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Astrobiological Significance of Definitive Mineralogical Analysis of Martian Surface Samples Using the CheMin XRD/XRF Instrument

The search for evidence of habitability, or of extant or extinct life on Mars, will initially be a search for evidence of past or present conditions supportive of life. The three key requirements for the emergence of life are thought to be liquid water; a suitable energy source; and chemical building blocks. CheMin is a miniaturized XRD/XRF (X-Ray diffraction / X-ray fluorescence) instrument which has been developed for definitive mineralogic analysis of soils and rocks on the Martian surface. The CheMin instrument can provide information that is highly relevant to each of these habitability requirements as summarized below.

Feldman, S. M.↗

CheMin: A Definitive Mineralogy Instrument in the Analytical Laboratory of the Mars Science Laboratory (MSL '09)

An important goal of the Mars Science Laboratory (MSL 09) mission is the determination of definitive mineralogy and chemical composition. CheMin is a miniature X-ray diffraction/X-ray fluorescence (XRD/XRF) instrument that has been chosen for the analytical laboratory of MSL. CheMin utilizes a miniature microfocus source cobalt X-ray tube, a transmission sample cell and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D X-ray diffraction patterns and X-ray fluorescence spectra from powdered or crushed samples. A diagrammatic view of the instrument is shown.

Blake, D. F.↗

CheMin: A Definitive Mineralogy Instrument in the Analytical Laboratory of the Mars Science Laboratory

An important goal of the Mars Science Laboratory (MSL '09) mission is the determination of definitive mineralogy and chemical composition. CheMin is a miniature X-ray diffraction/X-ray fluorescence (XRD/XRF) instrument that has been chosen for the analytical laboratory of MSL. CheMin utilizes a miniature microfocus source cobalt X-ray tube, a transmission sample cell and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D X-ray diffraction patterns and X-ray fluorescence spectra from powdered or crushed samples. A diagrammatic view of the instrument is shown. Additional information is included in the original extended abstract.

Blake, David F.↗

Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in the Rocknest samples.

Rampe, E. B.↗

Coordinated Analyses of Antarctic Sediments as Mars Analog Materials Using Reflectance Spectroscopy and Current Flight-Like Instruments for CheMin, SAM and MOMA

Coordinated analyses of mineralogy and chemistry of sediments from the Antarctic Dry Valleys illustrate how data obtained using flight-ready technology of current NASA and ESA missions can be combined for greater understanding of the samples. Mineralogy was measured by X-ray diffraction (XRD) and visible/ near-infrared (VNIR) reflectance spectroscopy. Chemical analyses utilized a quadrupole mass spectrometer (QMS) to perform pyrolysis-evolved gas analysis (EGA) and gas chromatography-mass spectrometry (GC/MS) both with and without derivatization, as well as laser desorption-mass spectrometry (LD/MS) techniques. These analyses are designed to demonstrate some of the capabilities of near-term landed Mars missions, to provide ground truthing of VNIR reflectance data acquired from orbit by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on MRO and to provide detection limits for surface- operated instruments: the Chemistry and Mineralogy (CheMin) and Sample Analysis at Mars (SAM) instrument suites onboard Mars Science Laboratory (MSL) and the Mars Organic Molecule Analyzer (MOMA) onboard ExoMars-2018. The new data from this study are compared with previous analyses of the sediments performed with other techniques. Tremolite was found in the oxic region samples for the first time using the CheMin-like XRD instrument. The NIR spectral features of tremolite are consistent with those observed in these samples. Although the tremolite bands are weak in spectra of these samples, spectral features near 2.32 and 2.39 micrometers could be detected by CRISM if tremolite is present on the martian surface. Allophane was found to be a good match to weak NIR features at 1.37-1.41, 1.92, and 2.19 micrometers in spectra of the oxic region sediments and is a common component of immature volcanic soils. Biogenic methane was found to be associated with calcite in the oxic region samples by the SAM/EGA instrument and a phosphoric acid derivative was found in the anoxic region sample using the SAM/MTBSTFA technique.

