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A lunar core of Fe-Ni-S.

It has been proposed that lunar samples were magnetized by a field created by a lunar core of molten Fe. Low abundances of siderophile elements in lunar rocks are compatible with formation of a metallic lunar core. A molten Fe core requires that the bulk of the moon was above, or close to, the melting point, a requirement which disagrees with most models of the lunar thermal regime. A core (or perhaps a layer or pockets) of molten Fe-Ni-S, at or close to the eutectic composition would act as a lunar dynamo, and be at a temperature (approximately 1000 C) consistent with some reasonable models of lunar thermal history. The existence of a Fe-Ni-S core would also partly explain the depletion in volatile elements in lunar basalts. Such a core, occupying up to 20% of the moon's radius, requires a bulk S content for the moon of only 0.3 wt %.

Brett, R.↗

Partitioning of siderophile elements in the Fe-Ni-S system - 1 bar to 80 kbar

Partition coefficients for Au, Ni, P, and Ge between solid Fe-Ni metal and sulfur-bearing metallic liquids have been measured at 7, 27 and 80 kbar. These are the only such data for Au, P, and Ge at high pressure. Comparison of the present partitioning results to those obtained at 1 bar indicate that only the 80-kbar Ge data differ significantly from the 1-bar experiments. Thus, many low-pressure partitioning experiments in the Fe-Ni-S-P system may have applicability to the greater portion of the earth's upper mantle or, alternatively, the entire mantle of Mars.

Jones, J. H.↗

Influence of temperature and the role of chromium on the kinetics of sulfidation of 310 stainless steel

The sulfidation of 310 stainless steel was studied over the temperature range from 910 K to 1285 K. By adjusting the ratio of hydrogen sulfide, variations in sulfur potential were obtained. The effect of temperature on sulfidation was determined at three different sulfur potentials: 39/sqNm, 0.014/sqNm, and 0.00015/sqNm. All sulfide scales contained one or two surface layers in addition to a subscale. The second outer layer (OL-II), furthest from the alloy, contained primarily Fe-Ni-S. The first outer layer (OL-I), nearest the subscale, contained FE-Cr-S. The subscale consisted of sulfide inclusions in the metal matrix. At a given temperature and sulfur potential, the weight gain data obeyed the parabolic rate law after an initial transient period. The parabolic rate constants obtained at the sulfur potential of 39/sqNm did not show a break when the logarithm of the rate constant was plotted as a function of the inverse of absolute temperature. Sulfidation carried out at sulfur potentials below 0.02/sqNm, however, did show a break at 1145 K, which is termed as the transition temperature. This break was found to be associated with the changes which had occurred in the Fe:Cr ratio of OL-I. Below the transition temperature the activation energy was found to be approximately 125 kj/mole. Above the transition temperature the rate of sulfidation decreased with temperature but dependent on the Fe:Cr ratio in the iron-chromium-sulfide layers of the OL-I. A reaction mechanism consistent with the experimental results has been proposed.

Rao, D. B.↗

Metamorphic effects in experimentally heated Krymka /L3/ chondrite

Experimental charges of the Krymka unequilibrated ordinary chondrite heated from 500-1000 C have been examined petrographically for evidence of metamorphism. Of the petrologic criteria commonly used to distinguish types 4-6 chondrites, only changes in opaque mineral compositions are observed. Chemical and textural observations indicate development of a fine-grained intergrowth of taenite + troilite beginning at 700 C due to melting within the metal-rich portion of the Fe-Ni-S system, and minor reduction of troilite to metal, possibly through sulfur loss at higher temperatures. Overall textural integration, glass devitrification, and significant Fe-enrichment of ferromagnesian minerals are not observed because the short duration of these experiments was not sufficient for the development of other changes normally attributed to metamorphism in ordinary chondritic meteorites.

