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At least 19 records

Depletion of Vandium in Planetary Mantles: Controlled by Metal, Oxide, or Silicate?

Vanadium concentrations in planetary mantles can provide information about the conditions during early accretion and differentiation. Because V is a slightly siderophile element, it is usually assumed that any depletion would be due to core formation and metal-silicate equilibrium. However, V is typically more compatible in phases such as spinel, magnesiowuestite and garnet. Fractionation of all of these phases would cause depletions more marked than those from metal. In this paper consideration of depletions due to metal, oxide and silicate are critically evaluated.

Righter, Kevin↗

Terrestrial magma ocean and core segregation in the earth

According to the recent theories of formation of the earth, the outer layer of the proto-earth was molten and the terrestrial magma ocean was formed when its radius exceeded 3000 km. Core formation should have started in this magma ocean stage, since segregation of metallic iron occurs effectively by melting of the proto-earth. Therefore, interactions between magma, mantle minerals, and metallic iron in the magma ocean stage controlled the geochemistry of the mantle and core. We have studied the partitioning behaviors of elements into the silicate melt, high pressure minerals, and metallic iron under the deep upper mantle and lower mantle conditions. We employed the multi-anvil apparatus for preparing the equilibrating samples in the ranges from 16 to 27 GPa and 1700-2400 C. Both the electron probe microanalyzer (EPMA) and the Secondary Ion Mass spectrometer (SIMS) were used for analyzing the run products. We obtained the partition coefficients of various trace elements between majorite, Mg-perovskite, and liquid, and magnesiowustite, Mg-perovskite, and metallic iron. The examples of the partition coefficients of some key elements are summarized in figures, together with the previous data. We may be able to assess the origin of the mantle abundances of the elements such as transition metals by using the partitioning data obtained above. The mantle abundances of some transition metals expected by the core-mantle equilibrium under the lower mantle conditions cannot explain the observed abundance of some elements such as Mn and Ge in the mantle. Estimations of the densities of the ultrabasic magma Mg-perovskite at high pressure suggest existence of a density crossover in the deep lower mantle; flotation of Mg-perovskite occurs in the deep magma ocean under the lower mantle conditions. The observed depletion of some transition metals such as V, Cr, Mn, Fe, Co, and Ni in the mantle may be explained by the two stage process, the core-mantle equilibrium under the lower mantle conditions in the first stage, and subsequent downwards separation of the ultrabasic liquid (and magnesiowustite) and flotation of Mg-perovskite in the lower mantle.

Ohtani, Eiji↗

Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

Depletions of volatile siderophile elements (VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd) in mantles of Earth and Moon, constrain the origin of volatile elements in these bodies, and the overall depletion of volatile elements in Moon relative to Earth. A satisfactory explanation has remained elusive [1,2]. We examine the depletions of VSE in Earth and Moon and quantify the amount of depletion due to core formation and volatility of potential building blocks. We calculate the composition of the Earth's PUM during continuous accretion scenarios with constant and variable fO2. Results suggest that the VSE can be explained by a rather simple scenario of continuous accretion leading to a high PT metal-silicate equilibrium scenario that establishes the siderophile element content of Earth's PUM near the end of accretion [3]. Core formation models for the Moon explain most VSE, but calculated contents of In, Sn, and Zn (all with Tc < 750 K) are all still too high after core formation, and must therefore require an additional process to explain the depletions in the lunar mantle. We discuss possible processes including magmatic degassing, evaporation, condensation, and vapor-liquid fractionation in the lunar disk.

Righter, Kevin↗

Winds, Water Budgets and Stable Isotopes in Tropical Cyclones using TRMM and QUICKSCAT

