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Globally distributed kimberlites with broadly chondritic initial (143)Nd-(176)Hf isotopic systematics may be derived from a chemically homogenous, relatively primitive mantle source that remained isolated from the convecting mantle for much of the Earth’s history. To assess whether this putative reservoir may have preserved remnants of an early Earth process, we report (182)W/(184)W and (142)Nd/(144)Nd data for “primitive” kimberlites from 10 localities worldwide, ranging in age from 1,153 to 89 Ma. Most are characterized by homogeneous μ(182)W and μ(142)Nd values averaging −5.9 ± 3.6 ppm (2SD, n = 13) and +2.7 ± 2.9 ppm (2SD, n = 6), respectively. The remarkably uniform yet modestly negative μ(182)W values, coupled with chondritic to slightly suprachondritic initial (143)Nd/(144)Nd and (176)Hf/(177)Hf ratios over a span of nearly 1,000 Mya, provides permissive evidence that these kimberlites were derived from one or more long-lived, early formed mantle reservoirs. Possible causes for negative μ(182)W values among these kimberlites include the transfer of W with low μ(182)W from the core to the mantle source reservoir(s), creation of the source reservoir(s) as a result of early silicate fractionation, or an overabundance of late-accreted materials in the source reservoir(s). By contrast, two younger kimberlites emplaced at 72 and 52 Ma and characterized by distinctly subchondritic initial (176)Hf/(177)Hf and (143)Nd/(144)Nd have μ(182)W values consistent with the modern upper mantle. These isotopic compositions may reflect contamination of the ancient kimberlite source by recycled crustal components with μ(182)W ≥ 0.

International audience; Rhenium-Os, Ptsingle bondOs, Smsingle bondNd, Lusingle bondHf, and Hfsingle bondW isotope data, together with lithophile trace element and highly siderophile element (HSE: Re, Os, Ir, Ru, Pt, and Pd) abundances, are reported for 2.05 Ga Jeesiörova and Kevitsa komatiites from the Central Lapland Greenstone Belt, Fennoscandia, Finland. Both komatiites are closely genetically related, with the Kevitsa dikes having served as feeding magma conduits to the Jeesiörova pillowed and massive lavas. The parental komatiite magma is estimated to have contained ~25 wt% MgO and was, thus, derived from a mantle source at least as hot as those of some of its late Archean counterparts. A suite of Jeesiörova and Kevitsa whole-rock komatiite samples and olivine and chromite separates define an internal Resingle bondOs isochron with an age of 2049 ± 13 Ma and an initial γ187Os = −0.2 ± 0.2 (2SE), indicating long-term chondritic Re/Os in the mantle source. By contrast, Ptsingle bondOs data for a set of Jeesiörova chromite separates define an average initial μ186Os = +29 ± 2 (2SE), indicating a long-term history of suprachondritic Pt/Os in the mantle source. The absolute HSE abundances in the mantle source of the Jeesiörova-Kevitsa komatiite system are estimated to have been 120 ± 5% of the present-day Bulk Silicate Earth (BSE). This is the first komatiite system for which excess HSE in the mantle source, relative to modern BSE, has been documented.The 147Smsingle bond143Nd and 176Lusingle bond176Hf data yield isochron ages and initial ratios of, respectively, 2046 ± 22 Ma with ε143Nd = +3.7 ± 0.3, and 2072 ± 20 Ma with ε176Hf = +8.7 ± 0.4 (2SE), indicating a long-term history of depletions of Nd relative to Sm, and Hf relative to Lu. The measured μ182W = +1.5 ± 3.3 is indistinguishable from the modern mantle value. Despite being strongly depleted in highly incompatible lithophile trace elements, the Th-Nb-La systematics of the komatiites indicate ~1% crustal contamination of the original komatiite magma, assuming the contaminant was similar in composition to the calculated Fennoscandian Tonalite Average (FTA). This level of contamination would have also significantly modified the Nd, Hf, and W isotope compositions of the original komatiitic magma, but not the Os isotope compositions or HSE abundances. The calculated original komatiite magma, corrected for the effects of crustal contamination, would have had initial ε143Nd ~ +4.9, ε176Hf ~ +10.2, and μ182W ~ −10.Our modeling indicates that the initial 186,187Os/188Os isotopic compositions and suprachondritic HSE abundances, coupled with the projected negative μ182W, are best explained by either (1) derivation from a mantle domain characterized by an excess of late accreted, differentiated planetesimal core metal, i.e., “grainy” late accretion, or (2) addition of chemically fractionated terrestrial core metal to the mantle source domain of the komatiites. The presence of these characteristics in the Jeesiörova-Kevitsa komatiite mantle source provides further evidence for the early creation and long-term survival of chemically diverse domains within the mantle.

