Highly siderophile elements in ureilites

The abundances of the highly siderophile elements (HSE) Ru, Pd, Re, Os, Ir, and Pt were determined by isotope dilution mass spectrometry for 22 ureilite bulk rock samples, including monomict, augite-bearing, and polymict lithologies. This report adds significantly to the quantity of available Pt and Pd abundances in ureilites, as these elements were rarely determined in previous neutron activation studies. The CI-normalized HSE abundance patterns of all ureilites analyzed here except ALHA 81101 show marked depletions in the more volatile Pd, with CI chondrite-normalized Pd/Os ratios (excluding ALHA 81101) averaging 0.19 ± 0.23 (2σ). This value is too low to be directly derived from any known chondrite group. Instead, the HSE bulk rock abundances and HSE interelement ratios in ureilites can be understood as physical mixtures of two end member compositions. One component, best represented by sample ALHA 78019, is characterized by superchondritic abundances of refractory HSE (RHSE—Ru, Re, Os, Ir, and Pt), but subchondritic Pd/RHSE, and is consistent with residual metal after extraction of a S-bearing metallic partial melt from carbonaceous chondrite-like precursor materials. The other component, best represented by sample ALHA 81101, is RHSE-poor and has HSE abundances in chondritic proportions. The genesis of the second component is unclear. It could represent regions within the ureilite parent body (UPB), in which metallic phases were completely molten and partially drained, or it might represent chondritic contamination that was added during disruption and brecciation of the UPB. Removal of carbon-rich melts does not seem to play an important role in ureilite petrogenesis. Removal of such melts would quickly deplete the ureilite precursors in Re/Os and As/Au, which is inconsistent with measured osmium isotope abundances, and also with literature As/Au data for the ureilites. Removal of ²⁶Al during silicate melting may have acted as a switch that turned off further metal extraction from ureilite source regions.     

Iron meteorites: Crystallization,thermal history,parent bodies,and origin

We review the crystallization of the iron meteorite chemical groups, the thermal history of the irons as revealed by the metallographic cooling rates, the ages of the iron meteorites and their relationships with other meteorite types, and the formation of the iron meteorite parent bodies. Within most iron meteorite groups, chemical trends are broadly consistent with fractional crystallization, implying that each group formed from a single molten metallic pool or core. However, these pools or cores differed considerably in their S concentrations, which affect partition coefficients and crystallization conditions significantly. The silicate-bearing iron meteorite groups, IAB and IIE, have textures and poorly defined elemental trends suggesting that impacts mixed molten metal and silicates and that neither group formed from a single isolated metallic melt. Advances in the understanding of the generation of the Widmanstätten pattern, and especially the importance of P during the nucleation and growth of kamacite, have led to improved measurements of the cooling rates of iron meteorites. Typical cooling rates from fractionally crystallized iron meteorite groups at 500–700 °C are about 100–10,000 °C/Myr, with total cooling times of 10 Myr or less. The measured cooling rates vary from 60 to 300 °C/Myr for the IIIAB group and 100–6600 °C/Myr for the IVA group. The wide range of cooling rates for IVA irons and their inverse correlation with bulk Ni concentration show that they crystallized and cooled not in a mantled core but in a large metallic body of radius 150±50 km with scarcely any silicate insulation. This body may have formed in a grazing protoplanetary impact. The fractionally crystallized groups, according to Hf–W isotopic systematics, are derived originally from bodies that accreted and melted to form cores early in the history of the solar system, <1 Myr after CAI formation. The ungrouped irons likely come from at least 50 distinct parent bodies that formed in analogous ways to the fractionally crystallized groups. Contrary to traditional views about their origin, iron meteorites may have been derived originally from bodies as large as 1000 km or more in size. Most iron meteorites come directly or indirectly from bodies that accreted before the chondrites, possibly at 1–2 AU rather than in the asteroid belt. Many of these bodies may have been disrupted by impacts soon after they formed and their fragments were scattered into the asteroid belt by protoplanets.     

