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The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

Lauretta, D. S.↗

The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

During the three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. At the time the grant started, our collaborating PI, Dante Lauretts, was a postdoctoral research associate working with Peter Buseck at Arizona State University. The work on chondritic Hg was done in collaboration with Dante Lauretta and Peter Buseck and this study was published in Lauretta et a1 (2001a). In July, 2001 Dante Lauretta accepted a position as an Assistant Professor in the Lunar and Planetary Laboratory at the University of Arizona. His funding was transferred and this grant has supported much of his research activities during his first two years at the U of A. Several other papers are in preparation and will be published soon. We presented papers on this topic at Goldschmidt Conferences, the Lunar and Planetary Science Conferences, and the Annual Meetings of the Meteoritical Society. The work done under this grant has spurred several new directions of inquiry, which we are still pursuing. Included in this paper are the studies of bulk abundances and isotopic compositions of metreoritic Mercury, and the development of a thermal analysis ICP-MS technique applied to thermally liable elements.

Blum, J. D.↗

Osmium Isotope Evidence for an S-Process Carrier in Primitive Chondrites

The degree of isotopic mixing in the solar nebula and the nature of pre-solar components that have contributed to our solar system remain subjects of vigorous debate. Isotopic anomalies have been identified in Ca-Al inclusions in chondrites [1-4]. This indicates that refractory pre-solar components were not completely homogenized or processed away at the high temperatures experienced by CAIs. Pre-solar grains (SiC, C, etc.) are prevalent in primitive chondrites, and preserve isotopic heterogeneity resulting from the nucleosynthetic processes occurring in the stars from which these grains formed [2,4]. Several recent studies employing precise techniques for measuring Ru, Mo and Zr isotopes in bulk meteorites, have come up with varying conclusions on the degree of effectiveness of nebular mixing on the scale of bulk meteorite material. Some of these studies have reported isotopic anomalies in Mo and Ru [3,5-7], while others have not observed anomalies in Mo, Ru, or Zr [8-10]. Debate over the quality of the data, the normalization techniques employed, the absence or presence of isobaric interferences during the measurements on different types of instruments (e.g. TIMS versus ICP-MS), and other factors, has ensued [11,12].

Brandon, A. D.↗

Lunar and Planetary Science XXXVI, Part 17

The following topics were discussed: A Model for the Formation of Paterae on Io; LIBS-based Detection of As, Br, C, Cl, P, and S in the VUV Spectral Region in a Mars Atmosphere; Mass Independent Sulfur in Achondrites: Possible Evidence of Photochemistry in the Solar Nebula; Grain Size-dependent Viscosity and Oceans in Icy Satellites; Claritas Paleolake Studied from the MEX HRSC Data; Mars Express HRSC Colors of White Rock, Arabia, Mars; Lava and Flows of the Arcadia Region of Mars; Isotopic Composition of Lunar Soils and the Early Differentiation of the Moon; Trace Element Analysis of Lunar Soils by ICP-MS; Highly Siderophile Elements and Osmium Isotope Systematics in Ureilites: Are the Carbonaceous Veins Primary Components?; Evaporative Evolution of Martian Brines Based on Halogens in Nakhlites and MER Samples; Io from High-Resolution Galileo PPR Data Taken Simultaneously with SSI or NIMS Observations; Loki, Io: Groundbased Observations and a Model for Periodic Overturn; Deconstructing a Few Myths in the Interpretation of Satellite-Altitude Crustal Magnetic Field: Examples from Mars Global Surveyor; Semi-Autonomous Rover Operations: A Mars Technology Program Demonstration; Rotational Studies of Asteroids with Small Telescopes; Mineralogy and Temperature-induced Spectral Investigations of A-type Asteroids 246 Asporina and 446 Aeternitas; and Thermal History Calculations Versus Full Convection Models: Application to the Thermal Evolution of Mercury. Recent Solar-Proton Fluxes

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Genesis of Augite-Bearing Ureilites: Evidence From LA-ICP-MS Analyses of Pyroxenes and Olivine

Ureilites are ultramafic achondrites composed primarily of coarse-grained low-Ca pyroxene and olivine with interstitial carbonaceous material, but a number of them contain augite [1]. Ureilites are considered to be restites after partial melting of a chondritic precursor, although at least some augite-bearing ureilites may be partially cumulate [1, 2]. In this scenario, the augite is a cumulus phase derived from a melt that infiltrated a restite composed of typical ureilite material (olivine+low-Ca pyroxene) [2]. To test this hypothesis, we examined the major and trace element compositions of silicate minerals in select augite-bearing ureilites with differing mg#. Polished thick sections of the augite-bearing ureilites ALH 84136 , EET 87511, EET 96293, LEW 88201, and META78008 and augite-free typical ureilite EET 90019 were examined by EPMA for major and minor elements and laser ablation ICP-MS (LA-ICP-MS) for trace elements, REE in particular. Although EET 87511 is reported to contain augite, the polished section that we obtained did not.

