Phosphates on Mars and Their Importance as Igneous, Aqueous, and Astrobiological Indicators
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E. M. Hausrath↗
Engineering topics
V. M. Tu
Publications and source records attributed to V. M. Tu.
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↗
Thermal and Evolved Gas Analysis of Mars Analog Paleosols
Decades of space exploration have shown that three to four billion-year old surface environments on Mars may have been habitable. Ancient surface environments which resemble paleosols (buried sedimentary deposits which formed from subaerial weathering) on Mars have recently been named a high-priority target for biosignature investigation and Mars Sample Return because paleosol mineralogy records valuable information about past climates, and because Archean (~2.6 Ga) paleosols from Earth preserve some of the oldest biosignatures of life on land. However, there has been little effort to characterize terrestrial paleosols with Mars-like mineralogy using instruments analogous to those on current and future missions to Mars, which is imperative for understanding if putative paleosols on Mars should be targeted for future exploration. The objectives of this study were to perform the first comprehensive analysis of Mars-analog paleosols with Mars flight-analog instrumentation and to determine if organic carbon in these paleosols is detectable in the presence of a perchlorate salt.
A. P. Broz↗
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↗
Importance of Sulfur for Phosphorus Mobility on the Martian Surface
Sulfur and phosphorus were mobile on the martian surface, and we present evidence that sulfate was likely a control on phosphate mobility. Mobility of the two elements on the martian surface is crucial for the habitability of Mars because their availability for biochemical reactions and biological structures is a major constraint on life. In the sedimentary rocks of Gale crater, the rover Curiosity has discovered evidence of mobile S and P with the alpha particle X-ray spectrometer (APXS). Sulfur-rich fluids are evident in ubiquitous Ca-sulfate veins that crosscut the bedrock. Compelling evidence of P mobility is in nodules, veins, crusts, and haloes with P2O5 enrichments (1.5-7.5 wt%) relative to the median bedrock (0.9-1.2 wt%) and average basaltic crust (~0.9 wt%). We have investigated phosphorus mobility in Hawaiian analogues, where the primary P2O5 (0.2-2.1 wt%) is contained in Ca-apatite. Four relevant processes have emerged: (1) In open-system, circumneutral regolith weathering profiles, we found up to 40% of the P was leached over 10s-100s ka. (2) Natural acid-sulfate alteration at the Maunakea summit resulted in the dissolution of apatite and mobilization of phosphate 10s-1000s µm to rock surfaces where it formed Al-phosphates and substituted into crystalline sulfates (alunite and jarosite). (3) Experimental results indicate that basaltic sediment chemisorbs phosphate (pH < 7). (4) In experimental systems containing water, basaltic sediment, and a starting pH = 2-7, phosphate has higher solubility in chloride-rich fluids, but significantly lower solubility in sulfate-rich fluids. For example, in water doped with phosphate (~100-500 mg/L), ~60-80% of the PO43- was removed from the sulfate-rich fluid, whereas ~20% of the PO43- was removed from the Cl-rich and pure water fluids (likely via adsorption). Gypsum precipitated from the sulfate-rich fluids; the fate of phosphate in the solid residue is unconfirmed. The potential for phosphate incorporation in martian sulfates is reflected in the enrichment of P2O5 in Gale Ca-sulfate veins, based on preliminary analyses of APXS data. Models for the mobility of phosphorus in Gale crater should consider these conflicting P characteristics: (1) P solubility may have been inhibited by sulfate and (2) P¬ is enriched in diagenetic features and was therefore mobile.
Jeff A. Berger↗
Mineralogical Evidence for Environmental Change in the Clay-Sulfate Transition at Gale Crater, Mars
A primary reason for selecting Gale crater as the Mars Science Laboratory (MSL) Curiosity rover landing site was a clear mineralogical transition from Fe/Mg smectite in older strata to hydrated Mg sulfate salts in younger strata observed in orbital visible/shortwave-infrared reflectance data. This transition has been observed in other early-Hesperian terrains on Mars and has been hypothesized to signal a planet-wide change in climate from relatively warm and wet to cold and dry. Curiosity studied the sedimentology and geochemical and mineralogical composition of rocks in this “clay-sulfate transition” region from sols 3052 to 3572 (i.e., March 2021 to August 2022), with arrival at the sulfate unit on sol 3574. Here, we report on the mineralogical measurements made by the CheMin X-ray diffractometer of the six drill targets in the clay-sulfate transition and the first drill target in the sulfate unit. We use compositional data and sedimentological observations to interpret depositional and diagenetic environments and present hypotheses to explain the transition from clay minerals to hydrated Mg sulfates.
