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A paleoweathering profile from Griqualand West, South Africa: evidence for a dramatic rise in atmospheric oxygen between 2.2 and 1.9 bybp

A core drilled near Wolhaarkop in Griqualand West, South Africa, intersected highly oxidized Kuruman Iron Formation below red beds of the Gamagara Formation. The lateral equivalents of the Kuruman Iron Formation in this drill hole consist largely of siderite, ankerite, magnetite, greenalite, and quartz. The oxidation of the Kuruman Iron Formation in WOL 2 occurred almost certainly during weathering prior to the deposition of the Gamagara Formation. The date of this weathering episode is bracketed between about 2.2 and 1.9 bybp by the age of the Ongeluk lavas in the Transvaal sequence below the unconformity and by the age of the Hartley lavas in the Olifantshoek Group above the unconformity. The ratio of iron to SiO2 in the several facies of the weathered Kuruman Iron Formation in WOL 2 is nearly the same as that in their unweathered equivalents. Since SiO2 loss during weathering was almost certainly minor, the similarity of the Fe/SiO2 ratio in the weathered and unweathered BIF indicates that nearly all the "FeO" in the Kuruman Iron Formation was oxidized and retained as FeO3 during weathering. Such a high degree of iron retention is best explained by an O2 content of the atmosphere > or = 0.03 atm at the time of weathering. Such an O2 pressure is very much greater than that suggested by the composition of paleosols developed on basalt > or = 2.2 bybp but is consistent with the highly oxidized nature of the 1.85 by Flin Flon paleosol. The new data suggest that PO2 rose dramatically from about 1 percent PAL (present atmospheric level) to > or = 15 percent PAL between 2.2 and 1.9 bybp.

NASA Discipline Number 52-20↗

Process for Making Single-Domain Magnetite Crystals

A process for making chemically pure, single-domain magnetite crystals substantially free of structural defects has been invented as a byproduct of research into the origin of globules in a meteorite found in Antarctica and believed to have originated on Mars. The globules in the meteorite comprise layers of mixed (Mg, Fe, and Ca) carbonates, magnetite, and iron sulfides. Since the discovery of the meteorite was announced in August 1996, scientists have debated whether the globules are of biological origin or were formed from inorganic materials by processes that could have taken place on Mars. While the research that led to the present invention has not provided a definitive conclusion concerning the origin of the globules, it has shown that globules of a different but related chemically layered structure can be grown from inorganic ingredients in a multistep precipitation process. As described in more detail below, the present invention comprises the multistep precipitation process plus a subsequent heat treatment. The multistep precipitation process was demonstrated in a laboratory experiment on the growth of submicron ankerite crystals, overgrown by submicron siderite and pyrite crystals, overgrown by submicron magnesite crystals, overgrown by submicron siderite and pyrite. In each step, chloride salts of appropriate cations (Ca, Fe, and Mg) were dissolved in deoxygenated, CO2- saturated water. NaHCO3 was added as a pH buffer while CO2 was passed continuously through the solution. A 15-mL aliquot of the resulting solution was transferred into each of several 20 mL, poly(tetrafluoroethylene)-lined hydrothermal pressure vessels. The vessels were closed in a CO2 atmosphere, then transferred into an oven at a temperature of 150 C. After a predetermined time, the hydrothermal vessels were removed from the oven and quenched in a freezer. Supernatant solutions were decanted, and carbonate precipitates were washed free of soluble salts by repeated decantations with deionized water.