Water vapor is the most abundant greenhouse gas in the atmosphere. Changes in its concentration and distribution are controlled by the hydrologic cycle. Because of its capacity to absorb and emit long wave radiation, release latent heat during condensation in storms and reflect short wave radiation when clouds form it has a major impact on Global climate change. The stable isotope ratios of water are H20 H2l6O and H0 H2l6O. These ratios change whenever water undergoes a phase change. They also change in both rain and water vapor whenever an air parcel is exposed to rain. In addition the relative changes in the two ratios differ as a &nction of the relative humidity. In short, the stable isotope ratios in water vapor in the atmosphere contain an integrated history of the processes affecting the concentration and distribution of water vapor in the atmosphere. Therefore the measurement and interpretation of changes in these stable isotope ratios are a powerful tool matched by no other method in tracing the transport history of water in the atmosphere. Our initial studies under this grant focused on the changes of the stable isotope ratios of precipitation and water vapor in tropical cyclones. The changes in time and space were found to be very large and to trace the transport of water in the storms reflecting changes in basic structural features. Because the stable isotope ratios of rains from tropical cyclones are so low flooding associated with land falling tropical cyclones introduces a negative isotopic spike into the coastal surface waters. In addition the stable isotope ratios of water vapor in the vicinity of tropical cyclones is anomalously low. This suggests that carbonate shelled organisms such as ostracoda living in coastal waters have the potential to record the isotopic spike and thereby provide a long term record of tropical storm activity in sediment cores containing fossil shells. Likewise, tree rings in coastal environments offer a similar potential. We have analyzed the oxygen isotopic composition of ostrcoda shells formed in the floodwaters of Tropical Storm Allison (2001) and discovered the negative isotopic 1 16 spike. Because we had learned that storm activity has a major impact on the stable isotope ratios of water vapor in the tropics and sub-tropics we decided to analyze the isotopic compositions of water vapor in different locations in the tropics. We did this in Puerto Escondido, Mexico in July 1998, near Kwajalein Island in the Pacific in 1999 as part of a TRMM summer field program and in 2001 in Key West, Florida as part of the CAMEX 4 summer field program. Our isotopic studies along with our earlier tropical cyclone studies showed that the low isotopic ratios in water vapor induced by exposure to rains the storms persisted for 48 hours often far away from the original storm site. We also noted that positive isotopic spikes were introduced into atmospheric water vapor if winds were high and extensive sea spray was present. These findings have a significant impact on the interpretation of the stable isotope studies of tropical ice cores found in the high mountain regions of the tropics. The assumption made in interpreting the ice core record is that the source water vapor evaporated from the sea surface is in near isotopic equilibrium with the seawater and undergoes a decrease during its transport that reflects the change in temperature from the sea surface to the site of the ice core. Because an additional isotopic depletion occurs at the sea surface source area that depends on the intensity, duration and size of the tropical rain system the isotopic variations found in the ice cores must take into account changes in past storm activity in the tropics. These systems must be an important source of water vapor to the ice cores because they charge the troposphere with water vapor to a far greater vertical height than evaporation in quiescent regions. Finally, an interest in increased heat transfer in thnterior of tropical cyclones resulting from greater amounts of sea spray is a topic of considerable interest to the research community. Increases in sea spray may be related to rapid changes in the intensity of hurricanes, a feature of hurricanes that currently is very poorly forecast. Project CBLAST of the Hurricane Research Division of NOAA is an active program that uses P3 research aircraft to evaluate this problem. An instrument has been designed and built at the University of Houston that will be placed on the P3 research aircraft during the 2004 hurricane season. It continuously measures the salt content of rain in hurricanes. Changes in the salt content of the rains should reflect the abundance of sea spray at the sea surface. In this way maps of sea spray intensity in hurricanes may be forthcoming. This should help computer modelers who simulate hurricanes to better understand the potential of changes in sea spray to change the intensity of hurricanes. The cost of designing, building and installing this instrument was borne largely by funding from this NASA grant. A list of presentations at national meetings and publications that were as the result of funding from this NASA grant are found in the report.

Lawrence, James R.↗

Geochemical affinities of cobalt and germanium toward metal, silicate, and sulfide phases at high temperature

Hydrothermal studies indicate that Co and Ge are strongly siderophile when metallic iron is in equilibrium with olivine at 900 C and 500 bars. If the metal is replaced by troilite (FeS), Ge is strongly lithophile whereas Co tends to concentrate in the sulfide phase. If iron meteorites were formed in a core derived from the sulfide phase, they would be depleted in Ge but retain Co.

