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Materials Refining for Solar Array Production on the Moon

Silicon, aluminum, and glass are the primary raw materials that will be required for production of solar arrays on the moon. A process sequence is proposed for producing these materials from lunar regolith, consisting of separating the required materials from lunar rock with fluorine. The fluorine is brought to the moon in the form of potassium fluoride, and is liberated from the salt by electrolysis in a eutectic salt melt. Tetrafluorosilane produced by this process is reduced to silicon by a plasma reduction stage; the fluorine salts are reduced to metals by reaction with metallic potassium. Fluorine is recovered from residual MgF and CaF2 by reaction with K2O.

Landis, Geoffrey A.↗

Coatings on Atacama Desert Basalt: A Possible Analog for Coatings on Gusev Plains Basalt

Surface coatings on Gusev Plains basalt have been observed and may contain hematite and nanophase Fe-oxides along with enrichments in P, S, Cl, and K relative to the underlying rock. The Gusev coatings may be derived from the dissolution of adhering soil and/or parent rock along with the addition of S and Cl from outside sources. Transient water for dissolution could be sourced from melting snow during periods of high obliquity, acid fog, and/or ground water (Haskin et al., 2005). Coatings on basalt in the hyper-arid (less than 2mm y(sup -1)) Atacama Desert may assist in understanding the chemistry, mineralogy and formation mechanisms of the Gusev basalt coatings. The Atacama Desert climate is proposed to be analogous to a paleo-Mars climate that was characterized by limited aqueous activity when the Gusev coatings could have formed. The objectives of this work are to (i) determine the chemical nature and extent of surface coatings on Atacama Desert basalt, and (ii) assess coating formation mechanisms in the Atacama Desert. Preliminary backscattered electron imaging of Atacama basalt thin-sections indicated that the coatings are as thick as 20 m. The boundary between the coating and the basalt labradorite, ilmenite, and augite grains was abrupt indicating that the basalt minerals underwent no chemical dissolution. The Atacama coatings have been added to the basalt instead of being derived from basalt chemical weathering. Semi-quantitative energy dispersive spectroscopy shows the coatings to be chemically homogeneous. The coating is depleted in Ca (0.9 wt% CaO) and enriched in K (1.3 wt.% K2O) and Si (69.1 wt.% SiO2) relative to the augite and labradorite grains. A dust source enriched in Si (e.g., poorly crystalline silica) and K and depleted in Ca appears to have been added to the basalt surface. Unlike the Gusev coatings, no P, S, and Cl enrichment was observed. However, Fe (3.2 wt.% FeO) was present in the Atacama coatings suggesting the present of Fe-oxides. While the chemistry of Atacama coating does not mirror the Gusev coating, the coating formation mechanism may be similar. The Atacama coatings of surface basalt are derived completely from exogenous sources. If surface Mars rocks have experienced limited wetting conditions as in the Atacama, then Mars coatings may be derived only from dissolution of material adhering to rock.

Sutter, B.↗

Experimental and Petrological Constraints on Lunar Differentiation from the Apollo 15 Green Picritic Glasses

