in the martian regolith. Apparently, Fe(2+) ions in primary minerals in parent igneous rocks on the martian surface have been oxidized to ferric iron, which occurs in degradation products that now constitute the regolith. The mineralogy of the unweathered igneous rocks prior to weathering on the martian surface is reasonably well constrained, mainly as a result of petrographic studies of the SNC meteorites. However, the alteration products resulting from oxidative weathering of these rocks are less well-constrained. The topics covered include the following: primary rocks subjected to chemical weathering; dissolution processes; oxidation of dissolved Fe(2+); mechanism of polymerization of hydrous ferric oxides; terrestrial occurrences of ferromagnesian smectites; and dehydroxylated Mg-Fe smectites on Mars.

Burns, Roger G.↗
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

Ferric sulfate montmorillonites as Mars soil analogs

Spectroscopic analyses have shown that Fe(3+)-doped smectites prepared in the laboratory exhibit important similarities to the soils on Mars. Ferrihydrite in these smectites has features in the visible to near-infrared region that resemble the energies and band-strengths of features in reflectance spectra observed for several bright regions on Mars. Ferric - sulfate - montmorillonite samples have been prepared more recently because they are a good compositional match with the surface material on Mars as measured by Viking. Reflectance spectra of montmorillonite doped with ferric sulfate in the interlayer regions include a strong 3 micron band that persists under dry conditions. This is in contrast to spectra of similarly prepared ferric-doped montmorillonites, which exhibit a relatively weaker 3 micron band under comparable dry environmental conditions. Presented here are reflectance spectra of a suite of ferric-sulfate exchanged montmorillonites prepared with variable ferric sulfate concentrations and variable pH conditions.

Bishop, J. L.↗
NASA NTRS1997

Trace Element Geochemistry of Martian Iddingsite in the Lafayette Meteorite

The Lafayette meteorite contains abundant iddingsite, a fine-grained intergrowth of smectite clay, ferrihydrite, and ionic salt minerals. Both the meteorite and iddingsite formed on Mars. Samples of iddingsite, olivine, and augite pyroxene were extracted from Lafayette and analyzed for trace elements by instrumental neutron activation. Our results are comparable to independent analyses by electron and ion microbeam methods. Abundances of most elements in the iddingsite do not covary significantly. The iddingsite is extremely rich in Hg, which is probably terrestrial contamination. For the elements Si, Al, Fe, Mn, Ni, Co, and Zn, the composition of the iddingsite is close to a mixture of approximately 50% Lafayette olivine + approximately 40% Lafayette siliceous glass + approximately 1O% water. Concordant behavior among these elements is not compatible with element fractionations between smectite and water, but the hydrous nature and petrographic setting of the iddingsite clearly suggest an aqueous origin. These inferences are both consistent, however, with deposition of the iddingsite originally as a silicate gel, which then crystallized (neoformed) nearly isochemically. The iddingsite contains significantly more magnesium than implied by the model, which may suggest that the altering solutions were rich in Mg(2+).

Treiman, Allan H.↗
NASA NTRS1996

CM-like Interplanetary Dust Particles in Lower Stratosphere During 1989 October and 1991 June/July

The stratospheric interplanetary dust particles L2005T12 and L2011O3 are linked to CM chondrite matrix. Particle L2005T12 is dominated by tabular grains of partially dehydrated greenalite-rich serpentine. Its amorphous matrix contains abundant smectite nanocrystals and annular Fe,Ni,S units. A uniquely stratified (partial) maghemite rim occurs only on S-rich parts of the matrix. Formation of this rim and Mg depletions in the matrix occurred during atmospheric entry heating of this particle. Particle L2011O3 has large iron sulfide and magnesiowustite grains in an amorphous low-Al, ferromagnesiosilica matrix. Hydrous crystallisation of this matrix produced ultrafine-grained smectites and disseminated iron sulfides. Atmospheric entry heating of both particles is indicated by the partial iron oxide rim, vesicular sulfides, and the scatter of matrix compositions due to loss of Mg. While many uncertainties remain, the high incidence of chondritic rough particles, which include an unknown amount of CM-like particles, in the lower stratosphere during 1984, 1989, and 1991 suggests annual variations in their abundances. The timing of lower stratospheric dust samplings is critical to collect these particles.

