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At least 217 records · Page 12

Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (Xsite), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al., recently reported that the exchange coefficients vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

McCubbin, F. M.↗

The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.

Holzheid, Astrid↗

Europium anomaly in plagioclase feldspar - Experimental results and semiquantitative model.

The partition of europium between plagioclase feldspar and magmatic liquid is considered in terms of the distribution coefficients for divalent and trivalent europium. A model equation is derived giving the europium anomaly in plagioclase as a function of temperature and oxygen fugacity. The model explains europium anomalies in plagioclase synthesized under controlled laboratory conditions as well as the variations of the anomaly observed in natural terrestrial and extraterrestrial igneous rocks.

Weill, D. F.↗

Experimental Constraints on the Partitioning Behavior of F, Cl, and OH Between Apatite and Basaltic Melt

The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations induced by changes in temperature (T) or pressure (P) . In regions where apatite undergoes ideal mixing of F, Cl, and OH, temperature has a stronger effect than pressure on the partitioning behavior, but both are important. Furthermore, fluorine becomes less compatible in apatite with increasing pressure and temperature. We are still in the process of analyzing our experimental run products, but we plan to quantify the effects of P and T on apatite-melt partitioning of F, Cl, and OH.

McCubbin, Francis M.↗

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.↗

Improving a Spectral Bin Microphysical Scheme Using TRMM Satellite Observations

Comparisons between cloud model simulations and observations are crucial in validating model performance and improving physical processes represented in the mod Tel.hese modeled physical processes are idealized representations and almost always have large rooms for improvements. In this study, we use data from two different sensors onboard TRMM (Tropical Rainfall Measurement Mission) satellite to improve the microphysical scheme in the Goddard Cumulus Ensemble (GCE) model. TRMM observed mature-stage squall lines during late spring, early summer in central US over a 9-year period are compiled and compared with a case simulation by GCE model. A unique aspect of the GCE model is that it has a state-of-the-art spectral bin microphysical scheme, which uses 33 different bins to represent particle size distribution of each of the seven hydrometeor species. A forward radiative transfer model calculates TRMM Precipitation Radar (PR) reflectivity and TRMM Microwave Imager (TMI) 85 GHz brightness temperatures from simulated particle size distributions. Comparisons between model outputs and observations reveal that the model overestimates sizes of snow/aggregates in the stratiform region of the squall line. After adjusting temperature-dependent collection coefficients among ice-phase particles, PR comparisons become good while TMI comparisons worsen. Further investigations show that the partitioning between graupel (a high-density form of aggregate), and snow (a low-density form of aggregate) needs to be adjusted in order to have good comparisons in both PR reflectivity and TMI brightness temperature. This study shows that long-term satellite observations, especially those with multiple sensors, can be very useful in constraining model microphysics. It is also the first study in validating and improving a sophisticated spectral bin microphysical scheme according to long-term satellite observations.

Li, Xiaowen↗

Theoretical Study of the Transverse Dielectric Constant of Superlattices and Their Alloys

The optical properties of III to V binary and ternary compounds and GaAs-Al(x)Ga(1-x)As superlattices are determined by calculating the real and imaginary parts of the transverse dielectric constant. Emphasis is given to determining the influence of different material and superlattice parameters on the values of the index of refraction and absorption coefficient. In order to calculate the optical properties of a material, it is necessary to compute its electronic band structure. This was accomplished by introducing a partition band structure approach based on a combination of the vector k x vector p and nonlocal pseudopotential techniques. The advantages of this approach are that it is accurate, computationally fast, analytical, and flexible. These last two properties enable incorporation of additional effects into the model, such as disorder scattering, which occurs for alloy materials and excitons. Furthermore, the model is easily extended to more complex structures, for example multiple quantum wells and superlattices. The results for the transverse dielectric constant and absorption coefficient of bulk III to V compounds compare well with other one-electron band structure models and the calculations show that for small frequencies, the index of refraction is determined mainly by the contibution of the outer regions of the Brillouin zone.

Kahen, K. B.↗

The washout of combustion-generated hydrogen chloride

The coefficient for the washout from a rocket exhaust cloud of HCl generated by the combustion of an ammonium perchlorate-based solid rocket propellant such as that to be used for the Space Shuttle Booster is determined. A mathematical model of HCl scavenging by rain is developed taking into account rain droplet size, fall velocity and concentration under various rain conditions, partitioning of exhaust HCl between liquid and gaseous phases, the tendency of HCl to promote water vapor condensation and the concentration and size of droplets within the exhaust cloud. The washout coefficient is calculated as a function of total cloud water content, total HCl content at 100% relative humidity, condensation nuclei concentration and rain intensity. The model predictions are compared with experimental results obtained in scavenging tests with solid rocket exhaust and raindrops of different sizes, and the large reduction in washout coefficient at high relative humidities predicted by the model is not observed. A washout coefficient equal to 0.0000512 times the -0.176 power of the mass concentration of HCl times the 0.773 power of the rainfall intensity is obtained from the experimental data.