Mars↗

A Decade of Mineralogical Discoveries in Gale Crater, Mars from the CheMin XRD Instrument

Curiosity landed in Gale crater in August 2012 and has traversed ~28 km through sedimentary rocks that comprise the lower slopes of a ~5 km-high mound, informally known as Mount Sharp, to investigate depositional/diagenetic environments and potential habitability. Orbital visible/short-wave infrared spectra revealed some strata on lower 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-five powdered rock samples have been analyzed by the CheMin XRD instrument to evaluate mineralogical changes within the stratigraphic section. Curiosity began studying the strata that show mineralogical signatures from orbit in 2018, with the investigation of Vera Rubin ridge. Here, we describe the mineralogical diversity in these strata using X-ray diffraction data collected by the CheMin instrument. We report on the mineral assemblages from: 1) Hematite-rich Vera Rubin ridge; 2) Smectite-rich Glen Torridon region that progresses from tri- to di-octahedral phyllosilicate; 3) Transition unit from smectite to sulfate-bearing rocks with lower layers dominated by Ca-sulfates. We will present hypotheses explaining the changes in mineralogy throughout the strata, including changes in depositional environment, diagenetic reactions with saline groundwater, and groundwater-lake water interactions (e.g., 5-7). Continued exploration of sulfate-rich rocks will elucidate this environmental transition above the phyllosilicate-rich sediments.

V M Tu↗

Hematite Formation and Growth in Gale Crater Seen Through MSL Chemin X-Ray Diffraction Data

For more than 10 Earth years, the Mars Science Laboratory (MSL) Curiosity rover has been studying modern sediments and ancient sedimentary rocks deposited by lacustrine, fluvial, deltaic, and eolian processes in Gale crater. The mineral and X-ray amorphous abundances in rocks and sediments have been quantified via X-ray diffraction (XRD) data from the CheMin instrument. The received data demonstrate significant mineralogical variations within the stratigraphy, including changes in the type and abundances of Fe-oxides/oxyhydroxides silica polymorphs, phyllosilicates, and sulfate minerals. Characterizing Fe-oxides/oxyhydroxide minerals in Gale crater is especially important for constraining past aqueous environments because their formation depends on a variety of conditions, including pH, Eh, temperature, and salinity. Hematite, magnetite, goethite, and akaganeite have been identified by CheMin in different portions of the stratigraphic section. Hematite is the most prevalent Fe-bearing oxide mineral and has been detected (>1 wt.%) in 34 of the studied 36 drill targets. Variations in hematite crystallite size were reported in association with Vera Rubin ridge, which has a strong hematite signature in orbital reflectance spectroscopy. Here, we calculate hematite crystallite sizes and shapes for the entire stratigraphic section to date, to characterize trends and evaluate the processes by which hematite formed and transformed in Gale crater.

M. Szczerba↗

In Situ Analysis of Martian Phyllosilicates Using the Chemin Minerological Instrument on Mars Science Laboratory

The CheMin minerological instrument on Mars Science Laboratory (MSL'09) [1] will return quantitive Xray diffraction data (XRD) and quantative X-ray fluorescence data (XRF;14<Z<92) from scooped soil samples and drilled rock powders collected from the Mars surface. Samples of 45-65 mm 3 from material sieved to less than 150 micrometers will be delivered through a funnel to one of 27 reusable sample cells (five additional cells on the sample wheel contain diffraction of fluorescence standards). Sample cells are 8-mm diamater discs with 7-micrometer thick Mylar or Kapton windows spaced 170 micrometers apart. Within this volume, the sample is shaken by piezoelectric vibration at sonic frequencies, causing the powder to flow past a narrow, collimated -ray beam in random orientation can be obtained even from minnerals exhibiting strong preferred orientation such as phylosilicates.

Blake, David F.↗

Test and Delivery of the Chemin Mineralogical Instrument for Mars Science Laboratory

The CheMin mineralogical instrument on MSL will return quantitative powder X-ray diffraction data (XRD) and qualitative X-ray fluorescence data (XRF; 14<Z<92) from scooped soil samples and drilled rock powders collected on the Mars surface. The geometry of the source, sample, and detector is shown. A transmission geometry was chosen so that diffracted intensities in the low-20 region (5-15 deg), important for phyllosilicate identification, could be detected.

