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R.J. Walker

Publications and source records attributed to R.J. Walker.

At least 19 recordsLinked to original sources

Osmium isotope and highly siderophile element systematics of the lunar crust

Coupled 187 Os/ 188 Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for pristine lunar crustal rocks 60025, 62255, 65315 (ferroan anorthosites, FAN) and 76535, 78235, 77215 and a norite clast in 15455 (magnesian-suite rocks, MGS). Osmium isotopes permit more refined discrimination than previously possible of samples that have been contaminated by meteoritic additions and the new results show that some rocks, previously identified as pristine, contain meteorite-derived HSE. Low HSE abundances in FAN and MGS rocks are consistent with derivation from a strongly HSE-depleted lunar mantle. At the time of formation, the lunar floatation crust, represented by FAN, had 1.4 ?? 0.3 pg g - 1 Os, 1.5 ?? 0.6 pg g - 1 Ir, 6.8 ?? 2.7 pg g - 1 Ru, 16 ?? 15 pg g - 1 Pt, 33 ?? 30 pg g - 1 Pd and 0.29 ?? 0.10 pg g - 1 Re (??? 0.00002 ?? CI) and Re/Os ratios that were modestly elevated ( 187 Re/ 188 Os = 0.6 to 1.7) relative to CI chondrites. MGS samples are, on average, characterised by more elevated HSE abundances (??? 0.00007 ?? CI) compared with FAN. This either reflects contrasting mantle-source HSE characteristics of FAN and MGS rocks, or different mantle-crust HSE fractionation behaviour during production of these lithologies. Previous studies of lunar impact-melt rocks have identified possible elevated Ru and Pd in lunar crustal target rocks. The new results provide no supporting evidence for such enrichments. If maximum estimates for HSE in the lunar mantle are compared with FAN and MGS averages, crust-mantle concentration ratios (D-values) must be ??? 0.3. Such D-values are broadly similar to those estimated for partitioning between the terrestrial crust and upper mantle, with the notable exception of Re. Given the presumably completely different mode of origin for the primary lunar floatation crust and tertiary terrestrial continental crust, the potential similarities in crust-mantle HSE partitioning for the Earth and Moon are somewhat surprising. Low HSE abundances in the lunar crust, coupled with estimates of HSE concentrations in the lunar mantle implies there may be a 'missing component' of late-accreted materials (as much as 95%) to the Moon if the Earth/Moon mass-flux estimates are correct and terrestrial mantle HSE abundances were established by late accretion. ?? 2009 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗

Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35??years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9??wt.%, with temperatures prior to quench ranging from 1140????C to ambient (110????C). Five eruption samples were also analyzed. Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006-1.40??ppb for Os and 0.0006-2.01??ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples. Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials. Estimated mineral (olivine + chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~ 7 to 27??wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar. Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained. ?? 2008 Elsevier B.V.

Chemical Geology↗

Osmium isotope and highly siderophile element systematics of lunar impact melt breccias: Implications for the late accretion history of the Moon and Earth

To characterize the compositions of materials accreted to the Earth-Moon system between about 4.5 and 3.8 Ga, we have determined Os isotopic compositions and some highly siderophile element (HSE: Re, Os, Ir, Ru, Pt, and Pd) abundances in 48 subsamples of six lunar breccias. These are: Apollo 17 poikilitic melt breccias 72395 and 76215; Apollo 17 aphanitic melt breccias 73215 and 73255; Apollo 14 polymict breccia 14321; and lunar meteorite NWA482, a crystallized impact melt. Plots of Ir versus other HSE define excellent linear correlations, indicating that all data sets likely represent dominantly two-component mixtures of a low-HSE target, presumably endogenous component, and a high-HSE, presumably exogenous component. Linear regressions of these trends yield intercepts that are statistically indistinguishable from zero for all HSE, except for Ru and Pd in two samples. The slopes of the linear regressions are insensitive to target rock contributions of Ru and Pd of the magnitude observed; thus, the trendline slopes approximate the elemental ratios present in the impactor components contributed to these rocks. The 187Os/188Os and regression-derived elemental ratios for the Apollo 17 aphanitic melt breccias and the lunar meteorite indicate that the impactor components in these samples have close affinities to chondritic meteorites. The HSE in the Apollo 17 aphanitic melt breccias, however, might partially or entirely reflect the HSE characteristics of HSE-rich granulitic breccia clasts that were incorporated in the impact melt at the time of its creation. In this case, the HSE characteristics of these rocks may reflect those of an impactor that predated the impact event that led to the creation of the melt breccias. The impactor components in the Apollo 17 poikilitic melt breccias and in the Apollo 14 breccia have higher 187Os/188Os, Pt/Ir, and Ru/Ir and lower Os/Ir than most chondrites. These compositions suggest that the impactors they represent were chemically distinct from known chondrite types, and possibly represent a type of primitive material not currently delivered to Earth as meteorites. ?? 2008 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

