Stacking Defects in Synthetic and Meteoritic Hibonites: Implications for High-Temperature Processes in the Solar Nebula

Hibonite (CaAl12O19) is a primary, highly refractory phase occurring in many Ca-Al-rich inclusions (CAIs) from different chondrite groups, except CI chondrites. Hibonite is predicted to be one of the earliest minerals to condense during cooling of the solar nebula at higher temperatures than any other major CAI mineral. Therefore, hibonite has great potential to reveal the processes and conditions of the very early, high-temperature stages of the solar nebular evolution. Previous microstructural studies of hibonite in CAIs and their Wark-Lovering (WL) rims showed the presence of numerous stacking defects in hibonite. These defects are interpreted as the modification of the stacking sequences of spinel and Ca-containing blocks within the ideal hexagonal hibonite structure, as shown by experimental studies of reaction-sintered ceramic CaO-Al2O3 compounds. We performed preliminary experiments in the CaO-Al2O3-MgO system to understand the formation processes and conditions of defect-structured hibonite found in meteorites

Iron Redox Systematics of Shergottites and Martian Magmas

Martian meteorites record a range of oxygen fugacities from near the IW buffer to above FMQ buffer [1]. In terrestrial magmas, Fe(3+)/ SigmaFe for this fO2 range are between 0 and 0.25 [2]. Such variation will affect the stability of oxides, pyroxenes, and how the melt equilibrates with volatile species. An understanding of the variation of Fe(3+)/SigmaFe for martian magmas is lacking, and previous work has been on FeO-poor and Al2O3-rich terrestrial basalts. We have initiated a study of the iron redox systematics of martian magmas to better understand FeO and Fe2O3 stability, the stability of magnetite, and the low Ca/high Ca pyroxene [3] ratios observed at the surface

On carbon and oxygen isotope ratios in starburst galaxies: New data from NGC253 and Mrk231 and their implications

Using the IRAM 30-m telescope, CN and CO isotopologues have been measured toward the central regions of the nearby starburst galaxy NGC253 and the prototypical ultraluminous infrared galaxy Mrk231. In NGC253, the 12C/13C ratio is 40+-10. Assuming that the ratio also holds for the CO emitting gas, this yields 16O/18O = 145+-36 and 16O/17O = 1290+-365 and a 32S/34S ratio close to that measured for the local interstellar medium (20-25). No indication for vibrationally excited CN is found. Peak line intensity ratios between NGC253 and Mrk231 are ~100 for 12C16O and 12C18O J=1-0, while the ratio for 13C16O J=1-0 is ~250. This and similar 13CO and C18O line intensities in the J=1-0 and 2-1 transitions of Mrk231 suggest 12C/13C ~ 100 and 16O/18O ~ 100, in agreement with values obtained for the less evolved ultraluminous merger Arp220. Also accounting for other extragalactic data, 12C/13C ratios appear to vary over a full order of magnitude, from >100 in ultraluminous high redshift galaxies to ~100 in more local such galaxies to ~40 in weaker starbursts not undergoing a large scale merger to 25 in the Central Molecular Zone of the Milky Way. With 12C being predominantly synthesized in massive stars, while 13C is mostly ejected by longer lived lower mass stars at later times, this is qualitatively consistent with our results of decreasing carbon isotope ratios with time and rising metallicity. It is emphasized, however, that both infall of poorly processed material, initiating a nuclear starburst, as well as the ejecta from newly formed massive stars (in particular in case of a top-heavy stellar initial mass function) can raise the carbon isotope ratio for a limited amount of time.Comment: Accepted by Astronomy & Astrophysics, 6 figures, 4 table

Effect of Silicon on Activity Coefficients of Siderophile Elements (P, Au, Pd, As, Ge, Sb, and In) in Liquid Fe, with Application to Core Formation

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

Melting of the Primitive Mercurian Mantle, Insights into the Origin of Its Surface Composition