Blake, D. F.↗

Confidence Hills Mineralogy and Chemin Results from Base of Mt. Sharp, Pahrump Hills, Gale Crater, Mars

The Mars Science Laboratory (MSL) rover Curiosity recently completed its fourth drill sampling of sediments on Mars. The Confidence Hills (CH) sample was drilled from a rock located in the Pahrump Hills region at the base of Mt. Sharp in Gale Crater. The CheMin X-ray diffractometer completed five nights of analysis on the sample, more than previously executed for a drill sample, and the data have been analyzed using Rietveld refinement and full-pattern fitting to determine quantitative mineralogy. Confidence Hills mineralogy has several important characteristics: 1) abundant hematite and lesser magnetite; 2) a 10 angstrom phyllosilicate; 3) multiple feldspars including plagioclase and alkali feldspar; 4) mafic silicates including forsterite, orthopyroxene, and two types of clinopyroxene (Ca-rich and Ca-poor), consistent with a basaltic source; and 5) minor contributions from sulfur-bearing species including jarosite.

Cavanagh, P. D.↗

Mineralogy, Provenance, and Diagenesis of a Potassic Basaltic Sandstone on Mars: CheMin X-Ray Diffraction of the Windjana Sample (Kimberley Area, Gale Crater)

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, approximately Or(sub 95)); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (approximately 25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, approximately 1.8 times that of Windjana, implying a sediment component with greater than 40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g.,mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

Treiman, Allan H.↗

The Mineralogical Record of Ancient Fluvio-Lacustrine Environments in Gale Crater as Measured by the MSL CheMin Instrument

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to investigate early Hesperian-aged sedimentary rocks on the lower slopes of Aeolis Mons (i.e., Mount Sharp) that show variations in phyllosilicates, hematite, and sulfates from orbital reflectance spectroscopy, suggesting changes in ancient aqueous environments. During the Eighth International Conference on Mars in July 2014, Curiosity was still traversing the Bradbury group on the plains of Gale crater (Aeolis Palus) and had only analyzed four samples in its internal laboratories. Soon after Mars 8, Curiosity began its investigation of Mount Sharp and has since driven through ~350 m of vertical stratigraphy, the majority of which is part of the Murray formation. The Murray fm is comprised primarily of laminated mudstone with occasional sandstone and heterolithic facies and represents a long-lived fluvio-lacustrine environment. Curiosity has analyzed 13 drilled rock samples from the Murray formation and 4 from the ancient eolian Stimson fm with the Chemistry and Mineralogy (CheMin) instrument. Here, we discuss the mineralogy of all fluvio-lacustrine samples analyzed to date and what these results tell us about sources of the sediments, aqueous environments, and habitability of ancient Gale crater.

Rampe, E. B.↗

Mineralogy of Vera Rubin Ridge in Gale Crater from the Mars Science Laboratory CheMin instrument

Gale crater was selected as the landing site for the Mars Science Laboratory Curiosity rover because of orbital evidence for a variety of secondary minerals in the lower slopes of Aeolis Mons (aka Mount Sharp) that indicate changes in aqueous conditions over time. Distinct units demonstrate orbital spectral signatures of hematite, phyllosilicate (smectite), and sulfate minerals, which suggest that ancient aqueous environments in Gale crater varied in oxidation potential, pH, and water activity. Vera Rubin ridge (VRR) is the first of these units identified from orbit to have been studied by Curiosity. Orbital near-infrared data from VRR show a strong band at 860 nm indicative of hematite. Before Curiosity arrived at VRR, the hypotheses to explain the formation of hematite included (1) precipitation at a redox interface where aqueous Fe2+ was oxidized to Fe3+, and (2) acidic alteration of olivine in oxic fluids. Studying the composition and sedimentology of the rocks on VRR allow us to test and refine these hypotheses and flesh out the depositional and diagenetic history of the ridge. Here, we focus on the mineralogical results of four rock powders drilled from and immediately below VRR as determined by CheMin.

Rampe, E. B.↗

Mineralogy of Vera Rubin Ridge from the Mars Science Laboratory CheMin Instrument

