Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation during late fractional crystallization. These results show that shergottite HSE contents are controlled by silicates, oxides, and sulfides. In addition, the mantle producing the most primitive shergottites did not contain near chondritic relative ratios of the HSEs like the terrestrial mantle, and did not experience a late chondritic veneer

Depletion of Vandium in Planetary Mantles: Controlled by Metal, Oxide, or Silicate?

Vanadium concentrations in planetary mantles can provide information about the conditions during early accretion and differentiation. Because V is a slightly siderophile element, it is usually assumed that any depletion would be due to core formation and metal-silicate equilibrium. However, V is typically more compatible in phases such as spinel, magnesiowuestite and garnet. Fractionation of all of these phases would cause depletions more marked than those from metal. In this paper consideration of depletions due to metal, oxide and silicate are critically evaluated

Late Chondritic Additions and Planet and Planetesimal Growth: Evaluation of Physical and Chemical Mechanisms

Studies of terrestrial peridotite and martian and achondritic meteorites have led to the conclusion that addition of chondritic material to growing planets or planetesimals, after core formation, occurred on Earth, Mars, asteroid 4 Vesta, and the parent body of the angritic meteorites [1-4]. One study even proposed that this was a common process in the final stages of growth [5]. These conclusions are based almost entirely on the highly siderophile elements (HSE; Re, Au, Pt, Pd, Rh, Ru, Ir, Os). The HSE are a group of eight elements that have been used to argue for late accretion of chondritic material to the Earth after core formation was complete (e.g., [6]). This idea was originally proposed because the D(metal/silicate) values for the HSE are so high, yet their concentration in the mantle is too high to be consistent with such high Ds. The HSE also are present in chondritic relative abundances and hence require similar Ds if this is the result of core-mantle equilibration. Since the work of [6] there has been a realization that core formation at high PT conditions can explain the abundances of many siderophile elements in the mantle (e.g., [7]), but such detailed high PT partitioning data are lacking for many of the HSE to evaluate whether such ideas are viable for all four bodies. Consideration of other chemical parameters reveals larger problems that are difficult to overcome, but must be addressed in any scenario which calls on the addition of chondritic material to a reduced mantle. Yet these problems are rarely discussed or emphasized, making the late chondritic (or late veneer) addition hypothesis suspect

Conditions of Core Formation in the Early Earth: Single Stage or Heterogeneous Accretion?

Since approx.1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients [D(met/sil)] for siderophile (iron-loving) elements are much different than those measured at low PT conditions [1,2]. The high PT data have been used to argue for a magma ocean during growth of the early Earth [3,4]. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements (> 80 experiments published for Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd). At the same time several different models have been advanced to explain the siderophile elements in Earth's mantle: a) shallow depth magma ocean 25-30 GPa [3,5]; b) deep magma ocean; up to 50 GPa [6,7], and c) early reduced and later oxidized magma ocean [8,9]. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to identify issues that have lead to a difference in interpretation, and to present updated predictive expressions based on new experimental data. The resulting expressions will be applied to the siderophile element depletions in Earth's upper mantle

Antarctic Meteorite Newsletter, Volume 29, Number 1

This newsletter contains classifications for 597 new meteorites from the 2003 and 2004 ANtarctic Search for METeorites (ANSMET) seasons. They include samples from the Cumulus Hills, Dominion Range, Grosvenor Mountains, LaPaz Icefield, MacAlpine Hills, and the Miller Range. Macroscopic and petrographic descriptions are given for 25 of the new meteorites: 1 acapulcoite/Iodranite, 1 howardite, 1 diogenite, 2 eucrites, 1 enstatite chondrite, four L3 and two H3 chondrites, 2 CM, 3 CK and 1 CV chondrites, three R chondrites, and four impact melt breccias (with affinities for H and L). Likely the most interesting sample announced in this newsletter is LAP04840, with affinity to R chondrites. This meteorite contains approximately 15% horneblende, and has mineral compositional ranges and oxygen isotopic values similar to those of R chondrites. The presence of an apparently hydrous phase in this petrologic grade 6 chondrite is very unusual, and should be of great interest to many meteoriticists

Volatile Siderophile Elements in Shergottites: Constraints on Core Formation and Magmatic Degassing