Herrin, J. S.↗

Analysis of Moderately Siderophile Elements in Angrites: Implications for Core Formation of the Angrite Parent Body

Angrites are an enigmatic group of achondrites, that constitute the largest group of basalts not affiliated with the Moon, Mars or Vesta (HEDs). Chemically, angrites are exceptionally refractory element- enriched (e.g., Al, Ca) and volatile element-depleted (e.g., Na and K) achondrites. Highly volatile siderophile and chalcophile elements (Zn, Ge and Se) may be less depleted than alkalis and Ga taken to imply a fractionation of plagiophile elements. Core formation on the angrite parent body (APB) is not well understood due to the dearth of moderately siderophile element (Ga, Ge, Mo, Sb, W) data for angrites, with the exception of Ni and Co [2]. In particular, there are no data for Mo abundances of angrites, while Sb and W abundances are reported for only 3 angrites, and have not always been determined on the same sample. The recent increase in angrite numbers (13) has greatly increased our knowledge of the compositional diversity of the angrite parent body (APB). In this study, we report new Co, Ni, Ga, Mo, Sb and W abundances for angrites by laser ablation inductively coupled plasma mass spectrometry (ICP-MS) in order to place constraints on core formation of the APB.

Righter, K.↗

In Situ Determination of Siderophile Trace Elements in Metals and Sulfides in Enstatite Achondrites

Enstatite meteorites are identified by their extremely reduced mineralogy (1) and similar oxygen isotope composition (2). The enstatite meteorite clan incorporates both EH and EL chondrites, as well as a wide variety of enstatite achondrites, such as aubrites or anomalous enstatite meteorites (e.g. Mt. Egerton, Shallowater, Zaklodzie, NWA 2526). The role of nebular versus planetary processes in the formation of enstatite meteorites is still under debate (e.g. 3-5). Past studies showed a significant influence of metal segregation in the formation of enstatite achondrites. Casanova et al. (6) suggested incomplete metal-silicate segregation during core formation and attributed the unfractionated siderophile element patterns in aubrites metals to a lack of fractional crystallization in a planetary core. Recent studies suggest a significant role of impact melting in the formation of primitive enstatite chondrites (7) and identified NWA 2526 as a partial melt residue of an enstatite chondrite (8). To understand the nature of siderophile element-bearing phases in enstatite achondrites, establish links between enstatite achondrites and enstatite chondrites (9), and constrain planetary differentiation on their respective parent bodies and their petrogenetic histories, we present laser ablation ICP-MS measurements of metal and sulfide phases in Shallowater, Mt. Egerton, and the aubrites Aubres, Cumberland Falls, and Mayo Belwa.