Wai, C. M.↗

Metal-olivine associations and Ni-Co contents in two Apollo 12 mare basalts

Olivine crystals in mare basalts 12004,8 and 12022,12 are normally zoned with Cr-poor rims. The Ni content of rare 2- to 10-micron metal inclusions in olivine decreases markedly as Fe/Mg in their immediate olivine hosts increases. Each metal grain appears to have been enclosed by late olivine almost immediately after it crystallized. The fractionation trend for the olivine and metal contrasts with the subsolidus equilibration trend for pallasites. For the basalts, not even local equilibrium of Fe, Ni and Co at metal/olivine interfaces can be detected by microprobe. Ni and Co concentrations range from about 300 ppm in olivine cores to about 70 ppm in rims. The limits of detection, at 95% confidence, are 36 ppm (Ni) and 25 ppm (Co). The distribution of Ni and Co in olivine, like that of Mg and Cr, records the depletion of these elements in the melt.

Hewins, R. H.↗

Constraints on the Parental Melts of Enriched Shergottites from Image Analysis and High Pressure Experiments

Martian basalts can be classified in at least two geochemically different families: enriched and depleted shergottites. Enriched shergottites are characterized by higher incompatible element concentrations and initial Sr-87/Sr-86 and lower initial Nd-143/Nd-144 and Hf-176/Hf-177 than depleted shergottites [e.g. 1, 2]. It is now generally admitted that shergottites result from the melting of at least two distinct mantle reservoirs [e.g. 2, 3]. Some of the olivine-phyric shergottites (either depleted or enriched), the most magnesian Martian basalts, could represent primitive melts, which are of considerable interest to constrain mantle sources. Two depleted olivine-phyric shergottites, Yamato (Y) 980459 and Northwest Africa (NWA) 5789, are in equilibrium with their most magnesian olivine (Fig. 1) and their bulk rock compositions are inferred to represent primitive melts [4, 5]. Larkman Nunatak (LAR) 06319 [3, 6, 7] and NWA 1068 [8], the most magnesian enriched basalts, have bulk Mg# that are too high to be in equilibrium with their olivine megacryst cores. Parental melt compositions have been estimated by subtracting the most magnesian olivine from the bulk rock composition, assuming that olivine megacrysts have partially accumulated [3, 9]. However, because this technique does not account for the actual petrography of these meteorites, we used image analysis to study these rocks history, reconstruct their parent magma and understand the nature of olivine megacrysts.

Collinet, M.↗

Experimental determination of the partitioning of gallium between solid iron metal and synthetic basaltic melt Electron and ion microprobe study

The distribution of Ga between solid Fe metal and synthetic basaltic melt is investigated experimentally at temperatures of 1190 and 1330 C, and over a narrow range of oxygen fugacities. Metal-silicate reversal experiments were conducted, indicating a close approach to equilibrium. The analysis of the partitioned products was performed using electron and ion microprobes. At one bar total pressure, the solid metal/silicate melt partition coefficient D(Ga) is used to evaluate metal-silicate fractionation processes in the earth, moon, and Eucrite Parent Body (EPB). It is found that the depletion of Ga abundances in the EPB is due to the extraction of Ga into a metallic core. Likewise, the depletion of Ga in the lunar mantle is consistent with the extraction of Ga into a smaller lunar core if Ga was originally present in a subchondritic concentration. The relatively high Ga abundances in the earth's mantle are discussed, with reference to several theoretical models.

Drake, M. J.↗

Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: new constraints from Bi, Pd, and Ag metal-silicate partitioning.

The Earth’s timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Be-cause Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion for Earth and Mars and show that the Pd/Ag ratio is significantly fractionated during accretion, allowing for the production of detectable 107Ag anomalies produced while 107Pd (half life = 6.5 M.y.) was still extant. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) precursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the PUM Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.