Rietmeijer, Frans J. M.↗
NASA NTRS1999

Possible Bacteria in Nakhla

Mars Agueous Alteration Nakhla contains alteration products in an extensive network of which fill cracks, veins, and void spaces, composed of smectite, although in some cases they are amorphous and gel-like. Strong evidence presented show that these alteration products developed on Mars: some veins are offset by impact faulting of olivine followed by annealing of the olivine, and veins near the fusion crust show partial vesicle development suggesting heating and volatile liberation. The smectite-containing cracks and veins are interpreted as low temperature aqueous alteration on Mars. We have been studying these veins with optical microscopy and high resolution SEM.

McKay, David S., Jr.↗
NASA NTRS2000

Visible Wavelength Spectroscopy of Ferric Minerals: A Key Tool for Identification of Ancient Martian Aqueous Environments

The mineralogic signatures of past aqueous alteration of a basaltic Martian crust may include iron oxides and oxyhydroxides, zeolites, carbonates, phyllosilicates, and silica. The identities, relative abundances, and crystallinities of the phases formed in a particular environment depend on physicochemical conditions. At one extreme, hot spring environments may be characterized by smectite-chlorite to talc-kaolinite silicate assemblages, plus crystalline ferric oxides dominated by hematite. However, most environments, including cold springs, pedogenic layers, and ponded surface water, are expected to deposit iron oxides and oxyhydroxides, carbonates, and smectite-dominated phyllosilicates. A substantial fraction of the ferric iron is expected to occur in nanophase form, with the exact mineralogy strongly influenced by Eh-pH conditions. Detection of these phases has been an objective of a large body of terrestrial telescopic, Mars orbital, and landed spectral investigations and in situ compositional measurements. However, clear identifications of many of these phases is lacking. Neither carbonate nor silica has been unequivocally detected by any method. Although phyllosilicates may occur near the limit of detection by remote sensing, in general they appear to occur in only poorly crystalline form. In contrast, compelling evidence for ferric iron minerals has been gathered by recent telescopic investigations, the Imager for Mars Pathfinder (IMP), and the Thermal Emission Spectrometer (TES) on the Mars Global Surveyor (MGS). These data yield two crucial findings: (1) In the global, high spatial resolution TES data set, highly crystalline ferric iron (as coarse-grained 'gray' hematite) has been recognized but with only very limited spatial occurrence and (2) Low-resolution telescopic reflectance spectroscopy, very limited orbital reflectance spectroscopy, and landed multispectral imaging provide strong indications that at least two broad classes of ferric iron minerals are commonplace in non-dust covered regions.

Murchie, Scott L.↗
NASA NTRS2003

A Study of Olivine Alteration to Iddingsite Using Raman Spectroscopy

A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.

Kuebler, K. E.↗
NASA NTRS2000

Geology and geochemistry of paleosols developed on the Hekpoort Basalt, Pretoria Group, South Africa

