Highly Siderophile Elements Abundances Research Articles

Significance of highly siderophile element and Re–Os isotope systematics in global carbonatites

The systematics of highly siderophile elements (HSE) in carbonatites have rarely been investigated although carbonatite melts are among key metasomatic agents in the Earth's mantle. Thus, establishing the Os isotope systematics of carbonatites is of prime importance because carbonatite metasomatism might play a determining role in driving 187Os/188Os signature of the Earth's mantle as a consequence of extreme mobility of carbonatite liquids. In this study, a suite of carbonatites from continental settings was analyzed for HSE abundances and Re–Os isotope systematics, combined with detailed petrography of sulfide phases, to provide constraints on the HSE behavior during the formation of carbonatite melts, the role of sulfides in distribution of HSE and the reliability of Re–Os isotope compositions. All investigated carbonatites display low ΣHSE <1 ppb whereby calciocarbonatites exhibit supra-chondritic OsN/IrN ratios from ∼1.4 to 15, in contrast to magnesiocarbonatites and Mg/Fe-rich carbonatites showing exclusively sub-chondritic OsN/IrN. We posit that preferential removal of Os over Ir during the segregation of calcite-normative melts from the co-existing S-rich silicate melts is the main driver of Os/Ir elemental fractionation. The present-day 187Os/188Os ratios in carbonatites range from mildly unradiogenic (∼0.124) to extremely radiogenic values (∼115–152), with 187Os/188Os(i) ratios spanning from negative to highly radiogenic (∼17) values, paralleled by highly variable 187Re/188Os ratios between 0.096 and ∼ 26,000, and without any clear relationship to the carbonatite type or emplacement age. The Re–Os systematics of carbonatites appear to be significantly modified by hydrothermal processes resulting in either removal of both Re and Os, or Re addition and, consequently, commonly negative calculated γOs values, which may indicate a rather limited potential of the Re–Os systematics to evaluate the nature of carbonatite melts. Conversely, limited Re–Os data for the samples that were likely not affected by late-stage perturbation indicate a largely radiogenic 187Os/188Os nature of carbonatite melts. Nevertheless, carbonatite melts may, in part, be responsible for the radiogenic γOs values commonly observed in mantle-derived silicate melts influenced by carbonatite-like metasomatism.

Ni isotopes provide a glimpse of Earth’s pre-late-veneer mantle

Moderately siderophile (e.g., Ni) and highly siderophile elements (HSEs) in the bulk silicate Earth (BSE) are believed to be partly or near-completely delivered by late accretion after the depletion caused by metallic core formation. However, the extent and rate of remixing of late-accreted materials that equilibrated with Earth’s pre-late-veneer mantle have long been debated. Observing evidence of this siderophile element-depleted pre-late-veneer mantle would provide powerful confirmation of this model of early mantle evolution. We find that the mantle source of the ~3.8-billion-year-old (Ga) Narssaq ultramafic cumulates from Southwest Greenland exhibits a subtle 60 Ni/ 58 Ni excess of ~0.05 per mil and contains a clear HSE deficiency of ~60% relative to the BSE. The intermediate Ni isotopic composition and HSE abundances of the ~3.8-Ga Narssaq mantle mark a transitional Eoarchean snapshot as the poorly mixed 3.8-Ga mantle containing elements of pre-late-veneer mantle material transitions to modern Earth’s mantle.

Highly siderophile element fractionation during chondrite melting inferred from olivine-rich primitive achondrites