Effects of mother lode-type gold mineralization on 187Os/188Os and platinum group element concentrations in peridotite: Alleghany District, California

Osmium isotope compositions and concentrations of Re, platinum group elements (PGE), and Au were determined for host peridotites (serpentinites and barzburgites) and hydrothermally altered ultramafic wall rocks associated with Mother Lode-type hydrothermal gold-quartz vein mineralization in the Alleghany district, California. The host peridotites have Os isotope compositions and Re, PGE, and Au abundances typical of the upper mantle at their presumed formation age during the late Proterozoic or early Paleozoic. The hydrothermally altered rocks have highly variable initial Os isotope compositions with ??os, values (% deviation of 187OS/188OS from the chondritic average calculated for the approx. 120 Ma time of mineralization) ranging from -1.4 to -8.3. The lowest Os isotope compositions are consistent with Re depletion of a chondritic source (e.g., the upper mantle) at ca. 1.6 Ga. Most of the altered samples are enriched in Au and have depleted and fractionated abundances of Re and PGE relative to their precursor peridotites. Geoehemical characteristics of the altered samples suggest that Re and some PGE were variably removed from the ultramafic rocks during the mineralization event. In addition to Re, the Pt and Pd abundances of the most intensely altered rocks appear to have been most affected by mineralization. The 187Os-depleted isotopic compositions of some altered rocks are interpreted to be a result of preferential 187Os loss via destruction of Re-rich phases during the event. For these rocks, Os evidently is not a useful tracer of the mineralizing fluids. The results do, however, provide evidence for differential mobility of these elements, and mobility of 187Os relative to the initial bulk Os isotope composition during hydrothermal metasomatic alteration of ultramafic rocks. ?? 2007 Society of Economic Geologists, Inc.

Economic Geology↗

Confirmation of a meteoritic component in impact-melt rocks of the Chesapeake Bay impact structure, Virginia, USA - Evidence from osmium isotopic and PGE systematics

The osmium isotope ratios and platinum-group element (PGE) concentrations of impact-melt rocks in the Chesapeake Bay impact structure were determined. The impact-melt rocks come from the cored part of a lower-crater section of suevitic crystalline-clast breccia in an 823 m scientific test hole over the central uplift at Cape Charles, Virginia. The 187Os/188Os ratios of impact-melt rocks range from 0.151 to 0.518. The rhenium and platinum-group element (PGE) concentrations of these rocks are 30-270?? higher than concentrations in basement gneiss, and together with the osmium isotopes indicate a substantial meteoritic component in some impact-melt rocks. Because the PGE abundances in the impact-melt rocks are dominated by the target materials, interelemental ratios of the impact-melt rocks are highly variable and nonchondritic. The chemical nature of the projectile for the Chesapeake Bay impact structure cannot be constrained at this time. Model mixing calculations between chondritic and crustal components suggest that most impact-melt rocks include a bulk meteoritic component of 0.01-0.1% by mass. Several impact-melt rocks with lowest initial 187Os/188Os ratios and the highest osmium concentrations could have been produced by additions of 0.1%-0.2% of a meteoritic component. In these samples, as much as 70% of the total Os may be of meteoritic origin. At the calculated proportions of a meteoritic component (0.01-0.1% by mass), no mixtures of the investigated target rocks and sediments can reproduce the observed PGE abundances of the impact-melt rocks, suggesting that other PGE enrichment processes operated along with the meteoritic contamination. Possible explanations are 1) participation of unsampled target materials with high PGE abundances in the impact-melt rocks, and 2) variable fractionations of PGE during syn- to post-impact events. ?? The Meteoritical Society, 2006.