Fenton, D. L.↗

The Influence of Tungsten on the Chemical Composition of a Temporally Evolving Nanostructure of a Model Ni-Al-Cr Superalloy

The influence of W on the temporal evolution of gamma' precipitation toward equilibrium in a model Ni-Al-Cr alloy is investigated by three-dimensional atom-probe (3DAP) microscopy and transmission electron microscopy (TEM). We report on the alloys Ni-10 Al-8.5 Cr (at.%) and Ni-10 Al-8.5 Cr-2 W (at.%), which were aged isothermally in the gamma + gamma' two-phase field at 1073 K, for times ranging from 0.25 to 264 h. Spheroidal-shaped gamma' precipitates, 5-15 nm diameter, form during quenching from above the solvus temperature in both alloys at a high number density (approx. 10(exp 23/cu m). As gamma' precipitates grow with aging at 1073 K, a transition from spheriodal- to cuboidal-shaped precipitates is observed in both alloys. The elemental partitioning and spatially resolved concentration profiles across the gamma' precipitates are obtained as a function of aging time from three-dimensional atom-by-atom reconstructions. Proximity histogram concentration profiles of the quaternary alloy demonstrate that W concentration gradients exist in gamma' precipitates in the as-quenched and 0.25-h aging states, which disappear after 1 h of aging. The diffusion coefficient of W in gamma' is estimated to be 6.2 x 10(exp -20) sq m/s at 1073 K. The W addition decreases the coarsening rate constant, and leads to stronger partitioning of Al to gamma' and Cr to gamma.

Sudbrack, Chantal K.↗

Petrogenesis of KREEP

Solid/liquid distribution coefficients were experimentally determined for a number of trace elements for olivine, orthopyroxene, plagioclase and ilmenite. Major- and trace-element partitioning and relevant phase equilibria are used to study possible parent-daughter relationships between a number of highland samples and highly evolved KREEP-rich materials. A model is proposed in which low-K Fra Mauro basalt type material was produced by fractionation of large amounts of olivine and lesser amounts of plagioclase from undifferentiated lunar material at about 4.4 AE.

Mckay, G. A.↗

Measurements of surface energy budgets in the rocky mountains of Colorado

The surface energy balance of a mountain valley and a mountain peak were continuously monitored for periods of 126 and 34 days, respectively. The data yielded temporally resolved, high-quality measurements of the radiative, soil, and total atmospheric turbulent heat fluxes. Comparative data for the two sites reveal the effects of terrain setting and surface cover in modulating the heat balance. A procedure is suggested for accommodating local advective affects due to variable terrain and surface cover to allow partitioning of the total turbulent flux into values for sensible and latent heat. This procedure relies on a stability-dependent coefficient of turbulent transfer which is locally calibrated to systematically minimize advection-related errors. Scaling functions for the transfer coeffient are based on the effective blackbody temperature of the surface. Consequently, the procedure offers an opportunity for developing reliable bulk representations of heat transfer at the surface for use with remote sensing data and with models of the soil and surface cover in complex terrain.

Sheaffer, John D.↗

Diagnosing Bias in Modeled Soil Moisture/runoff Coefficient Correlation Using the SMAP Level 4 Soil Moisture Product

The physical parameterization of key processes in land surface models (LSMs) remains uncertain, and new techniques are required to evaluate LSM accuracy over coarse spatial scales. Given the role of soil moisture in the partitioning of surface water fluxes (between infiltration, runoff and evapotranspiration), surface soil moisture (SSM) estimates represent an important observational benchmark for such evaluations. Here, we apply SSM estimates from the NASA Soil Moisture Active Passive Level 4 product (SMAP_L4) to diagnose bias in the coupling between SSM and surface runoff for multiple Noah-Multiple Physics (Noah-MP) LSM parameterization cases. Results demonstrate that Noah-MP surface runoff parameterizations often underestimate the coupling strength between pre-storm SSM and the event-scale runoff coefficient (RC; defined as the ratio between event-scale streamflow and precipitation volumes). This bias squanders RC information contained in pre-storm SSM and reduces RC estimation skill. Such bias can be quantified against an observational benchmark calculated using streamflow observations and SMAP_L4 SSM and applied to explain a substantial fraction of the observed basin-to-basin (and case-to-case) variability in the skill of event-scale Noah-MP RC estimates. Based on this concept, a novel case selection strategy for ungauged basins is introduced and demonstrated to successfully identify poorly performing Noah-MP parameterization cases.