Metal-silicate segregation is one of the most fundamental mechanisms in planetary differentiation, with primitive achondrites offering important constraints on this process. Brachinites and brachinite-like achondrites (BLA) are olivine-dominated primitive achondrites that experienced up to ∼20% partial melt removal under relatively oxidized (ΔIW ∼ −1) conditions within an initially chondritic parent body and represent residues after inefficient metal-loss. We present bulk rock and in situ lithophile and highly siderophile element (HSE) abundance systematics as well as 187Re-187Os data for five olivine-rich primitive achondrites. These new data confirm classification of Reid 013 as a brachinite, three of the samples as BLA (Northwest Africa [NWA] 6874, NWA 7499, and Miller Range 090805), and the final sample as an ungrouped primitive olivine-rich achondrite (NWA 7680). An aliquot of MIL 090805 shows amongst the highest total HSE contents (>35 ppm) and the highest Pt content (∼23 ppm) of any primitive achondrite. Compiled HSE data for brachinites and BLA show correlations between total HSE abundance, Pt enrichment, and average olivine Fo. This correlation can be explained by variable melting (∼10–20%) of an H ordinary chondrite-like protolith, with retention of both Fe-metal and a Pt-rich alloy phase distinct from the observed Fe-metal phases in more depleted residues. Such a Pt-alloy phase is likely stabilized by elevated abundances of the HSE during chondrite melting and the low solubility of HSE in melts. Rhenium-Os isotope data in the studied samples has been modified by recent mobilization of Re during terrestrial weathering, with the limited range of measured 187Os/188Os in brachinites and BLA supporting minor fractionation of Re/Os during melting and an ancient (∼4.5 Ga) partial melting event to explain their compositions. These results indicate that models of planetary differentiation should consider the low solubility of Pt in chondrite melts and the potential for alloy formation to modify HSE abundances of silicate mantles.

Genetics, age, and crystallization history of group IC iron meteorites

The IC iron meteorite group is characterized utilizing nucleosynthetic mass-independent isotopic compositions and 182W age constraints, coupled with siderophile element concentration measurements and modeling of crystal-liquid fractionation processes. The six IC irons analyzed, Arispe, Bendego, Chihuahua City, Nocoleche, NWA 2743, and Winburg have indistinguishable Mo and W genetic isotopic compositions and are consistent with derivation from the same parent body, which formed in the non-carbonaceous (NC) nebular reservoir. A pre-exposure µ182W value (parts-per-million deviations in isotopic ratios from terrestrial standards) for the six IC irons of −337 ± 5 corresponds to a metal-silicate segregation age of 1.0 ± 0.4 Myr after calcium-aluminum-rich inclusion (CAI) formation. This age is similar to those determined for other NC iron groups. Siderophile element abundances of the IC irons are generally similar and characterized by minor depletions in the more volatile siderophile elements. Highly siderophile element (HSE) distributions among the IC group suggest that the initial parent body core was S-rich, with preferred model results indicating an initial melt composition with ∼ 18 wt% S, 2 wt% P and 0.03 wt% C. Processes in addition to fractional crystallization, such as late-stage parent body modification, possibly as a result of impacts, and subsequent metal-melt mixing, are required within the first 100 Myr of Solar System history to explain the range of HSE abundances.

Compositions of carbonaceous-type asteroidal cores in the early solar system.

The parent cores of iron meteorites belong to the earliest accreted bodies in the solar system. These cores formed in two isotopically distinct reservoirs: noncarbonaceous (NC) type and carbonaceous (CC) type in the inner and outer solar system, respectively. We measured elemental compositions of CC-iron groups and used fractional crystallization modeling to reconstruct the bulk compositions and crystallization processes of their parent asteroidal cores. We found generally lower S and higher P in CC-iron cores than in NC-iron cores and higher HSE (highly siderophile element) abundances in some CC-iron cores than in NC-iron cores. We suggest that the different HSE abundances among the CC-iron cores are related to the spatial distribution of refractory metal nugget–bearing calcium aluminum–rich inclusions (CAIs) in the protoplanetary disk. CAIs may have been transported to the outer solar system and distributed heterogeneously within the first million years of solar system history.

Partitioning of Ru, Pd, Ag, Re, Pt, Ir and Au between sulfide-, metal- and silicate liquid at highly reduced conditions: Implications for terrestrial accretion and aubrite parent body evolution

