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NASA NTRS2007

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.↗
NASA NTRS2006

Acid Sulfate Weathering on Mars: Results from the Mars Exploration Rover Mission

Sulfur has played a major role in the formation and alteration of outcrops, rocks, and soils at the Mars Exploration Rover landing sites on Meridiani Planum and in Gusev crater. Jarosite, hematite, and evaporite sulfates (e.g., Mg and Ca sulfates) occur along with siliciclastic sediments in outcrops at Meridiani Planum. The occurrence of jarosite is a strong indicator for an acid sulfate weathering environment at Meridiani Planum. Some outcrops and rocks in the Columbia Hills in Gusev crater appear to be extensively altered as suggested by their relative softness as compared to crater floor basalts, high Fe(3+)/FeT, iron mineralogy dominated by nanophase Fe(3+) oxides, hematite and/or goethite, corundum-normative mineralogies, and the presence of Mg- and Casulfates. One scenario for aqueous alteration of these rocks and outcrops is that vapors and/or fluids rich in SO2 (volcanic source) and water interacted with rocks that were basaltic in bulk composition. Ferric-, Mg-, and Ca-sulfates, phosphates, and amorphous Si occur in several high albedo soils disturbed by the rover's wheels in the Columbia Hills. The mineralogy of these materials suggests the movement of liquid water within the host material and the subsequent evaporation of solutions rich in Fe, Mg, Ca, S, P, and Si. The presence of ferric sulfates suggests that these phases precipitated from highly oxidized, low-pH solutions. Several hypotheses that invoke acid sulfate weathering environments have been suggested for the aqueous formation of sulfate-bearing phases on the surface of Mars including (1) the oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials by solutions enriched by volcanic gases (e.g., SO2); and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials.

Ming, Douglas W.↗
NASA NTRS2006

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.↗
NASA NTRS2010

Principal Components Analysis of Reflectance Spectra Returned by the Mars Exploration Rover Opportunity

The Mars Exploration Rover Opportunity has spent over six years exploring the Martian surface near its landing site at Meridiani Planum. Meridiani bedrock observed by the rover is largely characterized by sulfate-rich sandstones and hematite spherules, recording evidence of ancient aqueous environments [1]. The region is a deflationary surface, allowing hematite spherules, fragments of bedrock, and "cobbles" of foreign origin to collect loosely on the surface. These cobbles may be meteorites (e.g., Barberton, Heat Shield Rock, Santa Catarina) [2], or rock fragments of exotic composition derived from adjacent terranes or from the subsurface and delivered to Meridiani Planum as impact ejecta [3]. The cobbles provide a way to better understand Martian meteorites and the lithologic diversity of Meridiani Planum by examining the various rock types located there. In the summer of 2007, a global dust storm on Mars effectively disabled Opportunity's Miniature Thermal Emission Spectrometer (Mini-TES), which served as the Athena Science Team s primary tool for remotely identifying rocks of interest on a tactical timescale for efficient rover planning. While efforts are ongoing to recover use of the Mini-TES, the team is currently limited to identifying rocks of interest by visual inspection of images returned from Opportunity's Panoramic Camera (Pancam). This study builds off of previous efforts to characterize cobbles at Meridiani Planum using a database of reflectance spectra extracted from Pancam 13-Filter (13F) images [3]. We analyzed the variability of rock spectra in this database and identified physical characteristics of Martian rocks that could potentially account for the observed variance. By understanding such trends, we may be able to distinguish between rock types at Meridiani Planum and regain the capability to remotely identify locally unique rocks.

Mercer, C. M.↗
NASA NTRS2012

Chemical and Mineralogical Characterization of Acid-Sulfate Alteration of Basaltic Material on Mauna Kea Volcano, Hawaii: Jarosite and Hydrated Halloysite

Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH <3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO-CRISM and MEx OMEGA, MERMB, MSL-CheMin, and MER and MSL APXS, respectively.