Phase equilibrium experiments on the most magnesian Apollo 15C green picritic glass composition indicate a multiple saturation point with olivine and orthopyroxene at 1520 C and 1.3 GPa (about 260 km depth in the moon). This composition has the highest Mg# of any lunar picritic glass and the shallowest multiple saturation point. Experiments on an Apollo 15A composition indicate a multiple saturation point with olivine and orthopyroxene at 1520 C and 2.2 GPa (about 440 km depth in the moon). The importance of the distinctive compositional trends of the Apollo 15 groups A, B, and C picritic glasses merits the reanalysis of NASA slide 15426,72 with modern electron microprobe techniques. We confirm the compositional trends reported by Delano (1979, 1986) in the major element oxides SiO2, TiO2, Al2O3, Cr2O3, FeO, MnO, MgO, and CaO, and we also obtained data for the trace elements P2O5, K2O, Na2O, NiO, S, Cu, Cl, Zn, and F. Petrogenetic modeling demonstrates that the Apollo 15 A-B-C glass trends could not have been formed by fractional crystallization or any continuous assimilation/fractional crystallization (AFC) process. The B and C glass compositional trends could not have been formed by batch or incremental melting of an olivine + orthopyroxene source or any other homogeneous source, though the A glasses may have been formed by congruent melting over a small pressure range at depth. The B compositional trend is well modeled by starting with an intermediate A composition and assimilating a shallower, melted cumulate, and the C compositional trend is well modeled by a second assimilation event. The assimilation process envisioned is one in which heat and mass transfer were separated in space and time. In an initial intrusive event, a picritic magma crystallized and provided heat to melt magma ocean cumulates. In a later replenishment event, the picritic magma incrementally mixed with the melted cumulate (creating the compositional trends in the green glass data set), ascended to the lunar surface, and erupted as a fire fountain. A barometer created from multiple saturation points provides a depth estimate of other glasses in the A-B-C trend and of the depths of assimilation. This barometer demonstrates that the Apollo 15 A-B-C trend originated over a depth range of approx.460 km to approx.260 km within the moon.

Elkins-Tanton, Linda T.↗

Calculation of Oxygen Fugacity in High Pressure Metal-Silicate Experiments and Comparison to Standard Approaches

Calculation of oxygen fugacity in high pressure and temperature experiments in metal-silicate systems is usually approximated by the ratio of Fe in the metal and FeO in the silicate melt: (Delta)IW=2*log(X(sub Fe)/X(sub FeO)), where IW is the iron-wustite reference oxygen buffer. Although this is a quick and easy calculation to make, it has been applied to a huge variety of metallic (Fe- Ni-S-C-O-Si systems) and silicate liquids (SiO2, Al2O3, TiO2, FeO, MgO, CaO, Na2O, K2O systems). This approach has surely led to values that have little meaning, yet are applied with great confidence, for example, to a terrestrial mantle at "IW-2". Although fO2 can be circumvented in some cases by consideration of Fe-M distribution coefficient, these do not eliminate the effects of alloy or silicate liquid compositional variation, or the specific chemical effects of S in the silicate liquid, for example. In order to address the issue of what the actual value of fO2 is in any given experiment, we have calculated fO2 from the equilibria 2Fe (metal) + SiO2 (liq) + O2 = Fe2SiO4 (liq).

Righter, K.↗

Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

"Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston-cylinder experiments at 1 GPa between 950 and 1700 C using a mixture of 70wt% tholeiitic basalt + 15wt% anhydrite + 15wt% calcite. Up to ~1440 C, an ultracalcic (CaO>13.5 wt%; CaO/Al2O3>1 wt%) picrobasaltic (SiO2~40-45 wt%; Na2O+K2O<2 wt%) melt containing up to 5 wt% SO3 and up to 5.3 wt% CO2+H2O (calculated by difference) is present in equilibrium with clinopyroxene, anhydrite, spinel-chromite, a CAS-phase and a gas composed mainly of CO and an aliphatic thiol (CH2)4SH. Hydrogen was incorporated either by contact between the starting material and air or by diffusion through the capsule during the experiments. The S content in the gas increases with temperature and run duration, implying that gases with various C/S ratios might be released during an impact or at subduction zones, depending on the P-T-t path and on the H content. Above approx.1440 C, a Ca-rich carbonate-sulfate melt forms (in equilibrium with the picrobasaltic melt) which contains a few percents of Na and K. Such melt is not expected to form at Earth s subduction temperatures. If it forms by meteorite impact, it might crystallize too fast to explain long flows like Venus canali. A different basalt/anhydrite/calcite ratio might, however, decrease its formation temperature.

Martin, A. M.↗

Technology for Solar Array Production on the Moon

Silicon, aluminum, and glass are the primary raw materials that will be required for production of solar arrays on the moon. A process sequence is proposed for producing these materials from lunar regolith is proposed, consisting of separating the required materials from lunar rock with fluorine. Fluorosilane produced by this process is reduced to silicon; the fluorine salts are reduced to metals by reaction with metallic potassium. Fluorine is recovered from residual MgF and CaF2 by reaction with K2O. Aluminum, calcium oxide, and magnesium oxide are recovered to manufacture structural materials and glass.

