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Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

Oxygen fugacity (fO2) plays an important role in thephysicochemical properties of that system because fO2 has asubstantial impact on the partitioning behavior between andsolubility of elements in various phases. The reduced nature ofMercury and the aubrite parent bodies (APB) have raised manyquestions regarding the geochemical behavior of typicallylithophile, heat-producing, and rare-earth elements (REE) inmagmas at low fO2. In fact, interpretations of magmaticprocesses on reduced rocky bodies are difficult at presentbecause of the small number of experimental studies relevant tothe extremely low fO2 and high sulfur content of Mercury andthe APB, and our only natural analogs are the highly reducedenstatite chondrites and aubrites [e.g., 1]. Preliminaryobservations suggest that major and minor elements exhibitdifferent geochemical affinities in highly reduced, S-richsystems compared to terrestrial rocks. The partitioning behavior of major, minor, and traceelements between silicate melt, sulfide melt, and metal underhighly reduced conditions will be determined in a suite of super-liquidus experiments at a range of pressures (1 bar to 4 GPa) atNASA Johnson Space Center (JSC). Based on previous studies,heat-producing elements U and Th become more chalcophile,while K becomes less chalcophile, with more reducingconditions [2]. The nominally lithophile elements Mg and Cabecoming more chalcophile and appear as minor elements in(Fe,Mg,Ca)-S with more reducing conditions [3]. Additionally, itappears that nominally siderophile elements become moresiderophile and chalcophile with more reducing conditions,although the partitioning behavior into Mg- and Ca-bearingsulfide melts, rather than FeS, is less understood. Current workis focused on investigating elements for which we currently haveMESSENGER data as well as a host of geochemically relevanttrace elements such as REE.

Brendan A Anzures↗
NASA NTRS2023

Temperature Effect on Silicate Melt-Sulfide-Metal Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

The reduced nature of Mercury, enstatite chondrites, and the aubrite parent bodies (APB) have raised many questions regarding the geochemical behavior of typically lithophile, heat-producing, and rare-earth elements (REE) in magmas at low oxygen fugacity (fO2). Due to decreasing O availability at these low fO2, and an abundance of S(sup 2(-)), sulfur (S) acts as an important anion that changes the partitioning behavior of many elements and modifies the physical properties of silicate melts. Preliminary observations suggest that major and minor elements exhibit different geochemical affinities in highly reduced, S-rich systems compared to terrestrial rocks. The speciation and bonding environment of S, dictated by P/T/fO2 conditions, may strongly influence the degree to which S affects partitioning behavior. Here we investigate the partitioning behavior of major, minor, and trace elements between silicate melt, sulfide melt, and metal as well as the coordination chemistry of S in highly reduced silicate melts. Our work is focused on investigating solely the entropy-dependent temperature effect on partitioning of elements for which we currently have MESSENGER data (K, Na, Th, U, Si, Mg, Fe, Ti, Ca, Al, Cr, Mn, S, Cl) as well as a host of geochemically relevant trace elements such as REEs (P, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb). Previous studies in which temperature, pressure, and fO2 were co-varied found that as fO2 decreases, heat-producing elements U and Th become more chalcophile, while K becomes less chalcophile. Concurrently, nominally lithophile elements Mg and Ca become more chalcophile and were observed as minor elements in exsolved sulfides and bonded with S species in silicate melt. These studies, however, could not disentangle entropic effects from changes in the fO2. New temperature-dependent partitioning data from our work will be used to determine which elements are most likely to retain their lithophile character and hence be incorporated into silicates, and which elements are likely contained within the sulfide (chalcophile) and metal core (siderophile), setting the stage for the thermal and magmatic evolution of reduced planetary bodies.

B A Anzures↗
NASA NTRS1973

Auroral electron spectra

Discussion of the suitability of available differential electron flux data for auroral analyses. The differential energy spectra of auroral electrons at several altitudes computed by Berger et al. (1973) and Rees and Jones (1973) for initial electron energies of 10, 5, and 2 keV are reviewed, and it is concluded that they are suitable for auroral analyses.

