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The sulfur content of the Martian mantle is critical to understanding volcanic volatiles supplied to the surface of Mars and possibly climate. In the absence of Martian mantle rocks, sulfur content of the mantle has been inferred from S contents of Martian meteorites or from sedimentary sulfate abundances. Estimates of the sulfur content of the Martian mantle vary from 390-2,000 ppm, all of which are higher than that of the terrestrial mantle (~250 ppm;). Residual sulfide in the Martian mantle controls the distribution of chalcophile elements during partial melting. In this study, we report new analyses of Martian meteorites, and use the incompatible behavior of As, Tl and Pb to infer the sulfide mode of the Martian mantle using a different set of assumptions than those of prior studies.

Meteorites from Mars lack field context but chemical and chronologic studies have revealed remarkable links between nakhlites and chassignites. A widely held consensus is that nakhlites and chassignites originated from a large, single differentiated flow or shallow intrusive [1-5]. An Ar-Ar study assumed multiple flows based on resolvable age differences between meteorites [6], but did not address the possibility of differential cooling in a large, shallowly emplaced intrusion [1]. REE abundances in pyroxenes from nakhlites and Chassigny led [7] to argue for derivation of these rocks from distinct magmas. Volatile abundances (F, Cl, OH) in chlorapatites indicated that the entire suite of nakhlites and chassignites experienced hydrothermal interaction with a single fluid supporting a single body origin [4]. The discovery of a new chassignite, NWA 8694, extended the Mg# range from 80-54, providing a closer link to nakhlites but revealed the petrological difficulty of fractionating a single body of liquid to yield a series of olivine cumulates with such a large Mg# range [8]. When mafic magmas are emplaced into the crust, crustal assimilation can impart distinct elemental signatures if the country rock has experienced sedimentary or hydrothermal processing [9]. In this work, we used Sn abundances of nakhlites and chassignites to show that these rocks were crystallized from distinct magma batches, providing vital contextual clues to their origin.

Light elements can alloy into the iron cores of terrestrial planetary bodies. It is estimated that the Earth’s core contains ~10% of a light element, most likely a combination of S, C, Si, and O with Si probably being the most abundant. Si dissolved into Fe metal liquids can have a significant influence on the activity coefficients of siderophile elements, and thus the partitioning behavior of those elements between the core and mantle. Many of these elements have been investigated extensively at ambient pressure, and studies up to 1 GPa are becoming more common, but few have been studied at pressures above this. The formation of the Earth’s core has been estimated to have formed at pressures between 40-60 GPa, so investigating the effect pressure has on Si’s influence on siderophile element partitioning is important for modeling core formation in the Earth and smaller planets. Pressure is well known to influence volumetric properties of metallic and silicate liquids, and oxygen fugacity (e.g., [10,11]), but less is known about its effect on activity coefficients (e.g., [12]). Some activity coefficients depend strongly upon the Si content of Fe liquids, and the concentration of siderophile elements such as P, Sb, and As in the terrestrial mantle is easily influenced by dissolved Si in the core. Thus, isolating the effect of pressure on activity coefficients in general is critical in quantitative analysis of core formation models. In this work, we investigate the effect variable Si content has on the partitioning of Au between Fe metal and silicate melt at 10 GPa and 2373 K, with the intention of comparing the behavior to that already investigated at lower pressures. In addition, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb were also measured and could thus be included in the assessment of potential pressure effects.

Olivine-hosted melt inclusions (MIs) may retain trapped parent magma compositions as well as record progressive differentiation while magmas crystallize and ascend towards the surface [1,2 and references therein]. Major element compositions of the MIs, especially Fe and Mg, can be affected by post-entrapment re-equilibration with their host olivine [1,2]. Therefore, Fe/Mg ratio correction is required to obtain MI bulk compositions following equilibrium with their host olivine. Partition coefficients of most of the trace elements in olivine are very low (i.e. DOL/melt<0.001). Thus, ratios of trace elements of olivine-hosted MIs are unlikely to be affected by post-entrapment re-equilibration and no correction is necessary [2]. Hence, tracking trace element behavior in MIs may constrain the composition of the parent magma and its evolution yielding insights on magma differentiation of shergottites. However, analyzing MIs for chemical compositions is a challenging task due to their low abundances and small sizes. Using a highly sensitive and precise micro-beam technique is essential to examine olivine-hosted MIs in order to measure trace element abundances. For this purpose, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an excellent tool due to its wide range of laser spot sizes (1-150 μm), ability to obtain raster analysis (several mm2) and lower detection limits (0.1 ppb) [3].

