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At least 109 records · Page 6

Valence State Partitioning of Cr and V Between Olivine-Melt and Pyroxene-Melt in Experimental Basalts of a Eucritic Composition

The partitioning of multivalent elements in basaltic systems can elucidate the oxygen fugacity (fO2) conditions under which basalts formed on planetary bodies (Earth, Moon, Mars, asteroids). Chromium and V are minor and trace elements in basaltic melts, partition into several minerals that crystallize from basaltic melts, exist in multiple valence states at differing fO2 conditions, and can therefore be used as oxybarometers for basaltic melts. Chromium is mostly 3+ in terrestrial basaltic melts at relatively high fO2 values (≥ IW+3.5), and mostly 2+ in melts at low fO2 values (≤ IW-1), such as those on the Moon and some asteroids. At intermediate fO2s, (i.e., IW-1 to IW+3.5), basaltic melts contain both Cr3+ and Cr2+. Vanadium in basaltic melts is mostly 4+ at high fO2, mostly 3+ at low fO2, and a mix of V3+ and V4+ at intermediate fO2 con-ditions. Understanding the partitioning of Cr and V into silicate phases with changing fO2 is therefore critical to the employment of Cr and V oxybarometers. In this abstract we examine the equilibrium partitioning of Cr and V between olivine/melt and pyroxene/melt in experimental charges of a eucritic composition produced at differing fO2 conditions. This study will add to the experimental data on DCr and DV (i.e., olivine/melt, pyroxene/melt) at differing fO2, and in turn these D values will be used to assess the fO2 of eucrite basalts and perhaps other compositionally similar planetary basalts.

Karner, J. M.↗

Experimental Study into the Partitioning Behavior of Fluorine, Chlorine, Hydroxyl, and Sulfur (S2-) Between Apatite and a Synthetic Kreep Basalt Melt

The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wüstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to the melting temperature of the materials. To make sure crystals grow large enough for the necessary analyses, the sample will be kept at the crystallization temperature for 8 hours. This extended run time should also allow the sample to achieve a steady state which is necessary to accurately assess the partitioning of these elements between apatite and melt. The results from this experimental study will allow us to determine the fate of F-, Cl-, OH-, and S2- during the magmatic evolution of the Moon.

Turner, Amber↗

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↗

Effect of Sulfur on siderophile element partitioning between olivine and martian mantle primary melt

Ni and Co variations in primary martian magmas exhibit anomalous incompatible behavior, which has remained an unexplained conundrum. Because martian magmas are S-rich, and some trace metals are reported to have enhanced solubility in S-bearing magmas, we have carried out a series of experiments to evaluate the effect of high-S melts on the olivine/melt partitioning of Ni, Co, Mn, V, and Cr. Near-liquidus experiments on a synthetic primary martian mantle melt (Yamato-980459 [Y98]) were completed in a piston-cylinder apparatus at 0.75 GPa. Previous studies in S-free systems illustrate that the partition coefficients for these elements are dependent chiefly on D(Mg(Ol/melt)) (the partition coefficient defined as wt% Mg in olivine/wt% Mg in melt, a proxy for temperature), and were used to calibrate a predictive expression that includes the effects of temperature [i.e., D(Mg(Ol/melt))], melt composition, and oxygen fugacity. These predictive expressions are then used to isolate any effect in DM olivine/melt due to dissolved sulfur. The results show that S might have a small effect for Co, but not enough to change Co partitioning from compatible to incompatible in our experiments. The addition of a sulfur term to the D(Co) predictive expressions shows that nearly 8000 ppm of sulfur would be required in the melt (at liquidus temperature of Y98) for D(Co) to become <1. These S contents are two times higher than those of a sulfide-saturated melt at the P-T conditions of a martian mantle source region. Therefore, the anomalous incompatible behavior observed in these primary magma suites must be due to another mechanism. High temperature, oxygen fugacity, and diffusion are not viable mechanisms, but magma mixing, assimilation, or kinetic crystallization effects remain possibilities.