vanAcken, D.↗

In Situ Trace Element Measurements on Roda and the Origin of Diogenites

The origin of diogenites remains poorly understood. A recent model interprets many diogenites to have been formed from melts that were derived by remelting initial magma ocean cumulates, and these penultimate parent melts were then contaminated by melts derived from remelting of the basaltic (eucritic) crust to form the ultimate diogenite parent melts [1] (hereafter the remelting model). This is a very complicated petrogenesis that has profound implications for the geological evolution of 4 Vesta if correct. This model was developed based on trace element analyses of bulk rock samples that had been leached in acids to remove phosphates; the compositions of the residues were interpreted to be close to those of cumulus orthopyroxenes plagioclase, chromite and olivine [1]. In situ measurements of phases in diogenites can be used to test this model. We have begun a campaign of laser ablation ICP-MS of orthopyroxene grains in diogenites for this purpose. Here we report our first results on one diogenite, Roda. We have determined a suite of trace lithophile elements on nine, mm-sized pyroxene grains separated from Roda that have previously been studied [2, 3]. A key observation supporting the remelting model is the very low Eu/Eu* of leached residues; values too low to represent orthopyroxene that crystallized from melts with chondritic Sm/Eu and Gd/Eu [1]. (Eu* = Eu interpolated from REE diagrams.) Crustal remelts have low Sm/Eu and Gd/Eu, and orthopyroxenes that crystallized from parent melts contaminated by them would have very low Eu/Eu* [1]. Roda grains have Eu/Eu* of 0.243 to 0.026; the latter a value lower than any measured on bulk diogenite leached residues (0.041) [1]. There is a general negative correlation between Eu/Eu* and some incompatible elements (Zr, Nb, Hf), but not others (LREE). This appears inconsistent with the remelting model as it would suggest an evolving parent melt with La de-creasing as Zr increased and Eu/Eu* decreased. Grain R-15 includes trace-element-rich trapped melt phases [2, 3]. This grain has the highest Eu/Eu* and LREE contents, indicating that the trapped melt had a high Eu/Eu*. Thus, our first data on one diogenite do not provide support for the remelting model [1]. Roda is unusual in that its orthopyroxene grains show wide ranges in trace element contents [4]. Previous in situ REE analyses of grain R-15 did not reveal evidence for subsolidus equilibration with trace-element-rich trapped melt phases, and led to the suggestion that Roda may be polymict, with different grains representing different lithologies of diverse compositions [3]. Thus, based on our results on Roda, it is perhaps premature to abandon the remelting model. In situ measurements on a suite of diogenites is planned to further address this issue.

Mittlefehldt, David W.↗

NASA Tech Briefs, February 2003

opics covered include: Integrated Electrode Arrays for Neuro-Prosthetic Implants; Eroding Potentiometers; Common/Dependent-Pressure-Vessel Nickel-Hydrogen Batteries; 120-GHz HEMT Oscillator With Surface-Wave-Assisted Antenna; 80-GHz MMIC HEMT Voltage-Controlled Oscillator; High-Energy-Density Capacitors; Microscale Thermal-Transpiration Gas Pump; Instrument for Measuring Temperature of Water; Improved Measurement of Coherence in Presence of Instrument Noise; Compact Instruments Measure Helium-Leak Rates; Irreversible Entropy Production in Two-Phase Mixing Layers; Subsonic and Supersonic Effects in Bose-Einstein Condensate; Nanolaminate Mirrors With "Piston" Figure-Control Actuators; Mixed Conducting Electrodes for Better AMTEC Cells; Process for Encapsulating Protein Crystals; Lightweight, Self-Deployable Wheels; Grease-Resistant O Rings for Joints in Solid Rocket Motors; LabVIEW Serial Driver Software for an Electronic Load; Software Computes Tape-Casting Parameters; Software for Tracking Costs of Mars Projects; Software for Replicating Data Between X.500 and LDAP Directories; The Technical Work Plan Tracking Tool; Improved Multiple-DOF SAW Piezoelectric Motors; Propulsion Flight-Test Fixture; Mechanical Amplifier for a Piezoelectric Transducer; Swell Sleeves for Testing Explosive Devices; Linear Back-Drive Differentials; Miniature Inchworm Actuators Fabricated by Use of LIGA; Using ERF Devices to Control Deployments of Space Structures; High-Temperature Switched-Reluctance Electric Motor; System for Centering a Turbofan in a Nacelle During Tests; Fabricating Composite-Material Structures Containing SMA Ribbons; Optimal Feedback Control of Thermal Networks; Artifacts for Calibration of Submicron Width Measurements; Navigating a Mobile Robot Across Terrain Using Fuzzy Logic; Designing Facilities for Collaborative Operations; and Quantitating Iron in Serum Ferritin by Use of ICP-MS.

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Composition and Petrology of HED Polymict Breccias: The Regolith of (4) Vesta