Compositions of group IVB iron meteorites and their parent melt

The concentrations of P, V, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the group IVB iron meteorites Cape of Good Hope, Hoba, Skookum, Santa Clara, Tawallah Valley, Tlacotepec, and Warburton Range have been measured by laser ablation inductively coupled plasma mass spectrometry. The data were fitted to a model of fractional crystallization of the IVB parent body core, from which the composition of the parent melt and metal/melt distribution coefficients for each element in the system were determined, for a chosen value of D(Ni). Relative to Ni and chondritic abundances, the parent melt was enriched in refractory siderophiles, with greatest enrichment of 5× chondritic in the most refractory elements, and was strongly volatile-depleted, down to 0.00014× chondritic in Ge. Comparison to an equilibrium condensation sequence from a gas of solar composition indicates that no single temperature satisfactorily explains the volatility trend in the IVB parent melt; a small (<1%) complement of ultrarefractory components added to metal that is volatile-depleted but otherwise has nearly chondritic abundances (for Fe, Co and Ni) best explains the volatility trend. In addition to this volatility processing, which probably occurred in a nebular setting, there was substantial oxidation of the metal in the IVB parent body, leading to loss of Fe and other moderately siderophile elements such as Cr, Ga, and W, and producing the high Ni contents that are observed in the IVB irons. By assuming that the entire IVB parent body underwent a similar chemical history as its core, the composition of the silicate that is complementary to the IVB parent melt was also estimated, and appears to be similar to that of the angrite parent.     

Highly siderophile element evidence for early solar system processes in components from ordinary chondrites

Separated magnetic and nonmagnetic components from the ordinary chondrites Dhajala (H3.8) and Ochansk (H4) were analyzed for their Re-Os isotopic compositions, as well as for the abundances of the highly siderophile elements (HSE) Re, Os, Ir, Ru, Pt and Pd. The Re-Os isotopic systematics of these components are used to constrain the timing of HSE fractionations, and assess the level of open-system behavior of these elements in each of the different components. The high precision, isotope dilution mass spectrometric analyses of the HSE are used to constrain the origins of, and possible relations between some of the diverse components present in these chondrites. The relative and absolute abundances of the HSE differ considerably among the components. Metal fractions have Re/Os that are factors of ∼2 (Dhajala) to ∼3 (Ochansk) higher than those of their nonmagnetic fractions. The isotopic data for both meteorites are consistent with the largest Re-Os fractionations occurring between metal and nonmagnetic components early in solar system history, although minor to moderate late stage, open-system behavior, and limited variations in Re/Os preclude a precise determination of the age for that fractionation. Open-system behavior is generally absent to minor in the metal fractions, and highly variable in nonmagnetic fractions. Re/Os ratios of nonmagnetic fractions deviate as much as 40% from a primordial isochron. Although some deviations are large for isochron applications, nearly all are negligible with respect to consideration of fractionation processes controlling the HSE.Metal from both meteorites contains about 90% of the total budget of HSE. Metal in Ochansk has ∼2 to 10 times the abundances of the bulk meteorite, while metal from the matrix of Dhajala has ∼2 to 4 times the abundances of the bulk. Fine metal in both meteorites has higher abundances than coarse metal, as has been previously observed. Nonmagnetic components, consisting of chondrules and matrix from which metal was removed in the laboratory, have highly fractionated HSE, characterized by much lower Re/Os than the bulk meteorites, as well as large relative depletions in Pd. The abundances of Re, Os, Ir, Ru and Pt in the nonmagnetic fractions are 14-120 ng/g, much higher than would be expected if they had equilibrated with the metal phases present (150-16,000 ng/g). Collectively, the data are consistent with the HSE budget in ordinary chondrites being dominated by two HSE-bearing carrier phases with distinct compositions. These phases formed separately, and never subsequently equilibrated. Metal components incorporated a HSE carrier that formed at high through moderate temperatures and relatively high pressures, such that the relatively volatile Pd behaved coherently with the more refractory HSE. Nonmagnetic fractions from both chondrules and matrix have HSE compositions that likely require at least two processes that fractionated the HSE. Depletions in Pd are consistent with the presence of HSE carriers that formed as either highly refractory condensates, or residues of high degrees of metal melting. Depletions in Re may implicate a period of relatively high f_O2 during which a volatile form of Re was separated from the other HSE.     