shergottite↗

Thermodynamic Modeling of Calcium and Magnesium Partitioning Between Sulfide and Silicate and Implications for Mercury’s Differentiation

Mercury is the least oxidized terrestrial planet of the solar system and is enriched in sulfur, which may be saturated in its mantle, possibly forming Ca- and Mg-rich sulfides. Using literature experimental data, we developed a thermodynamic model for calcium and magnesium partitioning between sulfide and silicate melts to enhance our understanding of the chemical equilibria involved in Mercury’s mantle-crust differentiation. Our models show that temperature and carbon abundance in sulfide have a positive effect on Ca partitioning into sulfides, while pressure decreases it. In addition, carbon abundance and sulfur concentration in the silicate melt are the primary controls on Mg partitioning, both favoring Mg partitioning into sulfides. Our results will be used to better understand the abundance as well as presence of calcium and magnesium sulfides within Mercury’s mantle and crust.

Taylor McCombs↗

Insights Into Reconstructing REE Compositions of Melt From Zircon-Melt Partition Coefficients Using Zircon-Hosted Melt Inclusions From the Yellowstone Volcanic Province

Establishing the major and trace element composition of the Earth’s melts (Hadean to recent) is essential for understanding crustal evolution. Due to its physical-chemical resilience, zircon spans the complete age spectra of Earth’s history, and thus provides the only physical record from the early Earth. However, the petrological context i.e., the melt from which zircon crystallised, is often lost, except for inclusions of melt preserved within zircon. Melt inclusions in zircon (MI) provide a valuable tool to constrain zircon-melt REE partition coefficients (D REE ), which are used with the zircon REE chemistry to reconstruct melt compositions. Such reconstruction requires accurate partition coefficients, which are particularly sensitive to temperature, but also to pressure and melt composition. We determined the major and trace element compositions of 60 co-existing zircon-MI pairs from two ~ 2 Ma age rhyolites (the caldera-forming Huckleberry Ridge Tuff; HRT-C and the post-caldera Blue Creek Flow; BC-1) of the Yellowstone Plateau volcanic field by EPMA and SIMS, and calculated a set of 60 zircon-MI partition coefficients. The MI from both units are glassy with average silica contents of 78.30 ± 0.74 and 77.19 ± 1.11 wt %, and Ti-in-zircon crystallisation temperatures are 839 ± 36 and 835 ± 35 oC. Measured D REE patterns for each population (n = 30) are tightly constrained and exhibit a smooth pattern spanning ~ six orders of magnitude from La to Lu, (with exceptions at Ce and Eu), and for the HRT exhibit greater curvature (i.e., flatter) between the MREE to HREE compared to the BC-1. D REE patterns for the HRT have small to moderate Ce anomalies (Ce/Ce* Di 50 ± 40), whereas those in the BC-1 are larger (98 ± 45), and both units exhibit negligible to positive Eu anomalies (Eu/Eu* Di 1.07 ± 0.89 and 1.80 ± 2.01, respectively). We compare the trace element compositions of the MI to bulk-glass compositions from Yellowstone to assess any differences, which are small, then compare the measured MI compositions to those reconstructed using published partition coefficients (natural, empirical and experimental). The choice of D REE for reconstruction of the melt REE pattern results in differing petrogenetic interpretations.

Laura J. Crisp↗

Use of strainrange partitioning to predict high temperature low-cycle fatigue life

The fundamental concepts of the strainrange partitioning approach to high temperature, low low-cycle fatigue are reviewed. Procedures are presented by which the partitioned strainrange versus life relationships for any material can be generated. Laboratory tests are suggested for further verifying the ability of the method of strainrange partitioning to predict life.

