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At least 73 records · Page 4

Highly Siderophile Element Abundances in Martian Meteorites

Critical evaluation of new and literature data for highly siderophile elements (HSE) in Martian (SNC) meteorites allows several first order conclusions to be drawn. (i) Re concentrations in SNC meteorites are nearly constant (within a factor of two) and do not correlate with rock type. Exceptions to this rule are Chassigny and Dar al Gani (DaG) 476, both of which are inferred to have experienced terrestrial Re contamination. (ii) Fractionations between Rh and Pd are small. Excluding Shergotty, the Rh/Pd ratio of the SNC suite is 0.22\pm0.05. (iii) Os and Ir contents vary by about four orders of magnitude; and positive correlations with MgO, Cr, and Ni suggest that these variations are not controlled by sulfide fractionation. A possible exception is the orthopyroxenite ALH84001, whose HSE's (including Ni, which is compatible in opx) are very low. (iv) Zagami, Shergotty, and Nakhla have nearly identical HSE signatures. Shergotty and Zagami have experienced assimilation-fractional crystallization (AFC) and have "crustal" Sr and Nd isotopic signatures. Conversely, the Nakhla parent was a small degree partial melt of a depleted mantle that interacted little with the Martian crust. These observations suggest that "evolved" HSE signatures can be produced by either fractional crystallization or small degrees of partial melting. (v) Chassigny and other mafic SNC's have HSE signatures that are very distinct from those of Nakhla-Zagami-Shergotty. The HSE elemental ratios of mafic SNC's approach chondritic, implying that the Martian mantle has nearly chondritic relative abundances of the HSE's. (vi) This chondritic HSE signature is observed in SNC's of various ages, suggesting that this is an ancient feature that has not evolved over time. (vii) No correlation is observed between HSE's and signatures of crustal contamination (e.g., Sr isotopes), indicating that the HSE signatures of the SNC suite are not derived from the crust. (vii) The Ru/Pd for the SNC suite ratio is about 0.5 chondritic. We attribute this depletion of Ru to the presence of spinel in the SNC source regions. (viii) Assignment of this depletion of Ru to spinel seems to also imply that spinel is not the cause of Os and Ir fractionations, requiring some other mafic phase to account for the observed variations. -----.

Jones, J. H.

Parent-body models for the formation of iron meteorites.

The iron meteorites appear to have formed by both igneous and non-igneous processes in asteroid-sized parent bodies. Evidence regarding the IIIA-IIIB irons (the most common iron meteorite group) favors their having originated as a central core, which experienced fractional crystallization during solidification. A reevaluation of available data does not confirm earlier reports of variable cooling rates within group IIIA. Members of group IA-IB contain chondritic silicates, have short I-Xe formation intervals and do not show evidence of fractional crystallization. They appear to have formed nonigneously by inhomogeneous agglomeration and accretion of solar nebular condensates.

Wasson, J. T.

Fe-Mg-Mn relations of ureilite olivines and pyroxenes and the genesis of ureilites

Microprobe analyses of ureilite and pigeonite cores are studied. The Fe/Mn-Fe/Mg relationship in the olivine core is examined. It is observed that magnetic processs such as fractional crystallization and partial melting, and FeO reduction contribute to the olivine core composition. The study of the Mg/Mn and Fe/Mn distributions reveals that these two distributions are not in equilibrium in the olivine and pigeonite cores. The effect of a reducing agent, carbon, on the ureilite genesis is investigated. It is concluded that fractional crystallization and FeO reduction are the major processes of ureilite genesis.

Mittlefehldt, D. W.

Causes of compositional variations within mare basalt suites

The short-range unmixing model, which explains compositional variations produced during crystallization of a single undifferentiated basalt flow, has been applied to the variations found within each of the suites of mare basalts. Based on this modelling, the following suites of mare basalts could represent random samples from single, undifferentiated lava flows: Apollo 11 A (high K), Apollo 15 olivine, Apollo 17 A-U, Apollo 17 B, Apollo 17 C. The short range unmixing model fails to account for variations within the Apollo 12 olivine-pigeonite group and Apollo 12 ilmenite group, which are well explained by fractional crystallization. The fact that the compositional variations within a suite of samples of unknown affinity can be explained in terms of short-range unmixing of a single lava does not mean that they are necessarily related in that way. It does, however, mean that independent evidence (stratigraphic, petrographic, isotropic, or age) is required to support arguments for the variations being caused by fraction crystallization or different magma batches.

Lindstrom, M. M.