Rees, M. H.↗
NASA NTRS1983

A comparison of wind observations of the upper thermosphere from the Dynamics Explorer satellite with the predictions of a global time-dependent model

Experimental and theoretical investigations of high-latitude circulation in the upper thermosphere are reported. Vector-wind plots constructed by combining remotely sensed meridional-wind and in situ zonal-wind data obtained during four south-polar and three north-polar passes of the NASA Dynamics Explorer satellite in October and December, 1981, are presented and analyzed, taking the geomagnetic activity level and local solar time into account. The results are then compared with the predictions of 3D time-dependent global models of thermospheric neutral winds (Fuller-Rowell and Rees, 1980, 1981, 1983) adjusted to account for both solar-UV/EUV heating and ionization effects and quiet (Kp from 1 to 2) or moderately disturbed (Kp from 3 to 4) geomagnetic conditions (models Q and MD). An MD model incorporating a self-consistent description of the high-latitude ionosphere and a Q model excluding high-latitude effects are found to give the most accurate predictions for the respective geomagnetic conditions.

Rees, D.↗
NASA NTRS1988

Observations of a gradual transition between Ps 6 activity with auroral torches and surgelike pulsations during strong geomagnetic disturbances

This paper describes a long-lasting large-amplitude pulsation event, which occurred on January 10, 1983 in the ionosphere and magnetosphere and was characterized by Steen and Rees (1983). Over the 4-h period (0200-0600 UT), the characteristics of the pulsations in the ionosphere changed from being Ps 6 auroral torches toward substorms and back to Ps 6. At GEO, the corresponding characteristics were a modulation of the high-energy particle intensity and plasma dropouts. Based on the ideas presented by Rostoker and Samson (1984), an interpretation of the event is offered, according to which the pulsations are caused by the Kelvin-Helmholtz instability during an interval of strong magnetospheric convection. On the basis of this explanation, a new interpretation of the substorm time sequence is proposed.

Steen, A.↗
NASA NTRS1993

Faint blue counts from formation of dwarf galaxies at z approximately equals 1

The nature of faint blue objects (FBO's) has been a source of much speculation since their detection in deep CCD images of the sky. Their high surface density argues against them being progenitors of present-day bright galaxies and since they are only weakly clustered on small scales, they cannot be entities that merged together to form present-day galaxies. Babul & Rees (1992) have suggested that the observed faint blue counts may be due to dwarf elliptical galaxies undergoing their initial starburst at z is approximately equal to 1. In generic hierarchical clustering scenarios, however, dwarf galaxy halos (M is approximately 10(exp 9) solar mass) are expected to form at an earlier epoch; for example, typical 10(exp 9) solar mass halos will virialize at z is approximately equal to 2.3 if the power-spectrum for the density fluctuations is that of the standard b = 2 cold dark matter (CDM) model. Under 'ordinary conditions' the gas would rapidly cool, collect in the cores, and undergo star-formation. Conditions at high redshifts are far from 'ordinary'. The intense UV background will prevent the gas in the dwarf halos from cooling, the halos being released from their suspended state only when the UV flux has diminished sufficiently.

Babul, Arif↗
NASA NTRS2020

Cerium Stable Isotope Analysis of Synthetic and Terrestrial Rock Reference Materials by MC-ICPMS

Cerium is the most abundant rare earth element (REE) in the solar photosphere, CI chondrites, and the Earth. It has four main stable isotopes (masses: 136,138,140, and 142), with 138Ce being the most studied species, used in geochronology and petrogenesis. In addition, more abundant 140Ce and 142Ce are suggested to be potentially applicable in geochemical investigations. In this work, we developed a modified four-step ion chromatography procedure for Ce chemical separation. Using a MC-ICPMS, we designed a cup configuration to measure 142Ce/140Ce ratio of the samples with an optimized Nd correction equation. A 0.03‰ (2SD) reproducibility was obtained for Ce Ames metal standard. We analyzed ten different igneous and one sedimentary geochemical reference materials. Mean δ142Ce range from −0.07 to 0.32‰. Most of the samples show a heavier Ce isotopic composition than the Ce Ames standard. The majority of rocks have a homogenous δ142Ce. The δ142Ce does not show any correlation with rock chemical composition including their Ce content or rock types. A carbonatite (SARM 40) has a mean δ142Ce of −0.07 ± 0.13‰ (2SD), lower than the other rocks, suggesting the possibility of a pronounced isotopic fractionation. Our work demonstrates the applicability of the developed methodology and the potential of Ce stable isotopes for future geochemical studies. Production of a larger database of δ142Ce values is required to obtain a clearer view on the similarities and differences between different geological material and explaining Ce stable isotope dynamics.

Cerium↗
NASA NTRS1971

Uranium-bearing minerals of lunar rock 12013.

