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Siderophile Element Profile Measurements in Iron Meteorites Using Laser Ablation ICP-MS

Understanding the behaviour of siderophile elements during cooling of iron meteorites can lead to insight into the general thermal histories of the meteorites as well as their respective parent bodies. Traditionally trace element analyses in meteorites have been done using techniques that only measure the average concentration in each phase. With these methods, all of the spatial information with respect to the distribution of an element within one phase is lost. Measuring concentration profiles of trace elements in meteorites is now possible, with the advent of high-resolution analytical techniques such as laser ablation, inductively coupled plasma mass spectrometry (LA-ICP-MS) with spatial resolution <20 microns. [e.g. 1,2] and secondary ion mass spectrometry [3]. These profiles can give more insight into both the partitioning and diffusive behavior of siderophile elements in metal systems relevant to iron meteorites, as well as parent body cooling rates.

Watson, H. C.↗

History of Metal Veins in Acapulcoite-Lodranite Clan Meteorite GRA 95209

Graves Nunataks (GRA) 95209 has been hailed as the missing link of core formation processes in the acapulcoitelodranite parent asteroid because of the presence of a complex cm-scale metal vein network. Because the apparent liquid temperature of the metal vein (approximately 1500 C) is higher than inferred for the metamorphic grade of the meteorite, questions regarding the vein s original composition, temperature, and mechanism of emplacement have arisen. We have determined trace siderophile element compositions of metals in veins and surrounding matrix in an effort to clarify matters. We analyzed metals in GRA 95209 in a portion of thick metal vein and adjacent metal-rich (30-40 modal%), sulfide poor (less than 1%) matrix by EPMA and LA-ICP-MS for major and trace siderophile elements using methods described by [3]. We also examined metals from a metal-poor (approximately 15 modal%) and relatively sulfide-rich (2-5 modal%) region of the sample. Kamacite is the dominant metal phase in all portions of the sample. In comparison to matrix metal, vein metal contains more schreibersite and less tetrataenite, and is less commonly associated with Fe,Mn,Mg-bearing phosphates and graphite. Vein kamacite contains higher Co, P, and Cr and lower Cu and Ge. These minor variations aside, all metal types in GRA 95209 are fairly homogeneous in terms of their levels of enrichment of compatible siderophile elements (e.g. Pt, Ir, Os) relative to incompatible siderophile elements (e.g. As, Pd, Au), consistent with the loss of metal-sulfide partial melt that characterizes much of the clan. Whatever compositional differences between matrix and vein metal that may have originally existed, they have since largely co-equilibrated to similar restitic trace element compositions. We agree with [2] that metal veins, in their present state, do not represent a liquid composition. The original vein liquid was much more S-rich and emplaced at correspondingly lower liquid temperatures. Much of the Fe,Ni component solidified in cm scale conduits while S-rich melts were expelled and continued to migrate by percolation. The higher troilite content in metal poor regions of the sample results mostly from trapping of a small portion of these melts. The troilite is not remnant primary sulfide. Strong depletions of W, Mo, and especially Ga (greater than 50%, greater than 60%, and greater than 90% depletion, respectively) in metals of the metalpoor GRA 95209 lithology are localized at scales of 10-100 micrometers in the vicinity of graphite spherules. These depletions must have occurred below the temperatures at which cm-scale equilibration occurred, and future work will seek to determine their cause.

Herrin, J. S.↗

Northwest Africa 5298: A Basaltic Shergottite

NWA 5298 is a single 445 g meteorite found near Bir Gandouz, Morocco in March 2008 [1]. This rock has a brown exterior weathered surface instead of a fusion crust and the interior is composed of green mineral grains with interstitial dark patches containing small vesicles and shock melts [1]. This meteorite is classified as a basaltic shergottite [2]. A petrologic study of this Martian meteorite is being carried out with electron microprobe analysis and soon trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Oxygen fugacity is calculated from Fe-Ti oxides pairs in the sample. The data from this study constrains the petrogenesis of basaltic shergottites.