Germanium (Ge) and Zn enrichment in martian sedimentary rocks has been reported from rocks at Gale Crater, showing concentrations of Ge from tens to hundreds ppm [1]. The Ge concentrations in martian meteorites are significantly lower (0.5-2.5 ppm) [2]. Our recent studies [3-4] have revealed that Ge is lost from shergottites due to volatility. Recent experimental studies confirm that Ge and Zn are both significantly volatile under magmatic conditions [5-7]. Further, Ge is moderately incompatible during magmatic differentiation [8] so Ge contents in olivines or pyroxenes increase during igneous fractionation in nakhlites and chassignites [4]. Shergottites for which Ge abundances had been determined included rocks with ages of 150-600 Ma, while the enrichments reported from Gale Crater rocks likely occurred over 3 Ga ago. The recent discovery of two unpaired ancient (2.4 Ga) depleted shergottites, NWA 7635 [9] and NWA 8159 [10], afforded the prospect of obtaining an extended history of martian volcanic outgassing. Both of the ancient shergottites are depleted in incompatible elements and share a similar GCR exposure age to younger depleted shergottites implying derivation from a single, long-lived (>2 Ga) volcanic center [9].

Knowing the distribution and origin of water in terrestrial planets is crucial to understand their formation, evolution and the source of their atmospheres and surface water. Mantle D/H ratios may be used to determine what type of material contributed water to the terrestrial planets [1]. However, other processes, magmatic or surface alteration processes, can also modify D/H ratios, and for Mars, we only have samples from the crust, as meteorites. The D/H ratio of igneous phases of Martian meteorites is generally explained in terms of the mixing contributions of two reservoirs: surficial with high D/H (dD > 700 ‰) related to interaction with the martian atmosphere (dD ~ 5000‰), and mantle-derived with lower D/H (dD < 500 ‰ but the exact value is still debated)[2]. However, our present study evidences that H loss in clinopyroxene during degassing can significantly fractionate H isotopes and increase their D/H ratios. In situ analyses of H isotopes, and of water, major and trace element contents were performed on the pyroxenes of 5 nakhlites. Nakhlites are clinopyroxenites that likely originated from the same lava flow or shallow magma chamber. Water contents decrease (380 to <5 ppm H2O) with increasing dD (-268 to 4860 ‰). Significant influence from spallation, exchange with the martian atmosphere, shock, surface alteration, and hydrothermal processes is ruled out. Together with the evidence of less water at the edge of individual pyroxene grains compared to their interior, we interpret this correlation as the result of preferential diffusive loss of H relative to D from the already crystallized pyroxenes during ascent of the partially-crystallized magma. Similar H isotope fractionations have been observed in another nominally anhydrous mineral, garnet, during experimental dehydration [3]. These results emphasize that caution is warranted when interpreting H isotope analyses of igneous, nominally anhydrous minerals in terms of planetary processes.

UNKNOWN

Seeking the signs of life on Mars is often considered the "first among equal" objectives for any potential Mars Sample Return (MSR) campaign. Among the geological settings considered to have the greatest potential for recording evidence of ancient life or its pre-biotic chemistry on Mars are lacustrine (and marine, if ever present) sedimentary depositional environments. This potential, and the possibility of returning samples that could meaningfully address this objective, have been greatly enhanced by investigations of an ancient redox stratified lake system in Gale crater by the Curiosity rover.

Highly promising locales for biosignature prospecting on Mars are ancient hydrothermal deposits, formed by the interaction of surface water with heat from volcanism or impacts. On Earth, they occur throughout the geological record (to at least approx. 3.5 Ga), preserving robust mineralogical, textural and compositional evidence of thermophilic microbial activity. Hydrothermal systems were likely present early in Mars' history, including at two of the three finalist candidate landing sites for M2020, Columbia Hills and NE Syrtis Major. Hydrothermal environments on Earth's surface are varied, constituting subaerial hot spring aprons, mounds and fumaroles; shallow to deep-sea hydrothermal vents (black and white smokers); and vent mounds and hot-spring discharges in lacustrine and fluvial settings. Biological information can be preserved by rapid, spring-sourced mineral precipitation, but also could be altered or destroyed by postdepositional events. Thus, field observations need to be followed by detailed laboratory analysis to verify potential biosignatures. See Attachment

Metallic cores contain light alloying elements that can be a combination of S, C, Si, and O, all of which have important chemical and physical influences. For Earth, Si may be the most abundant light element in the core. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE), and thus the partitioning behavior of those elements between core and mantle. The effect of Si on the highly siderophile elements is only beginning to be studied and the effects on Au, Pd and Pt are significant. Here we report new experiments designed to quantify the effect of Si on the partitioning of Re between metal and silicate melt. A solid understanding of Re partitioning is required for a complete understanding of the Re-Os isotopic systems. The results will be applied to understanding the HSEs and Os isotopic data for planetary mantles, and especially Earth.