accretion↗

Effective Forces Between Colloidal Particles

Colloidal suspensions have proven to be excellent model systems for the study of condensed matter and its phase behavior. Many of the properties of colloidal suspensions can be investigated with a systematic variation of the characteristics of the systems and, in addition, the energy, length and time scales associated with them allow for experimental probing of otherwise inaccessible regimes. The latter property also makes colloidal systems vulnerable to external influences such as gravity. Experiments performed in micro-ravity by Chaikin and Russell have been invaluable in extracting the true behavior of the systems without an external field. Weitz and Pusey intend to use mixtures of colloidal particles with additives such as polymers to induce aggregation and form weak, tenuous, highly disordered fractal structures that would be stable in the absence of gravitational forces. When dispersed in a polarizable medium, colloidal particles can ionize, emitting counterions into the solution. The standard interaction potential in these charged colloidal suspensions was first obtained by Derjaguin, Landau, Verwey and Overbeek. The DLVO potential is obtained in the mean-field linearized Poisson-Boltzmann approximation and thus has limited applicability. For more precise calculations, we have used ab initio density functional theory. In our model, colloidal particles are charged hard spheres, the counterions are described by a continuum density field and the solvent is treated as a homogeneous medium with a specified dielectric constant. We calculate the effective forces between charged colloidal particles by integrating over the solvent and counterion degrees of freedom, taking into account the direct interactions between the particles as well as particle-counterion, counterion-counterion Coulomb, counterion entropic and correlation contributions. We obtain the effective interaction potential between charged colloidal particles in different configurations. We evaluate two- and three-body forces in the bulk as well as study the influence of soft walls. We qualitatively explain the effects of the walls on the forces and demonstrate that many-body effects are negligible in our system. With adjustments in the parameters, the DLVO pair-potential can describe the results quantitatively. Besides electrostatic interactions, entropic depletion effects that arise from (hard-core) exclusion play an important role in determining the behavior of multi-component colloidal suspensions. A standard theory for depletion forces is due to Asakura and Oosawa and is based on the ideal gas approximation. To go beyond this approximation, we have studied entropic forces in molecular dynamics simulations of systems of hard spheres (the effects of the solvent have been ignored). The effective depletion forces for these systems can be found either from equilibrium distribution functions or from direct momentum transfer calculations. Our results obtained by either method show qualitative differences from the Asakura-Oosawa forces, indicating a longer range, higher value at contact and most importantly a more complicated structure, comprising of several maxima and minima. Our calculations include the determination of effective forces between two spheres, a hard sphere and a wall, and the behavior of a hard sphere near a step-edge and a corner. We also demonstrate that such entropic forces do not necessarily satisfy pairwise additivity.

Tehver, Riina↗

Mantle-melt Partitioning of the Highly Siderophile Elements: New Results and Application to Mars

Trace elements and extant and extinct isotopic attributes in martian meteorites have been used to argue that Mars accreted quickly, differentiated into core and mantle, and established several mantle reservoirs, possibly within 10 Ma of T0. The partitioning of trace elements in the deep mantle has been relatively unstudied, despite the need for such knowledge in understanding magma ocean crystallization and the origin of depleted and enriched mantle reservoirs. The siderophile element composition of the martian mantle, and lithophile isotopic systems such as Sr, Hf, and Nd, are thought to record evidence for early metal-silicate equilibrium and deep magma ocean at an intermediate depth and pressure of 800 km or 14 GPa. We have carried out experiments across this pressure range to better understand the mineral/melt partitioning of a wide range of elements. These new data are used to evaluate differentiation models for Mars and to help interpret the available isotopic data. The relatively incompatible nature of Re compared to mildly compatible Os means that the crystallization of a deep magma ocean will lead to residual liquids with super chondritic Re/Os, and solids with sub-chondritic Re/Os. Such material available in the mantle could be the source of enriched isotopic reservoir that produced shergottites with + Os values. On the other hand, slightly sub-chondritic Re/Os ratios in the crystallizing solids would provide a reservoir that could produce - Os values. Melting of mixtures of these two enriched and depleted end members could explain the Nd-Os isotopic correlations and systematics of shergottites.