Hui, Hejiu↗

LU-HF Age of Martian Meteorite Larkman Nunatek 06319

Lu-Hf isotopic data were collected on mineral separates and bulk rock powders of LAR 06319, yielding an age of 197+/- 29 Ma. Sm-Nd isotopic data and in-situ LA-ICP-MS data from a thin section of LAR 06319 are currently being collected and will be presented at the 2009 LPSC. These new data for LAR 06319 extend the existing data set for the enriched shergottite group. Martian meteorites represent the only opportunity for ground truth investigation of the geochemistry of Mars [1]. At present, approximately 80 meteorites have been classified as Martian based on young ages and distinctive isotopic signatures [2]. LAR 06319 is a newly discovered (as part of the 2006 ANSMET field season) martian meteorite that represents an important opportunity to further our understanding of the geochemical and petrological constraints on the origin of Martian magmas. Martian meteorites are traditionally categorized into the shergottite, nakhlite, and chassignite groups. The shergottites are further classified into three distinct isotopic groups designated depleted, intermediate, and enriched [3,4] based on the isotope systematics and compositions of their source(s).

Shafer, J. T.↗

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

King, C.↗

Towards a Regolith Maturity Index for Howardites

The Dawn spacecraft has just arrived at asteroid 4 Vesta, parent of the howardite, eucrite and diogenite (HED) meteorites [1], to begin a yearlong surface study from orbit [2]. As Dawn will view a debris-covered surface, understanding the formation and mixing processes for the debris layer will strongly aid surface data interpretations. Howardites are polymict breccias mainly composed of clasts derived from basaltic (eucritic) and orthopy-roxenitic (diogenitic) parent materials [3]. Some howardites are poorly reworked (fragmental howardites) whilst others have been extensively gardened in an active regolith (regolithic howardites) [4]. The latter may represent an ancient, well-mixed regolith, whilst the former may be from more recent ejecta deposits [4]. Due to environmental differences, regolith development on Vesta differs in detail from that on the Moon [4-6]. We have been developing petrological criteria to apply to howardite thin sections to determine their relative regolithic maturity, which we are fine-tuning with comparison to noble gas data [7, 8]. Whilst we previously emphasized the abundance of reworked clasts (fragmental and impact-melt breccia clasts), this is an imperfect criterion: one howardite with abundant re-worked clasts (EET 99408) shows no evidence of solar wind Ne (SW-Ne), yet, two of our alleged fragmental howardites have clear SW-Ne signatures (LEW 85313, MET 00423) [7, 8]. We are now investigating the diversity in minor and trace element contents of low-Ca pyroxene clasts in howardites as a measure of regolith grade, and will begin analyses of such grains within reworked clasts. Our hypothesis is that regolithic howardites (and the breccia clasts they contain) will show greater diversity because they sampled more diverse diogenitic plutons than fragmental howardites, which formed from ejecta from only a few impacts [e.g. 4]. Our initial LA-ICP-MS work showed ranges in trace element diversity in low-Ca pyroxenes (estimated from the standard error of the mean of analyses), where those howardites considered of medium to high regolithic grade showed greater diversity [9]. Our EMPA results (from a larger howardite suite) show an overall greater diversity in our putative medium to high regolithic grade howardites, though there are exceptions. The greatest diversity is found for paired howardites GRO 95574 and GRO 95581, which were not considered regolithic in our initial study. We will continue investigating avenues to determine regolith maturity in thin section, factoring in bulk rock compositional data, and will coordinate these studies with noble gas results.