Metallographic cooling rates and origin of IVA iron meteorites

We have determined the metallographic cooling rates for 13 IVA irons using the most recent and most accurate metallographic cooling rate model. Group IVA irons have cooling rates that vary from 6600 °C/Myr at the low-Ni end of the group to 100 °C/Myr at the high-Ni end of the group. This large cooling rate range is totally incompatible with cooling in a mantled core which should have a uniform cooling rate. Thermal and fractional crystallization models have been used to describe the cooling and solidification of the IVA asteroid. The thermal model indicates that a metallic body of 150 ± 50 km in radius with less than 1 km of silicate on the outside of the body has a range of cooling rates that match the metallographic cooling rates in IVA irons in the temperature range 700-400 °C where the Widmanstätten pattern formed. The fractional crystallization model for Ni with initial S contents between 3 and 9 wt% is consistent with the measured variation of cooling rate with bulk Ni and the thermal model. New models for impacts in the early solar system and the evolution of the primordial asteroid belt allow us to propose that the IVA irons crystallized and cooled in a metallic body that was derived from a differentiated protoplanet during a grazing impact. Other large magmatic iron groups, IIAB, IIIAB, and IVB, also show significant cooling rate ranges and are very likely to share a similar history.     

Silica and pyroxene in IVA irons; possible formation of the IVA magma by impact melting and reduction of L-LL-chondrite materials followed by crystallization and cooling

Group IVA is a large magmatic group of iron meteorites. The mean Δ¹⁷O (=δ¹⁷O − 0.52·δ¹⁸O) of the silicates is ∼+1.2‰, similar to the highest values in L chondrites and the lowest values in LL chondrites; δ¹⁸O values are also in the L/LL range. This strongly suggests that IVA irons formed by melting L-LL parental material, but the mean Ni content of IVA irons (83 mg/g) is much lower than that of a presumed L-LL parent (∼170 mg/g) and the low-Ca pyroxene present in two IVA meteorites is Fs13, much lower than the Fs20-29 values in L and LL chondrites. Thus, formation from L-LL precursors requires extensive addition of metallic Fe, probably produced by reduction of FeS and FeO. Group IVA also has S/Ni, Ga/Ni, and Ge/Ni ratios that are much lower than those in L-LL chondrites or any chondrite group that preserves nebular compositions, implying loss of these volatile elements during asteroidal processing. We suggest that these reduction and loss processes occurred near the surface of the asteroid during impact heating, and resulted partly from reduction by C, and partly from the thermal dissociation of FeS and FeO with loss of O and S. The hot (∼1770 K) low-viscosity melt quickly moved through channels in the porous asteroid to form a core. Two members of the IVA group, São João Nepomuceno (hereafter, SJN) and Steinbach, contain moderate amounts of orthopyroxene and silica, and minor amounts of low-Ca clinopyroxene. Even though SJN formed after ∼26% crystallization and Steinbach formed after ∼77% crystallization of the IVA core, both could have originated within several tens of meters of the core-mantle interface if 99% of the crystallization occurred from the center outwards. Two other members of the group (Gibeon and Bishop Canyon) contain tabular tridymite, which we infer to have initially formed as veins deposited from a cooling SiO-rich vapor. The silicates were clearly introduced into IVA irons after the initial magma crystallized. Because the γ-iron crystals in SJN are typically about 5 cm across, an order of magnitude smaller than in IVA irons that do not contain massive silicates, we infer that the metal was in the γ-iron field when the silicates were injected. The SJN and Steinbach silicate compositions are near the low-Ca-pyroxene/silica eutectic compositions. We suggest that a tectonic event produced a eutectic-like liquid and injected it together with unmelted pyroxene grains into fissures in the solid metal core. Published estimates of IVA metallographic cooling rates range from 20 to 3000 K/Ma, leading to a hypothesized breakup of the core during a major impact followed by scrambling of the core and mantle debris [Haack, H., Scott, E.R.D., Love, S.G., Brearley, A. 1996. Thermal histories of IVA stony-iron and iron meteorites: evidence for asteroid fragmentation and reaccretion. Geochim. Cosmochim. Acta60, 3103-3113]. This scrambling model is physically implausible and cannot explain the strong correlation of estimated cooling rates with metal composition. Previous workers concluded that the low-Ca clinopyroxene in SJN and Steinbach formed from protopyroxene by quenching at a cooling rate of 10¹² K/Ma, and suggested that this also supported an impact-scrambling model. This implausible spike in cooling rate by a factor of 10¹⁰ can be avoided if the low-Ca clinopyroxene were formed by a late shock event that converted orthopyroxene to clinopyroxene followed by minimal growth in the clinopyroxene field, probably because melt was also produced. We suggest that metallographic cooling-rate estimates (e.g., based on island taenite) giving similar values throughout the metal compositional range are more plausible, and that the IVA parent asteroid can be modeled by monotonic cooling followed by a high-temperature impact event that introduced silicates into the metal and a low-temperature impact event that partially converted orthopyroxene into low-Ca clinopyroxene.     