Volatile siderophile elements (e.g., As, Sb, Ge, Ga, In, Bi, Zn, Cd, Sn, Cu, Pb) can place constraints both on early differentiation as well as the origin of volatiles. This large group of elements has been used to constrain Earth accretion [1,2], and Earth-Moon geochemistry [3]. Application to Earth has been fostered by new experimental studies of these elements such as Ge, In, and Ga [4,5,6]. Application to Mars has been limited by the lack of data for many of these elements on martian meteorites. Many volatile elements are considered in the pioneering work by [7] but for only the small number of martian samples then available. We have made new measurements on a variety of martian meteorites in order to obtain more substantial datasets for these elements using the analytical approach of [8]. We use the new dataset, together with published data from the literature, to define martian mantle abundances of volatile siderophile elements. Then, we evaluate the possibility that these abundances could have been set by mid-mantle (14 GPa, 2100 C) metal-silicate equilibrium, as suggested by the moderately and slightly siderophile elements [9]. Finally, we examine the possibility that some elements were affected by volatility and magmatic degassing

Sample Curation in Support of the OSIRIS-REx Asteroid Sample Return Mission

The OSIRIS-REx asteroid sample return mission launched to asteroid Bennu Sept. 8, 2016. The spacecraft will arrive at Bennu in late 2019, orbit and map the asteroid, and perform a touch and go (TAG) sampling maneuver in July 2020. After sample is stowed and confirmed the spacecraft will return to Earth, and the sample return capsule (SRC) will land in Utah in September 2023. Samples will be recovered from Utah [2] and then transported and stored in a new sample cleanroom at NASA Johnson Space Center in Houston [3]. The materials curated for the mission are described here. a) Materials Archive and Witness Plate Collection: The SRC and TAGSAM were built between March 2014 and Summer of 2015, and instruments (OTES,OVIRS, OLA, OCAMS, REXIS) were integrated from Summer 2015 until May 2016. A total of 395 items were received for the materials archive at NASA-JSC, with archiving finishing ~30 days after launch (with the final archived items being related to launch operations)[4]. The materials fall into several general categories including metals (stainless steel, aluminum, titanium alloys, brass and BeCu alloy), epoxies, paints, polymers, lubricants, non-volatile-residue samples (NVR), sapphire, and various miscellaneous materials. All through the ATLO process (from March 2015 until late August 2016) contamination knowledge witness plates (Si wafer and Al foil) were deployed in the various cleanrooms in Denver and KSC to provide an additional record of particle counts and volatiles that is archived for current and future scientific studies. These plates were deployed in roughly monthly increments with each unit containing 4 Si wafers and 4 Al foils. We archived 128 individual witness plates (64 Si wafers and 64 Al foils); one of each witness plate (Si and Al) was analyzed immediately by the science team after archiving, while the remaining 3 of each are archived indefinitely. Information about each material archived is stored in an extensive database at NASA-JSC, and key summary information for each will be presented in an online catalog. b) Bulk Asteroid sample: The Touch and Go Sampling Mechanism (TAGSAM) head will contain up to 1.5 kg of asteroid material. Upon return to Earth, the TAGSAM head with the sample canister will be subjected to a nitrogen purge and then opened in a nitrogen cabinet in Houston. Once the TAGSAM head is removed from the canister, it will be dis-assembled slowly and carefully under nitrogen until the sample can be removed for processing in a dedicated nitrogen glovebox. Bennu surface samples are expected to be sub-cm sized, based on thermal infrared and radar polarization ratio measurements [1]. The upper limit on material collected by the TAGSAM head is ~2 cm. Therefore, we will be prepared to handle, subdivide, and characterize materials of a wide grain size (from ~10 m to 2 cm), and for both organic (UV fluorescence) and inorganic (SEM, FTIR, optical) properties. Representative portions of the bulk sample will be prepared for JAXA (0.5 %; see also [5]) and Canadian Space Agency (4%), with the remaining divided between the science team (75%). c) Contact Pad samples: The base of the TAGSAM head contains 24 contact pads that are designed to trap the upper surface layer of material and thus offer an opportunity to study asteroid samples that have resided at the very top surface of the regolith. Asteroid material is trapped on the pads in spring steel Velcro hooks, and material will have to be removed from these pads by curation specialists in the lab. d) Hardware: Some canister and SRC hardware items will contain information that will be important to understanding the collected samples, including the canister gas filter, temperature strips, flight witness plates, and the TAGSAM and canister parts that might have adhering dust grains. Some challenges remaining for both bulk sample and contact pad samples include: i) working with intermediate size range (200 to 500 micron) samples - a size range NASA has not previously worked in such detail; ii) techniques for removal of contact pad material from the spring steel hooks, iii) static electrical effects of dust sized particles during sample handling and curation is likely to be significant, and iv) the TAGSAM head and associated canister hardware will undoubtedly be coated with fine adhering dust grains from Bennu. In the case of collection of a large bulk sample mass, the adhering dust grains may be of lower priority. If a small sample mass is returned, the adhering dust may attain a higher priority, so recovery of adhering dust grains is an additional challenge to consider. In the year leading up to sample return we plan a variety of sample handling rehearsals that will enables the curation team to be prepared for many new aspects posed by this sample suite

