Mary F. Horan

Highly siderophile elements in chondrites

Abstract The abundances of the highly siderophile elements (HSE), Re, Os, Ir, Ru, Pt and Pd, were determined by isotope dilution mass spectrometry for bulk samples of 13 carbonaceous chondrites, 13 ordinary chondrites and 9 enstatite chondrites. These data are coupled with corresponding 187Re–187Os isotopic data reported by Walker et al. [Geochim. Cosmochim. Acta, 2002] in order to constrain the nature and timing of chemical fractionation relating to these elements in the early solar system. The suite of chondrites examined displays considerable variations in absolute abundances of the HSE, and in the ratios of certain HSE. Absolute abundances of the HSE vary by nearly a factor of 80 among the chondrite groups, although most vary within a factor of only 2. Variations in concentration largely reflect heterogeneities in the sample aliquants. Different aliquants of the same chondrite may contain variable proportions of metal and/or refractory inclusions that are HSE-rich, and sulfides that are HSE-poor. The relatively low concentrations of the HSE in CI1 chondrites likely reflect dilution by the presence of volatile components. Carbonaceous chondrites have Re/Os ratios that are, on average, approximately 8% lower than ratios for ordinary and enstatite chondrites. This is also reflected in 187Os/188Os ratios that are approximately 3% lower for carbonaceous chondrites than for ordinary and enstatite chondrites. Given the similarly refractory natures of Re and Os, this fractionation may have occurred within a narrow range of high temperatures, during condensation of these elements from the solar nebula. Superimposed on this major fractionation are more modest movements of Re or Os that occurred within the last 0–2 Ga, as indicated by minor open-system behavior of the Re–Os isotope systematics of some chondrites. The relative abundances of other HSE can also be used to discriminate among the major classes of chondrites. For example, in comparison to the enstatite chondrites, carbonaceous and ordinary chondrites have distinctly lower ratios of Pd to the more refractory HSE (Re, Os, Ir, Ru and Pt). Differences are particularly well resolved for the EH chondrites that have Pd/Ir ratios that average more than 40% higher than for carbonaceous and ordinary chondrite classes. This fractionation probably occurred at lower temperatures, and may be associated with fractionation processes that also affected the major refractory lithophile elements. Combined, 187Os/188Os ratios and HSE ratios reflect unique early solar system processing of HSE for each major chondrite class.

Comparative 187Re-187Os systematics of chondrites: Implications regarding early solar system processes

Abstract A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the 187Re/188Os and 187Os/188Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average 187Re/188Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the 187Os/188Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history. A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga. The 187Os/188Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.

Chondrite Barium, Neodymium, and Samarium Isotopic Heterogeneity and Early Earth Differentiation

Isotopic variability in barium, neodymium, and samarium in carbonaceous chondrites reflects the distinct stellar nucleosynthetic contributions to the early solar system. We used 148Nd/144Nd to correct for the observed s-process deficiency, which produced a chondrite 146Sm-142Nd isochron consistent with previous estimates of the initial solar system abundance of 146Sm and a 142Nd/144Nd at average chondrite Sm/Nd ratio that is lower than that measured in terrestrial rocks by 21 ± 3 parts per million. This result strengthens the conclusion that the deficiency in 142Nd in chondrites relative to terrestrial rocks reflects 146Sm decayand earlyplanetary differentiation processes.

RE-OS ISOTOPIC EVIDENCE FOR AN ENRICHED-MANTLE SOURCE FOR THE NORIL'SK-TYPE, ORE-BEARING INTRUSIONS, SIBERIA

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Norilsk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Norilsk I intrusion have γOs values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have γOs values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have γOs values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Norilsk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ϵNd values that range only from −0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. (1) incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. (2) derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. (3) persistence of primordial stratification of rhenium and osmium in the mantle.

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively.