Siderophile geochemistry of ureilites: A record of early stages of planetesimal core formation

New bulk-compositional data, including trace siderophile elements such as Ir, Os, Au, and Ni, are presented for 25 ureilites. Without exception, ureilites have siderophile abundances too high to plausibly have formed as cumulates. Ureilites undoubtedly underwent a variety of “smelting,” by which C was oxidized to CO gas while olivine FeO was reduced to Fe-metal. However, pressure-buffered equilibrium smelting is not a plausible model for engendering the wide range (75-96 mol%) of mafic-silicate core mg among ureilites. The smelting reaction produces too much CO gas. Even supposing a disequilibrium process with the smelt-gas leaking out of the mantle, none of the ureilites, least of all the ureilite with the most “reduced” (highest) olivine-core mg (ALH84136), has the high Fe-metal abundance predicted by the smelted-cores model. In principle, the Fe-metal generated by smelting could have been subsequently lost, but siderophile data show that ureilites never underwent efficient depletion of Fe-metal. Ureilites display strong correlations among siderophile ratios such as Au/Ir, Ni/Ir, Co/Ir, As/Ir, Se/Ir, and Sb/Ir. Ureilite siderophile depletion patterns loosely resemble siderophile fractionations, presumably nebular in origin, among carbonaceous chondrites. However, Zn, for an element of moderate volatility, is anomalously high in ureilites. A tight correlation between Au and Ni extrapolates to the low-Ni/Au side of the compositional range of carbonaceous chondrites. From this mismatch, mild but nonetheless significant depletions of refractory siderophile elements such as Ir and Os, and moderate depletions of strongly siderophile, weakly chalcophile elements such as Ni and Au, we infer that the ureilite siderophile fractionations are largely the result of a non-nebular process, i.e., removal of S-rich metallic melt, possibly with minor entrainment of Fe-metal. Several lines of trace-element evidence indicate that melt porosity during ureilite anatexis was at least moderate. The ureilite pattern of very mild depletions of extremely siderophile elements, but much deeper depletions of moderately siderophile, chalcophile elements, suggests that asteroidal core formation probably occurs in two discrete stages. In general, separation of a considerable proportion (several wt%) of S-rich metallic melt probably occurs long before, and at a far lower temperature than, separation of the remaining S-poor Fe-metal. Apart from the Fe-metal itself, only extremely siderophile elements wait until the second stage to sequester mainly into the core.     

Siderophile elements in Martian meteorites and implications for core formation in Mars

Noble metals, Mo, W, and 24 other elements were determined in six SNC meteorites of presumably Martian origin. Based on element correlations, representative siderophile element concentrations for the silicate mantle of Mars were inferred. From a comparison with experimentally determined metal/silicate partition coefficients of the moderately siderophile elements: Fe, Ni, Co, W, Mo, and Ga, it is concluded that equilibrium between core forming metal and silicates in Mars has occurred at high temperatures (around 2200°C) and low pressures (<1 GPa). This suggests that metal segregation occurred concurrently with rapid accretion of Mars, which is consistent with the inference from excess ¹⁸²W in Martian meteorites (Lee and Halliday, 1997). Concentrations of Ir, Os, Ru, Pt, and Au in the analyzed Martian meteorites, except ALH84001, are at a level of approximately 10⁻²–10⁻³ × CI. The comparatively high abundances of noble metals in Martian meteorites require the addition of chondritic material after core formation. The similarity in Au/La and Pt/Ca ratios between ALH84001 and the other Martian meteorites suggests crystallization of ALH84001 after complete accretion of Mars.     

Metal-silicate partitioning and constraints on core composition and oxygen fugacity during Earth accretion

We present the results of new partitioning experiments between metal and silicate melts for a series of elements normally regarded as refractory lithophile and moderately siderophile and volatile. These include Si, Ti, Ni, Cr, Mn, Ga, Nb, Ta, Cu and Zn. Our new data obtained at 3.6 and 7.7 GPa and between 2123 and 2473 K are combined with literature data to parameterize the individual effects of oxygen fugacity, temperature, pressure and composition on partitioning. We find that Ni, Cu and Zn become less siderophile with increasing temperature. In contrast, Mn, Cr, Si, Ta, Nb, Ga and Ti become more siderophile with increasing temperature, with the highly charged cations (Nb, Ta, Si and Ti) being the most sensitive to variations of temperature. We also find that Ni, Cr, Nb, Ta and Ga become less siderophile with increasing pressure, while Mn becomes more siderophile with increasing pressure. Pressure effects on the partitioning of Si, Ti, Cu and Zn appear to be negligible, as are the effects of silicate melt composition on the partitioning of divalent cations. From the derived parameterization, we predict that the silicate Earth abundances of the elements mentioned above are best explained if core formation in a magma ocean took place under increasing conditions of oxygen fugacity, starting from moderately reduced conditions and finishing at the current mantle-core equilibrium value.     