The Hekpoort paleosols comprise a regional paleoweathering horizon developed on 2.224 +/- 0.021 Ga basaltic andesite lavas at the top of the Hekpoort Formation of the Pretoria Group, Transvaal Supergroup, South Africa. In five separate profiles, from outcrops along road cuts near Waterval Onder and the Daspoort Tunnel and in three drill cores from the Bank Break Area (BB3, BB8, and BB14), the top of the paleosol is a sericite-rich zone. The sericite zone grades downward into a chlorite-rich zone. In core BB8 and in the road cut at the Daspoort Tunnel, we sampled the underlying or parent basaltic andesite into which the chlorite zone grades. We did not obtain samples of the parent material at Waterval Onder and in cores BB3 and BB14, but chemical analyses indicate that the chlorite and sericite zones in these profiles derive from underlying lavas similar to the ones we sampled in core BB8 and at the Daspoort Tunnel. The presence of apparent rip-up clasts of the paleosol in the overlying ironstones of the Strubenkop Formation in the cores from Bank Break makes it very unlikely that most of the alteration was a result of interactions with hydrothermal fluids. Desiccation cracks at the top of the paleosol that were filled with sand during the deposition of the overlying sediments at Waterval Onder point to a subaerial weathering origin. Very little, if any, Al, Ti, Zr, V, or Cr moved a discernible distance during weathering of any of the five profiles. The vertical distribution of Fe, Mg, Mn, Ni, and Co indicates that these elements were largely removed from the top of the soil during weathering. The overall abundance of these elements in each of the profiles indicates that a significant fraction of the complement lost from the top subsequently reprecipitated in the lower portion of the soil as constituents of an Fe2(+) -rich smectite. The loss of Fe from the top of the soil during weathering of the Hekpoort paleosols indicates that atmospheric PO2 was less than 8 x 10(-4) atm about 2.22 Ga. Fe2(+) -rich smectite should only precipitate during soil formation if atmospheric PCO2 is less than or equal to 2 x 10(-2) atm (Rye, Kuo, and Holland, 1995). Ca and Na were largely lost during weathering. Some Na was apparently added to the sericite zone in cores BB3, BB8, and BB14 after weathering. All five profiles are enriched in K and Rb, and most are enriched in Ba. The distribution of these elements indicates that they all were added during post-weathering hydrothermal metasomatism. Rb-Sr analysis of the paleosol at the Daspoort Tunnel indicates that metasomatism last affected that profile 1.925 +/- 0.032 Ga (Macfarlane and Holland, 1991).

Non-NASA Center↗
NASA NTRS1995

Reflectance spectroscopy of ferric sulfate-bearing montmorillonites as Mars soil analog materials

Spectroscopic analyses have shown that smectites enhanced in the laboratory with additional ferric species exhibit important similarities to those of the soils on Mars. Ferrihydrite in these chemically treated smectites has features in the visible to near-infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. New samples have been prepared with sulfate as well, because S was found by Viking to be a major component in the surface material on Mars. A suite of ferrihydrite-bearing and ferric sulfate-bearing montmorillonites, prepared with variable Fe3+ and S concentrations and variable pH conditions, has been analyzed using reflectance spectroscopy in the visible and infrared regions, Mossbauer spectroscopy at room temperature and 4 K, differential thermal analysis, and X-ray diffraction. These analyses support the formation of ferrihydrite of variable crystallinity in the ferrihydrite-bearing montmorillonites and a combination of schwertmannite and ferrihydrite in the ferric sulfate-bearing montmorillonites. Small quantities of poorly crystalline or nanophase forms of other ferric materials may also be present in these samples. The chemical formation conditions of the ferrihydrite-bearing and ferric sulfate-bearing montmorillonites influence the character of the low temperature Mossbauer sextets and the visible reflectance spectra. An absorption minimum is observed at 0.88-0.89 micrometers in spectra of the ferric sulfate-bearing samples, and at 0.89-0.92 micrometers in spectra of the ferrihydrate-bearing montmorillonites. Mossbauer spectra of the ferric sulfate-bearing montmorillonites indicate variable concentrations of ferrihydrite and schwertmannite in the interlaminar spaces and along grain surfaces. Dehydration under reduced atmospheric pressure conditions induces a greater effect on the adsorbed and interlayer water in ferrihydrite-bearing montmorillonite than on the water in ferric sulfate-bearing montmorillonite. Reflectance spectra of ferric sulfate-bearing montmorillonite include a strong 3-micrometers band that is more resistant to dry atmospheric conditions than the 3-micrometers band in spectra of similarly prepared ferrihydrite-bearing montmorillonites.