Graff, Trevor G.↗
NASA NTRS2012

Dissolution of Olivine, Siderite, and Basalt at 80 Deg C in 0.1 M H2SO4 in a Flow Through Process: Insights into Acidic Weathering on Mars

The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

Golden, D. C.↗
NASA NTRS2015

Aram Chaos: a Long Lived Subsurface Aqueous Environment with Strong Water Resources Potential for Human Missions on Mars

Aram Chaos, Mars is a crater 280 kilometers in diameter with elevations circa. minus 2 to minus 3 kilometers below datum that provides a compelling landing site for future human explorers as it features multiple scientific regions of interest (ROI) paired with a rich extensible Resource ROI that features poly-hydrated sulfates [1]. The geologic history of Aram Chaos suggests several past episodes of groundwater recharge and infilling by liquid water, ice, and other materials [1-3]. The creation of the fractured region with no known terrestrial equivalent may have been caused by melting of deep ice reservoirs that triggered the collapse of terrain followed by catastrophic water outflows over the region. Aram Chaos is of particular scientific interest because it is hypothesized that the chaotic terrain may be the source of water that contributed to the creation of nearby valleys such as Ares Vallis flowing toward Chryse Planitia. The liquid water was likely sourced as groundwater and therefore represents water derived from a protected subsurface environment making it a compelling astrobiological site [2]. The past history of water is also represented by high concentrations of hematite, Fe-oxyhydroxides, mono-hydrated and poly-hydrated sulfates [1, 2]. Poly-hydrated sulfates are likely to contain abundant water that evolves at temperatures below 500 degrees Centigrade thus conferring Aram Chaos a potentially high value for early in-situ resource utilization (ISRU) [4]. The geologic history also calls for future prospecting of deep ice deposits and possibly liquid water via deep drilling. The most recent stratigraphic units in the central part of Aram Chaos are not fractured, and are part of a dome-shaped formation that features bright, poorly-consolidated material that contains both hydrated sulfates and ferric oxides according to OMEGA (Observatoire pour la Minéralogie, l'Eau, les Glaces et l'Activité) data [5]. These surface material characteristics are preliminary indications of their potential use in civil engineering activities that involve regolith moving and hauling, while further study is needed to assess traverse-ability challenges. The widespread distribution of sulfates is also of interest as a resource for the use of sulfur as a binding compound in regolith-based concrete for constructions. The terrain depressions caused by the rock fracturing events may challenge surface mobility but also suggest the possibility of using such natural features for additional shielding from space radiation and as emplacement of nuclear surface power reactors for the same reason. The high concentration of hematite (up to 16 percent) in some of the smoother recent terrains of the central part of Aram Chaos [2] is a favorable attribute for metal extraction ISRU to create iron-based feedstock for in-situ fabrication of replacement parts or their repairs. Preliminary data on Aram Chaos indicate that it offers a combination of many critical criteria for human missions to the surface of Mars: equatorial region at low Mars Orbiter Laser Altimeter (MOLA), evidence of hydrated minerals over large areas and at high concentrations tied to historic evidence of liquid water over long periods.

Sibille, L.↗
NASA NTRS2017

Effects of Martian Surface Materials on the Thermal Decomposition of Hydrogen Peroxide

While hydrogen peroxide (H2O2) has been detected in the martian atmosphere, it has not been detected in surface materials. Since the Viking lander mission, we have sent instruments to Mars with the capability to detect H2O2. The Sample Analysis at Mars (SAM) instrument onboard the Curiosity Rover and Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander both detected water and oxygen releases from analyzed sediments but whether or not peroxide could be the source of these gases has not been investigated. We are investigating the possible presence of H2O2 in martian materials by analyzing Mars-relevant minerals that have been mixed with hydrogen peroxide using lab instruments configured as analogs to Mars mission instruments. The object of this research is to use lab instruments to find the effects of Mars analog minerals on hydrogen peroxide gas release temperatures, specifically gas releases of water and oxygen and also determine the effect of the peroxide on the minerals. Data that we get from the lab can then be compared to the data collected from Mars. The minerals hematite, siderite, San Carlos olivine, magnetite and nontronite were chosen as our Mars analog minerals. ~20 mg of analog Mars minerals with 5μl of 50% H2O2, and were either run immediately or placed in a sealed tube for 2, 4, or 9 days to look for changes over time with two reps being done at each time step to determine repeatability. Each sample was heated from -60 degC to 500 degC at 20 degC/min and the evolved gases were monitored with a mass spectrometer. Each sample was also analyzed with an X-ray diffraction instrument to look for changes in mineralogy. Preliminary results show three potential outcomes: 1) peroxide has no effect on the sample (e.g., hematite), 2) the mineral is unaffected but catalyzes peroxide decomposition (magnetite, siderite), or 3) peroxide alters the mineral (pyrrhotite, San Carlos olivine).