Neodymium-142 isotope data from young Reunion Island volcanic rocks reflect the effects of geological processes that occurred more than four billion years ago, showing that the deep mantle may preserve geochemical signatures of the primordial Earth. Certain volcanic hotspots are thought to sample sections of Earth's deep interior that were formed more than two billion years ago, with some having witnessed differentiation events—the separation of planetary materials into chemically distinct regions, such as the core and mantle—that occurred within the first 50 million years of Earth's history. Bradley Peters and colleagues report neodymium isotopic data from Reunion Island volcanic rocks. The data correlate with helium isotopic data, suggesting parallel behaviour of the isotopic systems during silicate differentiation, perhaps as early as 4.39 billion years ago. They conclude that Reunion magmas tap an unusually ancient, primitive source compared to other volcanic hotspots, which could offer a window into the formation and preservation of ancient heterogeneities in Earth's interior. Active volcanic hotspots can tap into domains in Earth’s deep interior that were formed more than two billion years ago1,2. High-precision data on variability in tungsten isotopes have shown that some of these domains resulted from differentiation events that occurred within the first fifty million years of Earth history3,4. However, it has not proved easy to resolve analogous variability in neodymium isotope compositions that would track regions of Earth’s interior whose composition was established by events occurring within roughly the first five hundred million years of Earth history5,6. Here we report 142Nd/144Nd ratios for Reunion Island igneous rocks, some of which are resolvably either higher or lower than the ratios in modern upper-mantle domains. We also find that Reunion 142Nd/144Nd ratios correlate with helium-isotope ratios (3He/4He), suggesting parallel behaviour of these isotopic systems during very early silicate differentiation, perhaps as early as 4.39 billion years ago. The range of 142Nd/144Nd ratios in Reunion basalts is inconsistent with a single-stage differentiation process, and instead requires mixing of a conjugate melt and residue formed in at least one melting event during the Hadean eon, 4.56 billion to 4 billion years ago. Efficient post-Hadean mixing nearly erased the ancient, anomalous 142Nd/144Nd signatures, and produced the relatively homogeneous 143Nd/144Nd composition that is characteristic of Reunion basalts. Our results show that Reunion magmas tap into a particularly ancient, primitive source compared with other volcanic hotspots7,8,9,10, offering insight into the formation and preservation of ancient heterogeneities in Earth’s interior.

New Sm-Nd, Lu-Hf, Hf-W, and Re-Os isotope data, in combination with highly siderophile element (HSE, including Re, Os, Ir, Ru, Pt, and Pd) and W abundances, are reported for the 3.55 Ga Schapenburg komatiites, South Africa. The Schapenburg komatiites define a Re-Os isochron with an age of 3550 ± 87 Ma and initial γ187Os = +3.7 ± 0.2 (2SD). The absolute HSE abundances in the mantle source of the Schapenburg komatiite system are estimated to be only 29 ± 5% of those in the present-day bulk silicate Earth (BSE). The komatiites were derived from mantle enriched in the decay products of the long-lived 147Sm and 176Lu nuclides (initial ɛ143Nd = +2.4 ± 0.1, ɛ176Hf = +5.7 ± 0.3, 2SD). By contrast, the komatiites are depleted, relative to the modern mantle, in 142Nd and 182W (μ182W = −8.4 ± 4.5, μ142Nd = −4.9 ± 2.8, 2SD). These results constitute the first observation in terrestrial rocks of coupled depletions in 142Nd and 182W. Such isotopic depletions require derivation of the komatiites from a mantle domain that formed within the first ∼30 Ma of Solar System history and was initially geochemically enriched in highly incompatible trace elements as a result of crystal-liquid fractionation in an early magma ocean. This mantle domain further must have experienced subsequent melt depletion, after 182Hf had gone extinct, to account for the observed initial excesses in 143Nd and 176Hf. The survival of early-formed 182W and 142Nd anomalies in the mantle until at least 3.55 Ga indicates that the products of early planetary differentiation survived both later planetary accretion and convective mantle mixing during the Hadean. This work moreover renders unlikely that variable late accretion, by itself, can account for all of the observed W isotope variations in Archean rocks.