The polymict breccias of the howardite, eucrite and diogenite (HED) clan of meteorites preserve records of regolith processes that occur on Vesta, their putative home world. These breccias -- howardites, polymict eucrites and polymict diogenites -- are impact-engendered mixtures of diogenites and eucrites. The compositions of polymict breccias can be used to constrain the lithologic diversity of the vestan crust and the excavation depths of these materials. We have done petrological and compositional studies of multiple samples of 5 polymict eucrites and 28 howardites to investigate these issues. Older analyses were done on samples of approx 0.5 gram mass by INAA; newer analyses on samples of approx 5 gram mass by XRF and ICP-MS. We estimate the percentage of eucritic material (POEM) of polymict breccias by comparing their Al and/or Ca contents to those of average basaltic eucrite and diogenite. Our samples have POEM ranging from 28 to 98; adding two polymict diogenites from extends the range to POEM 10. One hypothesis is that ancient, well-mixed vestan regolith has POEM approx 67 and has a higher content of admixed impactor material. Several of our howardites have POEM of 59-74 (Al and/or Ca contents +/- 10% of POEM 67); about a third have Ni contents >300 micro g/g suggesting they contain >2% chondritic material (CM and/or CR). These may be regolithic howardites. Only one (LEW 85313) contains Ne dominated by a solar wind (SW) component. PCA 02066 is dominated by impact-melt material of polymict parentage and petrologically appears to be a mature regolith breccia, yet it does not contain SW-Ne. GRO 95602 falls within the POEM window, contains SW-Ne], yet has a Ni content of 193 micro g/g. Its petrologic characteristics suggest it was formed from immature regolith (no polymict breccia clasts; no glass). Trace element characteristics of the polymict breccias demonstrate the dominance of main-group eucrites as the basaltic component. Mixing diagrams of Zr, Nb, Ba, Hf and Ta with Al show no evidence for a significant contribution from Stannern-trend eucrites. An exception is polymict eucrite LEW 86001 (POEM 92), which is dominated by Stannern-trend basaltic debris. Howardite LAP 04838 (POEM 84) has higher incompatible trace concentrations than other polymict breccias (excluding LEW 86001), and either contains a Stannern-trend basaltic component, or has a significant contributions from evolved eucrites like Nuevo Laredo.

Mittlefehldt, David W.↗

Testing the Origins of Basalt Fragments fro Apollo 16

Several 2-4 mm regolith fragments of basalt from the Apollo 16 site were recently described by [1]. These included a high-Ti vitrophyric basalts (60603,10-16) and one very-low-titanium (VLT) crystalline basalt (65703,9-13). As Apollo 16 was the only highlands sample return mission distant from the maria, identification of basaltic samples at the site indicates input from remote sites via impact processes [1]. However, distinguishing between impact melt and pristine basalt can be notoriously difficult and requires significant sample material [2-6]. The crystal stratigraphy method utilizes essentially non-destructive methods to make these distinctions [7,8]. Crystal stratigraphy combines quantitative petrography in the form of crystal size distributions (CSDs) coupled with mineral geochemistry to reveal the petrogenetic history of samples. The classic CSD plot of crystal size versus population density can reveal insights on growth/cooling rates, residence times, and magma history which in turn can be used to evaluate basaltic vs impact melt origin [7-9]. Electron microprobe (EMP) and laser ablation (LA)-ICP-MS analyses of mineral phases complement textural investigations. Trace element variations document subtle changes occurring during the formation of the samples, and are key in the interpretation and preservation of this rare lunar sample collection.

Donohue, P. H.↗

Potassium Isotopic Compositions of NIST Potassium Standards and 40Ar/39Ar Mineral Standards

Knowledge of the isotopic ratios of standards, spikes, and reference materials is fundamental to the accuracy of many geochronological methods. For example, the 238U/235U ratio relevant to U-Pb geochronology was recently re-determined [1] and shown to differ significantly from the previously accepted value employed during age determinations. These underlying values are fundamental to accurate age calculations in many isotopic systems, and uncertainty in these values can represent a significant (and often unrecognized) portion of the uncertainty budget for determined ages. The potassium isotopic composition of mineral standards, or neutron flux monitors, is a critical, but often overlooked component in the calculation of K-Ar and 40Ar/39Ar ages. It is currently assumed that all terrestrial materials have abundances indistinguishable from that of NIST SRM 985 [2]; this is apparently a reasonable assumption at the 0.25per mille level (1σ) [3]. The 40Ar/39Ar method further relies on the assumption that standards and samples (including primary and secondary standards) have indistinguishable 40K/39K values. We will present data establishing the potassium isotopic compositions of NIST isotopic K SRM 985, elemental K SRM 999b, and 40Ar/39Ar biotite mineral standard GA1550 (sample MD-2). Stable isotopic compositions (41K/39K) were measured by the peak shoulder method with high resolution MC-ICP-MS (Thermo Scientific NEPTUNE Plus), using the accepted value of NIST isotopic SRM 985 [2] for fractionation [4] corrections [5]. 40K abundances were measured by TIMS (Thermo Scientific TRITON), using 41K/39K values from ICP-MS measurements (or, for SRM 985, values from [2]) for internal fractionation corrections. Collectively these data represent an important step towards a metrologically traceable calibration of 40K concentrations in primary 40Ar/39Ar mineral standards and improve uncertainties by ca. an order of magnitude in the potassium isotopic compositions of standards.