The abundances of highly siderophile elements (HSE) in planetary mantles and achondrites potentially provide important constraints on several aspects of planet formation, including the nature and composition of late accreted materials. Here, we experimentally and systematically assess the distribution of the HSE between silicate melts, sulfide and/or metal liquids at the highly to moderately reduced conditions thought to have characterized Earth accretion. The results show that the chalcophile behavior of all elements, except for Re, is strongly decreased at low FeO and/or high S concentrations in the silicate melt. There are considerable differences between how FeO and/or S contents of the silicate melt affect the D values of the various HSE, with the largest effects observed for Pd, Pt, Ir and Au. If liquid metal is Si-rich and S-poor, the siderophile behavior of the HSE mimics that in the presence of sulfide liquids, but with an offset due to differences in HSE activities in metal and sulfide liquids.Using our new experimental data, we quantify the relative effects of O in sulfide and S in silicate melt on the sulfide liquid-silicate melt partitioning behavior of the HSE using a thermodynamic approach. The resulting expressions were used to model the distribution of the HSE in highly reduced and differentiated EH- and EL chondritic parent bodies and during differentiation of the aubrite parent body. Our results show that even with their strongly decreased chalcophile and siderophile behavior at highly reduced conditions, HSE abundances in the mantles of these parent bodies remain extremely low. However, if such bodies accreted to Earth, any residual metal present in the parent body mantle and subsequently retained in Earth’s mantle would dramatically affect HSE abundances and produce chondritic ratios, making it impossible to track the potential accretion of a large reduced impactor to the BSE using HSE abundance systematics. In terms of the aubrite parent body, our results confirm previous hypotheses related to the importance of (un)differentiated core forming metals in establishing the HSE contents of unbrecciated aubrites. Finally, our results confirm that sulfides are likely a minor source of HSE abundances in aubrites, particularly for Re, consistent with sample observations.

Geochemical constraints on the formation of chondrules: Implication from Os and Fe isotopes and HSE abundances in metals from CR chondrites

CR chondrites are suitable for understanding the genetic linkage between metals and chondrules due to the unique characteristics of the coexisting metal phases with chondrules. Metal grains are found in three different locations of CR chondrites; chondrule interior (“interior grain”), chondrule surficial shells (“margin grain”), and the matrix (“isolated grain”). Here we report the abundances of highly siderophile elements (HSEs) and major elements in three types of metals (interior, margin, and isolated grains) from three CR chondrites (NWA 801, NWA 7184, and Dhofar 1432) by using femtosecond LA-ICP-MS (fs LA-ICP-MS) and EPMA. Additionally, we report the isotopic compositions of Os and Fe in the metals by using micro-milling sampling coupled with N-TIMS and MC-ICP-MS. The CR metals have variations in 187Os/188Os and δ57Fe values ranging from 0.1193 to 0.1314 and from −1.05 to +0.25, respectively. HSE abundances, except for Pd and Au, in the three types of metals increase as the abundance of Ir increases. A possible explanation for the variations of HSE abundances within and among grains, 187Os/188Os values within each grain, and δ57Fe values among grains, is the condensation of liquid metal from a gaseous reservoir followed by fractional crystallization. Most of the CR metals have negative δ57Fe values, suggesting that Fe in metal phases might have formed by condensation prior to Fe condensation in silicate phases. The chondrules and three types of metal grains in CR chondrites are believed to have formed contemporaneously in the same region. The existence of large isolated metals in matrix and compound chondrules might be the result of collision and merging of the metal and silicate droplets.

Ancient Melt-Depletion in Fresh to Strongly Serpentinized Tonga Trench Peridotites