Several nucleosynthetic processes contributed material to the Solar System, but the relative contributions of each process, the timing of their input into the solar nebula, and how well these components were homogenized in the solar nebula remain only partially constrained. The Ba isotope system is particularly useful in addressing these issues because Ba isotopes are synthesized via three nucleosynthetic processes (s-, r-, p-process). In this study, high precision Ba isotope analyses of 22 different whole rock chondrites and achondrites (carbonaceous chondrites, ordinary chondrites, enstatite chondrites, Martian meteorites, and eucrites) were performed to constrain the distribution of Ba isotopes on the regional scale in the Solar System. A melting method using aerodynamic levitation and CO2-laser heating was used to oxidize SiC, a primary carrier of Ba among presolar grains in carbonaceous chondrites. Destruction of these grains during the fusion process enabled the complete digestion of these samples. The Ba isotope data presented here are thus the first for which complete dissolution of the bulk meteorite samples was certain. Enstatite chondrites, ordinary chondrites, and all achondrites measured here possess Ba isotope compositions that are not resolved from the terrestrial composition. Barium isotope anomalies are evident in most of the carbonaceous chondrites analyzed, but the 135Ba anomalies are generally smaller than previously reported for similarly sized splits of CM2 meteorites. Variation in the size of the 135Ba anomaly is also apparent in fused samples from the same parent body (e.g., CM2 meteorites) and in different pieces from the same meteorite (e.g., Orgueil, CI). Here, we investigate the potential causes of variability in 135Ba, including the contribution of radiogenic 135Ba from the decay of 135Cs and incomplete homogenization of the presolar components on the

co-auteur étranger; International audience; Taking the example of Nd, we present a method based on a 4-mass-step acquisition scheme to measure all isotope ratios dynamically by thermal ionization mass spectrometry (TIMS); the aim being to minimize the dependency of all mass fractionation-corrected ratios on collector efficiencies and amplifier gains. The performance of the method was evaluated from unprocessed JNdi-1 Nd standards analyzed in multiple sessions on three different instruments over a period of ~ 1.5 years (n = 61), as well as from standards (18 JNdi-1 and 19 BHVO-2) processed through different chemical purification procedures. The Nd isotopic compositions of standards processed through fine-grained (25–50 μm) Ln-spec resin show a subtle but clear fractionation caused by the nuclear field shift effect. This effect contributes to the inaccuracy of Nd isotope measurements at the ppm level of precision.Following a comprehensive evaluation of the mass spectrometer runs, we suggest several criteria to assess the quality of data acquired by TIMS, in particular to see whether the measurements were affected by domain mixing effects on the filaments. We define maximum tolerable Ce and Sm interference corrections and the minimum number of ratios to acquire to ensure the best possible accuracy and precision for all Nd isotope ratios. Changes in fractionation of Nd isotope ratios in between acquisition steps can result in significant inaccuracy and bias dynamic μ142 values by > 15 ppm. To correct for these effects, we developed a systematic drift-correction based on the monitoring of Nd isotope ratios through time. The residual components of scatter in the JNdi-1 and BHVO-2 datasets were further investigated in binary isotopic plots in which we modeled the theoretical effects of domain mixing on filaments, nuclear field shift and correlated errors from counting statistics using Monte-Carlo simulations. These plots indicate that the 4-step method returns precisions limited by counting errors only for drift-corrected dynamic Nd isotope ratios. Data acquired on three different TIMS instruments suggest the following composition for the JNdi-1 reference standard: 142Nd/144Nd = 1.141832 ± 0.000006 (2s), 143Nd/144Nd = 0.512099 ± 0.000005 (2s), 145Nd/144Nd = 0.348403 ± 0.000003 (2s), 148Nd/144Nd = 0.241581 ± 0.000003 (2s), and 150Nd/144Nd = 0.236452 ± 0.000006 (2s) when normalized to 146Nd/144Nd = 0.7219. Measurements performed on different instruments (Triton™ vs. Triton Plus™) show resolvable differences of about 10 ppm for absolute 143Nd/144Nd, 145Nd/144Nd and 148Nd/144Nd ratios. The different criteria and corrections developed in this study could be applied to other isotopic systematics to improve and better evaluate the quality of high-precision data acquired by TIMS.