Landis, Geoffrey A.↗

APXS of First Rocks Encountered by Curiosity in Gale Crater: Geochemical Diversity and Volatile Element (K and ZN) Enrichment

The Alpha Particle X-ray spectrometer (APXS) on the Curiosity rover in Gale Crater [1] is the 4th such instrument to have landed on Mars [2]. Along the rover's traverse down-section toward Glenelg (through sol 102), the APXS has examined four rocks and one soil [3]. Gale rocks are geochemically diverse and expand the range of Martian rock compositions to include high volatile and alkali contents (up to 3.0 wt% K2O) with high Fe and Mn (up to 29.2% FeO*).

Schmidt, M. E.↗

Mineralogical, Chemical, and Isotopic Heterogeneity in Zagami: Evidence for a Complex Petrogenesis

Textural variations in the shergottite Zagami were initially interpreted as evidence that it formed in a heterogeneous lava flow. Variations in initial Sr-87/Sr-86 ratios between a Coarse Grained (CG) and a Fine Grained (FG) lithology and evidence for more extensive fractionation of the Rb/Sr ratio in a Dark Mottled Lithology (DML) are consistent with such an interpretation. More recently, Niihara et al. and Misawa et al. have reported the mineralogy and Sr-isotopic systematics of an Olivine Rich Lithology (ORL) found in association with the coarse-grained DML lithology in the Kanagawa Zagami specimen [6,7]. Here we call this lithology DML(Ka) to maintain a distinction with DML(USNM) as studied. An Ar-Ar study by Park et al. of a late stage K-rich melt enriched in K2O to approx 7% and intruded into ORL yielded an Ar-Ar age of 202+/0 7 Ma. The present work extends the study of Kanagawa Zagami to Nd-isotopes.

Nyquist, L. E.↗

Impact History on Vesta: Petrographic, Compositional and Future Chronological Studies of Melt Clasts in Howardites

Howardite meteorites are polymict breccias composed mainly of eucritic and diogenitic material that likely originate from the surface of the Asteroid 4 Vesta. They can be separated into two subtypes: Regolithic, which represent the lithified remains of the active vestan regolith; Fragmental, which represent simpler polymict breccias. Amongst the regolithic features observed in the former, melt clasts are particularly striking for their appearance and compositional variability. They range from glassy spherules to finely crystalline (i.e., devitrified) clasts, and clasts containing only relict mineral grains to those containing only phenocrysts. Glasses can be separated into compositional sub-types including those with low FeO/MgO ratios (less than 5) -low alkali glasses, K-rich (K2O greater than 0.2 wt.%), Na-rich (Na2O greater than 0.6 wt.%) and CaO-rich, and those with high FeO/MgO ratios (greater than 10). There is also a distinction to be made between primary volcanic melt clasts and those produced by impacts. While suggested that a lack of chemical homogeneity among their studied melt clasts ruled out a primary volcanic origin, the low siderophile element contents observed in such clasts suggest less compositional influence from impactors than commonly assumed. Studying the chronology of the impact melt clasts in howardites can help us to better determine the timing of impact events on Vesta and the asteroid belt. In this research, we are launching an investigation into the petrology, composition (major/trace element and noble gas) and chronology of melt clasts in howardites. We have selected a set of howardites known to contain large quantities of melt clasts, and have begun the petrological and compositional studies of these materials. Once the melt clasts have been fully classified, we aim to perform chronological studies of individual clasts using both the Ar-40/Ar-39 and Pb-Pb chronometers, as well as determine the noble gas components present. Of particular note, the study will take advantage of the laser ablation techniques associated with the noble gas facilities at ASU, which will allow high-resolution, in-situ analysis of individual clasts. The broader aim of this work is to ascertain whether the impact flux in the region of the asteroid belt was similar to that on the Moon. Our understanding of impact events in the inner Solar System relies heavily on our analyses of lunar meteorites and returned samples, and there is currently some debate regarding whether there was a "Lunar Cataclysm" event around approx. 3.9 Ga, or the end of an epoch of "Late Heavy Bombardment" (LHB) at this time. New and more comprehensive constraints on howardite melt clast ages may help determine whether the asteroid belt experienced such a cataclysm or LHB.