K Righter↗

Partitioning of Pd Between Fe-S-C and Mantle Liquids at High Pressure and Temperature: Implications for Core Formation

One of the most elusive geochemical aspects of the early Earth has been explaining the near chondritic relative abundances of the highly siderophile elements (HSE; Au, Re and the platinum group elements) in Earth's primitive upper mantle (PUM). Perhaps they were delivered to the Earth after core formation, by late addition of carbonaceous chondrite material. However, the recognition that many moderately siderophile elements can be explained by high pressure and temperature (PT) metal-silicate equilibrium, leads to the question whether high PT equilibrium can also explain the HSE concentrations. Answers to this question have been slowed by experimental difficulties (nugget effect and very low solubilities). But two different perspectives have emerged from recent studies. One perspective is that D(M/S) for HSE at high PT are not low enough to explain terrestrial mantle depletions of these elements (for Pd and Pt). A second perspective is D(M/S) are reduced substantially at high PT and even low enough to explain terrestrial mantle depletions (for Au and Pt). Issues complicating interpretation of all experiments include use of MgO- and FeO-free silicate melts, and S-free and FeNi metal-free systems. In addition, conclusions for Pt rest on an interpretation that the tiny metallic nuggets plaguing many such experiments, were formed upon quench. There is not agreement on this issue, and the general question of HSE solubility at high PT remains unresolved

Righter, K.↗

Water in the Oceanic Lithosphere: Salt Lake Crater Xenoliths, Oahu, Hawaii

Water can be present in nominally anhydrous minerals of peridotites in the form of hydrogen bonded to structural oxygen. Such water in the oceanic upper mantle could have a significant effect on its physical and chemical properties. However, the water content of the MORB source has been inferred indirectly from the compositions of basalts. Direct determinations on abyssal peridotites are scarce because they have been heavily hydrothermally altered. Here we present the first water analyses of minerals from spinel peridotite xenoliths of Salt Lake Crater, Oahu, Hawaii, which are exceptionally fresh. These peridotites are thought to represent fragments of the Pacific oceanic lithosphere that was refertilized by alkalic Hawaiian melts. A few have unradiogenic Os and radiogenic Hf isotopes and may be fragments of an ancient (~2 Ga) depleted and recycled lithosphere. Water contents in olivine (Ol), orthopyroxene (Opx), and clinopyroxene (Cpx) were determined by FTIR spectrometry. Preliminary H_{2}O contents show ranges of 8-10 ppm for Ol, 151-277 ppm for Opx, and 337-603 ppm for Cpx. Reconstructed bulk rock H_{2}O contents range from 88-131 ppm overlapping estimates for the MORB source. Water contents between Ol minerals of the same xenolith are heterogeneous and individual OH infrared bands vary within a mineral with lower 3230 cm^{-1} and higher 3650-3400 cm^{-1} band heights from core to edge. This observation suggests disturbance of the hydrogen in Ol likely occurring during xenolith entrainment to the surface. Pyroxene water contents are higher than most water contents in pyroxenes from continental peridotite xenoliths and higher than those of abyssal peridotites. Cpx water contents decrease with increasing degree of depletion (e.g. increasing Fo in Ol and Cr# in spinel) consistent with an incompatible behavior of water. However Cpx water contents also show a positive correlation with LREE/HREE ratios and LREE concentrations consistent with refertilization. Opx water contents increase with increasing degree of depletion and decrease with LREE/HREE ratios which is inconsistent with the incompatible behavior of H. Calculated water contents of melts in equilibrium with Cpx or Opx range from 1.4 to 3.8 wt % which is higher than that of all Hawaiian lavas. Calculated melts in equilibrium with Cpx and Opx have variable but mostly high H_{2}O/Ce ratios (194 to 1146) consistent with those of rejuvenated stage lavas from Niihau and the South Arch volcanic field, but unlike the drier shield building stage tholeiites. Whether the high water contents recorded in Salt Lake Crater xenoliths were acquired before and/or during interaction of the oceanic lithosphere with the Hawaiian plume will be discussed.