SSM↗

New Analysis of Lunar Prospector Radio Tracking Data Brings the Nearside Gravity Field of the Moon with an Unprecedented Resolution

A new analysis of the Doppler tracking data from the Lunar Prospector mission in 1999 revealed a number of previously-unseen gravity anomalies at spatial scales as small as 27 km over the nearside. The tracking data at low altitudes (50 km or below) were better analyzed to resolve the nearside features without dampening from a power law constraint, by partitioning the gravity parameters concentrated on either the nearside or farside. The resulting model presents gravity anomalies correlated with topography with a correlation coefficient of 0.7 or higher from degree 50 to 150, the widest bandwidth yet. The gravity-topography admittance of approx. 70 mGal/km is found from numerous craters of which diameters are 60 km or less. In addition, the new model produces orbits that fit to independent radio tracking data from the Lunar Reconnaissance Orbiter and Kaguya (SELENE) better than previous gravity models. This high-resolution model can be of immediate use to geophysical analysis of small craters. Our technique could be applied to an upcoming mission, the Gravity Recovery And Interior Laboratory and useful to extract short wavelength signals from the MESSENGER Doppler data.

Han, Shin-Chan↗

Approximations for the Thermodynamic and Transport Properties of High-Temperature Air

The thermodynamic and transport properties of high-temperature air are found in closed form starting from approximate partition functions for the major components in air and neglecting all minor components. The compressibility, enthalpy, entropy, the specific heats, the speed of sound, the coefficients of viscosity and of thermal conductivity, and the Prandtl numbers for air are tabulated from 500 degrees to 15,000 degrees Kelvin over a range of pressure from 0.0001 to 100 atmospheres. The energy of air and the mol. fractions of the major components of air can be found from the tabulated values for compressibility and enthalpy. It is predicted that the Prandtl number for fully ionized air, which is in complete equilibrium, will become small compared to unity, the order of 0.01, and this implies that boundary layers in such flow will be very transparent to heat flux.

Hansen, C. Frederick↗

Analysis of segregation trends observed in iron meteorites using measured distribution coefficients

Fe-Ni alloys of meteoritic composition were solidified by a plane front solidification technique. Distribution coefficients of Ni, P, Ir, Ge, and Cu were determined from the composition data of the plane front solidified alloys. Equations that describe the distribution coefficients (P, Ni, Ir, Ge, and Cu) as a function of S and P content as well as S to P ratio were used to calculate solute partitioning between solid and liquid during the solidification of IIAB, IIIAB, and IVA parent bodies. The calculated P versus Ni, Ir versus Ni, Ge versus Ni, and Cu versus Ni trends are in good agreement with the observed meteorite data for each chemical group. It is concluded that each chemical group formed as a single molten pool in a parent body and that solute partitioning that occurred during solidification is responsible for the observed compositional trends within a single meteorite group.

Sellamuthu, R.↗

Copper and nickel partitioning in iron meteorites

Trace element analyses using proton induced X-ray emission and synchrotron X-ray fluorescence have been made on metal and troilite from nine iron meteorites representing five geochemical groups. Nickel and copper distribution coefficients D (troilite/metal) vary by factors of 600 and 20, respectively, correlate positively with kamacite bandwidth and correlate negatively with bulk nickel content. Meteorites with bulk Ni of less than 10 percent have Cu-enriched troilite while those with Ni greater than 10 percent have Cu-depleted troilite. Since magmatic evolution and partial melting will produce Cu-enriched troilite only, the observation of Cu-depleted troilite in Ni-rich meteorites is evidence for subsolidus reequilibration, a process which reduces D(Cu) by transfer of Cu to exsolving metal. Elemental redistribution may have played an important role in establishing the present chemical trends in iron meteorites.

Sutton, S. R.↗

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Iraci, L. T.↗

Design of a Dual Waveguide Normal Incidence Tube (DWNIT) Utilizing Energy and Modal Methods

This report investigates the partition design of the proposed Dual Waveguide Normal Incidence Tube (DWNIT). Some advantages provided by the DWNIT are (1) Assessment of coupling relationships between resonators in close proximity, (2) Evaluation of "smart liners", (3) Experimental validation for parallel element models, and (4) Investigation of effects of simulated angles of incidence of acoustic waves. Energy models of the two chambers were developed to determine the Sound Pressure Level (SPL) drop across the two chambers, through the use of an intensity transmission function for the chamber's partition. The models allowed the chamber's lengthwise end samples to vary. The initial partition design (2" high, 16" long, 0.25" thick) was predicted to provide at least 160 dB SPL drop across the partition with a compressive model, and at least 240 dB SPL drop with a bending model using a damping loss factor of 0.01. The end chamber sample transmissions coefficients were set to 0.1. Since these results predicted more SPL drop than required, a plate thickness optimization algorithm was developed. The results of the algorithm routine indicated that a plate with the same height and length, but with a thickness of 0.1" and 0.05 structural damping loss, would provide an adequate SPL isolation between the chambers.

Betts, Juan F.↗