Systematics of metal-silicate partitioning for many siderophile elements applied to Earth’s core formation

Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO₂ conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO₂ yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO₂ conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.     

Chemical Analysis of Iron Meteorites by Inductively Coupled Plasma-Mass Spectrometry

Iron meteorites were analysed for nineteen siderophile and chalcophile elements by conventional inductively coupled plasma-mass spectrometry with the specific aim of demonstrating that this technique is an effective alternative to the more routine, yet complex, methodologies adopted in this field such as instrumental or radiochemical neutron activation analysis. Two aliquots of each meteorite sample, in the form of small shavings, were dissolved, one in 6 mol l^-1 HNO₃ and the other in aqua regia , and diluted to a final concentration of 1 mg sample per 1 ml of solution, without pre-concentrating the analytes. Nitric acid solutions were used for the determination of the elements Cr, Co, Ni, Cu, Ga, Ge and As; aqua regia solutions were analysed for the elements Mo, Ru, Rh, Pd, In, Sn, Sb, W, Re, Ir, Pt and Au. Samples were analysed by external calibration, carried out using synthetic multi-elemental solutions, and internal standardisation (with Be, Rb and Bi selected as internal standards). The results obtained from the analyses of nine geochemically well-characterized iron meteorites (Canyon Diablo, Odessa, Toluca, Coahuila, Sikhote-Alin, Buenaventura, Tambo Quemado, Gibeon, NWA 859) with widely variable chemical compositions are in good agreement with literature values for most elements. Detection limits were generally below the lowest concentration observed in iron meteorites. The most notable exception is for Ge, which cannot be successfully determined in the low-Ge meteorites of groups IVA, IVB and IIIF and a number of ungrouped irons. A test of the overall reproducibility of the adopted method, undertaken by repeatedly analysing the same Odessa IAB meteorite specimen, yielded relative standard deviations (1 s ) of between 1 and 6% for all elements except Cr (40%).     

Highly siderophile elements in the Earth, Moon and Mars: Update and implications for planetary accretion and differentiation

The highly siderophile elements (HSE) pose a challenge for planetary geochemistry. They are normally strongly partitioned into metal relative to silicate. Consequently, planetary core segregation might be expected to essentially quantitatively remove these elements from planetary mantles. Yet the abundances of these elements estimated for Earth's primitive upper mantle (PUM) and the martian mantle are broadly similar, and only about 200 times lower than those of chondritic meteorites. In contrast, although problematic to estimate, abundances in the lunar mantle may be more than twenty times lower than in the terrestrial PUM. The generally chondritic Os isotopic compositions estimated for the terrestrial, lunar and martian mantles require that their long-term Re/Os ratios were within the range of chondritic meteorites. Further, most HSE in the terrestrial PUM also appear to be present in chondritic relative abundances, although Ru/Ir and Pd/Ir ratios are slightly suprachondritic. Similarly suprachondritic Ru/Ir and Pd/Ir ratios have also been reported for some lunar impact melt breccias that were created via large basin forming events.Numerous hypotheses have been proposed to account for the HSE present in Earth's mantle. These hypotheses include inefficient core formation, lowered metal-silicate D values resulting from metal segregation at elevated temperatures and pressures (as may occur at the base of a deep magma ocean), and late accretion of materials with chondritic bulk compositions after the cessation of core segregation. Synthesis of the large database now available for HSE in the terrestrial mantle, lunar samples, and martian meteorites reveals that each of the main hypotheses has flaws. Most difficult to explain is the similarity between HSE in the Earth's PUM and estimates for the martian mantle, coupled with the striking differences between the PUM and estimates for the lunar mantle. More complex, hybrid models that may include aspects of inefficient core formation, HSE partitioning at elevated temperatures and pressures, and late accretion may ultimately be necessary to account for all of the observed HSE characteristics. Participation of aspects of each process may not be surprising as it is difficult to envision the growth of a planet, like Earth, without the involvement of each.     