The U distribution in rock 12013 was studied by fission track and elemental mapping techniques. Major U-bearing phases are whitlockite, apatite, zircon, and phase beta, which is a Zr-Ti mineral rich in Fe, Nb, Y, REE, and containing up to 3.6% UO2, 4.7% ThO2 and 4.2% PbO. Calculated microprobe ages for phase beta average 4.0 b.y. and are in reasonable agreement with Rb-Sr and K-Ar ages. Phase beta plays a significant role in the U-Th-Pb systematics of rock 12012 and may play a similar role in the model ages of lunar soil.

Haines, E. L.↗
NASA NTRS1971

Composition of island arcs and continental growth.

Island arc volcanism has contributed and is still contributing to continental growth, but the composition of island arcs differs from that of the upper continental crust in its lower abundance of Si, K, Rb, Ba, Sr and light rare earth elements. In their advanced stage of evolution, island arcs contain more than 80% of tholeiitic and 15% of ?island arc' calc-alkaline rocks with varied SiO2 contents. The larger proportion of tholeiitic rocks is in the lower crustal levels. The high stratigraphical levels of the island arcs are composed of tholeiitic plus calc-alkaline and/or high potash (shoshonitic) associations with higher abundances of K, Rb, Sr, and Ba. Stratification of the island arc crust is accentuated by another type of calc-alkaline volcanism (Andean type) originating at a late stage of arc evolution, probably by partial melting at the base of the crust. This causes enrichment of the upper crust in K, Rb, Ba and REE and accounts for upper crustal abundances of these elements as well as of SiO2.

Jakes, P.↗
NASA NTRS1972

Chemical features of the Luna 16 regolith sample.

The Luna 16 regolith sample differs from Apollo 11, 12 and 14 regolith and basalt samples by having smaller negative Eu and Sr anomalies and nearly chondritic Eu/Sm and Eu/Sr ratios although the overall REE, Ba, Sr and U concentrations are 25 to 45 times chondrites. Major element data, in particular FeO vs Al2O3, show that the Luna 16 regolith sample is composed of materials that follow a quantitatively different Fe/Al variation than do Apollo 11, 12, 14 and 15 samples. The small Eu and Sr anomalies and the displaced Fe/Al variation are two chemical features unique to the Luna 16 regolith sample. The Luna 16 regolith sample can contain little if any of the rock types abundant at Apollo sites, thus indicating that the unique chemical features are typical of local or nearby materials and indicate a separate petrogenetic province for major component rock types of the Luna 16 regolith.

Hubbard, N. J.↗
NASA NTRS1972

The moon as a high temperature condensate

The accretion during condensation mechanism is used to explain the differences in composition of the terrestrial planets and the moon. Many of the properties of the moon, including the enrichment in Ca, Al, Ti, U, Th, Ba, Sr and the REE and the depletion in Fe, Rb, K, Na and other volatiles can be understood if the moon represents a high temperature condensate from the solar nebula. Thermodynamic calculations show that Ca, Al and Ti rich compounds condense first in a cooling nebula. The high temperature mineralogy is gehlenite, spinel perovskite, Ca-Al-rich pyroxenes and anorthite. The model is consistent with extensive early melting, shallow melting at 3 A.E. and with presently high speed internal temperatures. It is predicted that the outer 250 km is rich in plagioclase and FeO. The low iron content of the interior in this model raises the interior temperatures estimated from electrical conductivity by some 800 C. The lunar crust is 80 percent gabbroic anorthosite, 20 percent basalt and is about 250-270 km thick. The lunar mantle is probably composed of spinel, merwinite and diopside with a density of 3.4 g/cu cm.

Anderson, D. L.↗
NASA NTRS1973

The composition and origin of the moon.

Many of the properties of the moon can be explained by early condensation processes in the solar nebula. Thermodynamic calculations show that Ca-, Al- and Ti-rich compounds condense first in a cooling nebula. The inital high-temperature mineralogy is gehlenite, spinel, perovskite, (Ca-Al)-rich pyroxenes and anorthite. Inclusions in type III carbonaceous chondrites such as the Allende meteorite are composed primarily of these minerals and are highly enriched in trace refractories such as REE relative to carbonaceous chondrites. These inclusions can yield basalt and anorthosite in the proportions required to eliminate the europium anomaly, leaving a residual spinel-melilite interior. A high-(Ca-Al) deep interior does not imply an unacceptable mean density of moment of inertia for the moon. The inferred high-U content of the lunar interior, both from the Allende analogy and the high heat flow, indicates a high-temperature interior. The model is consistent with extensive early melting, shallow melting at 3 AE, and with presently high deep internal temperatures.