Cartwright, J. A.↗

Distinct Igneous APXS Rock Compositions on Mars from Pathfinder, MER and MSL

The alpha particle x-ray spectrometer (APXS) on all four Mars Rovers returned geochemical data from about 1000 rocks and soils along the combined traverses of over 50 kilometers. Here we discuss rocks likely of igneous origin, which might represent source materials for the soils and sediments identified along the traverses. Adirondack-type basalts, abundant in the plains of Gusev Crater, are primitive, olivine bearing basalts. They resemble in composition the basaltic soils encountered at all landing sites, except the ubiquitous elevated S, Cl and Zn in soils. They have been postulated to represent closely the average Martian crust composition. The recently identified new Martian meteorite Black Beauty has similar overall geochemical composition, very distinct from the earlier established SNC meteorites. The rim of the Noachian crater Endeavour, predating the sulfate-bearing Burns formation at Meridiani Planum, also resembles closely the composition of Adirondack basalts. At Gale Crater, the MSL Curiosity rover identified a felsic rock type exemplified by the mugearitic float rock JakeM, which is widespread along the traverse at Gale. While a surprise at that time, possibly related more evolved, alkaline rocks had been previously identified on Mars. Spirit encountered the Wishstone rocks in the Columbia Hills with approx. 6% Na2O+K2O, 15 % Al2O3 and low 12% FeO. Pathfinder rocks with elevated K and Na and >50% SiO2 were postulated to be andesitic. Recently Opportunity encountered the rock JeanBaptisteCharbonneau with >15% Al2O3, >50% SiO2 and approx. 10% FeO. A common characteristic all these rocks is the very low abundance of Cr, Ni and Zn, and an Fe/Mn ratio of about 50, indicating an unaltered Fe mineralogy. Beside these likely igneous rock types, which occurred always in several rocks, a few unique rocks were encountered, e.g. Bounce Rock, a pyroxene-bearing ejecta rock fragment resembling the Shergottite EETA 79001B meteorite. The APXS data can be used to relate the findings of all 4 landing sites, constrain the water to rock ratio of sediments or imply source rock provenance. Beyond that the capability to quantify important volatile elements like P, S, Cl, and Br have provided new insights into the chemistry and the environment present during the formation of the sediments.

Gellert, Ralf↗

Discordant K-Ar and Young Exposure Dates for the Windjana Sandstone, Kimberley, Gale Crater, Mars

K-Ar and noble gas surface exposure age measurements were carried out on the Windjana sandstone, Kimberley region, Gale Crater, Mars, by using the Sample Analysis at Mars instrument on the Curiosity rover. The sandstone is unusually rich in sanidine, as determined by CheMin X-ray diffraction, contributing to the high K2O concentration of 3.09 +/- 0.20 wt % measured by Alpha-Particle X-ray Spectrometer analysis. A sandstone aliquot heated to approximately 915 C yielded a K-Ar age of 627 +/- 50 Ma. Reheating this aliquot yielded no additional Ar. A second aliquot heated in the same way yielded a much higher K-Ar age of 1710 +/- 110 Ma. These data suggest incomplete Ar extraction from a rock with a K-Ar age older than 1710 Ma. Incomplete extraction at approximately 900 C is not surprising for a rock with a large fraction of K carried by Ar-retentive K-feldspar. Likely, variability in the exact temperature achieved by the sample from run to run, uncertainties in sample mass estimation, and possible mineral fractionation during transport and storage prior to analysis may contribute to these discrepant data. Cosmic ray exposure ages from He-3 and Ne-21 in the two aliquots are minimum values given the possibility of incomplete extraction. However, the general similarity between the He-3 (57 +/- 49 and 18 +/- 32 Ma, mean 30 Ma) and Ne-21 (2 +/- 32 and 83 +/- 24 Ma, mean 54 Ma) exposure ages provides no evidence for underextraction. The implied erosion rate at the Kimberley location is similar to that reported at the nearby Yellowknife Bay outcrop.