Mittlefehldt, David W.↗

Trace Element Compositions of Pallasite Olivine Grains and Pallasite Origin

Pallasites are mixtures of metal with magnesian olivine. Most have similar metal compositions and olivine oxygen isotopic compositions; these are the main-group pallasites (PMG). The Eagle Station grouplet of pallasites (PES) have distinctive metal and olivine compositions and oxygen isotopic compositions. Pallasites are thought to have formed at the core-mantle boundary of their parent asteroids by mixing molten metal with solid olivine of either cumulatic or restitic origin. We have continued our investigation of pallasite olivines by doing in situ trace element analyses in order to further constrain their origin. We determined Al, P, Ca, Ga and first row transition element contents of olivine grains from suite of PMG and PES by LA-ICP-MS at JSC. Included in the PMG suite are some that have anomalous metal compositions (PMG-am) and atypically ferroan olivines (PMG-as). Our EMPA work has shown that there are unanticipated variations in olivine Fe/Mn, even within those PMG that have uni-form Fe/Mg. Manganese is homologous with Fe2+, and thus can be used the same way to investigate magmatic fractionation processes. It has an advantage for pallasite studies in that it is unaffected by redox exchange with the metal. PMG can be divided into three clusters on the basis of Mn/Mg; low, medium and high that can be thought of as less, typically and more fractionated in an igneous sense. The majority of PMG have medium Mn/Mg ratios. PMG-am occur in all three clusters; there does not seem to be any relationship between putative olivine igneous fractionation and metal composition. The PMG-as and one PMG-am make up the high Mn/Mg cluster; no PMG are in this cluster. The high Mn/Mg cluster ought to be the most fractionated (equivalent to the most Fe-rich in igneous suites), yet they have among the lowest contents of incompatible lithophile elements Al and Ti and the two PMG-as in this cluster also have low Ca and Sc contents. This is inconsistent with simple igneous fractionation on a single, initially homogeneous parent asteroid. For Al and Ti, the low and high Mn/Mg clusters have generally uniform contents, while the medium cluster has wide ranges. This is also true of analyses of duplicate grains from the medium cluster pallasites which can have very different Al and Ti contents. Those from the low and high clusters do not. These observations suggest that pallasite olivines are not cumulates, but rather are restites from high degrees of melting. The moderately siderophile elements P and Ga show wide ranges in the high Mn/Mg cluster, but very uniform compositions in the medium cluster, opposite the case for Al and Ti. There is no correlation of P or Ga and Fe/Mn as might be expected if redox processes controlled the contents of moderately siderophile elements in the olivines. The lack of correlation of P could reflect equilibration with phosphates, although there is no correlation of Ca with P as might be expected

Mittlefehldt, David W.↗

Chemical Composition of Four Shergottites from Northwest Africa (NWA 2800, NWA, 5214, NWA 5990, NWA 6342)

Shergottites represent the majority of recovered Martian meteorites. As basic igneous rocks, they formed from magmas that were emplaced in the Martian crust [1]. Due to the low ambient pressure of the Martian atmosphere, subaerial lavas and shallow magma chambers are expected to outgas volatile metals (e.g., Cd, Te, Re, Bi) [2]. The planetary abundances of the volatile siderophile and chalcophile elements are important at establishing the depth of core formation for Mars, and must be known as a baseline for understanding volcanic outgassing on Mars, particularly the large enrichments of S and Cl observed in modern Martian soils [3]. There is little data on volatile siderophile and chalcophile elements from Martian meteorites, excluding a few well-analyzed samples [2]. Further, a large number of shergottites being recovered from North West Africa are in need of chemical analysis. All of the shergottites are in need of state-of-the art analysis for such ratios as Ge/Si and Ga/Al, which can now be accomplished by LA-ICP-MS [2].

Yang, S.↗

Expanding the REE Partitioning Database for Lunar Materials

Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. This is taken as evidence of a large-scale differentation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were later derived. However, the extent of the Eu anomaly in lunar rocks is variable. Some plagioclase grains in a lunar impact rock (60635) have been reported to display a negative Eu anomaly, or in some cases single grains display both positive and neagtive anomalies. Cathodoluminescence images reveal that some crystals have a negative anomaly in the core and positive at the rim, or vice versa, and the negative anomalies are not associated with crystal overgrowths. Oxygen fugacity is known to affect Eu partitioning into plagioclase, as under low fO2 conditions Eu can be divalent, and has an ionic radius similar to Ca2+ - significant in lunar samples where plagioclase compositions are predominantly anorthitic. However, there are very few experimental studies of rare earth element (REE) partitioning in plagioclase relevant to lunar magmatism, with only two plagioclase DEu measurements from experiments using lunar materials, and little data in low fO2 conditions relevant to the Moon. We report on REE partitioning experiments on lunar compositions. We investigate two lunar basaltic compositions, high-alumina basalt 14072 and impact melt breccia 60635. These samples span a large range of lunar surface bulk compositions. The experiments are carried out at variable fO2 in 1 bar gas mixing furnaces, and REE are analysed by and LA-ICP-MS. Our results not only greatly expand the existing plagioclase DREE database for lunar compositions, but also investigate the significance of fO2 in Eu partitioning, and in the interpretation of Eu anomalies in lunar materials.

