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NASA NTRS2016

Calibration of the Fluorine, Chlorine and Hydrogen Content of Apatites With the ChemCam LIBS Instrument

Determining the composition of apatites is important to understand the behavior of volatiles during planetary differentiation. Apatite is an ubiquitous magmatic mineral in the SNC meteorites. It is a significant reservoir of halogens in these meteorites and has been used to estimate the halogen budget of Mars. Apatites have been identified in sandstones and pebbles at Gale crater by ChemCam, a Laser-Induced Breakdown Spectroscometer (LIBS) instrument onboard the Curiosity rover. Their presence was inferred from correlations between calcium, fluorine (using the CaF molecular band centered near 603 nm, whose detection limit is much lower that atomic or ionic lines and, in some cases, phosphorus (whose detection limit is much larger). An initial quantification of fluorine, based on fluorite (CaF2)/basalt mixtures and obtained at the LANL laboratory, indicated that the excess of F/Ca (compared to the stoichiometry of pure fluorapatites) found on Mars in some cases could be explained by the presence of fluorite. Chlorine was not detected in these targets, at least above a detection limit of 0.6 wt% estimated from. Fluorapatite was later also detected by X-ray diffraction (with CheMin) at a level of approx.1wt% in the Windjana drill sample (Kimberley area), and several points analyzed by ChemCam in this area also revealed a correlation between Ca and F. The in situ detection of F-rich, Cl-poor apatites contrasts with the Cl-rich, F-poor compositions of apatites found in basaltic shergottites and in gabbroic clasts from the martian meteorite NWA 7034, which were also found to be more Cl-rich than apatites from basalts on Earth, the Moon, or Vesta. The in situ observations could call into question one of the few possible explanations brought forward to explain the SNC results, namely that Mars may be highly depleted in fluorine. The purpose of the present study is to refine the calibration of the F, Cl, OH and P signals measured by the ChemCam LIBS instrument, initiated for F, for Cl in soils, for P, and estimate their limit of detection. For this purpose, different types of apatites and mixtures of basalt powder and apatites were analyzed using ChemCam Engineering Qualification Model (EQM) at IRAP, Toulouse. The present abstract presents the initial results from the laboratory analyses. Differences between the response function of the EQM and the Flight Model of ChemCam are still to be refined to apply these new results to the Martian dataset.

Meslin, P.-Y.↗
NASA NTRS2016

Petrology and Geochemistry of New Paired Martian Meteorites Larkman Nunatak 12240 and Larkman Nunatak 12095

Two of the latest Martian meteorites found in Antarctica, paired olivine-phyric shergottites LAR 12240 and LAR 12095, are described in order to decipher their petrological context, and place constraints on the geological history of Mars. This project identifies all phases found in LAR 12240 and 12095 and analyzes them for major and trace elements. The textural relationships among these phases are examined in order to develop a crystallization history of the magma(s) that formed these basalts.

Funk, R. C.↗
NASA NTRS2016

Fluids During Diagenesis and Sulfate Vein Formation in Sediments at Gale Crater, Mars

We model the fluids involved in the alteration processes recorded in the Sheep bed Member mudstones of Yellowknife Bay (YKB), Gale crater, Mars, as revealed by the Mars Science Laboratory Curiosity rover investigations. We compare the Gale crater waters with fluids modeled for shergottites, nakhlites, and the ancient meteorite ALH 84001, as well as rocks analyzed by the Mars Exploration rovers, and with terrestrial ground and surface waters. The aqueous solution present during sediment alteration associated with phyllosilicate formation at Gale was high in Na, K, and Si; had low Mg, Fe, and Al concentrations relative to terrestrial ground waters such as the Deccan Traps and other modeled Mars fluids; and had near neutral to alkaline pH. Ca and S species were present in the 10(exp -3) to 10(exp -2) concentration range. A fluid local to Gale crater strata produced the alteration products observed by Curiosity and subsequent evaporation of this ground water- type fluid formed impure sulfate- and silica-rich deposits veins or horizons. In a second, separate stage of alteration, partial dissolution of this sulfate-rich layer in Yellowknife Bay,or beyond, led to the pure sulfate veins observed in YKB. This scenario is analogous to similar processes identified at a terrestrial site in Triassic sediments with gypsum veins of the Mercia Mudstone Group in Watchet Bay, UK.