K-Ar↗

Volatiles in High-K Lunar Basalts

Chlorine is an unusual isotopic system, being essentially unfractionated ((delta)Cl-37 approximately 0 per mille ) between bulk terrestrial samples and chondritic meteorites and yet showing large variations in lunar (approximately -4 to +81 per mille), martian, and vestan (HED) samples. Among lunar samples, the volatile-bearing mineral apatite (Ca5(PO4)3[F,Cl,OH]) has been studied for volatiles in K-, REE-, and P (KREEP), very high potassium (VHK), low-Ti and high-Ti basalts, as well as samples from the lunar highlands. These studies revealed a positive correlation between in-situ (delta)Cl-37 measurements and bulk incompatible trace elements (ITEs) and ratios. Such trends were interpreted to originate from Cl isotopic fractionation during the degassing of metal chlorides during or shortly after the differentiation of the Moon via a magma ocean. In this study, we investigate the volatile inventories of a group of samples for which new-era volatile data have yet to be reported - the high-K (greater than 2000 ppm bulk K2O), high-Ti, trace element-rich mare basalts. We used isotope imaging on the Cameca NanoSIMS 50L at JSC to obtain the Cl isotopic composition [((Cl-37/(35)Clsample/C-37l/(35)Clstandard)-1)×1000, to get a value in per thousand (per mille)] which ranges from approximately -2.7 +/- 2 per mille to +16.1 +/- 2 per mille (2sigma), as well as volatile abundances (F & Cl) of apatite in samples 10017, 10024 & 10049. Simply following prior models, as lunar rocks with high bulk-rock abundances of ITEs we might expect the high-K, high-Ti basalts to contain apatite characterized by heavily fractionated (delta)Cl-37 values, i.e., Cl obtained from mixing between unfractionated mantle Cl (approximately 0 per mille) and the urKREEP reservoir (possibly fractionated to greater than +25 per mille.). However, the data obtained for the studied samples do not conform to either the early degassing or mixing models. Existing petrogentic models for the origin of the high-K, high-Ti basalts do not include urKREEP assimilation into their LMO cumulate sources. Therefore, Cl in these basalts either originated from source region heterogeneity or through assimilation or metasomatism by volatile and incompatible trace element rich materials. The new data presented here could provide evidence for the existence of region(s) in the lunar interior that are ITE-enriched and contain Cl that does not share isotopic affinities with lunar urKREEP, possibly representing the composition of the purported 'neuKREEP'.

Barnes, Jessica J.↗

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.↗

Design and Characteristics of Hydroxyapatites: Effect of Radiation

Hydroxyapatites single crystals have been investigated their applications as the laser host material. Czochralksi and flux growth methods have been utilized to achieve single crystals. Because of their bioactivities with tissues these have attracted interest for bone applications. For low temperature processing we have used several techniques. We utilized some organic melt and oriented the grains by the directional solidification method. This organic treated material has different characteristics than coarsened oxide materials. Our approach involved low temperature processing using nano-engineered powders of the material system MgO-Na2O-K2O-CaO-SrO-SiO2 and also borates were processed by sintering and grain growth. Our results indicate that substitution of calcium and strontium with some other elements such as gallium and magnesium have great potential to improve the mechanical properties of bones.

Bhavsar, Jayati↗

Design and Characteristics of Hydroxyapatites: Effect of Radiation

We have prepared silicate based hard materials and have processed it with organic flux. Because of the bioactivities of hydroxyapatites with tissues, this class of materials have attracted interest for bone applications. We have utilized low temperature processing techniques. Organic melt was used and the directional solidification method to cast the shaped sample. This organic treated material has different characteristics than coarsened oxide materials. Our approach involved low temperature processing using nano and micron sized powders of the material system Na2O-K2O-CaO- MgO-Ga2O3-SiO2, and titanates were processed by sintering and grain growth. Our results indicate that substitution of gallium and magnesium or titanium with some variation in processing methods have great potential to improve the glassy characteristics without decreasing the mechanical properties of bones. Effect of radiation on bone was studied by exposing with commercially available Cs137 gamma ray source. It was observed that electrical resistivity increased due to radiation exposure for this system.