Active volcanic hotspots can tap into domains in Earth's deep interior that were formed more than two billion years ago. High-precision data on variability in tungsten isotopes have shown that some of these domains resulted from differentiation events that occurred within the first fifty million years of Earth history. However, it has not proved easy to resolve analogous variability in neodymium isotope compositions that would track regions of Earth's interior whose composition was established by events occurring within roughly the first five hundred million years of Earth history. Here we report

This paper presents geophysical and geochemical evidence for the possible existence of cold, subducted lithosphere beneath the Saint Paul Fracture Zone of the Equatorial Atlantic Ocean. The ocean floor along the fracture zone is characterized by a high percentage of abyssal peridotites. The abyssal peridotites were emplaced by tectonic uplift of the oceanic lithosphere. The top of the ridge is exposed at Saint Peter and Saint Paul islets. The Os isotopic composition of these abyssal peridotites indicate the presence of old depleted mantle material in this region with Re-depletion model ages (T RD) from 0.32 to 1.1Ga. Melt inclusions in plagioclase phenocrysts of the MORB close to this location have boninitic composition, suggesting that some basalts originated from low-degree mantle melting. The global tomography models show fast seismic velocities in the upper and lower mantle of the Equatorial Atlantic Ocean, consistent with the presence of cold subducted lithosphere. The range of Re-depletion model ages are consistent with paleo-reconstructions of plate motion, suggesting that the fossil subducted slab was formed during the closure of both the Iapetus and the Rheic oceans. O presente trabalho mostra evidências geofísicas e geoquímicas para a possível existência de fragmentos frios do manto originados da placa subductada abaixo da Zona de Fratura de São Paulo no Oceano Atlântico Equatorial. A planície abissal desta área é caracterizada por uma abundância de rochas peridotíticas, com presença de poucas rochas basálticas originadas de baixo grau de fusão parcial. Arquipélago de São Pedro e São Paulo se localiza no topo de uma elevação morfológica com mais de 4000m de altura, constituída por peridotitos abissais, posicionados por um soerguimento tectônico da litosfera oceânica. A razão isotópica de Os dos peridotitos da Zona de Fratura de São Paulo indica a presença de materiais originados de antigo manto depletado nesta região com as idades modelo de 0.32 a 1.1Ga. As inclusões de magma trapeadas nos fenocristais de plagioclásio nos basalto da cadeia meso-oceânica pouco mais ao sul apresentam composição boninítica, típicas de zona de arco. Os modelos da tomografia mundial do manto demonstram alta velocidade sísmica tanto no manto superior quanto no inferior do Oceano Atlântico Equatorial, o que corrobora a interpretação da presença de placa subductada de baixa temperatura. As idades do modelo de depleção de Re dos peridotitos são consistentes com a reconstituição de movimento das placas, sugerindo que os fragmentos de placa fóssil subductada são provenientes do fechamento tanto do Oceano Iapetus como o do Oceano Rheic.

We report new data for W concentrations, stable W isotopic compositions, high-precision 182W/184W ratios, highly siderophile element (HSE) abundances and 187Re–187Os systematics in a suite of 3.8–3.3 Ga mafic and ultramafic rocks from the Isua supracrustal belt, and the Paleoarchean terrane in the northwestern part of the belt. These data are compared with published data for 146Sm–142Nd systematics in the same samples. The samples from the Isua supracrustal belt show well resolved excesses of 182W/184W of up to ∼21 ppm, consistent with previous W isotopic data reported by Willbold et al. (2011) . While there is abundant evidence that W was mobilized in the crust accessed by the Isua supracrustal suite, the isotopic anomalies are interpreted to primarily reflect processes that affected the mantle precursors to these rocks. The origin of the 182W excesses in these rocks remains uncertain. The Isua mantle source could represent a portion of the post-core-formation mantle that was isolated from late accretionary additions (e.g., Willbold et al., 2011 ). However, the combined 182W, Re–Os isotopic systematics and HSE abundances estimated for the source of the Isua basalts are difficult to reconcile with this interpretation. The W isotope variations were more likely produced as a result of fractionation of the Hf/W ratio in the mantle during the lifetime of 182Hf, i.e., during the first 50 Ma of Solar System history. This could have occurred as a result of differentiation in an early magma ocean. The Isua suite examined is also characterized by variable 142Nd/144Nd, but the variations do not correlate with the variations in 182W/184W. Further, samples with ages between 3.8 and 3.3 Ga show gradual diminution of 142Nd anomalies until these are no longer resolved from the modern mantle isotopic composition. By contrast, there is no diminishment of 182W variability with time, suggesting different mechanisms of origin and retention of isotopic variations for these two extinct-radionuclide isotope systems. The presence of 182W isotopic anomalies in rocks as young as 3.3 Ga, implies that early-formed, high Hf/W domains survived for more than 1 Ga in the convective mantle.