Gale Crater↗
NASA NTRS2016

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.↗
NASA NTRS2019

Genetic Relationship Between Martian Chassignites and Nakhlites Revealed from Noble Gases

A group called as Martian meteorites is composed of shergottites, nakhlites, chassignites, and orthopyroxenite, and they are thought to be derived from Mars. Among the Martian meteorites nakhlites and chassignites show similar cosmic-ray exposure (CRE) ages of 11-12 million years, although petrologic characteristics are very different between them. Both nakhlites and chassignites indicate similar cooling rates, and would have cooled in identical scale of igneous bodies. However, the relationship between nakhlites and chassignites is still unclear, although they might have ejected at the same time, i.e., by accidentally coincidental impact events which occurred at different places on Mars or by a single impact which excavated both nakhlites and chassignites residing in a relatively small area. Here we propose that the chassignites show a genetically close relationship with nakhlites, i.e., both groups could be located within a relatively narrow area from where a single impact could have launched those meteorites, based on noble gas data obtained in our laboratory. If chassignites were really ejected with nakhlites by a single impact, both types of meteorites will provide us with geological/petrological profile in the area where both pyroxene-rich lava (nakhlites) and dunite-rich rocks (chassignites) are located close to the Martian surface. [i.e. discusses NWA 2737, etc. (Martian meteorites that fell in Northwest Africa)]

Nagao, K.↗
NASA NTRS2020

A Multi-Sims Investigation of Water Content and D/H Ratios in Roberts Massif 04262 with Insight to Sources of Hydrogen in Maskelynite

We want to define the H2O content ([H2O]) and hydrogen (H) isotope composition of meteoritic material from Mars [1-3] with motivation to understand Mars’ volatile history, constrain geochemical signatures of interior water reservoirs (i.e. the Martian mantle) and explore effects of planetary (e.g. planet formation, magma ocean degassing) and local (e.g. volcanic degassing, impact melting and degassing) processes on H incorporated in minerals. Secondary ion mass spectrometry (SIMS) allows multiple avenues to address these questions. However, application to (1) precious astromaterials and (2) low level H measurements, pose specific challenges that are further complicated when combined. We present preliminary data of a multi-approach (SIMS vs. NanoSIMS) study of H in Roberts Massif 04262 (RBT 04262), an enriched lherzolitic shergottite with nonpoikilitic (NP) and poikilitic (P) lithologies [4]. We analyze olivine, pyrox-ene, and melt inclusions to compare indigenous mantle water, with impact-generated maskelynite to investigate H signatures due to shock.

Dudley, J. M.↗
NASA NTRS2020

Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: new constraints from Bi, Pd, and Ag metal-silicate partitioning.

The Earth’s timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Be-cause Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion for Earth and Mars and show that the Pd/Ag ratio is significantly fractionated during accretion, allowing for the production of detectable 107Ag anomalies produced while 107Pd (half life = 6.5 M.y.) was still extant. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) precursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the PUM Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.

accretion↗
NASA NTRS2021

Chapter 3: Petrologic Evolution of Martian Volcanism and Clues from Meteorites

The formation and evolution of the Martian surface, and ultimately the fate of its various volcanic regions, are revealed in the chemistry of Martian meteorites, and the mineralogy of the crust. The interpretation of the chemistry from remote sensing instrumentation from orbiters and landers/rovers has been strongly influenced by our knowledge of geochemical processes on Earth, the Moon, and other asteroidal, rocky bodies [1]. The composition, and thus evolution, of the Martian crust has been resultant from SNC (shergottite –nakhlite –chassignite) meteorites, which are the igneous counterpart of rocks of Martian origin [2, 3, 4]. These meteorites are chemically similar to terrestrial basalts and cumulates, with the exception of higher concentrations of iron and other volatile elements (i.e., phosphorous, chlorine, chalcophile) [5]. From Tuff et al. [2], most Martian meteorites have relatively young crystallization ages ranging from 1.4 billion years to 180 million years ago [6]. These are considered to be derived from young, usually lightly-cratered volcanic regions, such as the Tharsis volcanic region [6, 7]. Though mainly basaltic in composition, surface rocks are richer in nickel and sulfur with lower manganese/iron ratios than Martian meteorites [2], which can be explained by the differences in oxygen fugacity during melting of the sulfur-rich mantle [2, 8]. From this difference, Martian meteorites are tied to surface rocks through an early (3.7 billion years ago) oxidation of the uppermost mantle, producing the more recent volcanic rocks [2]. The variety of compositions from basaltic, olivine volcanic rocks through pyroxene-cumulate nakhlites and peridotite chassignites, enable the hypothetical reconstructions of the silicic evolution of Mars similar to techniques used on Earth [2, 5, 9]. In this chapter, we will explore the basic Martian composition of the crust and mantle in regards to volcanic regions, the crustal components of the North-South dichotomy, and more detail of the SNC meteorites in relation to the evolution of the mantle for volcanism.