Bhavsar, Jayati↗

Effect of Radiation on Biologically Active Glasses

Multifunctional hydroxyapatites single crystals have been studied for their applications as the laser host material since past several decades. It is only recently their potential has been evaluated for bioactive materials. In the past researches, Czochralski and flux growth methods have been utilized to achieve single crystals. We have used low temperature processing techniques for synthesis. Organic melt was used to achieve oriented fibers by the directional solidification method. This organic treated material has different characteristics than coarsened oxide materials. Our approach involved low temperature processing using nano engineered powders of the material system Na2O-K2O-CaO- MgO-SrO-SiO2. Also, borates were processed by sintering and grain growth. Effect of -ray was studied by measuring the electrical characteristics of radiated samples. Our experiments to further improve mechanical characteristics indicate that substitution of calcium with some other elements such as gallium have great potential to improve the radiation hardening and mechanical properties of bones.

Tufail, Areeba↗

Reworking and Diagenesis of Martian Soil: Pathway to Murray Formation Sediments?

In Gale crater, the Curiosity Mars rover has climbed over 300 meters of the Murray formation from the base of the Pahrump Hills to the crest of Vera Rubin Ridge. We discuss the possibility that fine-grained mudstone of the Murray formation is a diagenetic product of sediments with a chemical and mineralogical composition similar to present-day martian soil. Typical (low Ca-sulfate) Murray samples have Na2O, Al2O3, SiO2, SO3, TiO2 and FeOT concentrations within 10% (relative) of average martian soil. These oxides constitute ~85% of each sample. The Al/Si and Ti/Si ratios of Murray samples are comparable to average martian soil but distinct from other martian geologic units. Percentage difference in P2O5, Cl, K2O, Cr2O3, MnO, Ni, Zn, Br, and Ge between soil and Murray samples generally exceed 10%, but these elements and oxides amount to less than 4% of the samples. These constituents are highly variable in Murray mudstone and may reflect mobility in fluid interactions. Large discrepancies in MgO and CaO with ~50% lower concentrations in the Murray samples (~2% absolute differences) are indicative of open-system alteration if the Murray mudstone originated from soil-like material. Mineralogically, martian soil is dominated by plagioclase feldspar, pyroxenes, and olivine with minor hematite, magnetite, and Ca-sulfate. In comparison, Murray samples generally have less feldspar and pyroxene, little to no olivine, more iron oxides and Ca-sulfates, and Fe-containing phyllosilicates. If Murray mudstone originated from a Mars soil composition, aqueous alteration could have converted olivine and pyroxenes to iron oxides and phyllosilicates. Intermixed or zoned plagioclase feldspars could have lost a larger portion of calcic constituents, consistent with susceptibility to weathering, resulting in a change from ~An55 (soil) to ~An40 (Murray). This alteration could be consistent with the major element chemistry, including the small decrease in MgO and CaO. A subsequent influx of minor/trace elements and Ca-sulfate, e.g. from groundwater, would be required. In this diagenetic scenario, the bulk of the alteration would have been nearly isochemical, suggesting limited mineral segregation and aqueous alteration during transport from the drainage basin or a significant direct aeolian contribution to the Murray sediments.

Yen, Albert S.↗

Post-Landing Major Element Quantification Using SuperCam Laser Induced Breakdown Spectroscopy

The SuperCam instrument on the PerseveranceMars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions andspectra are normalized to minimize signal fluctuations and effectsof target distance.In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositionsof diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well-characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g.,silicates, sulfates, carbonates, oxides),more unusual compositions (e.g.,Mn oreand sodalite), andreplicates of the sintered SuperCam calibration targets (SCCTs) onboardthe rover. For each major element (SiO2, TiO2, Al2O3, FeOT, MgO, CaO, Na2O, K2O), the database was subdivided into five“folds” with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining fourfolds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

Mars 2020↗