Re - Os isotopic constraints on the origin of volcanic rocks, Gorgona Island, Colombia: Os isotopic evidence for ancient heterogeneities in the mantle

The Re — Os isotopic systematics of komatiites and spatially associated basalts from Gorgona Island, Colombia, indicate that they were produced at 155±43 Ma. Subsequent episodes of volcanism produced basalts at 88.1±3.8 Ma and picritic and basaltic lavas at ca. 58 Ma. The age for the ultramafic rocks is important because it coincides with the late-Jurassic, early-Cretaceous disassembly of Pangea, when the North- and South-American plates began to pull apart. Deep-seated mantle upwelling possibly precipitated the break-up of these continental plates and caused a tear in the subducting slab west of Gorgona, providing a rare, late-Phanerozoic conduit for the komatiitic melts.Mantle sources for the komatiites were heterogeneous with respect to Os and Pb isotopic compositions, but had homogeneous Nd isotopic compositions (εNd+9±1). Initial 187Os/186Os normalized to carbonaceous chondrites at 155 Ma (γOs) ranged from 0 to +22, and model-initial μ values ranged from 8.17 to 8.39. The excess radiogenic Os, compared with an assumed bulk-mantle evolution similar to carbonaceous chondrites, was likely produced in portions of the mantle with long-term elevated Re concentrations. The Os, Pb and Nd isotopic compositions, together with major-element constraints, suggest that the sources of the komatiites were enriched more than 1 Ga ago by low (<20%) and variable amounts of a basalt or komatiite component. This component was added as either subducted oceanic crust or melt derived from greater depths in the mantle. These results suggest that the Re — Os isotope system may be a highly sensitive indicator of the presence of ancient subducted oceanic crust in mantle-source regions.

Rhenium-osmium concentration and isotope systematics in group IIAB iron meteorites

Rhenium and osmium abundances, and osmium isotopic compositions were measured by negative thermal ionization mass spectrometry in thirty samples, including replicates, of five IIA and eight IIB iron meteorites. Concentrations in HA irons range from 4800 ppb Re and 66000 ppb Os (Negrillos) to 160 ppb Re and 800 ppb Os (Lombard). In the IIB subgroup, concentrations vary from 28 ppb Re and 180 ppb Os (Navajo) down to 0.8 ppb Re and 9 ppb Os (Sao Juliao de Moreira and Santa Luzia). Log plots of Os vs. Re abundances for HA and IIB irons describe straight lines that approximately converge on Lombard, which has the lowest Re and Os abundances and highest 187Re/188Os measured in a IIA iron to date. The linear HA trend may be exactly reproduced by fractional crystallization with constant kRe and kOs, but is not well fitted using variable partition coefficients. The IIB iron trend, however, cannot be entirely explained by simple fractional crystallization. One explanation is that small amounts of Re and Os were added to the asteroid core during the final stages of crystallization. Another possibility is that diffusional enrichment of Os may have occurred in samples most depleted in Re and Os. The combined ReOs isotopic data for HA irons give the following results: slope = 0.07803 ± 0.00076; intercept = 0.09609 ± 0.00045; age = 4584 ± 43 Ma (neglecting the uncertainty in the decay constant of ±3%). Four IIB iron meteorites (Mount Joy, Central Missouri, DRPA 78009, Santa Luzia) also plot within the analytical uncertainty of the HA isochron. These results are consistent with rapid (probably <50 Ma) core segregation, differentiation, and crystallization in the IIAB parent. Several IIB irons (Navajo, Sandia Mountains, Smithsonian Iron, and perhaps Sao Juliao de Moreira) lie beyond analytical uncertainty above the IIA iron isochron, averaging 8 ± 2% higher in 187Os/188Os. These irons may have crystallized significantly after the HA irons and Mount Joy, but only if the 187Re/188Os of the melt was ≥2.2. There is no evidence for a IIA iron crystallizing in equilibrium with a melt having such a high ratio. Alternatively, the osmium isotopic systematics of these irons may have been slightly disturbed long after crystallization at ca. 3.3 Ga ago.