Archer, P. D., Jr.↗
NASA NTRS2017

Smectite Formation in the Presence of Sulfuric Acid: Implications for Acidic Smectite Formation on Early Mars

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (approximately 200 degC). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH less than or equal to 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH approximately 3 and trioctahedral smectite saponite at final pH approximately 4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Smectite↗
NASA NTRS2018

Curiosity's Investigation at Vera Rubin Ridge

The Curiosity rover is exploring Vera Rubin Ridge (VRR), a ~6.5 km long and ~200 m wide topographic feature trending northeast-southwest across Aeolis Mons (informally known as Mt. Sharp) (Fig 1). In orbital data, VRR is distinct from the underlying Murray formation due to its relative erosional resistance and greater exposure of bedrock. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) orbital data show a hematite spectral signature over much of the ridge (Fig. 2). On the ground, Curiosity also observed hematite associated with the sedimentary rocks of the underlying Murray formation, although these detections are difficult to see with CRISM due to mixing with sand and dust.

Fraeman, A. A.↗
NASA NTRS2019

Rock Hard Science: Multispectral and Mineralogical Investigations to Understand Bedrock Spectral Properties and Strength at Vera Rubin Ridge, Gale Crater, Mars

Since the beginning of the Mars Science Laboratory (MSL) mission, Vera Rubin Ridge (VRR) has been a location of interest to the MSL science team because of its apparent erosional resistance and strong near-IR (~860 nm) absorption feature seen from orbit in the Mars Reconnaissance Orbiter mission's Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) data. The strong CRISM absorption feature along VRR was hypothesized to be primarily associated with an increased abundance of crystal-line hematite compared to lower Mt. Sharp units. How-ever, surface multispectral and mineralogic data, from the Mastcam and CheMin instruments onboard the Curiosity rover, suggest hematite is not the only mineral contributing to the near-IR absorption feature measured in VRR or the reason for its relative hardness.

Jacob, S. R.↗
NASA NTRS2020

Evidence for Multiple Diagenetic Episodes in Ancient Fluvial‐Lacustrine Sedimentary Rocks in Gale Crater, Mars

The Curiosity rover's exploration of rocks and soils in Gale crater has provided diverse geochemical and mineralogical data sets, underscoring the complex geological history of the region. We report the crystalline, clay mineral, and amorphous phase distributions of four Gale crater rocks from an 80‐m stratigraphic interval. The mineralogy of the four samples is strongly influenced by aqueous alteration processes, including variations in water chemistries, redox, pH, and temperature. Localized hydrothermal events are evidenced by gray hematite and maturation of amorphous SiO 2 to opal‐CT. Low‐temperature diagenetic events are associated with fluctuating lake levels, evaporative events, and ground water infiltration. Among all mudstones analyzed in Gale crater, the diversity in diagenetic processes is primarily captured by the mineralogy and X‐ray amorphous chemistry of the drilled rocks. Variations indicate a transition from magnetite to hematite and an increase in matrix‐associated sulfates suggesting intensifying influence from oxic, diagenetic fluids up section. Furthermore, diagenetic fluid pathways are shown to be strongly affected by unconformities and sedimentary transitions, as evidenced by the intensity of alteration inferred from the mineralogy of sediments sampled adjacent to stratigraphic contacts.

C N Achilles↗
NASA NTRS2021

Quantifying the range of the dust direct radiative effect due to source mineralogy uncertainty

The large uncertainty in the mineral dust direct radiative effect (DRE) hinders projections of future climate change due to anthropogenic activity. Resolving modeled dust mineral speciation allows for spatially and temporally varying refractive indices consistent with dust aerosol composition. Here, for the first time, we quantify the range in dust DRE at the top of the atmosphere (TOA) due to current uncertainties in the surface soil mineralogical content using a dust mineral-resolving climate model. We propagate observed uncertainties in soil mineral abundances from two soil mineralogy atlases along with the optical properties of each mineral into the DRE and compare the resultant range with other sources of uncertainty across six climate models. The shortwave DRE responds region-specifically to the dust burden depending on the mineral speciation and underlying shortwave surface albedo: positively when the regionally averaged annual surface albedo is larger than 0.28 and negatively otherwise. Among all minerals examined, the shortwave TOA DRE and single scattering albedo at the 0.44–0.63 µm band are most sensitive to the fractional contribution of iron oxides to the total dust composition. The global net (shortwave plus longwave) TOA DRE is estimated to be within −0.23 to +0.35 W/sq. m. Approximately 97 % of this range relates to uncertainty in the soil abundance of iron oxides. Representing iron oxide with solely hematite optical properties leads to an overestimation of shortwave DRE by +0.10 W/sq. m at the TOA, as goethite is not as absorbing as hematite in the shortwave spectrum range. Our study highlights the importance of iron oxides to the shortwave DRE: they have a disproportionally large impact on climate considering their small atmospheric mineral mass fractional burden (∼2 %). An improved description of iron oxides, such as those planned in the Earth Surface Mineral Dust Source Investigation (EMIT), is thus essential for more accurate estimates of the dust DRE.