Recent findings of the MESSENGER mission on Mercury have brought new evidence for its reducing nature, widespread volcanism and surface compositional heteregeneity. MESSENGER also provided major elemental ratios of its surface that can be used to infer large-scale differentiation processes and the thermal history of the planet. Mercury is known as being very reduced, with very low Fe-content and high S and alkali contents on its surface. Its bulk composition is therefore likely close to EH enstatite chondrites. In order to elucidate the origin of the chemical diversity of Mercury's surface, we determined the melting properties of EH enstatite chondrites, at pressures between 1 bar and 3 GPa and oxygen fugacity of IW-3 to IW-5, using piston-cylinder experiments, combined with a previous study on EH4 melting at 1 bar. We found that the presence of Ca-rich sulfide melts induces significant decrease of Ca-content in silicate melts at low pressure and low degree of melting (F). Also at pressures lower than 3 GPa, the SiO2-content decreases with F, while it increases at 3 GPa. This is likely due to the chemical composition of the bulk silicate which has a (Mg+Fe+Ca)/Si ratio very close to 1 and to the change from incongruent to congruent melting of enstatite. We then tested whether the various chemical compositions of Mercury's surface can result from mixing between two melting products of EH chondrites. We found that the majority of the geochemical provinces of Mercury's surface can be explained by mixing of two melts, with the exception of the High-Al plains that require an Al-rich source. Our findings indicate that Mercury's surface could have been produced by polybaric melting of a relatively primitive mantle

The Origin of Mercury's Surface Composition, an Experimental Investigation

Introduction: Results from MESSENGER spacecraft have confirmed the reduced nature of Mercury, based on its high core/mantle ratio and its FeO-poor and S-rich surface. Moreover, high resolution images revealed large volcanic plains and abundant pyroclastic deposits, suggesting major melting stages of the Mercurian mantle. In addition, MESSENGER has provided the most precise data to date on major elemental compositions of Mercury's surface. These results revealed considerable chemical heterogeneities that suggested several stages of differentiation and re-melting processes. This interpretation was challenged by our experimental previous study, which showed a similar compositional variation in the melting products of enstatite chondrites, which are a possible Mercury analogue. However, these experimental melts were obtained over a limited range of pressure (1 bar to 1 gigapascal) and were not compared to the most recent elemental maps. Therefore, here we extend the experimental dataset to higher pressures and perform a more quantitative comparison with Mercury's surface compositions measured by MESSENGER. In particular, we test whether these chemical heterogeneities result from mixing between polybaric melts. Our experiments and models show that the majority of chemical diversity of Mercury's surface can result from melting of a primitive mantle compositionally similar to enstatite chondrites in composition at various depths and degrees of melting. The high-Mg region's composition is reproduced by melting at high pressure (3 gigapascals) (Tab. 1), which is consistent with previous interpretation as being a large degraded impact basin based on its low elevation and thin average crust. While low-Mg NVP (North Volcanic Plains) are the result of melting at low pressure (1 bar), intermediate-Mg NVP, Caloris Basin and Rachmaninoff result from mixing of a high-pressure (3 gigapascals) and low-pressure components (1 bar for Rachmaninoff and 1 gigapascal for the other regions) (Tab. 1). Moreover, all compositions suggest mixing between low and high degree melts that indicate important differentiation processes

Unusual Iron Redox Systematics of Martian Magmas

Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite. Morris et al. proposed that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks. Magnetite stability in terrestrial magmas is well understood, as are the stabilities of FeO and Fe2O3 in terrestrial magmas. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas, we have undertaken an experimental study with two emphases. First, we determine the FeO and Fe2O3 contents of super- and sub-liquidus glasses from a shergottite bulk composition at 1 bar to 4 GPa, and variable fO2. Second, we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition

Metal-Silicate-Sulfide Partitioning of U, Th, and K: Implications for the Budget of Volatile Elements in Mercury

During formation of the solar system, the Sun produced strong solar winds, which stripped away a portion of the volatile elements from the forming planets. Hence, it was expected that planets closest to the sun, such as Mercury, are more depleted in volatile elements in comparison to other terrestrial planets. However, the MESSENGER mission detected higher than expected K/U and K/Th ratios on Mercury's surface, indicating a volatile content between that of Mars and Earth. Our experiments aim to resolve this discrepancy by experimentally determining the partition coefficients (D(sup met/sil)) of K, U, and Th between metal and silicate at varying pressure (1 to 5 GPa), temperature (1500 to 1900 C), oxygen fugacity (IW-2.5 to IW-6.5) and sulfur-content in the metal (0 to 33 wt%). Our data show that U, Th, and K become more siderophile with decreasing fO2 and increasing sulfur-content, with a stronger effect for U and Th in comparison to K. Using these results, the concentrations of U, Th, and K in the bulk planet were calculated for different scenarios, where the planet equilibrated at a fO2 between IW-4 and IW-7, assuming the existence of a FeS layer, between the core and mantle, with variable thickness. These models show that significant amounts of U and Th are partitioned into Mercury's core. The elevated superficial K/U and K/Th values are therefore only a consequence of the sequestration of U and Th into the core, not evidence of the overall volatile content of Mercury