Rapp, Jennifer F.↗

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.↗

In Situ Trace Element Analysis of an Allende Type B1 CAI: EK-459-5-1

Variations in refractory major and trace element composition of calcium, aluminum-rich inclusions (CAIs) provide constraints on physical and chemical conditions and processes in the earliest stages of the Solar System. Previous work indicates that CAIs have experienced complex histories involving, in many cases, multiple episodes of condensation, evaporation, and partial melting. We have analyzed major and trace element abundances in two core to rim transects of the melilite mantle as well as interior major phases of a Type B1 CAI (EK-459-5-1) from Allende by electron probe micro-analyzer (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to investigate the behavior of key trace elements with a primary focus on the REEs Tm and Yb.

Jeffcoat, C. R.↗

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.↗

Trace Element Abundances of Olivine-Hosted Melt Inclusions in Shergottites Northwest Africa 7397 and Robert Massif 04262

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].

Ferdous, J.↗

Spatial U-Pb Age Distribution in Shock-Recrystallized Zircon – A Case Study from the Rochechouart Impact Structure, France

Age determination of impact structures via the zircon U–Pb system remains challenging and often ambiguous due to highly variable effects of shock metamorphism on U-Pb geochronology. It is, therefore, crucial to link the observed zircon microtextures, including their temperature and pressure conditions associated with their formation, directly to the U–Pb ages preserved. Here, we analyzed three recrystallized zircon grains and one plastically deformed zircon crystal from the medium-sized Rochechouart impact structure in the northwestern Massif Central of France. For the Rochechouart impact structure the impact age (206.92 ± 0.32 Ma [40Ar/39Ar]) as well as the 2 tectono-themal history is well established making this study site ideal to test concepts about U-Pb systematics in shocked zircon and to differentiate between shock-driven age resetting and preimpact crystallization and metamorphic overprinting. Zircon microstructures were studied using scanning electron imaging, cathodoluminescence imaging, and electron backscatter diffraction (EBSD) mapping. Further, we conducted U–Pb Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) depth-profiling analysis, allowing us to interpret the resultant age data in discrete steps with increasing ablation time/depth. The U–Pb depth profiling data demonstrate that plastically strained grains are incompletely reset and preserve rim and interior age domains reflecting typical pre-impact (pre-Variscan and Variscan) regional tectonic ages. Our results also reveal that the granular crystals encountered contain microstructural evidence for “former reidite in granular neoblastic” (FRIGN) zircon, reflecting both high-pressure (⩾30GPa) and high temperature (⩾1200℃) conditions. This signifies that FRIGN zircon is now known from an additional, medium sized, impact structure further supporting the hypothesis that this impact induced microstructure is commonly preserved. In addition, FRIGN zircon has a high potential to preserve completely impact-reset crystal domains (~204 to 207 Ma) that can be identified by our combined analytical approach of U–Pb depth profiling and EBSD mapping, and thus are suitable for determining reliable impact ages