Mk-IV Salt Crystallization Hot Finger Apparatus for Partitioning Used Electrorefiner Salt

Electrorefining is a controlled redox process used to regulate the behavior of ionic species. Through this process, metals can be deposited onto a cathode from an electrolyte solution in a controlled manner. The Mk-IV electrorefiner (Mk-IV ER) at Idaho National Laboratory is an engineering-scale, molten salt-based electrorefining cell that has been used for decades to recover metallic uranium from spent fuel. As a result, highly stable fission product chlorides have accumulated in the electrolyte. This accumulation results in changes to the salt’s properties, such as melting temperature, thermal conductivity, and density, as well as elevated product impurity and fissile materials criticality margin. These factors prompt the need for a salt regeneration process, such as melt-crystallization and species drawdown. This work focuses on providing a conceptual design to regenerate ER salt from used Mk-IV-ER salt in-situ, while minimizing salt waste volumes by concentrating the fission products in a final processed salt heal. We propose using a hot-finger crystallization apparatus design to fractionally crystallize salt in the Mk-IV-ER head space (or baffle space), allowing the collection of solid and liquid fractions. By using a cup-drain design, the used salt will be allowed to slowly solidify on the walls of a stainless-steel cup. The apparatus drain plug will then open to allow the liquid salt phase to drain to a lower cup, effectively separating the liquid phase from the solid phase. Under the hypothesis that the liquid phase salt concentrates the fission products, which is under examination in the accompanying work package, this separation allows the recovered solid salt to be reused while minimizing the high-level salt waste volume of used ER salt.

36 - MATERIALS SCIENCE

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.

Righter, Kevin

Petrogenesis of mare basalts - A record of lunar volcanism

The classification, sources, and overall petrogenesis of mare basalts are reviewed. All mare basalt analyses are used to define a sixfold classification scheme using TiO2 contents as the primary division. A secondary division is made using Al2O3 contents, and a tertiary division is defined using K contents. Such divisions and subdivisions yield a classification containing 12 categories, of which six are accounted for by the existing Apollo and Luna collections. A variety of postmagma-generation such as fractional crystallization, either alone or combined with wallrock assimilation, are invoked to explain the compositional ranges of the various mare basalt suites. High-Ti mare basalts are found at Apollo 1 and Apollo 17 sites; the A-11 basalts contain lower TiO2 abundances, a considerably larger range in trace-element contents, and the only occurrence of high-Ti/high-K mare basalts. The low-Ti basalts exhibit a wide range of major-and trace-element compositions and require source heterogeneity, fractional crystallization, and some assimilation.

Neal, Clive R.

Phase equilibrium constraints on the howardite-eucrite-diogenite association

Model determinations of fractional crystallization and equilibrium partial melting in the 0-10-kbar range have been performed for a series of compositions relevant to diogenite and eucrite petrogenesis. Olivine is found to react with diogenite parent liquids along the plagioclase-absent olivine/low-Ca pyroxene liquidus boundary under conditions of both fractional and equilibrium crystallization up to about 2 kbar. Olivine also reacts with eucritic liquids saturated with plagioclase and low-Ca pyroxene to pressures in excess of 2 kbar. The ability of simple fractional crystallization at 2 kbar to account for mineralogical and chemical features of the diogenite-eucrite association is discussed.

Longhi, John

Experimental study of pyroxene-liquid interaction in quartz-normative basalt 15597

Equilibrium and controlled cooling rate experiments on a synthetic analog of Apollo 15 quartz normative basalt 15597 are reported. While the partitioning of the major elements Ca, Mg, and Fe between pyroxene and liquid is rate independent, the K sub D parameter for Fe/Mg, which is calculated for low-Ca pyroxene, is temperature dependent. It is suggested that chemical trends observed in lunar pyroxenes are a consequence of three rate processes. The processes are (1) rate-dependent suppression of crystallization of other phases until lower temperature alters liquid composition and, therefore, the composition of the pyroxene that crystallizes; (2) the efficiency of fractional crystallization and the extent of crystal zoning are rate dependent; and (3) the partitioning of Al2O3, TiO2, and Cr2O3 between pyroxene and liquid depends on cooling rate.

Grove, T. L.

Systematic chemical variations in large 3AB iron meteorites: Clues to core crystallization

Analysis of numerous individual iron meteorites have shown that fractional crystallization of iron cores result in variations in chemical concentration of the solid core which span several orders of magnitude. The magnitude and direction of the resulting spatial gradients in the core can provide clues to the physical nature of the core crystallization process. We have analyzed suites of samples from three large 3AB irons (Cape York, 58t; Chupaderos, 24t; Morito, 10t) in order to estimate local chemical gradients. Initial results for the concentrations of Ge, Pd, Pt (Massey group), Ir, Au, As, Co, Os, and Rh (Dalhouse group), and P (Arizona group) show significant ranges among the Cape York and Chupaderos samples and marginally significant ranges among the Morito samples. Measurements of Au, Ir, Co, Ni, Cu, Ga, As, W, Re (from UCLA) and Ni and Co (Arizona group) are in progress. We find a spatial Ir gradient in Chupaderos with a magnitude similar to the one reported for Agpalilik (Cape York iron) by Esbensen et al.