C Ahrens↗
NASA NTRSDate not supplied

First in-situ Nitrogen Isotope Measurements in Martian Meteorites

The origin and timing of the accretion of volatile elements on the terrestrial planets remains a subject of controversy. Nitrogen and hydrogen isotopes are powerful tools to constrain the source(s) of primordial volatiles accreted by planetary bodies because their isotope ratios (15N/14N; D/H) differ significantly between different solar system reservoirs (e.g., solar, chondritic, cometary). Hf-W data of martian samples indicate that Mars accreted very rapidly in the inner solar system and reached half ofits size in 1.8 Myr [1]. Therefore, martian samples are key to understand the distribution of volatile elements in the inner solar system during the early stages of planetary formation. Since no space missions have yet returned samples from Mars, martian meteorites (Shergottites, Nakhlites, Chassignites) are unique samples to constrain the source(s) of volatiles present in the martian mantle. The goal of this study was to target pristine phases(e.g., melt inclusions, mesostasis) for in-situ measurements of their nitrogen content and isotopic ratios to access the most primitive melt of the Chassignites and Nakhlites reservoirs. Five different Nakhlites (Nakhla, NWA 998, MIL 03346, Y 000593,NWA 6148) and Chassigny were analysed [2] using a recent high-resolution analytical technique that allows constraining the nitrogen composition of both carbon-bearing and carbon-free phases in natural and synthetic samples. Nitrogen was measured in the form of 14N16O- and 15N16O- with the CAMECA 1280-HR2 at the CRPG [3]. A significant amount of nitrogen was detected in melt inclusions in Chassigny and in the mesostasis of Nakhla, Y000593, MIL 03346, and NWA 6148. Nitrogen isotope signatures of Chassigny and Nakhlites exhibit a heavy isotope enrichment compared to Earth's mantle, and are consistent with a carbonaceous chondrite-like source [4]. This suggests that Earth and Mars accreted nitrogen from different chondritic sources. Overall, our in-situ technique is a unique and powerful tool to characterize the nitrogen abundance and isotopic composition of natural samples.

C Deligny↗
NASA NTRSDate not supplied

Comparing Analysis of Hydrogen Concentration in Astromaterials Nominally Anhydrous Minerals by Multiple SIMS

Secondary Ion Mass Spectrometry (SIMS) is utilized to determine hydrogen (H) concentration in astromaterials nominally anhydrous minerals (NAMs) and their inclusions [e.g., 1]. This data is interpreted to refine the volatile history of planetary bodies. Four instruments are being used to compare H concentration analysis: a large geometry SIMS (The University of Hawaiʻi Cameca IMS 1280), a compact SIMS (Arizona State University (ASU) Cameca IMS 6f), and two Cameca NanoSIMS 50L at ASU and NASA-Johnson Space Center (JSC). Results on the first three instruments are available. Although fundamentally similar, SIMS instruments and their modifications [2] may produce different values or pose advantages for H analysis, especially for shocked samples that are susceptible to contamination filling their fractures. New data from the IMS 1280 is reported, using its microchannel plate (MCP) to image high H signals in grain fractures during pre-sputtering to avoid them as much as possible. Between fractures, 16 OH/ 30 Si was measured with a Cs + 4 nA primary beam, 30 micron spot size, and central ~5x5 micron collection area. First order comparison of H concentration (reported in ppm H 2 O) is achieved on a terrestrial gem quality clinopyroxene (SLP114, 162±12 ppm H 2 O [3]), with 157±7 and 215±40 ppm H 2 O by the IMS 1280 and 6f respectively. SIMS comparison is then extended to analysis of two Martian shergottites: RBT 04262 and NWA 5789. Due to a dense fracture network (< 20 micron) in RBT 04262, only one clinopyroxene hosted glassy inclusion was analyzed (n=6, ≤1 ppm H 2 O), while six olivine grains in NWA 5789 (n=12, ≤ 2 ppm H 2 O) (1s ±0.21) were analyzed. Higher concentrations were obtained for RBT 04262 olivine by the ASU NanoSIMS 50L (up to 350 ppm H 2 O [4]), and IMS 6f (300+ ppm H 2 O, [5]), for which contamination in fractures could not be avoided. Work on the JSC NanoSIMS 50L will further develop the SIMS comparison.