Meteoritics and Planetary Science↗

Sources of osmium to the modern oceans: New evidence from the 190Pt-186Os system

High precision Os isotope analysis of young marine manganese nodules indicate that whereas the composition of modern seawater is radiogenic with respect to 187Os/188Os, it has 186Os/188Os that is within uncertainty of the chondritic value. Marine Mn nodule compositions thus indicate that the average continental source of Os to modern seawater had long-term high Re/Os compared to Pt/Os. Analyses of loess and freshwater Mn nodules support existing evidence that average upper continental crust (UCC) has resolvably suprachondritic 186Os/188Os, as well as radiogenic 187Os/188Os. Modeling the composition of seawater as a two-component mixture of oceanic/cosmic Os with chondritic Os compositions and continentally-derived Os demonstrates that, insofar as estimates for the composition of average UCC are accurate, congruently weathered average UCC cannot be the sole continental source of Os to seawater. Our analysis of four Cambrian black shales confirm that organic-rich sediments can have 187Os/188Os ratios that are much higher than average UCC, but 186Os/188Os compositions that are generally between those of chondrites and average-UCC. Preferential weathering of black shales can result in dissolved Os discharged to the ocean basins that has a much lower 186Os/188Os than does average upper crust. Modeling the available data demonstrates that augmentation of estimated average UCC compositions with less than 0.1% additional black shale and 1.4% additional ultramafic rock can produce a continental end-member Os isotopic composition that satisfies the requirements imposed by the marine Mn nodule data. The interplay of these two sources provides a mechanism by which the 187Os/188Os of seawater can change as sources and weathering conditions change, yet seawater 186Os/188Os varies only minimally. ?? 2004 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

Highly siderophile elements in chondrites

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. ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗

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

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 (1?? 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 (1?? 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. ?? 2002 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

Rhenium-osmium systematics of calcium-aluminium-rich inclusions in carbonaceous chondrites

The Re-Os isotopic systematics of calcium-aluminium-rich inclusions (CAIs) in chondrites were investigated in order to shed light on the behavior of the Re-Os system in bulk chondrites, and to constrain the timing of chemical fractionation in primitive chondrites. CAIs with relatively unfractionated rare earth element (REE) patterns (groups I, III, V, VI) define a narrow range of 187Re/188Os (0.3764-0.4443) and 187Os/188Os (0.12599-0.12717), and high but variable Re and Os abundances (3209-41,820 ppb Os). In contrast, CAIs that show depletions in highly refractory elements and strongly fractionated REE patterns (group II) also show a much larger range in 187Re/188Os (0.409-0.535) and 187Os/188Os (0.12695-0.13770), and greater than an order of magnitude lower Re and Os abundances than other groups (e.g., 75.7-680.2 ppb Os). Sixteen bulk CAIs and CAI splits plot within analytical uncertainty of a 4558 Ga reference isochron, as is expected for materials of this antiquity. Eight samples, however, plot off the isochron. Several possible reasons for these deviations are discussed. Data for multiple splits of one CAI indicate that the nonisochronous behavior for at least this CAI is the result of Re-Os reequilibration at approximately 1.6 Ga. Thus, the most likely explanation for the deviations of most of the nonisochronous CAIs is late-stage open-system behavior of Re and Os in the asteroidal environment. The 187Os/188Os-Os systematics of CAIs are consistent with previous models that indicate group II CAIs are mixtures of components that lost the bulk of their highly refractory elements in a previous condensation event and a minor second component that provided refractory elements at chondritic relative proportions. The high Re/Os of group II CAIs relative to other CAIs and chondrite bulk rocks may have been caused by variable mobilization of Re and Os during medium- to low-temperature parent body alteration ??4.5 Ga ago. This model is favored over nebular models, which pose several difficulties. The narrow range of 187Os/188Os in group I, III, V, and VI bulk CAIs, and the agreement with 187Os/188Os of whole rock carbonaceous chondrites suggest that on a bulk inclusion scale, secondary alteration only modestly fractionated Re/Os in these CAIs. The average of 187Os/188Os for group I, III, V, and VI CAIs is indistinguishable from average CI chondrites, indicating a modern solar system value for 187Os/188Os of 0.12650, corresponding to a 187Re/188Os of 0.3964. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

Osmium isotopes demonstrate distal transport of contaminated sediments in Chesapeake Bay

Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post- Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post-Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.