Mcsween, H. Y., Jr.↗

On the chemical composition of L-chondrites

Radiochemical neutron activation analysis of Ag, As, Au, Bi, Co, Cs, Ga, In, Rb, Sb, Te, Tl, and Zn and major element data in 14 L4-6 and 3 LL5 chondrites indicates that the L group is unusually variable and may represent at least 2 subgroups differing in formation history. Chemical trends in the S/Fe rich subgroup support textural evidence indicating late loss of a shock formed Fe-Ni-S melt; the S/Fe poor subgroup seemingly reflects nebular fractionation only. Highly mobile In and Zn apparently reflect shock induced loss from L chondrites. However, contrasting chemical trends in several L chondrite sample sets indicate that these meteorites constitute a more irregular sampling of, or more heterogeneous parent material than do carbonaceous or enstatite chondrites. Data for 15 chondrites suggest higher formation temperatures and/or degrees of shock than for LL5 chondrites.

Neal, C. W.↗

Chemical studies of L-chondrites. I - A study of possible chemical sub-groups

Radiochemical neutron activation analysis of Ag, As, Au, Bi, Co, Cs, Ga, In, Rb, Sb, Te, Tl and Zn and major element data in 14 L4-6 and 3 LL5 chondrites indicates that the L-group is unusually variable and may represent at least 2 sub-groups differing in formation history. Chemical trends in the S/Fe-rich sub-group support textural evidence indicating late loss of a shock-formed Fe-Ni-S melt; the S/Fe-poor sub-group seemingly reflects nebular fractionation only. Highly mobile In and Zn apparently reflect shock-induced loss from L-chondrites. Data for L5 chondrites suggest higher formation temperatures and/or degrees of shock than for LL5 chondrites.

Neal, C. W.↗

Experimental investigations of trace element fractionation in iron meteorites. III - Elemental partitioning in the system Fe-Ni-S-P

Measurements of solid metal/liquid metal trace element partition coefficients, which are used to interpret the crystallization history of magmatic iron meteorite groups differ greatly between different research groups, using different experimental techniques. Specifically, partition coefficients measured utilizing 'static' experiments which approach equilibrium cannot be reconciled with the results of 'dynamic' experiments which mimic fractional crystallization. We report new tests of our 'static' experimental technique and demonstrate that our methodology yields reliable equilibrium values for Ni, P and Ge partition coefficients. Partition coefficients in the Fe-Ni-S-P system are well matched by interpolation between the Fe-Ni-S and Fe-Ni-P subsystems. In contrast, the predictions of 'dynamic' experiments do not agree with our measurements and, consequently, the ability of 'dynamic' experiments to reproduce iron meteorite Ge vs. Ni fractionation trends successfully must be regarded as fortuitous.

Malvin, D. J.↗

Metal with anomalously low Ni and Ge concentrations in the Allan Hills A77081 winonaite

The Ge content of metal in the Allan Hills A77081 winonaite was determined by high-sensitivity electron microprobe analysis. By optimizing analytical conditions for Ge determination, a detection limit of about 75 ppm could be achieved. In A77081 some small kamacite grains contain less Ni and Ge and more Co than coarse-grained metal. These small grains are always associated with sulfide, raising the possibility that anomalous metal is related to eutectic melting. However, when published partition coefficients for Ni and Ge in the Fe-Ni-S system are used to model fractionation of these elements during eutectic melting, one finds that secondary metal should be enriched in Ni and depleted in Ge. Thus, the positive Ni-Ge correlation found in this study is the opposite of the expected trend. No explanation for this discrepancy has yet been found. Nonetheless, the existence of anomalous metal is an indication that A77081, and probably other winonaites as well, have undergone some fractionation. This supports the notion that the high-temperature history of winonaites is related to the formation of IAB iron meteorites, whose silicate inclusions are very similar to winonaites.