Haack, H.

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.

A note on the Apollo 15 green glass vitrophyres

The paper discusses the vitrophyric fraction of Apollo 15 green glasses which contain skeletal crystals of olivine. Although the crystals are uniform in composition, the coexisting glass shows a range in composition and an olivine subtraction trend. The data suggest that the vitrophyres are part of the traditional Apollo 15 green glass suite composition; the natural trend of rapid low pressure crystal-fractionation suggests that other VLT rock types cannot be derived from Apollo 15 green glass magma.

Basu, A.

Equilibrium Fe isotope fractionation between olivine, pyroxene, spinel and MORB glass: Implications for mantle partial melting to generate MORBs

Primitive mid-ocean ridge basalts (MORBs) exhibit Fe isotopic compositions heavier than the upper mantle by +0.074 ± 0.028 ‰ for δ 56 Fe. The processes responsible for this isotopic difference remain unclear. Modeling of Fe isotope fractionation during mantle partial melting requires reliable equilibrium Fe isotope fractionation factors between minerals and melts, for which consistent data are still lacking. Here, in this study, we used Nuclear Resonant Inelastic X-ray Scattering (NRIXS) technique to measure Fe force constants for a MORB glass (ALV 519-4-1) and natural mantle minerals (olivine, orthopyroxene, clinopyroxene, and spinel) to determine the equilibrium Fe isotope fractionation factors between them. The force constants determined in this study, in increasing order, are 167 ± 26 N/m for spinel, 175 ± 17 N/m for olivine, 176 ± 20 N/m for MORB glass, 205 ± 26 N/m for clinopyroxene, and 219 ± 36 N/m for orthopyroxene. We evaluated the previously proposed mechanisms for the heavy Fe isotopic composition of MORBs, including (i) mantle partial melting, (ii) mantle lithological heterogeneity, with pyroxenite in the source, (iii) mantle metasomatism by low-degree melts, and (iv) fractional crystallization of olivine from melts. For (i), we used the pMELTS program to simulate adiabatic decompression melting of mantle peridotites, and calculated Fe isotope fractionation based on Fe 3+ –Fe 2+ equilibrium-controlled fractionation, where Fe 3+ forms stronger bonds and is more incompatible than Fe 2+ . At 10 wt% peridotite melting, corresponding to MORB generation, only +0.03 ‰ Fe isotope fractionation between the melt and the original bulk composition (Δ 56 Fe = δ 56 Fe melt - δ 56 Fe 0 ) was produced, insufficient to account for the observed MORB-upper mantle difference. For (ii), melting of pyroxenites yields smaller Fe isotope fractionation than melting of peridotites, making it unlikely the cause for the MORB-upper mantle isotopic difference. For (iii), both the Fe 3+ /ΣFe ratio and the δ 56 Fe of melts increase with the degree of partial melting, indicating that low-degree melts are not isotopically heavy enough to significantly alter the isotopic composition of lithospheric mantle through metasomatism. For (iv), equilibrium isotope fractionation between olivine and melt is near zero. These results suggest that equilibrium Fe isotope fractionation alone cannot explain the MORB isotopic signature, highlighting the potential role of kinetic isotope fractionation. Using a diffusion model, we calculated kinetic Fe and Mg isotope fractionations associated with (iv) olivine crystallization from a melt, and found that the predicted Fe and Mg isotope fractionations were inconsistent with observations in MORBs. Qualitatively, two processes could have induced kinetic Fe isotope fractionation during MORB generation: (a) Fe-Mg interdiffusion between melt and solid during melt migration and (b) reactive melt-rock interactions during melt focusing. However, a quantitative understanding of their role in modifying the melt isotopic composition remains limited and requires further investigation.

Fe isotopes

Trapped Melt in IIIAB Irons: Solid/Liquid Elemental Partitioning During the Fractionation of the IIIAB Magma

Group IIIAB, the largest iron-meteorite group, shows compositional trends (including a three-order-of-magnitude It concentration range) indicating that it formed by fractional crystallization of a metallic magma. Because about 200 irons are available, and all degrees of crystallization are well represented, IIIAB offers an excellent set of samples for the study of crystallization at all depths of the asteroidal core. On log-log Ir-Au, and Ir-As diagrams IIIAB forms a broad band; the breadth represents real meteorite-to-meteorite variations, far outside experimental or sampling uncertainties. A successful model must explain the width of this band; I suggest that it mainly resulted from the trapping of parental magma within the crystallizing solid. Because S is essentially insoluble in metal, the abundance of FeS is a measure of the fraction of trapped liquid. The trapped-melt model is supported by the observation that irons having higher S contents plot closer to the inferred composition of the magmatic parental liquid. The lowest S values are found in the irons occupying the left envelope of the IIIAB Ir-Au or Ir-As compositional fields, thus it is this set of irons that should be interpreted as the solid products of a fractionating magma. This simplifies the modeling of the crystallization process and allows inferences regarding the distribution ratios for other elements in the evolved IIIAB system. The large (multiton) Cape York irons show wide variations in their trapped-melt fractions; their compositions seem best understood in terms of a low initial S content of the IIIAB magma, about 20 mg/g. The inferred initial IIIAB distribution coefficient for Ir, 4.6, is much higher than published values based on laboratory studies of low-S systems; I suggest that low-S (and low-P) partition-ratio measurements tend to err in the direction of unity. In IIIAB distribution coefficients for Au, As, and Ni were still < 1 when the most evolved IIIAB irons formed, another indication of a low initial S content.