U-Pb depth profiling↗

Thermodynamic constraints on the textural evolution of eucrite, EET 90020

Basaltic eucrites, which are possibly parts of the Vestan crust, formed as either lava flows or intrusions, and can offer insights into early crust formation. However most eucrites have experienced thermal metamorphism, which exacerbates the challenges of understanding these samples. A variety of petrogenetic models such as, partial melting of a primitive source, fractional crystallization of magmas emplaced in a primitive crust, and/or partial melting of a eucritic source coupled with melt mixing and assimilation have been proposed in order to explain observed petrologic and chemical characteristics of eucrites. EET 90020 is an unbrecciated eucrite that has experienced significant thermal metamorphism, with temperatures of metamorphic equilibration calculated to be ~840-1040°C. Its petrologic history remains contentious, in part due to differences in trace element analyses [10,17, this work], which has led to multiple metamorphic interpretations [8,10-11]. Here, we combined petrologic observations, chemical analyses, and thermodynamic modeling, to interpret micro-domain textures identified in EET 90020 and better constrain its petrologic history. Ultimately, the development of such textures is a direct result of the geologic processes operating on a young Vesta or similar asteroid. Sample description: We identified three textural domains in EET 90020 (Figure 1); (I) A coarse grain domain with granoblastic plagioclase and pyroxene, (II) a medium grain domain with curved grain boundaries between plagioclase and pyroxene, and (III) a fine grain domain dominated by tridymite that fills in interstitial space between spherical plagioclase. Major element chemistry in phases is consistent across domains. Pyroxene have distinctive high Ca lamellae (Wo40.92En28.1Fs31.0) forming from the low-Ca pigeonite host (Wo3.5En33.7Fs62.8). There are small amounts of fayalitic olivine along pyroxene/oxide grain boundaries, where pyroxenes have reacted with ilmenite/chromite clasts. Plagioclase is anorthitic (Avg ~An88), with little variation (An86-92.5). Trace element bulk rock analyses were collected via ICP-MS and individual mineral analyses with LA-ICP-MS (Figure 2). The bulk sample has an observable enrichment in light rare earth elements, with a notable depletion in Eu. Plagioclase is enriched in LREEs, depleted in HREEs, and has a positive Eu anomaly while pyroxene is enriched in HREEs with a negative Eu anomaly. Variations in trace element analyses is likely influenced by the presence of phosphates because are highly enriched in REEs and have a dramatic effect on the bulk domain compositions. Thermodynamic modeling: The software package, Perple_X, was used to calculate mineral phase equilibria over a range of conditions using a Gibbs free energy minimization approach [12]. Models used all major/minor elements except P2O5. Thermodynamic properties from [13] were used to constrain endmember phase stabilities. Activity models were used to describe mixing in phases with solid solution. Isochemical P-T phase diagrams were constructed for the bulk thin section, and the coarse, medium and fine grain domain compositions. Domain compositions were determined using microprobe analyses of phases identified in each domain and observed modal mineral abundancies. Thermodynamically stable pyroxene compositions were extracted from model results and compared to pyroxene compositions collected via EMPA, allowing us to calculate temperatures for metamorphic equilibrium. Results: Results that use the coarse domain composition (Fig. 3a) demonstrate overlap at T ~ 1020°C indicating high T equilibration. There was no overlap for the medium and fine grain domains, or the bulk composition (e.g., Fig. 3b) indicating that these are not equilibrium assemblages. These results were replicated using data from [8,20]. Discussion: The disequilibrium results from the bulk rock, fine grain and medium grain models imply that EET 90020 was modified during and/or after peak metamorphism (open system behavior). However, this is in contrast to the coarse domain where it appears as if equilibrium was maintained. We suggest that this conflict is explained by highly localized equilibrium occurring at millimeter length-scales, which has been observed in terrestrial metamorphism where aqueous fluid infiltrate [14] or melt loss occurs [15]. It is unlikely that aqueous alteration was significant in modifying the bulk composition of EET 90020, because it lacks hydrated minerals. However, the presence of melt is supported by the presence of an abundance of curved grain boundaries and spherical grains in the medium and fine grain domains This contrasts the coarse domain, where grain boundaries are angular. Given the evidence for disequilibrium in the medium and fine grain domains, it would be inappropriate to draw additional conclusions about textural evolution using thermodynamic models of those domains. However, modeling results of the coarse grain domain, where equilibrium was maintained, can provide useful insights into the geologic evolution of EET 90020. We approximate maximum metamorphic temperatures, using the Ca component in pyroxene, at ~1020°C (Fig. 4), which is consistent with previous two-pyroxene thermometry [11]. At this temperature, up to 10 vol % melt can be produced in the coarse grain domain, which is at the boundary of minimum melt needed in order to segregate and form a melt network [16]. Tridymite and plagioclase would be the first minerals to melt out during heating starting ~990°C. This is consistent with the observed melt textures formed by tridymite and plagioclase in the fine grain domain. We suggest that a partial melting model best explains the textural development of EET 90020. Upon heating, melt generated was either trapped, resulting in no net change in the localized rock composition, or migrated, resulting in disequilibrium between pyroxene and the surrounding matrix. A positive Eu anomaly in plagioclase indicates that all of the plagioclase was melted previously. This is consistent with previous studies that have suggested that EET 90020 represents a residual eucrite that experienced partial melting and subsequent melt loss [8]. We speculate that partial melting could have occurred when EET 90020 was heated in the asteroid’s lower crust or adjacent to an intrusion [7]. Future work will study other, texturally heterogeneous samples to see if EET 90020 presents a unique circumstance or whether crustal partial melting was ubiquitous on the eucrite asteroid.