Peslier, Anne H.↗

Metamorphism of Cosmic Dust: Processing from Circumstellar Outflows to the Cometary Regolith

Nucleation is a non-equilibrium process: the products of this process are seldom the most thermodynamically stable condensates but are instead those which form fastest. It should therefore not be surprising that grains formed in a circumstellar outflow will undergo some degree of metamorphism if they are annealed or are exposed to a chemically active reagent. Metamorphism of refractory particles continues in the interstellar medium (ISM) where the driving forces are sputtering by cosmic ray particles, annealing by high energy photons and grain destruction in supernova generated shocks. Studies of the depletion of the elements from the gas phase of the interstellar medium tell us that if grain destruction occurs with high efficiency in the ISM, then there must be some mechanism by which grains can be formed in the ISM. Various workers have shown that refractory mantles could form on refractory cores by radiation processing of organic ices. A similar process may operate to produce refractory inorganic mantles on grain cores which survived the supernova shocks. Most grains in a cloud which collapses to form a star will be destroyed; many of the surviving grains will be severely processed. Grains in the outermost regions of the nebula may survive relatively unchanged by thermal processing or hydration. It is these grains which we hope to find in comets. However, only those grains encased in ice at low temperature can be considered pristine since a considerable degree of hydrous alteration might occur in a cometary regolith if the comet enters the inner solar system. Some discussion of the physical, chemical and isotopic properties of a refractory grain at each stage of its life cycle will be attempted based on the limited laboratory data available to date. Suggestions will be made concerning the types of experimental data which are needed in order to better understand the processing history of cosmic dust.

Nuth, Joseph A., III↗

Water Contents of the Mantle Beneath the Rio Grande Rift: FTIR Analysis of Kilbourne Hole Peridotite Xenoliths

Although nominally anhydrous mantle minerals contain only trace amounts of water, they are the main reservoir of water in the mantle. Added up at the scale of the Earth's mantle, these trace amounts of water represent oceans worth in mass]. Mantle xenoliths from Kilbourne Hole in southern New Mexico are ideal to study mantle water distribution in a rift tectonic setting as they come from a recently‐erupted maar in the middle of the Rio Grande Rift. Eleven lherzolites, one harzburgite, and one dunite are being analyzed for water contents by FTIR. The xenoliths will also be analyzed for major and trace element composition, Fe3+/Summation (Fe) ratios, and characterized petrologically. Olivines exhibit variable water contents with less water at the rims compared to the cores. This is probably due to H loss during decompression and xenolith transport by the host magma. Mantle water contents appear to have been primarily preserved in the core of the olivines, based on diffusion modeling of the typically plateau-shaped water content profiles across these grains. Water concentrations are in equilibrium between clino- and orthopyroxene, but olivine concentrations are typically not in equilibrium with those of either pyroxene. Lherzolites analyzed so far have water contents of 2‐12 ppm H2O in olivines, 125‐165 ppm H2O in orthopyroxenes, and 328‐447 ppm H2O in clinopyroxenes. These water contents are similar to, but with a narrower range, than those for the respective minerals in other continental peridotite xenoliths. The lherzolites have bulk-rock (BR) Al2O3 contents that range between 3.17 and 3.78 wt%, indicating similar degrees of partial melting, which could explain the narrow range of their pyroxene water contents. Primitive mantle normalized rare earth element (REE) profiles of the bulk lherzolites vary from light REE depleted to flat, with no significant differences between, nor relation to, their mineral water contents. Consequently, the metasomatic agents that enriched LREEs in these lherzolites were most likely water-poor. The harzburgite and the dunite have lower weight percent Al2O3 compared to the lherzolites (2.11% and 0.34% respectively) indicating higher degrees of melting. Their olivine water contents, however, are similar to those of the lherzolites. Moreover, no correlations are observed between pyroxene water contents and indices of melting or metasomatism between the lherzolite group, the harzburgite, and the dunite, although the latter has the lowest pyroxene water contents. More samples will be analyzed to determine if the water contents are controlled by melting, metasomatism, or a combination of the two in the Kilbourne Hole mantle.