Kracher, Alfred↗

Thermal diffusion in metal-sulfide liquids - Early results

Experiments were carried out to evaluate the Soret effect in liquid Fe-Ni-S-P alloys in order to gain a better understanding of the physical and thermodynamic properties of metallic liquids and to assess the possibility of systematic errors in Czochralski growth techniques. The metal-sulfide liquids were found to show a substantial Soret effect and, contrary to previous expectation, can be as large as that seen in the silicate system. The segregation is largely produced by S-Fe interactions. The P redistribution occurs to reduce activity gradients in P consequent upon S gradients, and P segregation can be approximately predicted in Fe-Ni-S liquids using the activity model of Jones and Malvin (1990). It is inferred that the sense of the Soret segregation, with P going to the cold end and S going to the hot end, is in accordance with the prediction of Malvin et al. (1986), who speculated that the crystal-pulling experiments of Sellamuthu and Goldstein (1985) was influenced by the Soret effect.

Jones, J. H.↗

Potassium-bearing Iron-Nickel Sulfides in Nature and High-Pressure Experiments: Geochemical Consequences of Potassium in the Earth's Core

Introduction: Potassium (K) as a large ion lithophile element has dominantly been concentrated in the Earth s crust and the mantle through differentiation, and in the form of K-40 contributes to the planet s heat budget. However, whether or not K also enters core-forming phases, has been debated for over three decades. Arguments favoring entry of K in the core are based on: (1) K-sulfide (with Fe, Ni, Cu, Na, and Cl; djerfisherite) found in highly reduced enstatite chondrites (or aubrites, enstatite achondrites); (2) demonstration that K, owing to an s-d electronic switch at high-pressure, exhibits transition- element like character, (3) solubility of measurable K in Fe-Ni-S liquids at high pressure, temperature conditions, and (4) models of cooling of the core that seem to require, besides convection, some form of radioactivity, and thus lending support to the experimental work. In this contribution, we assess the effect of sequestering K in the core, as it is perhaps an element that is a key to reconciling geochemistry, paleomagnetism, accretion, and thermal evolution models for the planet.

Keshav, S.↗

Asteroidal Differentiation Processes Deduced from Ultramafic Achondrite Ureilite Meteorites

Ureilites are the second largest achondrite group. They are ultramafic achondrites that have experienced igneous processing whilst retaining some degree of nebula-derived chemical heterogeneity. They differ from other achondrites in that they contain abundant carbon and their oxygen isotope compositions are very heterogeneous and similar to those of the carbonaceous chondrite anhydrous mineral line. Their carbonaceous nature and some compositional characteristics indicative of nebular origin suggest that they are primitive materials that form a link between nebular processes and early periods of planetesimal accretion. However, despite numerous studies, the exact origin of ureilites remains unclear. Current opinion is that they represent the residual mantle of an asteroid that underwent silicate and Fe-Ni-S partial melting and melt removal. Recent studies of short-lived chronometers indicate that the parent asteroid of the ureilites differentiated very early in the history of the Solar System. Therefore, they contain important information about processes that formed small rocky planetesimals in the early Solar System. In effect, they form a bridge between nebula processes and differentiation in small planetesimals prior to accretion into larger planets and so a correct interpretation of ureilite petrogenesis is essential for understanding this critical step.

Downes, Hilary↗

Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft, suggest that Vesta resembles H chondrites in bulk chemical composition, possibly with about 25% of a CM-chondrite like composition added in. For this model, the core is 15% by mass (or 8 volume %) of the asteroid. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. Melting in the Fe-Ni-S system begins at a cotectic temperature of ~940 deg. C. Only about 40% of the total metal phase, or 3-4 volume % of Vesta, melts prior to the onset of silicate melting. Liquid iron in solid silicate initially forms isolated pockets of melt; connected melt channels, which are necessary if the metal is to segregate from the silicate, are only possible when the metal phase exceeds about 5 volume %. Thus, metal segregation to form a core does not occur prior to the onset of silicate melting.

Kiefer, Walter S.↗