Eucrites↗

Additional Trials & Tribulations in Synthesizing a Sulfide Standard

Well-characterized sulfide reference materials that can serve as matrix-matched calibrants for in-situ trace element analyses via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain elusive. Here, we describe the creation an in-house sulfide standard at NASA JSC that will be used to measure siderophile and chalcophile trace elements in low pressure experimental products, specifically pentlandite ([FeNi]9S8) and pyrrhotite ([FeNi]1-xS), as well as natural sulfides in terrestrial and meteoritic mineral assemblages. Recent methods in creating a homogenous sulfide standard include pressed pellets, synthesized chips, or fused glass [e.g. 1-3]. Other studies, however, have had success in forming homogenous FeS standards via synthesization methods [e.g. 4-6]. We present a variation of the method described in [4], in which we create a pyrrhotite standard doped with a variety of trace elements (Zn, As, Se, Mo, Ru, Rh, Pd, Sn, Sb, Te, W, Os, Ir, Pt, Au) at ~10-40 ppm and Cu at ~200 ppm. Sulfide compositions were constructed using Fe and Ni metal and elemental sulfur powders. Trace elements were added to elemental sulfur from Atomic Absorption Spectroscopy (AAS) elemental standards as either nitrate or chloride solutions to prevent oxidation of the metal powders. The dried sulfur mixture was mixed with Fe and Ni powders and mechanically mixed before two aliquots were placed in separate SiO2 tubes. Each tube was held under vacuum for ~30 minutes, sealed under vacuum, and then heated at 800C for 48 hours. Like [4], the synthesis products were composed of pourous sulfide crystals. Major element analyses of both experimental aliquots, collected using an Electron Probe Microanalyser (EPMA), yield indistinguishable major element compositions (uncertainties in 2SE & 2RSE[%]), with an average of 57.90  0.09 (0.16 %), 4.95  0.03 (0.55 %), and 39.70  0.14 (0.34 %), for Fe, Ni, and S, respectively. Trace element data were measured using a Photon Machines 193nm laser ablation system coupled to a Thermo-Scientific Element-XR ICP-MS. Spot sizes were limited to 50 μm due to the porous nature of the sulfide target material. Trace element abundances, normalized to Fe as an internal standard, were also found to be homogenous between the two aliquots, with weighted mean 2RSE (%) values of <3.0 for all trace elements. Synthesized products were re-powdered and absolute concentrations measured via solution ICP-MS. Although the sulfide appears to be homogenous, sintering experiments will be performed to more closely match the standard density to natural sulfides and minimize differences in ablation behavior. Improved density also allows for higher sensitivity (i.e. more compact target material) and larger spot sizes or traverses, as void space is eliminated. Additional major and trace element analyses on the products of the sintering experiments will be undertaken.