This paper presents an improved technique for the precise and accurate determination of Ag isotopic composition in geologic samples. Following the separation of Ag from the rock matrix with a three-stage ion exchange procedure, the isotopic composition is measured by MC-ICPMS. Instrumental mass bias is corrected externally using a Pd standard, which was added to each sample, and sample-standard bracketing. The use of wet plasma significantly improves the analytical precision by eliminating variations in fractionation between Pd and Ag. A virtually identical behavior of the mass bias for Pd and Ag during the analyses is a prerequisite for the external correction method. Replicate dissolutions of the carbonaceous chondrite Allende with

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 Earth's core formed from several large impact events. Science , this issue p. 809 ; see also p. 768

International audience; We have measured Sm–Nd systematics, including the short-lived 146Sm–142Nd chronometer, in lunar ferroan anorthositic suite (FAS) whole rocks (15415, 62236, 62255, 65315, 60025). At least some members of the suite are thought to be primary crystallization products formed by plagioclase flotation during crystallization of the lunar magma ocean (LMO). Most of these samples, except 62236, have not been exposed to galactic cosmic rays for a long period and thus require minimal correction to their 142Nd isotope composition. These samples all have measured deficits in 142Nd relative to the JNdi-1 terrestrial standard in the range −45 to −21 ppm. The range is −45 to −15 ppm once the 62236 142Nd/144Nd ratio is corrected from neutron-capture effects. Analyzed FAS samples do not define a single isochron in either 146Sm–142Nd or 147Sm–143Nd systematics, suggesting that they either do not have the same crystallization age, come from different sources, or have suffered isotopic disturbance. Because the age is not known for some samples, we explore the implications of their initial isotopic compositions for crystallization ages in the first 400 Ma of solar system history, a timing interval that covers all the ages determined for the ferroan anorthositic suite whole rocks as well as different estimates for the crystallization of the LMO. 62255 has the largest deficit in initial 142Nd and does not appear to have followed the same differentiation path as the other FAS samples. The large deficit in 142Nd of FAN 62255 may suggest a crystallization age around 60–125 Ma after the beginning of solar system accretion. This result provides essential information about the age of the giant impact forming the Moon. The initial Nd isotopic compositions of FAS samples can be matched either with a bulk-Moon with chondritic Sm/Nd ratio but enstatite-chondrite-like initial 142Nd/144Nd (e.g. 10 ppm below modern terrestrial), or a bulk-Moon with superchondritic Sm/Nd ratio and initial 142Nd/144Nd similar to ordinary chondrites.