Final Paper and not the abstract is attached. Introduction: Germanium is generally thought to follow Si in its geochemical behavior, but little data has existed to rigorously understand the behavior of Ge in the Martian mantle. Germanium is known to be more siderophile than Si, and its partitioning into the martian core has been studied by. Typical abundances in igneous martian meteorites range from 0.5-3 ppm, a larger range than what is observed in terrestrial basalts (1.5 +/- 0.1 ppm). In situ measurements by the MER and MSL rovers have revealed a surprisingly large range in Ge abundances in surface rocks (30-650 ppm), but many igneous rocks and soils are shown to have greater than 30 ppm Ge (the detection limit of the APXS). Recently, reported that shergottite minerals showed a depletion of Ge with increasing fractionation, while nakhlites and chassignites exhibited Ge behavior compatible with closed system igneous differentiation. They interpreted their observations as tentatively indicating volcanic outgassing of Ge from shergottites (but not from nakhlite-chassignites) with recondensation of the Ge vapor into soils and breccias. Recent experimental studies show that Ge is significantly volatile from magmas. In this study, we followed up on those results by analyzing minerals in five nakhlites and five shergottites by laser ablation ICP-MS (LA-ICP-MS). See Attached

The 2011 Visions & Voyages Planeary Science Decadal Survey identified making significant progress toward the return of samples from Mars as the highest priority goal for flagship missions in next decade. Numerous scientific objectives have been identified that could be advanced through the potential return and analysis of martian rock, regolith, and atmospheric samples. The analysis of returned martian samples would be particularly valuable in in-creasing our understanding of Early Mars. There are many outstanding gaps in our knowledge about Early Mars in areas such as potential astrobiology, geochronology, planetary evolution (including the age, context, and processes of accretion, differentiation, magmatic, and magnetic history), the history of water at the martian surface, and the origin and evolution of the martian atmosphere. Here we will discuss scientific objectives that could be significantly advanced by Mars sample return.

The martian meteorite Northwest Africa 7034 (and pairings) is a breccia that provides important information about the rocks and processes of the martian crust (e.g., 1-3). Additional information can be gleaned from the components of the breccia. These components, specifically those designated as clasts, record the history of their parent rock (i.e., the rock that has been physically broken down to produce the clasts). In order to study these parent rocks, we must first determine which clasts within the breccia are de-rived from the same parent. Previous studies have be-gun this process (e.g., 4), but the search for genetic linkages between clasts has not integrated clasts with different grain sizes. We begin to take this approach here, incorporating igneous-textured clasts with both fine and coarse mineral grains. In NWA 7034, almost all materials (clasts and breccia matrix) are composed of the same mineral assemblages (feldspar, pyroxene, Fe-Ti oxides, apatite) with largely the same mineral compositions [1, 4-6]. Bulk breccia Sm-Nd systematics define a single isochron [7]. These observations are consistent with a majority of the components within NWA 7034 originating from the same geochemical source and crystallizing at roughly the same time.

The Mars 2020 rover will collect carefully selected samples of rock and regolith as it explores a potentially habitable ancient environment on Mars. Using the drill, rock cores and regolith will be collected directly into ultraclean sample tubes that are hermetically sealed and, later, deposited on the surface of Mars for potential return to Earth by a subsequent mission. Thorough characterization of any contamination of the samples at the time of their analysis will be essential for achieving the objectives of Mars returned sample science (RSS). We refer to this characterization as contamination knowledge (CK), which is distinct from contamination control (CC). CC is the set of activities that limits the input of contaminating species into a sample, and is specified by requirement thresholds. CK consists of identifying and characterizing both potential and realized contamination to better inform scientific investigations of the returned samples. Based on lessons learned by other sample return missions with contamination-sensitive scientific objectives, CC needs to be "owned" by engineering, but CK needs to be "owned" by science. Contamination present at the time of sample analysis will reflect the sum of contributions from all contamination vectors up to that point in time. For this reason, understanding the integrated history of contamination may be crucial for deciphering potentially confusing contaminant-sensitive observations. Thus, CK collected during the Mars sample return (MSR) campaign must cover the time period from the initiation of hardware construction through analysis of returned samples in labs on Earth. Because of the disciplinary breadth of the scientific objectives of MSR, CK must include a broad spectrum of contaminants covering inorganic (i.e., major, minor, and trace elements), organic, and biological molecules and materials.

