V Xanes in Spinels as an Oxy-Barometer in Meteorites with Implications for Redox Variations in the Inner Solar System

The variation of oxygen fugacity within inner solar system materials spans a range of nearly 15 orders of magnitude. Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or con-strained such as FeTi oxides, olivine-opx-spinel, or some other oxy-barometer. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these achondrites is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in achondrite. Because the V pre-edge peak intensity and energy in chromites varies with fO2, and this has been calibrated over a large fO2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints

L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted ~ 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2

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 [1]. Morris et al. [1] propose 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 [2,3]. Magnetite stability in terrestrial magmas is well understood, as are the stability of FeO and Fe2O3 in terrestrial magmas [4,5]. 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 document the stability of magnetite with temperature and fO2 in a shergottite bulk composition. Second, we determine the FeO and Fe2O3 contents of the same shergottite bulk composition at 1 bar and variable fO2 at 1250 C, and at variable pressure. These two goals will help define not only magnetite stability, but pyroxene-melt equilibria that are also dependent upon fO2

Using Vanadium in Spinel as a Sensor of Oxygen Fugacity in Meteorites: Applications to Mars, Vesta, and Other Asteroids

Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or constrained such as FeTi oxides, olivine-opx-spinel, or some other oxybarometer [1]. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these samples is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in natural meteorite samples. Because the V pre-edge peak intensity and energy in chromites varies with fO2 (Fig. 1) [2], and this has been calibrated over a large fO 2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints

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

Iron redox systematics of martian magmas.

第2回極域科学シンポジウム/第34回南極隕石シンポジウム 11月18日（金） 国立国語研究所 2階講

Molybdenum Valence in Basaltic Silicate Melts

The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (~IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo

The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+)

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo

Water–Energy Nexus: Addressing Stakeholder Preferences in Jordan

The water and energy sectors are fundamentally linked. In Jordan, especially in the face of a changing climate, the water–energy nexus holds a number of challenges but also opportunities. A key point in exploring synergies is the identification of such, as well as the communication between the water and energy sectors. This paper promotes the importance of using a co-creative approach to help resolve opposing views and assessing stakeholder preferences in the context of the water–energy nexus in Jordan. A computer-supported, co-creative approach was used to evaluate stakeholder preferences and opinions on criteria and future scenarios for the energy and water sector in Jordan, identifying common difficulties and possibilities. The criteria describe socio-ecological aspects as well as techno-economic aspects for both systems. Discussing a set of preliminary scenarios describing possible energy and water futures ranked under a set of sector relevant criteria, a consensus between both stakeholder groups is reached. The robustness of results is determined, using a second-order probabilistic approach. The results indicate that there are no fundamental conflicts between the energy and water stakeholder groups. Applying a participatory multi-stakeholder, multi-criteria framework to the energy-water nexus case in Jordan promotes a clear understanding of where different stakeholder groups stand. This understanding and agreement can form the basis of a joint water–energy nexus policy used in the continued negotiation process between and within national and international cooperation, as well as promoting and developing acceptable suggestions to solve complex problems for both sectors