Experimental investigations of trace element fractionation in iron meteorites,II: The influence of sulfur

We have investigated the partitioning of Ir. Ge, Ga, W, Cr, Au, P, and Ni between solid metal and metallic liquid as a function of temperature and S-concentration of the metallic liquid. Partition coefficients for siderophile elements such as Ir, W, Ga and Ge increase by factors of 10–100 as the Sconcentration of the metallic liquid increases from 0–30 wt%. Partition coefficients for other siderophile elements such as Ni, Au and P increase by only factors of 2–3. In contrast, partition coefficients for the more chalcophile element Cr decrease. These experimentally-determined partition coefficients have been used in conjunction with a fractional crystallization model to reproduce the geochemical behavior of Ni, P, Au and Ir during the magmatic evolution of groups IIAB, IIIAB, IVA and IVB iron meteorites. The mean S-concentration for each group increases in the order IVB, IVA, IIIAB, IIAB, in accord with cosmochemical prediction. However, we are unable to reproduce the geochemical behavior of Ge, Ga, W and Cr in an internally consistent way. We conclude that the magmatic histories of these iron meteorite groups are more complex than has been generally assumed.     

The compositional classification of some Chinese iron meteorites

Based on structural observations and the concentrations of Cr, Co, Ni, Cu, Ga, Ge, As, Sb, Re, Ir, and Au by neutron-activation analysis we have classified 14 Chinese iron meteorites. Thirteen are members of the large groups IAB, IIICD, IIIAB and IVA. Leshan is an ungrouped iron meteorite that falls within the IIE field on some element-Ni diagrams, but is distinctly outside this field on plots of Cu, W, and Ir vs. Ni; it is very similar in composition to Techado, another ungrouped iron. The high Cu content of Leshan in consistent with other evidence indicating that Cu is a valuable parameter for classifying iron meteorites. IIICD Dongling appears not to be a new meteorite, but to be paired with Nantan; Dongling was recovered about 50 km from the location of the Nantan shower. In view of the fact that Yongning is highly oxidized, we assign it to group IAB but cannot rule out IIICD. IVA-An Longchang has many characteristics of IVA irons, but has been remelted, probably in a terrestrial setting. Five irons belong to group IVA, a remarkably large number. Three are identical in composition, and we suspect that the two from Hubei, Guanghua and Huangling, are paired. Thus this set of 14 irons includes 12 independent falls.     

Petrogenetic relationships between diogenites and olivine diogenites: Implications for magmatism on the HED parent body

Diogenites are orthopyroxenites and harzburgites that are petrogenetically associated with basaltic magmatism linked to the earliest stages of asteroidal melting on the parent body for the howardite-eucrite-diogenite (HED) meteorites. There are several models proposed for their origin: (1) accumulation of orthopyroxene (OPX) + chromite (CHR) ± olivine (OL) during the crystallization of a magma ocean during the initial stages of asteroidal differentiation, (2) accumulation of OPX + CHR ± OL during the crystallization of compositionally distinct basaltic magmas emplaced into the crust of the HED parent body, and (3) the orthopyroxenites formed by the crystallization of basaltic magmas within the HED parent body crust, whereas the harzburgites represent the mantle of the HED parent body. Although OL and OPX experienced varying degrees of subsolidus reequilibration (1100-700 °C), their minor and trace element characteristics appear to partially preserve magmatic signatures that provide insights into distinguishing among different models for the origin of diogenites. The OPX exhibits a continuous and very systematic variation in incompatible elements such as Al, Ti, Zr, Y, and Yb. Polymict diogenites (i.e. Roda, EET 79002) can contain distinct lithologies with both different incompatible element characteristics and different model abundances of OL. There appears to be no relationship between the appearance and abundance of OL and the incompatible element characteristics of the OPX. The OL exhibits a range in Mg# and systematic variations Ni, Co, Ni/Co, and Mn. For examples, low Ni/Co appears to be closely associated with the harzburgites and Ni and Mn exhibit a negative correlation. Surprisingly, incompatible element concentrations in OPX are not negatively correlated to Ni concentrations in OL. The continuous nature of the minor and trace element characteristics of the OPX and OL is consistent with the all the diogenite lithologies forming through a single process such as crystallization within a magma ocean or a series of layered intrusions. Further, the range in incompatible element variability in the OPX, the Ni and Co systematics in the OL, and the association of distinctly different lithologies within polymict diogenites are most consistent with the diogenites representing lithologies from diverse layered intrusions. Alternatively, they may represent crystallization products of a magma ocean much more complex than has been thus far proposed (i.e. multiple MOs). There are some distinct differences between diogenites and the OL-rich achondrite QUE 93148 that was also analyzed during this study. These differences (such as Ni/Co in OL, estimated conditions of f_O2) suggest that QUE 93148 is closely related to main-group pallasites rather than the parent bodies for the HED meteorites.     