Schaffer, Lillian A.↗

Implications for Core Formation of the Earth from High Pressure-Temperature Au Partitioning Experiments

Siderophile elements in the Earth.s mantle are depleted relative to chondrites. This is most pronounced for the highly siderophile elements (HSEs), which are approximately 400x lower than chondrites. Also remarkable is the relative chondritic abundances of the HSEs. This signature has been interpreted as representing their sequestration into an iron-rich core during the separation of metal from silicate liquids early in the Earth's history, followed by a late addition of chondritic material. Alternative efforts to explain this trace element signature have centered on element partitioning experiments at varying pressures, temperatures, and compositions (P-T-X). However, first results from experiments conducted at 1 bar did not match the observed mantle abundances, which motivated the model described above, a "late veneer" of chondritic material deposited on the earth and mixed into the upper mantle. Alternatively, the mantle trace element signature could be the result of equilibrium partitioning between metal and silicate in the deep mantle, under P-T-X conditions which are not yet completely identified. An earlier model determined that equilibrium between metal and silicate liquids could occur at a depth of approximately 700 km, 27(plus or minus 6) GPa and approximately 2000 (plus or minus 200) C, based on an extrapolation of partitioning data for a variety of moderately siderophile elements obtained at lower pressures and temperatures. Based on Ni-Co partitioning, the magma ocean may have been as deep as 1450 km. At present, only a small range of possible P-T-X trace element partitioning conditions has been explored, necessitating large extrapolations from experimental to mantle conditions for tests of equilibrium models. Our primary objective was to reduce or remove the additional uncertainty introduced by extrapolation by testing the equilibrium core formation hypothesis at P-T-X conditions appropriate to the mantle.

Danielson, L. R.↗

High-resolution SOFIA/EXES Spectroscopy of SO2 Gas in the Massive Young Stellar Object MonR2 IRS3: Implications for the Sulfur Budget

Sulfur has been observed to be severely depleted in dense clouds leading to uncertainty in the molecules that contain it and the chemistry behind their evolution. Here, we aim to shed light on the sulfur chemistry in young stellar objects (YSOs) by using high-resolution infrared spectroscopy of absorption by the ν3 rovibrational band of SO2 obtained with the Echelon-Cross-Echelle Spectrograph on the Stratospheric Observatory for Infrared Astronomy. Using local thermodynamic equilibrium models we derive physical parameters for the SO2 gas in the massive YSO MonR2 IRS3. This yields a SO2/H abundance lower limit of 5.6 ± 0.5 × 10(exp -7), or >4% of the cosmic sulfur budget, and an intrinsic line width (Doppler parameter) of b < 3.20 km s(exp -1). The small line widths and high temperature (Tex = 234 ± 15 K) locate the gas in a relatively quiescent region near the YSO, presumably in the hot core where ices have evaporated. This sublimation unlocks a volatile sulfur reservoir (e.g., sulfur allotropes as detected abundantly in comet 67P/Churyumov–Gerasimenko), which is followed by SO2 formation by warm, dense gas-phase chemistry. The narrowness of the lines makes formation of SO2 from sulfur sputtered off grains in shocks less likely toward MonR2 IRS3.

Infrared ISM↗

Evaluation and optimization of lidar temperature analysis algorithms using simulated data

The middle atmosphere (20 to 90 km altitude) ha received increasing interest from the scientific community during the last decades, especially since such problems as polar ozone depletion and climatic change have become so important. Temperature profiles have been obtained in this region using a variety of satellite-, rocket-, and balloon-borne instruments as well as some ground-based systems. One of the more promising of these instruments, especially for long-term high resolution measurements, is the lidar. Measurements of laser radiation Rayleigh backscattered, or Raman scattered, by atmospheric air molecules can be used to determine the relative air density profile and subsequently the temperature profile if it is assumed that the atmosphere is in hydrostatic equilibrium and follows the ideal gas law. The high vertical and spatial resolution make the lidar a well adapted instrument for the study of many middle atmospheric processes and phenomena as well as for the evaluation and validation of temperature measurements from satellites, such as the Upper Atmosphere Research Satellite (UARS). In the Network for Detection of Stratospheric Change (NDSC) lidar is the core instrument for measuring middle atmosphere temperature profiles. Using the best lidar analysis algorithm possible is therefore of crucial importance. In this work, the JPL and CNRS/SA lidar analysis software were evaluated. The results of this evaluation allowed the programs to be corrected and optimized and new production software versions were produced. First, a brief description of the lidar technique and the method used to simulate lidar raw-data profiles from a given temperature profile is presented. Evaluation and optimization of the JPL and CNRS/SA algorithms are then discussed.

Leblanc, Thierry↗