ABSTRACT Peridotites from the Tonga Trench are some of the deepest-derived and freshest ever obtained from the seafloor. This study reports new bulk-rock major-, trace-, highly siderophile-element (HSE) abundance and 187Os/188Os data, as well as major- and trace-element abundances of mineral phases for NOVA88D dredge peridotites. The samples are harzburgites that experienced varying degrees of serpentinization, recorded in their loss on ignition (LOI) values, from zero to 16.7%. Degree of serpentinization in samples is correlated with Na, B, K, Sr, Ca, Rb and U, and weakly correlated with W, Fe, Pb, Cs and Li abundances, but is uncorrelated with other lithophile elements, most especially the rare earth elements (REE). Serpentinization had no systematic effect on the HSE abundances or 187Os/188Os compositions in the harzburgites. NOVA88D harzburgites record &amp;gt;18% melt depletion which has resulted in heterogenous distribution of the HSE within the rocks, likely due to retention of these elements within sub-micron sized alloy or sulphide phases. Time of rhenium depletion (TRD) ages, recorded by Os isotopes, average ~ 0.7 ± 0.4 Ga and can be as ancient as 1.5 Ga. Some harzburgite compositions are consistent with minor melt infiltration processes modifying incompatible trace element compositions and Re abundances, with a possible melt infiltration event at ~120 Ma based on 187Re-188Os, prior to the inception of subduction at the Tonga Trench at ~52 Ma. Evidence for ancient melt depletion, combined with limited melt processing since inception of subduction suggests that NOVA88D harzburgites represent melt residues incorporated into the Tonga arc, rather than their geochemical signatures being produced beneath the recent arc. Estimates of fO2 (~ − 0.4 ± 0.4 ΔFMQ) and olivine-spinel equilibration temperatures for the Tonga Trench samples (830 ± 120 ̊C) are similar to abyssal peridotites and some Izu-Mariana-Bonin peridotites. These values are unlikely to relate directly to recorded degrees of melt depletion and melt depletion ages in the rocks. Refractory residues from prior melt depletion events are probably common in the convecting mantle, and those with high degrees of melt depletion (&amp;gt;18%) and relatively ancient melt depletion ages (&amp;lt;2 Ga) are likely to have been formed during prior melting processes rather than melting processes within their current tectonic setting. These refractory peridotites can be incorporated into a range of tectonic settings, including into mid-ocean ridges, succeeding arcs, or within the continental lithospheric mantle, where they may play a limited role in melt generation processes.

Highly Siderophile Elements and Coupled Fe-Os Isotope Signatures in the Temagami Iron Formation, Canada: Possible Signatures of Neoarchean Seawater Chemistry and Earth's Oxygenation History.

Banded iron formations (BIFs) were deposited before and concurrent with the Great Oxidation Event at ∼2.33 Ga. They provide useful archives that document the transformation of the Precambrian hydrosphere from anoxic to progressively oxygenated conditions. Their formation involves removal of oceanic Fe by either inorganic or biologically promoted Fe2+ oxidation, or both. To evaluate depositional settings, elemental sources that affect seawater chemistry, and oxidation pathways, we present the first combined highly siderophile element (HSE) and Fe-Os isotope study for the ∼2.7 Ga Temagami BIF, Abitibi Greenstone Belt, Ontario (Canada). HSE abundances and 187Os/188Os ratios show no systematic variation between alternating magnetite and (meta)chert bands of the Temagami BIF. Whereas HSE concentrations mostly resemble modern crustal values, present-day 187Os/188Os ratios range from ∼0.17 to ∼10.8. Magnetite samples define a regression line corresponding to an age of 2661 ± 126 Ma. A chondrite-like 187Os/188Os initial value is in agreement with earlier studies on Neoarchean marine sediments and is thought to reflect seawater composition, which, unlike modern oceans, is dominated by mantle-like 187Os inventory most likely derived from deep-sea hydrothermal vents. Our δ56Fe data vary from about +0.6‰ to +0.9‰ and define a sawtooth-like pattern between alternating magnetite and (meta)chert layers. Partial oxidation of hydrothermally sourced Fe(II) and a lack of microbially mediated dissimilatory iron reduction provide the most plausible explanation for the positive δ56Fe values. Notably, our δ56Fe data for Temagami are in accord with trends defined by literature results for other Algoma-type BIFs that were deposited throughout the Archean.

Meter-Scale Chemical and Isotopic Heterogeneities in the Oceanic Mantle, Leka Ophiolite Complex, Norway