Anderson, D. L.↗
NASA NTRS1973

Petrology of some lithic fragments from Luna 20.

Microscopic and electron microprobe studies were made of polished thin sections of part of a 30-mg sample of 250- to 500-micron lunar soil returned by Luna 20 from a point between Mare Fecunditatis and Mare Crisium. Very fine-grained lithic (crystalline) rock fragments, composing about one-fifth of the total sample, have mineralogical compositions equivalent to various types of gabbro, anorthositic gabbro, gabbroic anorthosite, and troctolite, with minor basalt. The textures now observed in these fragments are in large part metamorphic. Twenty-seven electron microprobe analyses of minerals from these fragments are presented, including olivine, plagioclase, pyroxene, spinel, nickel-iron, and a Zr-Ti-REE mineral possibly similar to 'phase B' of Lovering and Wark (1971). Analyses of seven melt inclusions and 28 defocused beam analyses of lithic fragments are also given. Some of the fragments contain 'gas' inclusions which, along with the fine grain size, are believed to indicate final crystallization under low pressure near surface conditions.

Roedder, E.↗
NASA NTRS1973

The moon as a high temperature condensate.

The accretion during condensation mechanism, if it occurs during the early over-luminous stage of the sun, can explain the differences in composition of the terrestrial planets and the moon. An important factor is the variation of pressure and temperature with distance from the sun, and in the case of the moon and captured satellites of other planets, with distance from the median plane. Current estimates of the temperature and pressure in the solar nebula suggest that condensation will not be complete in the vicinity of the terrestrial planets, and that depending on location, iron, magnesium silicates and the volatiles will be at least partially held in the gaseous phase and subject to separation from the dust by solar wind and magnetic effects associated with the transfer of angular momentum just before the sun joins the Main Sequence. Many of the properties of the moon, including the 'enrichment' in Ca, Al, Ti, U, Th, Ba, Sr and the REE and the 'depletion' in Fe, Rb, K, Na and other volatiles can be understood if the moon represents a high temperature condensate from the solar nebula.

Anderson, D. L.↗
NASA NTRS1973

Major and trace elements in igneous rocks from Apollo 15.

The concentrations of major and trace elements have been determined in igneous rocks from Apollo 15. All materials analyzed have typical depletions of Eu except for minerals separated from sample 15085. Four samples have concentrations of trace elements that are similar to those of KREEP. The samples of mare basalt from Apollo 15 have higher concentrations of FeO, MgO, Mn, and Cr and lower concentrations of CaO, Na2O, K2O, and rare-earth elements (REE) as compared to the samples of mare basalt from Apollos 11, 12, and 14. The samples can be divided into two groups on the basis of their normative compositions. One group is quartz normative and has low concentrations of FeO while the other is olivine normative and has high concentrations of FeO. The trace element data indicate that the samples of olivine normative basalt could be from different portions of a single lava flow.

Helmke, P. A.↗
NASA NTRS1973

Lunar bulk sample trace element contents and KREEP.

The geochemical coherence of KREEP-related labile (Cl) and refractory (F, K, P, and REE) elements in lunar soils is shown to provide some insights into the evolution of the lunar samples studied. Thus, this coherence may help define the physical conditions under which the samples evolved. These conditions range from high temperatures and relatively open systems for mare basalts to moderate temperatures and closed systems for KREEP-related material. The water leachable Cl may be the residuum of the Cl-containing phase with which mare and KREEP source material equilibrated.

Reed, G. W., Jr.↗
NASA NTRS1974

K and U systematics and average concentrations on the moon

The K-U, Th-U, and Th-Al systematics for lunar samples from the Apollo 11-17 missions and the Luna 16 and 20 missions are summarized. With few exceptions (granitic portion of 12013 and the Apollo 17 mare basalts) the Th/U ratio is 3.8 plus or minus 0.2. The K/U ratio for lunar samples is about 2600 and is distinctly different from the K/U ratio found in terrestrial samples and in the majority of meteorites. The K-U systematics are similar to the K-La, K-Sm, K-Ba, and K-Zr systematics, suggesting that the moon accreted approximately homogeneously. Based on a model the moon contains an average abundance of about 80 ppb U, about 200 ppm K, and about 7 times chondritic abundances for all the refractory elements such as Al, Ca, Ti, Zr, Ba, Sr, and REE. The Th-Al systematics of many lunar highland rocks are dominated by the presence of the rock-type KREEP.

Schonfeld, E.↗