J.-M. Dudley↗
NASA NTRSDate not supplied

Quantitative 3D Textural and Petrofabric Analysis of the Northwest Africa 10645 Nakhlite Using X-Ray Computed Tomography

Martian meteorites are currently the only samples available from Mars to study and are critical for elucidating variability in martian igneous processes over time [e.g., 1]. Quantifying igneous textures and fabrics can help us understand how rocks are formed and emplaced [e.g., 2]. These features are innately three dimensional (3D) and are often strongly heterogeneous in cumulate rocks, like the nakhlites and poikilitic shergottites [2–3], where there can be substantial textural variations between and within individual samples. However, most quantitative textural and fabric analyses on these samples have been limited to two dimensions through measurements made on polished petrographic thin sections. Thus, 3D petrographic measurements are imperative for both representative sample characterization and accurately interpreting magmatic processes. The emplacement of martian meteorites at or near the surface of Mars (i.e., extrusive or intrusive, respectively) remains enigmatic due to the innate lack of geologic context [e.g., 1], but conducting 3D quantitative textural and fabric analyses can help elucidate emplacement mechanisms and settings on Mars.

S. Ramsey↗
NASA NTRS2022

Effect of Sulfur on siderophile element partitioning between olivine and martian mantle primary melt

Ni and Co variations in primary martian magmas exhibit anomalous incompatible behavior, which has remained an unexplained conundrum. Because martian magmas are S-rich, and some trace metals are reported to have enhanced solubility in S-bearing magmas, we have carried out a series of experiments to evaluate the effect of high-S melts on the olivine/melt partitioning of Ni, Co, Mn, V, and Cr. Near-liquidus experiments on a synthetic primary martian mantle melt (Yamato-980459 [Y98]) were completed in a piston-cylinder apparatus at 0.75 GPa. Previous studies in S-free systems illustrate that the partition coefficients for these elements are dependent chiefly on D(Mg(Ol/melt)) (the partition coefficient defined as wt% Mg in olivine/wt% Mg in melt, a proxy for temperature), and were used to calibrate a predictive expression that includes the effects of temperature [i.e., D(Mg(Ol/melt))], melt composition, and oxygen fugacity. These predictive expressions are then used to isolate any effect in DM olivine/melt due to dissolved sulfur. The results show that S might have a small effect for Co, but not enough to change Co partitioning from compatible to incompatible in our experiments. The addition of a sulfur term to the D(Co) predictive expressions shows that nearly 8000 ppm of sulfur would be required in the melt (at liquidus temperature of Y98) for D(Co) to become <1. These S contents are two times higher than those of a sulfide-saturated melt at the P-T conditions of a martian mantle source region. Therefore, the anomalous incompatible behavior observed in these primary magma suites must be due to another mechanism. High temperature, oxygen fugacity, and diffusion are not viable mechanisms, but magma mixing, assimilation, or kinetic crystallization effects remain possibilities.

shergottite↗
NASA NTRS2024

Formation and Interior Evolution of Mars

The formation and earliest evolution of Mars involved core formation followed by magma ocean solidification and primordial crust formation. Here, we review the formation and early interior evolution of Mars as understood through meteorite studies. Martian meteorites exhibit ages that span the entire history of the Solar System, but most derive from compositionally distinct sources that formed early in the history of Mars. Geochemical and isotopic studies of Martian meteorites have provided critical information on Mars’ building blocks, bulk composition, and its differentiation into a core, mantle and crust. Radiogenic isotope systems provide vital insights into the petrogenesis of Martian meteorite source regions and into the nature and timescales of primordial differentiation on Mars. Application of short-lived isotope chronometers to Martian meteorites indicates that the Martian core formed early within <10 million years (Ma), while magma ocean differentiation and crust formation occurred soon thereafter, within the first tens of Ma of Solar System history. Bulk silicate Mars is variably depleted in moderately volatile elements relative to chondrites, but to a lesser extent than the Earth. The nature and evolution of more volatile elements and volatile species on Mars (e.g., H 2 O, C, S, halogens) remains an active area of investigation, but overall suggest that Mars is more enriched in volatile elements than the Moon but less than the Earth. While geochemical exploration of Mars coupled with new discoveries of Martian meteorites has provided a wealth of information, the compositional and lithologic diversity on Mars significantly exceeds that seen in the suites of Martian meteorites currently studied. This implies that our current perspective on the planet’s evolution is very likely biased, highlighting the need for future sample return missions to Mars.

Accretion↗