NASA Discipline Exobiology↗
NASA NTRS2013

Mars Exploration Rover APXS Results from Matijevic Hill

Correlation analysis of APXS results on the eastern slope rocks indicate that the Matijevic Hill rocks are overall compositionally distinct from the Shoemaker Formation rocks [6]. Compared to the Shoemaker impactites, Matijevic Hill rocks are higher in Al, Si, and Ni, and lower in Ti, Fe, and Zn. No significant variation is evident in the APXS analyses that indicate the presence of a smectite or other phyllosilicate, as opposed to basaltic rocks. However, APXS data cannot in themselves rule out phyllosilicates. If indeed this material contains smectite, as seen from orbit, it implies that the rock has been isochemically altered to create the phyllosilicate content. The Cl content of the Cape York rocks is relatively high, and whereas the S/Cl ratio in the Burns Formation is 4x higher than in soil, in the Cape York rocks it is lower than in soil. These trends indicate that the alteration processes and types of aqueous salt loads were different between Cape York and Meridiani. In addition, significant deviations from the Martian Mn/Fe ratio are observed in Whitewater Lake coatings and the altered Grasford/Deadwood rocks (Fig. 3). These variations indicate that the redox/pH conditions during alteration of the Shoemaker Formation rocks and the Matijevic Hill rocks were similar, but that the Deadwood/Grasberg unit may have undergone alteration under different conditions, possibly at a later time. The Matijevic Hill outcrops appear to share a common genetic origin. It is not yet clear whether both the Shoemaker impactites and Matijevic Hill rocks are related to the formation of Endeavour Crater, or whether the Matijevic Hill suite represents a prior episode of Martian impact or volcanism. Opportunity continues to investigate both hypotheses.

Cohen, B. A.↗
NASA NTRS2013

Initial Estimates of Optical Constants of Mars Candidate Materials

Data obtained at visible and near-infrared wavelengths by OMEGA on Mars Express and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al- OH-bearing phyllosilicates were identified including the smectites, nontronite, saponite, and montmorillonite. To constrain the abundances of these phyllosilicates, spectral analyses of mixtures are needed. We report on our effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include two component mixtures of hydrated/ hydroxylated silicates with each other and with two analogs for other Martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass, hereafter referred to as palagonite). For the hydrated-hydroxylated silicates we include saponite and montmorillonite (Mg- and Al-rich smectites). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 micron.

Rousch, Ted L.↗
NASA NTRS2014

Optical Constants of Mars Candidate Materials used to Model Laboratory Reflectance Spectra of Mixtures

Data obtained at visible and nearinfrared wavelengths by OMEGA on MarsExpress and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al- OH-bearing phyllosilicates were identified including the smectites nontronite, saponite, and montmorillonite. To constrain the abundances of these phyllosilicates, spectral analyses of mixtures are needed. We report on our effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. Here we focus on two component mixtures of the hydrated/ hydroxylated silicates, saponite and montmorillonite (Mg- and Al-rich smectites) with each other and with two analogs for other Martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass, hereafter referred to as palagonite). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 micron. Here we focus upon mixtures of the 63-90 m size fractions.

MarsExpress and CRISM↗
NASA NTRS2014

SAM-Like Evolved Gas Analyses of Phyllosilicate Minerals and Applications to SAM Analyses of the Sheepbed Mudstone, Gale Crater, Mars

While in Yellowknife Bay, the Mars Science Laboratory Curiosity rover collected two drilled samples, John Klein (hereafter "JK") and Cumberland ("CB"), from the Sheepbed mudstone, as well as a scooped sample from the Rocknest aeolian bedform ("RN"). These samples were sieved by Curiosity's sample processing system and then several subsamples of these materials were delivered to the Sample Analysis at Mars (SAM) instrument suite and the CheMin X-ray diffraction/X-ray fluorescence instrument. CheMin provided the first in situ X-ray diffraction-based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., Fe-saponite) and comprise ~20 wt% of the mudstone samples [1]. SAM's evolved gas analysis (EGA) mass spectrometry analyses of JK and CB subsamples, as well as RN subsamples, detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases evolved during pyrolysis. The identity of evolved gases and temperature( s) of evolution can augment mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or those phases difficult to characterize with XRD (e.g., X-ray amorphous phases). Here we will focus on the SAM H2O data, in the context of CheMin analyses, and comparisons to laboratory SAM-like analyses of several phyllosilicate minerals including smectites.

McAdam, A. C.↗