The great majority of continental flood basalts (CFBs) have a marked lithospheric geochemical signature, suggesting derivation from the continental lithosphere, or contamination by it. Here we present new Pb and Os isotopic data and review previously published major element, trace element, mineral chemical, and Sr and Nd isotopic data for geochemically unusual mafic and ultramafic dikes located in the Antarctic segment (Ahlmannryggen, western Dronning Maud Land) of the Karoo CFB province. Some of the dikes show evidence of minor contamination with continental crust, but the least contaminated dikes exhibit depleted mantle –like initial εNd (+9) and 187Os/188Os (0.1244–0.1251) at 180 Ma. In contrast, their initial Sr and Pb isotopic compositions (87Sr/86Sr = 0.7035–0.7062, 206Pb/204Pb = 18.2–18.4, 207Pb/204Pb = 15.49–15.52, 208Pb/204Pb = 37.7–37.9 at 180 Ma) are more enriched than expected for depleted mantle, and the major element and mineral chemical evidence indicate contribution from (recycled) pyroxenite sources. Our Sr, Nd, Pb, and Os isotopic and trace element modeling indicate mixed peridotite-pyroxenite sources that contain ~10–30 % of seawater-altered and subduction-modified MORB with a recycling age of less than 1.0 Ga entrained in a depleted Os-rich peridotite matrix. Such a source would explain the unusual combination of elevated initial 87Sr/86Sr and Pb isotopic ratios and relative depletion in LILE, U, Th, Pb and LREE, high initial εNd, and low initial 187Os/188Os. Although the sources of the dikes probably did not play a major part in the generation of the Karoo CFBs in general, different kind of recycled source components (e.g., sediment-influenced) would be more difficult to distinguish from lithospheric CFB geochemical signatures. In addition to underlying continental lithosphere, the involvement of recycled sources in causing the apparent lithospheric geochemical affinity of CFBs should thus be carefully assessed in every case. The great majority of continental flood basalts (CFBs) have a marked lithospheric geochemical signature, suggesting derivation from the continental lithosphere, or contamination by it. Here we present new Pb and Os isotopic data and review previously published major element, trace element, mineral chemical, and Sr and Nd isotopic data for geochemically unusual mafic and ultramafic dikes located in the Antarctic segment (Ahlmannryggen, western Dronning Maud Land) of the Karoo CFB province. Some of the dikes show evidence of minor contamination with continental crust, but the least contaminated dikes exhibit depleted mantle –like initial εNd (+9) and 187Os/188Os (0.1244–0.1251) at 180 Ma. In contrast, their initial Sr and Pb isotopic compositions (87Sr/86Sr = 0.7035–0.7062, 206Pb/204Pb = 18.2–18.4, 207Pb/204Pb = 15.49–15.52, 208Pb/204Pb = 37.7–37.9 at 180 Ma) are more enriched than expected for depleted mantle, and the major element and mineral chemical evidence indicate contribution from (recycled) pyroxenite sources. Our Sr, Nd, Pb, and Os isotopic and trace element modeling indicate mixed peridotite-pyroxenite sources that contain ~10–30 % of seawater-altered and subduction-modified MORB with a recycling age of less than 1.0 Ga entrained in a depleted Os-rich peridotite matrix. Such a source would explain the unusual combination of elevated initial 87Sr/86Sr and Pb isotopic ratios and relative depletion in LILE, U, Th, Pb and LREE, high initial εNd, and low initial 187Os/188Os. Although the sources of the dikes probably did not play a major part in the generation of the Karoo CFBs in general, different kind of recycled source components (e.g., sediment-influenced) would be more difficult to distinguish from lithospheric CFB geochemical signatures. In addition to underlying continental lithosphere, the involvement of recycled sources in causing the apparent lithospheric geochemical affinity of CFBs should thus be carefully assessed in every case.

— The platinum group elements (PGE; Ru, Rh, Pd, Os, Ir, Pt), Re and Au comprise the highly siderophile elements (HSE). We reexamine selected isotopic and abundance data sets for HSE in upper mantle peridotites to resolve a longstanding dichotomy. Re-Os and Pt-Os isotope systematics, and approximately chondritic proportions of PGE in these rocks, suggest the presence in undepleted mantle of a chondrite-like component, which is parsimoniously explained by late influx of large planetisimals after formation of the Earth's core and the Moon. But some suites of xenolithic and orogenic spinel lherzolites, and abyssal peridotites, have a CI-normalized PGE pattern with enhanced Pd that is sometimes termed “non-chondritic”. We find that this observation is consistent with other evidence of a late influx of material more closely resembling enstatite, rather than ordinary or carbonaceous, chondrites. Regional variations in HSE patterns may be a consequence of a late influx of very large objects of variable composition. Studies of many ancient (>3.8 Ga) lunar breccias show regional variations in Au/Ir and suggest that “graininess” existed during the early bombardment of the Earth and Moon. Reliable Pd values are available only for Apollo 17 breccias 73215 and 73255, however. Differences in HSE patterns between the aphanitic and anorthositic lithologies in these breccias show fractionation between a refractory group (Re, Os and Ir) and a normal (Pd, Ni, and Au) group and may reflect the compositions of the impacting bodies. Similar fractionation is apparent between the EH and EL chondrites, whose PGE patterns resemble those of the aphanitic and anorthositic lithologies, respectively. The striking resemblance of HSE and chalcogen (S, Se) patterns in the Apollo aphanites and high-Pd terrestrial peridotites suggest that the “non-chondritic” abundance ratios in the latter may be reflected in the composition of planetisimals striking the Moon in the first 700 Ma of Earth–Moon history. Most notably, high Pd may be part of a general enhancement of HSE more volatile than Fe suggesting that the Au abundance in at least parts of the upper mantle may be 1.5 to 2x higher than previously estimated. The early lunar influx may be estimated from observed basin-sized craters. Comparison of relative influx to Earth and Moon suggests that the enrichment of HSE is limited to the upper mantle above 670 km. To infer enrichment of the whole mantle would require several large lunar impacts not yet identified.