Hirschberg, M. H.↗

Partition function corrections

The vibration-rotation interaction coupling in diatomic molecules is analyzed and first-order expressions for the energy levels are deduced. Corrections to the partition function to account for this coupling are derived. The effects of long-range intermolecular forces due to induced dipole-induced dipole interactions, dipole-induced dipole interactions, charge-dipole interactions, and charge-charge interactions are considered. London's quantized oscillator model of the induced dipole-induced dipole interaction is developed. The partition function including effects of such dispersion forces is derived and is shown to lead to the virial equation of state. For a model combining the hard sphere and long-range attractive type potentials, this is found to lead to the van der Waals equation of state. The equation of state near the critical point is presented in reduced form (thermodynamic variables expressed in units of critical point values). Finally, approximate corrections to the electronic partition functions are derived to account for perturbations of excited electronic states induced by neighboring neutral particles, heavy ions, and fast electron collisions.

Source record↗

The application of 'strain range partitioning method' to torsional creep-fatigue interaction

The method of strain range partitioning was applied to a series of torsional fatigue tests conducted on tubular 304 stainless steel specimens at 1200 F (649 C). Creep strain was superimposed on cycling strain, and the resulting strain range was partitioned into four components; completely reversed plastic shear strain followed by creep strain, creep strain followed by plastic strain and completely reversed creep strain. Each strain component was related to the cyclic life of the material. The paper describes the experimental procedure used to achieve strain partitioning and the torsional test results are compared to those obtained from axial tests. The damaging effects of the individual strain components were expressed by a linear life fraction rule. The shear strain plastic component showed the least detrimental factor when compared to creep strain reversal by plastic strain. In the latter case, a reduction of torsional fatigue life in the order of magnitude of 1.5 was observed.

Zamrik, S. Y.↗

Strain partitioning of three alloys in ultrahigh vacuum using the step stress method

The ultrahigh vacuum strain controlled thermal-mechanical strain cycling fatigue behavior of ASTAR 811C, 304 stainless steel and A-286 was studied. The step stress procedure of experimental strainrange partitioning was utilized to partition the inelastic strainranges for tests duplicating conditionings previously reported by TRW. An analytical method is described in which these partitioned inelastic strainrange data can be used to develop the four basic life relationships for these materials.

Kortovich, C. S.↗

Strainrange partitioning behavior of the nickel-base superalloys, Rene' 80 and in 100

A study was made to assess the ability of the method of Strainrange Partitioning (SRP) to both correlate and predict high-temperature, low cycle fatigue lives of nickel base superalloys for gas turbine applications. The partitioned strainrange versus life relationships for uncoated Rene' 80 and cast IN 100 were also determined from the ductility normalized-Strainrange Partitioning equations. These were used to predict the cyclic lives of the baseline tests. The life predictability of the method was verified for cast IN 100 by applying the baseline results to the cyclic life prediction of a series of complex strain cycling tests with multiple hold periods at constant strain. It was concluded that the method of SRP can correlate and predict the cyclic lives of laboratory specimens of the nickel base superalloys evaluated in this program.

Halford, G. R.↗

Strainrange partitioning behavior of the nickel-base superalloys, Rene 80 and 100

A study has been made to assess the ability of the method of Strainrange Partitioning (SRP) to both correlate and predict high-temperature low-cycle fatigue lives of nickel-base superalloys for gas turbine applications. SRP is shown to correlate the cyclic lives of the baseline tests to within factors of nearly two. The partitioned strainrage versus life relationships for uncoated Rene 80 and cast IN 100 have also been determined from the ductility normalized-strainrange partitioning equations. These were used to predict the cyclic lives of the baseline tests. Predicted and observed cyclic lives agreed to within factors of nearly three. The life predictability of the method is also verified for cast IN 100 by applying the baseline results to the cyclic-life prediction of a series of complex strain-cycling tests with multiple hold periods at constant strain. It is concluded that the method of SRP can correlate and predict the cyclic lives of laboratory specimens of the nickel-base superalloys evaluated in this program.