mineral dust↗
NASA NTRSDate not supplied

The Chemistry and Mineralogy of Mars Soils: A Tour of Landed Mission Results from the Last 45 years

Eight landed missions demonstrated that martian soils (defined as loose, unconsolidated surface material) consist of basaltic mineralogy, iron (hydr)oxides, amorphous material, sulfate, chloride, (per)chlorate, nitrate, carbonate, and possible organic C. The Viking Lander 1 and 2 (1976), Mars Pathfinder (1997), and Mars Exploration Rover (MER-A,B) (2004) missions determined that martian soil was similar at all landing sites by having mafic chemistry, high S (~ 7 wt.% SO3) and Cl (0.7 wt.%), and spectral detections of poorly crystalline and crystalline Fe-(hydr)oxide phases. The MER Mössbauer spectrometers detected Fe-bearing olivine and pyroxene along with magnetite, nano-phase Fe-oxides (npOx), hematite, and ferric sulfate. The 2008 Phoenix Lander instrumentation measured a soil pH of 7.7 and detected ~0.6 wt.% perchlorate, 3-5 wt.% Ca-rich carbonate and carbon (500 gC/g) consistent with oxidized organics and Fe-rich carbonate. The 2012 Mars Science Laboratory (MSL) rover (Gale Crater) through X-ray diffraction detected plagioclase feldspar, pyroxene, magnetite, hematite, anhydrite, and quartz, with the balance being composed of Si/Fe-containing amorphous (30 to 40 wt.%) material. MSL evolved gas analysis detected (per)chlorate (0.4 wt.% ClO4), nitrate (0.23 wt.%), along with minor Fe/Mg sulfate and oxidized organic C (~2000 gC/g). Limited pedogenesis may have occurred at the 2018 InSight landing site and in one Gusev Crater soil (MER-B) which have 3 to 10 cm-thick duricrust horizons consistent with atmospheric water vapor interactions with soil salts. Martian soil primary mineralogy was derived mostly from local rock (volcanic, sedimentary) that is largely basaltic planet wide. Secondary minerals [e.g., sulfate, chloride, perchlorate, nitrate, carbonate, Fe-(hydr)oxides] in martian soils formed from oxidative aqueous alteration processes and were likely derived from a combination of local sedimentary rock sources and the global bright dust. The Mars 2020 mission will collect soil for Earth return to enable a thorough assessment of the nature and origin of martian soil.

Mars↗
NASA NTRSDate not supplied

Implications of Deep UV Raman Spectra of Gypsum and Fe-Bearing Dust Mixtures for Gypsum Detectability by the SHERLOC M2020 Instrument

Key science objectives of the Mars2020 Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals (SHERLOC) instrument suite include identification and characterization of inorganic and bio-logic phases and investigation of the past habitability of Jezero crater [1, 2]. To fully interpret in situ data received from SHERLOC, databases of deep ultraviolet (DUV) Raman spectra from a wide variety of martian analogue materials are being developed by us and others [e.g., 3]. Ferrous and ferric iron are abundant on the martian surface in bas-alt and, depending on alteration and transport processes, its alteration products. Fe-bearing phases are important to characterize with respect to detect-ability by DUV Raman spectroscopy because they strongly absorb DUV radiation, thereby decreasing Raman peak intensity [3, 4]. Ca-sulfates and Fe-bearing minerals have been commonly detected on the martian surface [5, 6]. In this analogue study, we collected Raman spectra of mechanical mixtures of powders of hematite HMS3 (~120 nm discrete particle diameter [7]), palagonite HWMK919 (<5 μm size fraction [8]) and gypsum WD163 (<150 μm size fraction) t o ex-amine the detectability of gypsum in the presence of relatively finer-grained, Fe bearing material. Be-cause of the difference in particle diameters, hematite and palagonite powders act as surrogates for martian dust, coating at small concentrations and then enveloping larger gypsum particles.