Wasson, John T.

Iron isotope fractionation between solid and liquid metal in the Fe-P±Ni system: Experimental constraints and implications for meteorites

Iron meteorites record a range of Fe isotope compositions that hold valuable information regarding the evolution of their parent bodies. Interpreting this isotopic variability, however, requires experimental constraints on the equilibrium isotope fractionation between phases. It is thought that the cores of many iron meteorite parent bodies experienced fractional crystallization, during which crystallization of solid iron-nickel occurs from an increasingly non-metal-rich liquid alloy. Phosphorus is one component of this alloy, and this study provides the first constraints on Fe-isotope fractionation between solid and liquid alloys in the Fe-Ni-P system. Experiments comprising Fe and P show a clear enrichment in the light isotopes of Fe in the liquid phase, which increases with the amount of phosphorus. Nickel-bearing samples are offset from the trend defined by Ni-free experiments, which is accounted for by the change in the solid alloy phase from a body-centered cubic to face-centered cubic structure upon the addition of Ni. The increasing light isotope enrichment of the liquid with increasing P content suggests interstitial solution of P, which is known to lengthen Fe-Fe bonds in Fe-P liquids (Waseda and Shiraishi 1977). Results suggest a negligible effect of P on Fe isotope fractionation during planetesimal core crystallization. Iron isotopes may, however, prove useful for identifying the petrogenesis of schreibersite in pallasites and iron meteorites.

58 GEOSCIENCES

Modeling the evolution of Sm and Eu abundances during lunar igneous differentiation

The current work presents models for the evolution of europium and samarium abundances during lunar igneous processes. The effect of probable variations in lunar temperature and oxygen fugacity, mineral-liquid distribution coefficients, and the crystallization or melting progression are considered in the model calculations. Changes in the proportions of crystallizing phases strongly influence the evolution of trace element abundances during fractional crystallization, and models must include realistic estimates of the major phase equilibria during crystallization. The results are applied to evaluating the possibility of generating KREEP-rich materials by lunar igneous processes.

Weill, D. F.

The provenance of metal in anorthositic rocks

Calculated compositions for metal crystallized from anorthositic melt rocks or feldspathic basalts such as 14310, 68415, and 77017 are (1) meteoritic in the initial stages or if metal is the only phase crystallized, and (2) higher in Co than meteoritic metal as a result of fractional crystallization of metals and silicates. Metal in coarse anorthositic rocks 15415, 15455, 60015, 64435, and 78238 is not of meteoritic composition and has Co contents from 0 to 9% with a Ni/Co ratio of about 1. The formation of anorthosites and the composition of the earliest metal are discussed with attention to Ni concentrations and the Ni/Co ratio. It is shown that anorthositic hornfels and breccias contain metal of a composition not found in their source material, coarse anorthosite; it is suggested that the hornfels includes metal grains probably derived with little change in composition from ancient meteorites.

Hewins, R. H.

Moonage Daydream: Reassessing the Simple Model for Lunar Magma Ocean Crystallization

Details of the differentiation of a global-scale lunar magma ocean (LMO) remain enigmatic, as the Moon is not simply composed of highlands anorthosite and a suite of mare basalts as inferred from early studies. Results from recent orbital missions, and the increasingly detailed study of lunar samples, have revealed a much larger range of lithologies, from relatively MgO-rich and "purest anorthosite" discovered on the lunar far side by the M3 instrument on Chandraayan-1 to more exotic lithologies such as Si-rich domes and spinel-rich clasts distributed globally. To understand this increasingly complex geology, we must understand the initial formation and evolution of the LMO, and the composition of the cumulates this differentiation could have produced. Several attempts at modelling such a crystallization sequence have been made, and have raised as many questions as they have answered. We present results from our ongoing experimental simulations of magma ocean crystallization, investigating two end-member bulk compositions (TWM and LPUM) under fully fractional crystallization conditions. These simulations represent melting of the entire silicate portion of the Moon, as an end-member starting point from which to begin assessing the evolution of the lunar interior and formation of the lunar crust.

Rapp, J. F.