Origin of highly siderophile and chalcogen element fractionations in the components of unequilibrated H and LL chondrites

Osmium isotopic compositions, abundances of highly siderophile elements (HSE: platinum group elements, Re and Au), the chalcogen elements S, Se and Te and major and minor elements were analysed in physically separated size fractions and components of the ordinary chondrites WSG 95300 (H3.3, meteorite find) and Parnallee (LL3.6, meteorite fall). Fine grained magnetic fractions are 268-65 times enriched in HSE compared to the non-magnetic fractions. A significant deviation of some fractions of WSG 95300 from the 4.568 Ga ¹⁸⁷Re-¹⁸⁷Os isochron was caused by redistribution of Re due to weathering of metal. HSE abundance patterns show that at least four different types of HSE carriers are present in WSG 95300 and Parnallee. The HSE carriers display (i) CI chondritic HSE ratios, (ii) variable Re/Os ratios, (iii) lower than CI chondritic Pd/Ir and Au/Ir and (iv) higher Pt/Ir and Pt/Ru than in CI chondrites. These differences between components clearly indicate the loss of refractory HSE carrier phases before accretion of the components. Tellurium abundances correlate with Pd and are decoupled from S, suggesting that most Te partitioned into metal during the last high-temperature event. Tellurium is depleted in all fractions compared to CI chondrite normalized Se abundances. The depletion of Te is likely associated with the high temperature history of the metal precursors of H and LL chondrites and occurred independent of the metal loss event that depleted LL chondrites in siderophile elements. Most non-magnetic and slightly magnetic fractions have S/Se close to CI chondrites. In contrast, the decoupling of Te and Se from S in magnetic fractions suggests the influence of volatility and metal-silicate partitioning on the abundances of the chalcogen elements. The influence of terrestrial weathering on chalcogen element systematics of these meteorites appears to be negligible.     

Chemical classification of iron meteorites—X. Multielement studies of 43 irons,resolution of group IIIE from IIIAB,and evaluation of Cu as a taxonomic parameter

We report structural and compositional data leading to the classification of 41 iron meteorites, increasing the number of classified independent iron meteorites to 576. We also obtained data on a new metal-rich mesosiderite and on two new iron masses that are paired with previously studied irons. For the first time in this series we also report concentrations of Cr, Co, Cu, As, Sb, W, Re and Au in each of these 44 meteorites. We determined 7 of these elements (all except Sb) in 30 previously studied ungrouped or unusual irons, and obtained Cu data on 104 irons, 21 pallasites, and 3 meteorite phases previously studied by E. Scott. We show that Cu possesses characteristics well suited to a taxonomic element: a siderophile nature, a large range among all irons, and a low range within magmatic groups. For the first time we report the partial resolution of the C-rich group IIIE from its populous twin group IIIAB on element-Ni diagrams other than Ir-Ni. Cachiyuyal previously classified ungrouped and Armanty (Xinjiang) previously classified IIIAB are reclassified IIIE. Despite the addition of 3 new irons and the reanalysis of 3 previously studied irons the members of the set of 15 ungrouped irons having very low Ga (<3 μg/g) and Ge (<0.7 μg/g) contents remain individualists. The same is generally true for irons having $\text{100 ≤ Ni ≤ 180}\text{mg/g}$ and compositional similarities to IIICD, but A80104 increases the Garden Head trio to a quartet. Algoma is reclassified from ungrouped to IIICD-an and Hassi-Jekna and Magnesia from IIICD to IIICD-an. The metal of Horse Creek and Mount Egerton is compositionally closely related to metal from EH chondrites. We suggest that the P-rich Bellsbank trio irons formed in the IIAB core in topographic lows filled with an immiscible, P-rich second liquid.     