Environmental Science & Technology↗

Re-Os isotopic systematics of primitive lavas from the Lassen region of the Cascade arc, California

Rhenium-osmium isotopic systematics of primitive calc-alkaline lavas from the Lassen region appear to be controlled by mantle wedge processes. Lavas with a large proportion of slab component have relatively low Re and Os abundances, and have radiogenic Os and mid ocean ridge basalt-like Sr and Pb isotopic compositions. Lavas with a small proportion of slab component have higher Re and Os elemental abundances and display mantle-like Os, Sr, Nd, and Pb isotopic compositions. Assimilation with fractional crystallization can only generate the Re-Os systematics of the Lassen lavas from a common parent if the distribution coefficient for Re in sulfide is ~40-1100 times higher than most published estimates and if most incompatible element abundances decrease during differentiation. High Re/Os ratios in mid ocean ridge basalts makes subducted oceanic crust a potential source of radiogenic Os in volcanic arcs. The slab beneath the southernmost Cascades is estimated to have 187Os/188Os ratios as high as 1.4. Mixing between a slab component and mantle wedge peridotite can generate the Os isotopic systematics of the Lassen lavas provided the slab component has a Sr/Os ratio of ~7.5X105 and Os abundances that are 100-600 times higher than mid ocean ridge basalts. For this model to be correct, Os must be readily mobilized and concentrated in the slab component, perhaps as a result of high water and HCl fugacities in this subduction environment. Another possible mechanism to account for the correlation between the magnitude of the subduction geochemical signature and Os isotopic composition involves increasing the stability of an Os-bearing phase in mantle wedge peridotites as a result of fluxing with the slab component. Melting of such a source could yield low Os magmas that are more susceptible to crustal contamination, and hence have more radiogenic Os isotopic compositions, than magmas derived from sources with a smaller contribution from the slab. Thus, the addition of the slab component to the mantle wedge appears to result in either the direct or indirect addition of radiogenic Os to arc magmas. (C) 2000 Elsevier Science B.V. All rights reserved.

Earth and Planetary Science Letters↗

The absence of lithium isotope fractionation during basalt differentiation: New measurements by multicollector sector ICP-MS

We report measurements of the isotopic composition of lithium in basalts using a multicollector magnetic sector plasma-source mass spectrometer (MC-ICP-MS). This is the first application of this analytical technique to Li isotope determination. External precision of multiple replicate and duplicate measurements for a variety of sample types averages ±1.1‰ (2σ population). The method allows for the rapid (∼8 min/sample) analysis of small samples (∼40 ng Li) relative to commonly used thermal ionization methods. The technique has been applied to a suite of samples from Kilauea Iki lava lake, Hawaii. The samples range from olivine-rich cumulitic lava to SiO 2 − and K 2 O-enriched differentiated liquids, and have δ 7 Li (per mil deviation of sample 7 Li/ 6 Li relative to the L-SVEC standard) of +3.0 to +4.8. The data indicate a lack of per mil-level Li isotope fractionation as a result of crystal–liquid fractionation at temperatures greater than 1050°C. This conclusion has been tacitly assumed but never demonstrated, and is important to the interpretation of Li isotope results from such geochemically complex environments as island arcs.

Hawai'i↗

Applications of the 190Pt-186Os isotope system to geochemistry and cosmochemistry

Platinum is fractionated from osmium primarily as a consequence of processes involving sulfide and metal crystallization. Consequently, the 190 Pt 186 Os isotope system ( 190 Pt → 186 Os + α) shows promise for dating some types of magmatic sulfide ores and evolved iron meteorites. The first 190 Pt 186 Os isochrons are presented here for ores from the ca. 251 Ma Noril'sk, Siberia plume, and for group IIAB magmatic iron meteorites. Given the known age of the Noril'sk system, a decay constant for 190 Pt is determined to be 1.542 × 10 −12 a −1 , with ±1% uncertainty. The isochron generated for the IIAB irons is consistent with this decay constant and the known age of the group. The 186 Os/ 188 Os ratios of presumably young, mantle-derived osmiridiums and also the carbonaceous chondrite Allende were measured to high-precision to constrain the composition of the modern upper mantle. These compositions overlap, indicating that the upper mantle is chondritic within the level of resolution now available. Our best estimate for this 186 Os/ 188 Os ratio is 0.119834 ± 2 (2σ M ). The 190 Pt/ 186 Os ratios determined for six enstatite chondrites average 0.001659 ± 75, which is very similar to published values for carbonaceous chondrites. Using this ratio and the presumed composition of the modern upper mantle and chondrites, a solar system initial 186 Os/ 188 Os ratio of 0.119820 is calculated. In comparison to the modern upper mantle composition, the 186 Os/ 188 Os ratio of the Noril'sk plume was approximately 0.012% enriched in 186 Os. Possible reasons for this heterogeneity include the recycling of Pt-rich crust into the mantle source of the plume and derivation of the osmium from the outer core. Derivation of the osmium from the outer core is our favored model.