Morgan, Leah↗

Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.

Peretyazhko, Tanya↗

Identification of Martian Regolith Sulfur Components in Shergottites Using Sulfur K Xanes and Fe/S Ratios

Based on isotopic anomalies in Kr and Sm, Sr-isotopes, S-isotopes, XANES results on S-speciation, Fe/S ratios in sulfide immiscible melts [5], and major element correlations with S determined in impact glasses in EET79001 Lith A & Lith B and Tissint, we have provided very strong evidence for the occurrence of a Martian regolith component in some impact melt glasses in shergottites. Using REE measurements by LA-ICP-MS in shergottite impact glasses, Barrat and co-workers have recently reported conflicting conclusions about the occurrence of Martian regolith components: (a) Positive evidence was reported for a Tissint impact melt, but (b) Negative evidence for impact melt in EET79001 and another impact melt in Tissint. Here, we address some specific issues related to sulfur speciation and their relevance to identifying Martian regolith components in impact glasses in EET79001 and Tissint using sulfur K XANES and Fe/S ratios in sulfide immiscible melts. XANES and FE-SEM measurements in approx. 5 micron size individual sulfur blebs in EET79001 and Tissint glasses are carried out by us using sub-micron size beams, whereas Barrat and coworkers used approx. 90 micron size laser spots for LA- ICP-MS to determine REE abundances in bulk samples of the impact melt glasses. We contend that Martian regolith components in some shergottite impact glasses are present locally, and that studying impact melts in various shergottites can give evidence both for and against regolith components because of sample heterogeneity.

Sutton, S. R.↗

A Procedure to Simultaneously Determine the Calcium, Chromium, and Titanium Isotopic Compositions of Astromaterials

Many elements display both linear (mass-dependent) and non-linear (mass-independent) isotope anomalies (relative to a common reservoir). In early Solar System objects, with the exception of oxygen, mass-dependent isotope anomalies are most commonly thought to result from phase separation processes such as evaporation and condensation, whereas many mass-independent isotope anomalies likely reflect radiogenic ingrowth or incomplete mixing of presolar components in the proto-planetary disk. Coupling the isotopic characterization of multiple elements with differing volatilities in single objects may provide information regarding the location, source material, and/or processes involved in the formation of early Solar System solids. Here, we follow up on the work presented in, and detail new procedures developed to make high-precision multi-isotope measurements of Calcium, Chromium, and Titanium with small or limited amounts of sample using thermal ionization mass spectrometry and multi-collector ICP-MS, and characterize a suite of chondritic and terrestrial standards.

Tappa, M. J.↗

The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies

Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.

Righter, K.↗

The Contrast in Outgassing of Germanium Between Shergottites and Nakhlites

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

Yang, S.↗

Martian Magma Evolution from Olivine-Hosted Melt Inclusions in Shergottites Using MELTS Models

Shergottites, the largest martian meteorite group, come from at least two geochemically different source reservoirs i.e. incompatible trace element (ITE)-depleted and enriched. The depleted shergottites are thought to be derived from an ITE-depleted mantle reservoir, while enriched shergottites are thought to be derived from an ITE-enriched mantle reservoir that represents late stage residual melt from a magma ocean or interaction with martian crust. Moreover, the martian crust is distinct from shergottites, by being highly oxidized, distinctly ITE-enriched, and older. The link between the crust and shergottite compositions is poorly understood. Here we model shergottite differentiation to resolve the origin of enriched shergottites and why the bulk martian crust is compositionally distinct from shergottites. Early formed olivine-hosted melt inclusions can provide primary melt composition from which the parental magma had crystallized and also information at different stages of crystallization during parent magma differentiation that leads to shergottite magma evolution as well as crustal contribution assessment. We analyzed olivine-hosted melt inclusions of two enriched poikilitic shergottites for their major, minor and trace element concentrations using electron microprobe and laser ablation ICP-MS. We corrected the melt inclusion compositions for post-entrapment re-equilibration with their host olivine. To comprehend the crystallization sequence of these rocks and whether the melt entrapment is consistent with the crystallization, we use MELTS models for equilibrium and fractional crystallization. The results of these models suggest that all the melts were trapped in a closed system progressive crystallization at 1150-1210 ⁰C within 1 kbar to 1 bar pressure that is equivalent to <8.5 km, implying melt entrapment without any additional exogenous materials.

Ferdous, J.↗