Earth's core contains approximately 10% of a light element that is likely a combination of S, C, Si, and O, with Si possibly being the most abundant light element. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of Pt (with Re and Ru in progress or planned) between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle Pt concentrations.

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.

Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.

The Returned Sample Science Board (RSSB) was established in 2015 by NASA to provide expertise from the planetary sample community to the Mars 2020 Project. The RSSB's first task was to address the effect of heating during acquisition and storage of samples on scientific investigations that could be expected to be conducted if the samples are returned to Earth. Sample heating may cause changes that could ad-versely affect scientific investigations. Previous studies of temperature requirements for returned mar-tian samples fall within a wide range (-73 to 50 degrees Centigrade) and, for mission concepts that have a life detection component, the recommended threshold was less than or equal to -20 degrees Centigrade. The RSSB was asked by the Mars 2020 project to determine whether or not a temperature requirement was needed within the range of 30 to 70 degrees Centigrade. There are eight expected temperature regimes to which the samples could be exposed, from the moment that they are drilled until they are placed into a temperature-controlled environment on Earth. Two of those - heating during sample acquisition (drilling) and heating while cached on the Martian surface - potentially subject samples to the highest temperatures. The RSSB focused on the upper temperature limit that Mars samples should be allowed to reach. We considered 11 scientific investigations where thermal excursions may have an adverse effect on the science outcome. Those are: (T-1) organic geochemistry, (T-2) stable isotope geochemistry, (T-3) prevention of mineral hydration/dehydration and phase transformation, (T-4) retention of water, (T-5) characterization of amorphous materials, (T-6) putative Martian organisms, (T-7) oxidation/reduction reactions, (T-8) (sup 4) He thermochronometry, (T-9) radiometric dating using fission, cosmic-ray or solar-flare tracks, (T-10) analyses of trapped gasses, and (T-11) magnetic studies.

Germanium is a moderately volatile and siderophile element that follows silicon in its compatibility during partial melting of planetary mantles. Despite its obvious usefulness in planetary geochemistry germanium is not analyzed routinely, with there being only three prior studies reporting germanium abundances in Martian meteorites. The broad range (1-3 ppm) observed in Martian igneous rocks is in stark contrast to the narrow range of germanium observed in terrestrial basalts (1.5 plus or minus 0.1 ppm). The germanium data from these studies indicates that nakhlites contain 2-3 ppm germanium, while shergottites contain approximately 1 ppm germanium, a dichotomy with important implications for core formation models. There have been no reliable germanium abundances on chassignites. The ancient meteoritic breccia, NWA 7533 (and paired meteorites) contains numerous clasts, some pristine and some impact melt rocks, that are being studied individually. Because germanium is depleted in the Martian crust relative to chondritic impactors, it has proven useful as an indicator of meteoritic contamination of impact melt clasts in NWA 7533. The germanium/silicon ratio can be applied to minerals that might not partition nickel and iridium, like feldspars. We report germanium in minerals from the 3 known chassignites, 2 nakhlites and 5 shergottites by LAICP- MS using a method optimized for precise germanium analysis.

Earth's core contains approximately 10 percent light elements that are likely a combination of S, C, Si, and O, with Si possibly being the most abundant. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of P, Au, Pd, and many other SE between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle siderophile element concentrations.

The martian meteorite Northwest Africa 7034 (and pairings) is a breccia that samples a variety of materials from the martian crust. Several previous studies have identified multiple types of igneous-textured clasts within the breccia [1-3], and these clasts have the potential to provide insight into the igneous evolution of Mars. One challenge presented by studying these small rock fragments is the lack of field context for this breccia (i.e., where on Mars it formed), so we do not know how many sources these small rock fragments are derived from or the exact formation his-tory of these sources (i.e., are the sources mantle de-rived melt or melts contaminated by a meteorite impactor on Mars). Our goal in this study is to examine specific igneous-textured clast groups to determine if they are petrogenetically related (i.e., from the same igneous source) and determine more information about their formation history, then use them to derive new insights about the igneous history of Mars. We will focus on the basalt clasts, FTP clasts (named due to their high concentration of iron, titanium, and phosphorous), and mineral fragments described by [1] (Fig. 1). We will examine these materials for evidence of impactor contamination (as proposed for some materials by [2]) or mantle melt derivation. We will also test the petrogenetic models proposed in [1], which are igneous processes that could have occurred regardless of where the melt parental to the clasts was formed. These models include 1) derivation of the FTP clasts from a basalt clast melt through silicate liquid immiscibility (SLI), 2) derivation of the FTP clasts from a basalt clast melt through fractional crystallization, and 3) a lack of petrogenetic relationship between these clast groups. The relationship between the clast groups and the mineral fragments will also be explored.