AbstractMantle peridotites from three 3 × 3-meter grids sampled at kilometer distances from one another in the ca. 497 Ma Leka Ophiolite Complex (LOC), Norway, are examined to investigate the chemical and isotopic nature of oceanic mantle domains at the centimeter to kilometer scale. The lithology of each grid locality is predominantly harzburgite, but includes layers and lenses of dunite and pyroxenite. Major and lithophile trace element compositions indicate a history of prior melting at pressures at or slightly below the garnet stability field. The common presence of orthopyroxenite veins likely reflects infiltration of silicic melts associated with supra-subduction zone processes. Osmium isotopes and highly siderophile element (HSE) abundance data for centimeter-scale sampling of traverses from the pyroxenites into the harzburgites reveal that the formation of the veins had little effect on Os isotopic compositions, and Os, Ir, Ru and Re abundances in the harzburgites. Adjacent to one of the orthopyroxenite veins studied, however, Pt and Pd abundances appear to have been strongly modified by interactions with vein-forming melts or fluids at distances of as much as 4–6 cm from the pyroxenite-harzburgite contact. Leka harzburgites have initial γOs values (% deviation from a chondritic reference) that range from −4.7 to +2.2 (6.9% variation), with individual uncertainties of ±0.2 units. Averaged initial Os isotopic compositions for harzburgites from the three grid sites separated by as much as 6 km, by contrast, differ by only a maximum of 2.6%. Isotopic heterogeneity on the centimeter to meter scale is, therefore, larger than kilometer-scale heterogeneity, indicating that at least some of the Os isotopic heterogeneity commonly observed globally among mantle peridotites is the result of processes that acted on a local scale. The general uniformity of these isotopic compositions among the three grid sites suggests that the portion of the oceanic mantle sampled by the LOC was homogenous at the kilometer scale with respect to the long-term Re/Os ratio. The long-term projected Re/Os for LOC harzburgites is similar to the average required for modern abyssal peridotites. This observation strengthens previous interpretations, based largely on data for abyssal peridotites, that state the Os isotopic evolution of oceanic mantle is consistent with a long-term 187Re/188Os of ∼0.38. The present ∼3 to 4% difference between the Os isotopic composition of the modern oceanic mantle and estimates for primitive mantle suggests that at least ∼6% of the mass of the oceanic mantle has been removed from it in the form of Re-enriched, mafic oceanic crust. Despite the recycling of this crust back into the mantle, most of it has evidently not been mixed back into accessible portions of the upper oceanic peridotite mantle. Compared to composition estimates for the primitive mantle, the median HSE compositions for the three grid sites are moderately to strongly depleted in Pd and Re, consistent with the corresponding lithophile element evidence for 20–30% melt depletion. As with initial γOs values, most harzburgites from a given grid are characterized by greater variations in absolute and relative HSE abundances than the differences between the median abundances of the three grid sampling locales. This observation indicates that as with Os isotopes, the HSE abundance heterogeneity among the harzburgites most strongly reflects centimeter- to meter-scale melting and remobilization effects. Except for Ru, median HSE abundances for grid harzburgites are similar to median abundances for abyssal peridotites. The ∼30% lower median Ru/Ir in the LOC compared to the median ratio for abyssal peridotites suggests that the abundance of Ru in the oceanic mantle may be more variable than generally thought.

A new estimate for the age of highly-siderophile element retention in the lunar mantle from late accretion

Subsequent to the Moon's formation, late accretion to the terrestrial planets strongly modified the physical and chemical nature of silicate crusts and mantles. This alteration came in the form of melting through impacts, as well as the belated addition of volatiles and the highly siderophile elements (HSEs). Even though late accretion is well established as having been an important process in the evolution of the young solar system, its intensity and temporal decline remain subject to debate. Much of this deliberation hinges on what can be inferred about late accretion to the Moon from its computed mantle HSE abundances. Current debate centres on whether the lunar HSE record is representative of its whole late accretion history or alternatively that these were only retained in the mantle and crust after a particular time, and if so, when. Here we employ improved Monte Carlo impact simulations of late accretion onto the Moon and Mars and present an updated chronology based on new dynamical simulations of leftover planetesimals and the E-belt – a now-empty hypothesised inner extension of the asteroid belt (Bottke et al., 2012). We take into account the inefficient retention of colliding material. The source of impactors on both planetary bodies is assumed to be the same, hence we use constraints from both objects simultaneously. We compute the crater and basin densities on the Moon and Mars, the largest objects to strike these planets and the amount of material they accreted. Outputs are used to infer the mass in leftover planetesimals at a particular time period, which is then compared to the lunar HSE abundance. From this estimate we calculate a preferred lunar HSE retention age of ca. 4450 Ma which means that the modelled lunar mantle HSE abundances trace almost all of lunar late accretion. Based on our results, the surface ages of the lunar highlands are at least 4370 Ma. We find that the mass of leftover planetesimals with diameters Di < 300 km at 4500 Ma that best fits the crater chronology is approximately 2 × 10−3 Earth mass (ME) while the mass of the E-belt was fixed at 4.5 × 10−4 ME. We also find that a leftover planetesimal mass in excess of 0.01 ME results in a lunar HSE retention age younger than major episodes of lunar differentiation and crust formation, which in turn violates geochemical constraints for the timing and intensity of late accretion to the Earth (Mojzsis et al., 2019).