Golden, D. C.↗

Investigations Using Laboratory Testbeds to Interpret Flight Instrument Datasets from Mars Robotic Missions

The Astromaterials Research and Exploration Science Directorate at the NASA Johnson Space Center (JSC) has laboratory instrumentation that mimic the capabilities of corresponding flight instruments to enable interpretation of datasets returned from Mars robotic missions. The lab instruments have been and continue to be applied to datasets for the Moessbauer Spectrometer (MB) on the Mars Exploration Rovers (MER), the Thermal & Evolved Gas Analyzer (TEGA) on the Mars Phoenix Scout, the CRISM instrument on the Mars Reconnaissance Orbiter Missions and will be applied to datasets for the Sample Analysis at Mars (SAM), Chemistry and Mineralogy (CheMin) and Chemistry & Camera (ChemCam) instruments onboard the Mars Science Laboratory (MSL). The laboratory instruments can analyze analog samples at costs that are substantially lower than engineering models of flight instruments, but their success to enable interpretation of flight data depends on how closely their capabilities mimic those of the flight instrument. The JSC lab MB instruments are equivalent to the MER instruments except without flight qualified components and no reference channel Co-57 source. Data from analog samples were critical for identification of Mg-Fe carbonate at Gusev crater. Fiber-optic VNIR spectrometers are used to obtain CRISM-like spectral data over the range 350-2500 nm, and data for Fephyllosilicates show irreversible behavior in the electronic transition region upon dessication. The MB and VNIR instruments can be operated within chambers where, for example, the absolute H2O concentration can be measured and controlled. Phoenix's TEGA consisted of a calorimeter coupled to a mass spectrometer (MS). The JSC laboratory testbed instrument consisted of a differential scanning calorimeter (DSC) coupled to a MS configured to operate under total pressure (12 mbar), heating rate (20 C/min), and purge gas composition (N2) analogous to the flight TEGA. TEGA detected CO2 release at both low (400-680 C) and high (725-820 C) temperature and an endothermic reaction in concert with the high temperature release. The high-temperature thermal decomposition is consistent with calcite, dolomite, or ankerite, (3-6 wt.%) or any combination of these phase based upon laboratory testbed experiments. Recent laboratory experiments suggest that the low temperature CO2 release was caused by a reaction between calcium carbonate and hydrated magnesium perchlorate; although, CO2 release by the oxidation of organic materials and Fe-/Mg-rich carbonates cannot be ruled out. MSL landed in Gale crater on August 5, 2012. Although numerous analog samples have been analyzed on the JSC laboratory testbeds, no SAM, CheMin, or ChemCam analyses have been acquired by MSL to date. The JSC SAM laboratory testbed consists of a thermal analyzer coupled with a MS configured to operate under total pressure (30 mbar), heating rate (35 C/min), and purge gas composition (He) analogous to the flight SAM. The CheMin and ChemCam laboratory testbeds were developed and built by inXitu, Inc. and Los Alamos National Laboratory, respectively, to acquire datasets relevant to the MSL CheMin and ChemCam flight instruments.

Ming, D. W.↗

Relative Detectability of Iron-Bearing Phases for the Mars 2020 Sherloc Deep UV Raman Instrument: 1. Focusing on Carbonates

A deep ultraviolet (DUV) Raman and fluorescence instrument is a surface standoff instrument mounted on the robotic arm of the Mars 2020 (M2020) rover Perseverance, and it is a key element of the Scanning Habitable Environments with Luminescence for Organics and Chemicals (SHERLOC) investigation [1]. Measurement and science objectives include mineralogical and organic images (~100 μm/pixel) that map sub-millimeter spatial distributions and characterization of primary and secondary minerals, potential organics, and their interaction/alteration products. The results of data analysis pertain to understanding igneous and alteration processes on Mars through time, assessing habitability, evidencing in situ biosignatures, and, along with results from other Perseverance instruments, selecting samples to cache for Mars sample return. Acceptance of the SHERLOC investigation for the NASA M2020 mission [2] created a need for Mars-relevant DUV Raman spectra, particularly for inorganic materials [e.g., 3, 4]. As reported previously [e.g., 4, 5], phases with Fe cations as essential elements (e.g., siderite (FeCO3) and ankerite (FeCa(CO3)2) for carbonates) significantly hinder detection by DUV Raman because of intense absorption of incident and scattered DUV laser radiation by Fe cations. We report here the relative detectability of carbonates (Mg,Ca,Fe,Mn)CO3 by DUV Raman using a SHERLOC analog laboratory instrument.

R V Morris↗