The Miller Range Nakhlites: A Summary of the Curatorial Subdivision of the Main Mass in Light of Newly Found Paired Masses

The 2003-2004 ANSMET team re-covered a 715.2 g nakhlite from the Miller Range (MIL) region of the Transantarctic Mountains (MIL 03346). This was the first nakhlite for the US Antarctic meteorite program, and after the announcement in 2004 [1], JSC received over 50 requests for this sample for the Fall 2004 Meteorite Working Group meeting. Since then it has been subdivided into >200 splits, and distributed to approx.70 scientists around the world for study. The 2009-2010 ANSMET team recovered three additional masses of this nakhlite [2], making the total amount of mass 1.871 kg (Table 1). Given that the original find (MIL 03346) has been heavily studied and these new masses are available, we will present a comprehensive overview of the subdivision of the original mass as well as the scientific findings to date

Experimental Constraints on the Stability of Clinopyroxene (+) Magnesite in Iron Bearing Planetary Mantles: Implications for Nakhlite Formation

Carbon is present in various forms in the Earth s upper mantle (carbonate- or diamond-bearing mantle xenoliths, carbonatite magmas, CO2 emissions from volcanoes...). Moreover, there is enough carbon in chondritic material to stabilize carbonates into the mantles of Mars or Venus as well as in the Earth. However, the interactions with iron have to be constrained, because Fe is commonly thought to buffer oxygen fugacity into planetary mantles. [1] and [2] show evidences of the stability of clinopyroxene Ca(Mg,Fe)Si2O6 + magnesite (Mg,Fe)CO3 in the Earth s mantle around 6GPa (about 180km). The stability of oxidized forms of carbon (like magnesite) depends on the oxygen fugacity of the system. In the Earth s mantle, the maximum carbon content is 10000 ppm [3]. The fO2 parameter varies vertically as a function of pressure, but also laterally because of geodynamic processes like subduction. Thus, carbonates, graphite, diamond, C-rich gases and melts are all stable forms of carbon in the Earth s mantle. [4] show that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. [5] inferred from thermodynamic calculations that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond). After [6], a metasomatizing agent like a CO2-rich melt may infiltrate the mantle source of nakhlites. However, according to [7] and [8], the FeO wt% value in the Martian bulk mantle is more than twice that of the Earth s mantle (KLB-1 composition by [9]). As iron and carbon are two elements with various oxidation states, Fe/C interaction mechanisms must be considered

Antarctic Meteorite Classification and Petrographic Database

The Antarctic Meteorite collection, which is comprised of over 18,700 meteorites, is one of the largest collections of meteorites in the world. These meteorites have been collected since the late 1970's as part of a three-agency agreement between NASA, the National Science Foundation, and the Smithsonian Institution [1]. Samples collected each season are analyzed at NASA s Meteorite Lab and the Smithsonian Institution and results are published twice a year in the Antarctic Meteorite Newsletter, which has been in publication since 1978. Each newsletter lists the samples collected and processed and provides more in-depth details on selected samples of importance to the scientific community. Data about these meteorites is also published on the NASA Curation website [2] and made available through the Meteorite Classification Database allowing scientists to search by a variety of parameter