Geochimica et Cosmochimica Acta↗

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 (São Julião 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 187 Re/ 188 Os measured in a IIA iron to date. The linear HA trend may be exactly reproduced by fractional crystallization with constant k Re and k Os , 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 São Julião de Moreira) lie beyond analytical uncertainty above the IIA iron isochron, averaging 8 ± 2% higher in 187 Os/ 188 Os. These irons may have crystallized significantly after the HA irons and Mount Joy, but only if the 187 Re/ 188 Os 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.

Geochimica et Cosmochimica Acta↗

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

Picrites from the Gudchikhinsky suite, the oldest rocks examined, have ??Os of +5.3 to +6.1 and ??Nd 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 an mantle plume. Picrites from the stratigraphically higher Tuklonsky suite have similar ??Os of +3.4 to +6.5, but ??Nd of -0.9 to -2.6. The similar ??Os, but lower ??Nd , suggest that some magmas from the same OIB-type, mantle source were contaminated by lithospheric components. A differentiated ankaramite flow, associated with the top of the stratigraphically higher Morongovsky suite, has ??Os of +9.8 to +10.2 and ??Nd of +1.3 to +1.4. The higher ??Os 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. Mg-rich, alkaline rocks (meymechites) from the Guli area that erupted much nearer the end of the flood-basalt event have ??Os of -1.2 to -2.6 and ??Nd 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. -from Authors

Geochimica et Cosmochimica Acta↗

Osmium-187 enrichment in some plumes: Evidence for core-mantle interaction?

Calculations with data for asteroidal cores indicate that Earth's outer core may have a rhenium/osmium ratio at least 20 percent greater than that of the chondritic upper mantle, potentially leading to an outer core with an osmium-187/osmium-188 ratio at least 8 percent greater than that of chondrites. Because of the much greater abundance of osmium in the outer core relative to the mantle, even a small addition of metal to a plume ascending from the D" layer would transfer the enriched isotopic signature to the mixture. Sources of certain plume-derived systems seem to have osmium-187/osmium-188 ratios 5 to 20 percent greater than that for chondrites, consistent with the ascent of a plume from the core-mantle boundary.

Science↗

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 Noril'sk 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 Noril'sk I intrusion have γ Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have γ Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have γ Os 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 Noril'sk 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 ϵ Nd 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. incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. persistence of primordial stratification of rhenium and osmium in the mantle.

Siberia↗

Rhenium-osmium isotope systematics in meteorites I: Magmatic iron meteorite groups IIAB and IIIAB

Using resonance ionization mass spectrometry (RIMS), Re and Os abundances were determined by isotope dilution (ID) and 187 Os/ 186 Os ratios measured in nineteen iron meteorites: eight from group IIAB, ten from group IIIAB, and Treysa (IIIB anomalous). Abundances range from 1.4 to 4800 ppb Re, and from 13 to 65000 ppb Os, and generally agree well with previous ID and neutron activation (NAA) results. The Re and Os data suggest that abundance trends in these iron groups may be entirely explained by fractional crystallization. Addition of late-formed metal to produce Re Os variation in the B subgroups is not essential but cannot be excluded. Whole-rock isochrons for the IIAB and IIIAB groups are statistically indistinguishable. Pooled data yield an initial 187 Os/ 186 Os of 0.794 ± 0.010, with a slope of (7.92 ± 0.20) × 10 −2 corresponding to a magmatic iron meteorite age of 4.65 ± 0.11 Ga (using a decay constant of 1.64 × 10 −11 a −1 ). Given the errors in the slope and half life, this age does not differ significantly from the canonical chondrite age of 4.56 Ga, but could be as young as 4.46 Ga.

Earth and Planetary Science Letters↗