Vera Rubin ridge (VRR) is an erosion-resistant feature on the northwestern slope of Mount Sharp in Gale crater, Mars, and orbital visible/short-wave infrared measurements indicate it contains red-colored hematite. The Mars Science Laboratory Curiosity rover performed an extensive campaign on VRR to study its mineralogy, geochemistry, and sedimentology to determine the depositional and diagenetic history of the ridge and constrain the processes by which the hematite could have formed. X-ray diffraction (XRD) data from the CheMin instrument of four samples drilled on and below VRR demonstrate differences in iron, phyllosilicate, and sulfate mineralogy and hematite grain size. Hematite is common across the ridge, and its detection in a gray-colored outcrop suggested localized regions with coarse-grained hematite, which commonly forms from warm fluids. Broad XRD peaks for hematite in one sample below VRR and the abundance of FeOT in the amorphous component suggest the presence of nano-crystalline hematite and amorphous Fe oxides/oxyhydroxides. Well-crystalline akaganeite and jarosite are present in two samples drilled from VRR, indicating at least limited alteration by acid-saline fluids. Collapsed nontronite is present below VRR, but samples from VRR contain phyllosilicate with d(001) = 9.6 Å, possibly from ferripyrophyllite or an acid-altered smectite. The most likely cementing agents creating the ridge are hematite and opaline silica. We hypothesize late diagenesis can explain much of the mineralogical variation on the ridge, where multiple fluid episodes with variable pH, salinity, and temperature altered the rocks, causing the precipitation and crystallization of phases that are not otherwise in equilibrium.

E. B. Rampe↗

Mineralogy of the Greenheugh Pediment and Underlying Murray Formation from the Mars Science Laboratory CheMin Instrument

The Mars Science Laboratory Curiosity rover has been investigating a sequence of ancient fluvio-lacustrine and eolian units in Gale crater. For much of the mission, Curiosity has studied the fluvio-lacustrine deposits of the Murray formation. Curiosity has also studied the ancient eolian Stimson formation in a few locations, which unconformably overlies the Murray fm. The Stimson formation was previously studied at the Naukluft and Emerson Plateaus and recently studied at the Greenheugh pediment capping unit. The Curiosity science team also investigated the Murray formation directly underlying the pediment. Curiosity drilled the “Edinburgh” target within the pediment capping unit and the “Hutton” target in the Murray formation near the contact with the pediment and delivered these materials to the CheMin X-ray diffractometer to characterize bulk mineralogy. Edinburgh contains abundant plagioclase, pyroxene, magnetite, olivine, and X-ray amorphous materials, with 10 wt.% smectite and minor sanidine. The mineralogy of the Stimson at Greenheugh is distinct from the mineralogy of the Stimson at Naukluft and Emerson because previous Stimson targets did not contain olivine or clay minerals. This suggests sediments in the pediment may have a different source and/or different aqueous alteration history than those from Naukluft and Emerson. Hutton contains abundant plagioclase, pyroxene, magnetite, and X-ray amorphous materials, 6 wt.% smectite, and minor cristobalite, opal-CT, sanidine, hematite, fluorapatite, and anhydrite. Other Murray targets in the surrounding Glen Torridon region that are farther from the pediment contact contain ~30 wt.% smectite and lack cristobalite and opal-CT. Cristobalite and/or opal-CT are present in a few other targets elsewhere along the traverse, including the top of the nearby Vera Rubin ridge and the top of the Pahrump Hills outcrop. Stimson overlies the Pahrump Hills, and, based on projections of the pediment slope, the Stimson may have overlain Vera Rubin ridge. The proximity of the low-smectite and cristobalite- and/or opal-CT-bearing outcrops to the contact between the Murray and Stimson suggests the contact provided a conduit for diagenetic fluids that altered clay minerals and formed crystalline and paracrystalline silica.

E. B. Rampe↗

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↗

Recent Mineralogical Discoveries in Gale Crater, Mars from the CheMin XRD Instrument

Curiosity landed in Gale crater in August 2012 and has traversed ~27 km through sedimentary rocks that comprise the lower slopes of a ~5 km-high mound, informally known as Mount Sharp, to investigate depositional/diagenetic environments and potential habitability. Orbital visible/short-wave infrared spectra revealed some strata on lower 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). Curiosity began studying the strata that show mineralogical signatures from orbit in 2018, with the investigation of Vera Rubin ridge. Here, we describe the mineralogical diversity in these strata using X-ray diffraction data collected by the CheMin instrument. We report on the mineral assemblages from the hematite-rich Vera Rubin ridge, the smectite-rich Glen Torridon region, and the transition from the smectite-bearing rocks to the sulfate-bearing unit. We will present hypotheses explaining the changes in mineralogy throughout the strata, including changes in depositional environment, diagenetic reactions with saline groundwater, and groundwater-lake water interactions (e.g., 5-7).

V. M. Tu↗