N C Haney↗
NASA NTRSDate not supplied

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↗
NASA NTRSDate not supplied

Recent Mineralogical Discoveries in Gale Crater, Mars from the CheMin XRD Instrument, Demonstrating a Watery Past

Curiosity landed in Gale crater August 2012 and has traversed (~27 km) sedimentary rocks that comprise a ~5 km-high mound, informally known as Mount Sharp, to investigate depositional/diagenetic environments and potential habitability. VSWIR spectra revealed the lowermost slopes of Mount Sharp contain mineral assemblages that are indicative of water-rock interactions (1-3), with sulfate-bearing units overlying phyllosilicate-bearing units. This mineralogical succession may mark the beginning of the transition from a relatively wet/warm to a very dry/cold Mars (e.g., 1, 4). Thirty-four powdered rock samples have been analyzed by the CheMin XRD instrument and mineralogical results from the first 6 years of the mission are reviewed in [5]. Here we describe the mineralogical diversity observed over the most recent 4 years. Sediments in the Vera Rubin Ridge (VRR) and Glen Torridon (GT) region were deposited in a lacustrine-fluvial environment and are syndepositional. The mineralogy suggests post-depositional fluid-rock interaction. Differences in mineralogy could have been the result of silica-poor, briny groundwater that destabilized smectite and precipitated hematite in VRR [6]. Other hypotheses include lake water-groundwater mixing or diagenesis driven by deeply sourced fluids altering smectite to precipitate hematite and amorphous silica. Preserved bedforms in the clay-sulfate transition region indicate a change from lacustrine-fluvial to aeolian depositional environments. Mineralogical changes include the identification of goethite along with the disappearance of phyllosilicate. The absence of crystalline Mg-sulfate in drilled samples from this transition region may mean that: 1) Sulfates are concentrated in secondary concretions not sampled by Curiosity’s drill, or 2) Sulfate components are either X-ray amorphous or if crystalline, became amorphous in the relatively low-humidity environment of the rover. Continued exploration of sulfate-rich rocks will elucidate this environmental transition above the phyllosilicate-rich sediments.

V M Tu↗
NASA NTRSDate not supplied

The CheMin X-ray Diffractometer on MSL Curiosity: A Decade of Mineralogical Observations from Gale Crater, Mars

For more than a decade, the CheMin X-ray Diffraction instrument on the Mars Science Laboratory rover Curiosity has been returning quantitative mineralogical data from Gale crater, Mars. CheMin receives and analyzes sieved soil and powdered rock samples from Curiosity’s Sample Acquisition / Sample Processing and Handling (SA/SPaH) system. To date, 38 samples have been analyzed over the course of a 28 km transit. These samples document more than 600 vertical meters of flat-lying lacustrine, fluvial and aeolian sediments that comprise the lower part of the central mound of Gale crater (commonly called Mt. Sharp).The principal mineralogy of the sediments is basaltic, with evidence of early and late-stage diagenetic overprinting. The rocks in many cases preserve most of their primary mineralogy and sedimentary features, suggesting that they were never strongly heated or deformed. Using aeolian soil composition as a proxy for the composition of the deposited and lithified sediment, it appears that in many cases the diagenetic changes observed are principally isochemical. Exceptions to this include secondary nodules, calcium sulfate veining and rare alteration halos. A striking hematite-rich feature in lower Mt. Sharp called Vera Rubin Ridge is interpreted to be lake sediment diagenetically altered by silica-poor fluids. A surprising and as yet poorly understood observation is that nearly all of the 3.7 Gyr old sedimentary rocks analyzed to date are comprised of 25-50% X-ray amorphous material. Overall, this 600 m vertical section of sedimentary rock explored in lower Mt. Sharp documents a perennial shallow lake environment grading upward into alternating lacustrine/fluvial and aeolian environments. The mineralogical changes observed going up-section include a transition from trioctahedral to dioctahedral clay minerals and a transition from magnetite to hematite. More recently, in the last 150 m of section, CheMin has documented an overall decrease in clay minerals and increase in Fe3+ oxides and oxyhydroxides. The mineralogical changes observed in Gale crater may document the gradual drying out and oxidation of the martian hydrosphere.

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