Chromite separates within the Peridotite Zone of the 2,700 Ma-old Stillwater Complex are characterized by low 187Re/188Os (0.009 to 1.74) and relatively high Os concentrations (8.74 to 78.2 ppb). Their calculated initial Os isotopic compositions likely reflect the compositions of the magmas from which they crystallized. The chromites show variable initial Os isotopic compositions (γOs of +2.0 to +16.4) over the vertical extent of the Peridotite Zone, implicating at least two sources of Os. Both the range of γOs and values of γOs decrease upsection. These variations in γOs were caused by mixing of variable proportions of two magmas having different Os isotopic compositions. One of the magmatic components was a more primitive magma with a nearly chondritic Os isotopic composition. The other magma had a radiogenic Os isotopic composition as a result of assimilation of crust, perhaps of sedimentary rocks beneath the Stillwater Complex. The gradual decrease in the initial γOs values of the chromite layers with increasing stratigraphic height implies a decreasing relative contribution from the contaminated magma throughout the growth of the Peridotite Zone. Small variations in γOs between different chromite occurrences within the H multicyclic unit reflects the petrologic requirement that chromite layers crystallize from slightly different proportions of the magmas, compared to chromite from olivine- and orthopyroxene-rich layers.

Advances in the chemical, crystallographic and isotopic characterisation of geological and environmental materials can often be ascribed to technological improvements in analytical hardware or to innovative approaches to data acquisition and/or its interpretation. This biennial review addresses key laboratory methods that form much of the foundation for analytical geochemistry; again, this contribution is presented as a compendium of laboratory techniques. We highlight advances that have appeared since January 2012 and that are of particular significance for the chemical and isotopic characterisation of geomaterials. Prominent scientists from the selected analytical fields present publications they judge to be particular noteworthy, providing background information about the method and assessing where further opportunities might be anticipated. In addition to the well-established technologies such as thermal ionisation mass spectrometry and plasma emission spectroscopy, this publication also presents new or rapidly growing methods such as electron backscattered diffraction analysis and atom probe tomography – a very sensitive method providing atomic scale information.

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-l88 ratios 5 to 20 percent greater than that for chondrites, consistent with the ascent of a plume from the core-mantle boundary.

Advances in the chemical and isotopic characterisation of geological and environmental materials can often be ascribed to technological improvements in analytical hardware. Equally, the creation of novel methods of data acquisition and interpretation, including access to better reference materials, can also be crucial components enabling important breakthroughs. This biennial review highlights key advances in either instrumentation or data acquisition and treatment, which have appeared since January 2010. This review is based on the assessments by scientists prominent in each of the given analytical fields; it is not intended as an exhaustive summary, but rather provides insight from experts of the most significant advances and trends in their given field of expertise. In contrast to earlier reviews, this presentation has been formulated into a unified work, providing a single source covering a broad spectrum of geoanalytical techniques. Additionally, some themes that were not previously emphasised, in particular thermal ionisation mass spectrometry, accelerator-based methods and vibrational spectroscopy, are also presented in detail.

Earth's Silver Lining The age of the oldest rocks on Earth's surface is controversial, but, even if they are at their oldest estimate, hundreds of millions of years in our planet's earliest history are still missing. However, in some rocks that until relatively recently resided in the mantle, the isotopic signature from the time of Earth's 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.

Isotopic variability in barium, neodymium, and samarium in carbonaceous chondrites reflects the distinct stellar nucleosynthetic contributions to the early solar system. We used 148 Nd/ 144 Nd to correct for the observed s-process deficiency, which produced a chondrite 146 Sm- 142 Nd isochron consistent with previous estimates of the initial solar system abundance of 146 Sm and a 142 Nd/ 144 Nd 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 142 Nd in chondrites relative to terrestrial rocks reflects 146 Sm decayand earlyplanetary differentiation processes.

Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately +/-31 million years for meteorites approximately 4500 million years old. Although an absolute rheniumosmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of (187)Re, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isocbron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.