Modeling fractional crystallization of group IVB iron meteorites

A ¹⁸⁷Re-¹⁸⁷Os isochron including data for all twelve IVB irons gives an age of 4579 ± 34 Ma with an initial ¹⁸⁷Os/¹⁸⁸Os of 0.09531 ± 0.00022, consistent with early solar system crystallization. This result, along with the chemical systematics of the highly siderophile elements (HSE) are indicative of closed-system behavior for all of the HSE in the IVB system since crystallization.Abundances of HSE measured in different chunks of individual bulk samples, and in spot analyses of different portions of individual chunks, are homogeneous at the ±10% level or better. Modeling of HSE in the IVB system, therefore, is not impacted by sample heterogeneities. Concentrations of some other elements determined by spot analysis, such as P, Cr and Mn, however, vary by as much as two orders of magnitude and reflect the presence of trace phases.Assuming initial S in the range of 0 to 2 wt.%, the abundances of the HSE Re, Os, Ir, Ru, Pt, Rh, Pd and Au in bulk IVB irons are successfully accounted for via a fractional crystallization model. For these elements, all IVB irons can be interpreted as being representative of equilibrium solids, liquids, or mixtures of equilibrium solids and liquids.Our model includes changes in bulk D values (ratio of concentration in the solid to liquid) for each element in response to expected increases in S and P in the evolving liquid. For this system, the relative D values are as follow: Os > Re > Ir > Ru > Pt > Rh > Pd > Au. Osmium, Re, Ir and Ru were compatible elements (favor the solid) throughout the IVB crystallization sequence; Rh, Pd and Au were incompatible (favor the liquid). Extremely limited variation in Pt concentrations throughout the IVB crystallization sequence requires that D(Pt) remained at unity.In general, D values derived from the slopes of logarithmic plots, compared with those calculated from recent parameterizations of D values for metal systems are similar, but not identical. Application of D values obtained by the parameterization method is problematic for comparisons of the compatible elements with similar partitioning characteristics. The slope-based approach works well for these elements. In contrast, the slope-based approach does not provide viable D values for the incompatible elements Pd and Au, whereas the parameterization method appears to work well. Modeling results suggest that initial S for this system may have been closer to 2% than 0, but the elements modeled do not tightly constrain initial S.Consistent with previous studies, our calculated initial concentrations of HSE in the IVB parent body indicate assembly from materials that were fractionated via high temperature condensation processes. As with some previous studies, depletions in redox sensitive elements and corresponding high concentrations of Re, Os and Ir present in all IVB irons are interpreted as meaning that the IVB core formed in an oxidized parent body. The projected initial composition of the IVB system was characterized by sub-chondritic Re/Os and Pt/Os ratios. The cause of this fractionation remains a mystery. Because of the refractory nature of these elements, it is difficult to envision fractionation of these elements (especially Re-Os) resulting from the volatility effects that evidently affected other elements.     

Siderophile-element anomalies in CK carbonaceous chondrites: Implications for parent-body aqueous alteration and terrestrial weathering of sulfides

CK chondrites constitute the most oxidized anhydrous carbonaceous chondrite group; most of the Fe occurs in magnetite and in FeO-rich mafic silicates. The two observed CK falls (Karoonda and Kobe), along with thirteen relatively unweathered CK finds, have unfractionated siderophile-element abundance patterns. In contrast, a sizable fraction of CK finds (9 of 24 investigated) shows fractionated siderophile abundance patterns including low abundances of Ni, Co, Se and Au; the most extreme depletions are in Ni (0.24 of normal CK) and Au (0.14 of normal CK). This depletion pattern has not been found in other chondrite groups. Out of the 74 CK chondrites listed in the Meteoritical Bulletin Database (2006; excluded considerably paired specimens; see http://tin.er.usgs.gov/meteor/metbull.php) we analyzed 24 and subclassified the CK chondrites in terms of their chemical composition and sulfide mineralogy: sL (siderophiles low; six samples) for large depletions in Ni, Co, Se and Au (>50% of sulfides lost); sM (siderophiles medium; two CKs) for moderately low Ni and Co abundances (sulfides are highly altered or partly lost); sH (siderophiles high; one specimen) for enrichments in Ni, Co, Se and Au; ‘normal’ for unfractionated samples (13 samples). The sole sH sample may have obtained additional sulfide from impact redistribution in the parent asteroid. We infer that these elements became incorporated into sulfides after asteroidal aqueous processes oxidized nebular metal; thermal metamorphism probably also played a role in their mineral siting. The siderophile losses in the sL and sM samples are mainly the result of oxidation of pentlandite, pyrite and violarite by terrestrial alteration followed by leaching of the resulting phases. Some Antarctic CK chondrites have lost most of their sulfides but retained Ni, Co, Se and Au, presumably as insoluble weathering products.