Halford, G. R.↗

A review of experimental studies of crystal/liquid trace element partitioning

Experimental techniques for examining trace-element behavior are reviewed. Applications of these techniques are described for a variety of partition coefficients including: olivine/liquid, subcalcic pyroxene/liquid, calcic pyroxene/liquid, amphibole/liquid, plagioclase/liquid, alkali feldspar/liquid, garnet/liquid, apatite/liquid and whitlockite/liquid, ilmenite/liquid, armalcolite/liquid and pseudobrookite/liquid, magnetite/liquid and spinel/liquid, perovskite/liquid, and melilite/liquid partition coefficients. Partition coefficients between immiscible liquids are discussed and suggestions for further work are noted. A detailed bibliography is included.

Irving, A. J.↗

The Application of Strainrange Partitioning Method to Multiaxial Creep-Fatigue Interaction

The method of strain range partitioning was applied to a series of torsional fatigue tests conducted on tubular 304 stainless steel specimens at 1200 F (649 C). Creep strain was superimposed on cycling strain, and the resulting strain range was partitioned into four components: (1) completely reversed plastic shear strain, (2) plastic shear strain followed by creep strain, (3) creep strain followed by plastic strain, and (4) completely reversed creep strain. Each strain component was related to the cyclic life of the material. The experimental procedure used to achieve strain partitioning is described, and the torsional test results are compared to those obtained from axial tests. The damaging effects of the individual strain components were expressed by a linear life fraction rule.

Zamrik, S. Y.↗

Experimental partitioning of rare earth elements and scandium among armalcolite, ilmenite, olivine and mare basalt liquid

An experimental study was carried out to measure partition coefficients for two rare-earth elements (Sm and Tm) and Sc among armalcolite, ilmenite, olivine and liquid coexisting in a system modeled on high-Ti mare basalt 74275. This 'primitive' sample was chosen for study because its major and trace element chemistry as well as its equilibrium phase relations at atmospheric pressure are known from previous studies. Beta-track analytical techniques were used so that partition coefficients could be measured in an environment whose bulk trace element composition is similar to that of the natural basalt. Partition coefficients for Cr and Mn were determined in the same experiments by microprobe analysis. The only equilibrium partial melting model appears to be one in which ilmenite is initially present in the source region but is consumed by melting before segregation of the high-Ti mare basalt liquid from the residue.

Irving, A. J.↗

Laboratory studies of actinide partitioning relevant to 244Pu chronometry

Actinide partitioning and light lanthanide fractionation have been studied to gain an understanding of Pu chemistry under meteoritic and lunar conditions. The goal of the study was to identify conditions and samples from which chronological information can be retrieved. The laboratory investigations involved particle track radiography of the crystal/liquid partitioning of Th, U and Pu among diopsidic clinopyroxene, whitlockite and liquid. It is found that trivalent Pu plays an important role in partitioning for lunar and most meteoritic conditions. The use of Pu/Nd for relative age assessments is supported to some extent by the investigations; samples with unfractionated U, Th and Nd abundances (relative to average solar system values) may be suitable for Pu chronometry.

Benjamin, T.↗

Development of partitioning as an aid to spectral signature extension

Lists of spectrally similar LACIE sample segments may be constructed with the use of three basic information types: static, seasonal, and pass-specific variables. All are related directly or indirectly to spectral signature behavior and can be used to define spatial domains over which crop-specific signatures should be extendable. Topics covered include: (1) static spectral stratification; (2) evaluation of static partitions relative to variance control objectives; (3) evaluation of the relative importance of static versus seasonal and pass-specific partitioning variables in spectral variability; and (4) a current perspective on partitioning.

Thomas, R. W.↗

Partitioning as a cooling rate indicator

The paper presents a mathematical model for describing solute partitioning under continuous cooling conditions. It is shown that solute concentration profiles can be calculated for any cooling rate as a function of temperature provided that the appropriate data on diffusion and partitioning are known. As an example, the model is applied to zirconium partitioning between ilmenite and ulvospinel in a number of Apollo 15 Elbow Crater rocks in order to estimate the rates at which they cooled.

Onorato, P. I.↗