Osmium and neodymium isotopic constraints on the temporal and spatial evolution of Siberian flood basalt sources

High-Mg volcanic rocks from the ca. 250 Ma old Siberian Flood Basalt Province (SFBP) were analyzed for their osmium and neodymium isotopic compositions in order to help to constrain source characteristics as the system evolved. Picrites from the Gudchikhinsky suite, the oldest rocks examined, have γOs of +5.3 to +6.1 and ϵNd of +3.7 to +4.0. The osmium and neodymium isotopic compositions of these rocks are similar to some modern ocean-island basalts (OIB), consistent with their derivation from a mantle plume, and show little evidence for interaction with either subcontinental lithospheric mantle (SCLM), or the Precambrian Siberian craton through which the parental melts passed. Picrites from the stratigraphically higher Tuklonsky suite have similar γOs of +3.4 to +6.5, but ϵNd Of −0.9 to −2.6. The similar γOs but lower ϵNd for the Tuklonsky picrites as compared with the Gudchikhinsky picrites suggest that some magmas from the same OIB-type, mantle source were contaminated by lithospheric components. The osmium isotopic composition of the Tuklonsky picrites was not significantly affected by this interaction, possibly because Os concentrations in the magmas were substantially greater than those in the contaminant. A differentiated ankaramite flow, associated with the top of the stratigraphically higher Morongovsky suite, has γOs of +9.8 to +10.2 and ϵNd of +1.3 to +1.4. The higher γOs may indicate that the plume source was heterogeneous with respect to osmium isotopic composition, consistent with osmium isotopic measurements in rocks from other plume sources. In contrast to these rocks, Mg-rich, alkaline rocks (meymechites) from the Guli area that erupted much nearer the end of the flood-basalt event have γOs of −1.2 to −2.6 and ϵNd of +3.7 to +4.9. These rocks were probably produced by low degrees of partial melting of mantle after the main stages of flood-basalt production. The relatively low γOs and high ϵNd for the meymechites, together with a variety of trace-element characteristics, are most consistent with derivation from a mixed source—one that included both the 0113-type source that fed the majority of the flood-basalt system and a major component from the SCLM underlying the Siberian craton. These results, taken together with earlier investigations of the Norilsk-type ore-bearing intrusions, suggest that much of the SFBP consists dominantly of plume-derived material, until relatively late in the magmatic event, when the SCLM became a significant source of material.

Heterogeneous Accretion and the Moderately Volatile Element Budget of Earth

Earths Silver Lining The age of the oldest rocks on Earths surface is controversial, but, even if they are at their oldest estimate, hundreds of millions of years in our planets earliest history are still missing. However, in some rocks that until relatively recently resided in the mantle, the isotopic signature from the time of Earths formation is still preserved. Schönbächler et al. (p. 884) exploited this preservation to constrain models that describe the early material that assembled together to form Earth. Because the isotopic profile of silver in these rocks is nearly identical to that measured in a class of primitive meteorites, the earliest material probably had high volatile content. However, the fractionation of other isotopes suggests that the volatile content probably decreased over time in subsequent accretion events. With these isotopic model constraints, it is possible that one of the last major collisions—the Moon-forming giant impact—added considerable amounts of water and other volatile elements to Earth. Silver isotopes from mantle rocks suggest that Earth assembled from materials with variable volatile contents. Several models exist to describe the growth and evolution of Earth; however, variables such as the type of precursor materials, extent of mixing, and material loss during accretion are poorly constrained. High-precision palladium-silver isotope data show that Earth’s mantle is similar in 107Ag/109Ag to primitive, volatile-rich chondrites, suggesting that Earth accreted a considerable amount of material with high contents of moderately volatile elements. Contradictory evidence from terrestrial chromium and strontium isotope data are reconciled by heterogeneous accretion, which includes a transition from dominantly volatile-depleted to volatile-rich materials with possibly high water contents. The Moon-forming giant impact probably involved the collision with a Mars-like protoplanet that had an oxidized mantle, enriched in moderately volatile elements.

Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts

Isotopes isolated after impact Details about how Earth formed are gleaned from the daughter products of certain short-lived radioactive isotopes found in rocks. Rizo et al. describe subtle tungsten isotope variations in rocks from the very deep mantle in Baffin Island and the Ontong Java Plateau (see the Perspective by Dahl). The results suggest that portions of Earth have remained unmixed since it formed. The unmixed deep mantle rocks also imply that Earths core formed from several large impact events. Science, this issue p. 809; see also p. 768 Tungsten isotope ratios in certain rocks suggest an ancient primordial reservoir and early core formation from large impacts. How much of Earths compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth’s primary accretionary period have survived to the present.