E. B. Rampe↗
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↗
Using Mineralogy to Interpret Martian Geologic History
The surface mineralogy of Mars is key to interpreting the planet’s geologic history and constraining when and where Mars may have been habitable to microbial life. Orbital mineralogical data from infrared spectrometers collected over the last two decades have demonstrated that Mars is more than a basaltic planet. Thermal infrared (TIR) emission spectrometers have identified regional variations in igneous minerals, iron oxides, and chloride salts, showing evidence for magmatic evolution and aqueous alteration. Orbital visible/shortwave infrared reflectance spectra provide detailed information about the aqueous history of Mars through the identification of clay minerals, sulfates, carbonates, zeolites, and amorphous materials in ancient ~3-4-billion-year-old terrains. Mineralogical data from rovers allow us to better characterize mineral formation mechanisms by identifying mineral assemblages and placing them in geologic context using outcrop- to grain-scale images. TIR and Mössbauer data from the Mars Exploration Rovers helped identify an ancient dune-interdune playa environment with multiple episodes of groundwater at Meridiani Planum and volcanism-induced hydrothermalism at Gusev crater. The CheMin X-ray diffractometer on the Mars Science Laboratory Curiosity rover in Gale crater is the first fully quantitative mineralogical instrument sent to another planetary surface. CheMin data allow the quantification of minerals and X-ray amorphous materials with a mineral detection limit of <1 wt.% and provide crystal chemistry of major phases from refined unit-cell parameters. CheMin has revealed local mineralogical changes in ancient sedimentary rocks not seen from orbit and helped identify habitable environments. Throughout the 600+ m of vertical stratigraphy studied so far, changes in clay mineralogy, Fe-oxides/oxyhydroxides, sulfates, and carbonates demonstrate a long history of surface and groundwater at Gale crater with variable salinity, pH, Eh, and temperature. Recent CheMin data document a decrease in clay minerals and an increase in sulfate minerals in younger strata that corresponds with a change from fluvio-lacustrine to eolian depositional environments, potentially documenting a change to a drier climate across the planet.
E. B. Rampe↗
Advances in X-ray Instruments to Support Mars Sample Return
The Mars 2020 Perseverance rover is currently collecting drill cores of ancient igneous and sedimentary rock in and around Jezero crater for potential transport to Earth. These samples from the martian surface will enable detailed mineralogical, geochemical, and petrological measurements to characterize ancient depositional and diagenetic environments, quantitatively age-date the samples, and identify the building blocks for life or evidence for life itself. Furthermore, these drill cores are especially precious because they may represent the most pristine samples from the martian surface and our best chance at identifying martian life, as future sample return missions may be conducted by humans that can introduce biological contaminants to the samples. Because of the importance of these samples, we must take great care in their handling, curation, and preliminary analyses so that they are preserved for scientific measurements for decades to come. In-situ measurements by Perseverance have identified minerals that further warrant special treatment of the returned samples. Hydrated sulfate carbonate, swelling clay minerals, and oxychlorine salts are extremely sensitive to changes in temperature and relative humidity. The structures of hydrated sulfates and oxychlorine minerals, in particular, readily change when exposed to different conditions, meaning the mineral assemblage of the as-returned samples may be lost if the samples aren’t handled properly. Characterizing the as-returned mineral assemblage, particularly of the salts, is essential for reconstructing past aqueous conditions and habitability. To characterize the as-returned mineral assemblage, the samples must be analyzed rapidly before phase changes occur and/or under controlled conditions (e.g., within a glove box). Significant recent advances in X-ray instrumentation for robotic exploration of the solar system have resulted in high-resolution miniaturized instruments that would provide mineralogical, geochemical, and petrological information on the returned martian samples without degradation of the mineral assemblage. Here, we describe a combined X-ray diffractometer/X-ray fluorescence spectrometer (XRD/XRF), an X-ray computed tomographic (XCT) instrument, and a scanned beam XRF mapping instrument that could be used in a glove box so that the martian samples remain under controlled conditions.
E. B. Rampe↗