Jacob B Setera↗

Microstructural Changes and Pb Mobility During the Zircon to Reidite Transformation: Implications for Planetary Impact Chronology

Impact events modify and leave behind a complex history of rock metamorphism on terrestrial planets. Evidence for an impact event may be recorded in physical changes to minerals, such as mineral deformation and formation of high P-T polymorphs, but also in the form of chemical fingerprints, such as enhanced elemental diffusion and isotopic mixing. Here we explore laboratory shock-induced physical and chemical changes to zircon and feldspar, the former of which is of interest because its trace elements abundances and isotope ratios are used extensively in geochemistry and geochronology. To this end, a granular mixture of Bishop Tuff sanidine and Kuehl Lake zircon, both with well characterized Pb isotope compositions, was prepared and then shocked via a flat plate accelerator. The peak pressure of the experiment, as calculated by the impedance matching method, was ~24 GPa although a broader range of P-T conditions is anticipated due to starting sample porosity. Unshocked and shocked materials were characterized via scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and Raman spectroscopy. These methods show that the starting zircon material had abundant metamict regions, and the conversion of the feldspar to glass in the post-shock material. Analyses of the shocked product also yielded multiple occurrences of the high-pressure ZrSiO 4 polymorph reidite, with some domains up to 300 μm across. The possibility of U-Pb system disturbance was evaluated via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ion mass spectrometry (SIMS). The isotopic data reveal that disturbance of the U-Pb geochronometer in the reidite was minimal (<2% for the main U-Pb geochronometers). To better constrain the P-T conditions during the shock experiment, we complement impedance matching pressure calculations with iSALE2D impact simulations. The simulated results yield a range of P-T conditions experienced during the experiment and show that much of the sample may have reached >30 GPa, which is consistent with formation of reidite. In the recovered shocked material, we identified lamellae of reidite, some of which interlock with zircon lamellae. Reidite {112} twins were identified, which we interpret to have formed to reduce stress between the crystal structure of the host zircon and reidite. These two findings support the interpretation that shear transformation enabled the transition of zircon to reidite. The size and presence of reidite found here indicate that this phase is probably common in impact-shocked crustal rocks that experienced ~25 to ~35 GPa, especially when the target material has porosity. Additionally, shock loading of the zircon and transformation to reidite at these pressures in porous materials is unlikely to significantly disturb the U-Pb system in zircon and that the reidite inherits the primary U and Pb elemental and isotopic ratios from the zircon.

Bishop Tuff↗

The influence of water, diet, and temperature on 87 Sr/ 86 Sr in fin spines of juvenile Atlantic Sturgeon Acipenser oxyrinchus oxyrinchus

Analysis of microchemistry in fish fin spines offers a non-lethal approach to address key questions relating to spatial patterns and habitat use of fish. Reconstruction of life history is based on chemical changes within calcified structures with an underlying assumption of elemental incorporation relative to environmental concentration. However, information is limited on the relative influence of water and diet concentrations of elements to corresponding concentrations within fin spines. Strontium (Sr) is commonly used in trace element studies because of its predictable changes within watersheds, with recent applications showing utility of 87 Sr/ 86 Sr for greater spatial resolution. Therefore, this study evaluated the influence of water and diet 87 Sr/ 86 Sr on pectoral fin spines of Atlantic Sturgeon A. oxyrinchus oxyrinchus in controlled laboratory experiments. In the first experiment, fish were exposed to a control, water spiked with 0.10 mg/L of 87 Sr or diet spiked with 0.25 µg/g or 0.50 µg/g of 87 Sr in replicated tanks for 12 weeks. In a second experiment, to determine the time duration required to occupy a different environment for fin spine chemistry to change, fish were maintained in water- or diet-spiked treatments for 1, 2, 3, or 6 weeks. Additionally, to determine if temperature has an influence on 87 Sr/ 86 Sr in fin spines, fish were held at 15 and 25°C for 12 weeks. Fin spines were analyzed using laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), and water and diet samples were analyzed using solution based ICP-MS. Results from Experiment 1 indicate water is the primary contributor and diet a secondary contributor of 87 Sr/ 86 Sr in pectoral fin spines of Atlantic Sturgeon. Results from Experiment 2 indicate fin spine 87 Sr/ 86 Sr can be influenced by water after 1 week and diet after 12 weeks. Additionally, although sample size was limited (n=3), water temperature did not have an effect on 87 Sr/ 86 Sr fin spine chemistry. In conclusion, these results provide guidance for interpretation of 87 Sr/ 86 Sr in pectoral fin spines of sturgeon and indicate usefulness of the technique for retrospectively estimating movement and habitat use.

59 BASIC BIOLOGICAL SCIENCES↗