Genetics, age and crystallization history of group IIC iron meteorites

The eight iron meteorites currently classified as belonging to the IIC group were characterized with respect to the compositions of 21 siderophile elements. Several of these meteorites were also characterized for mass independent isotopic compositions of Mo, Ru and W. Chemical and isotopic data for one, Wiley, indicate that it is not a IIC iron meteorite and should be reclassified as ungrouped. The remaining seven IIC iron meteorites exhibit broadly similar bulk chemical and isotopic characteristics, consistent with an origin from a common parent body. Variations in highly siderophile element (HSE) abundances among the members of the group can be well accounted for by a fractional crystallization model with all the meteorites crystallizing between ∼10 and ∼26% of the original melt, assuming initial S and P concentrations of 8 wt.% and 2 wt.%, respectively. Abundances of HSE estimated for the parental melt suggest a composition with chondritic relative abundances of HSE ∼6 times higher than in bulk carbonaceous chondrites, consistent with the IIC irons sampling a parent body core comprising ∼17% of the mass of the body.Radiogenic 182W abundances of two group IIC irons, corrected for a nucleosynthetic component, indicate a metal-silicate segregation age of 3.2 ± 0.5 Myr subsequent to the formation of Calcium-Aluminum-rich Inclusions (CAI). When this age is coupled with thermal modeling, and assumptions about the Hf/W of precursor materials, a parent body accretion age of 1.4 ± 0.5 Myr (post-CAI) is obtained.The IIC irons and Wiley have 100Ru mass independent “genetic” isotopic compositions that are identical to other irons with so-called carbonaceous chondrite (CC) type genetic affinities, but enrichments in 94,95,97Mo and 183W that indicate greater s-process deficits relative to most known CC iron meteorites. If the IIC irons and Wiley are of the CC type, this indicates variable s-process deficits within the CC reservoir, similar to the s-process variability within the NC reservoir observed for iron meteorites. Nucleosynthetic models indicate that Mo and 183W s-process variability should correlate with Ru isotopic variability, which is not observed. This may indicate the IIC irons and Wiley experienced selective thermal processing of nucleosynthetic carriers, or are genetically distinct from the CC and NC precursor materials.

A compositionally heterogeneous martian mantle due to late accretion.

The approximately chondritic estimated relative abundances of highly siderophile elements (HSE) in the bulk martian mantle suggest that these elements were added after Mars' core formed. The shergottite-nakhlite-chassigny (SNC) meteorites imply an average mantle Pt abundance of ≈3 to 5 parts per billion, which requires the addition of 1.6 × 1021 kilograms of chondritic material, or 0.25% martian masses, to the silicate Mars. Here, we present smoothed particle hydro-dynamics impact simulations that show that Mars' HSE abundances imply one to three late collisions by large differentiated projectiles. We show that these collisions would produce a compositionally heterogeneous martian mantle. Based mainly on W isotopes, it has been argued that Mars grew rapidly in only about 2 to 4 million years (Ma). However, we find that impact generation of mantle domains with variably fractionated Hf/W and diverse 182W could imply a Mars formation time scale up to 15 Ma.

The highly siderophile elements and Re–Os isotope geochemistry of Variscan lamproites from the Bohemian Massif: implications for regionally dependent metasomatism of orogenic mantle

Orogenic lamproites represent a group of peralkaline, ultrapotassic and perpotassic mantle-derived igneous rocks that hold the potential to sample components with extreme compositions from highly heterogeneous orogenic mantle. In our pilot study, we present highly siderophile element (HSE) and Re–Os isotope systematics of Variscan orogenic lamproites sampled in the territories of the Czech Republic, Austria and Poland, i.e., from the termination of the Moldanubian and Saxo-Thuringian zones of the Bohemian Massif. Orogenic lamproites of the Bohemian Massif are distinguished by variably high contents of SiO2, high Mg# and predominant mineral associations of K-rich amphibole and Fe-rich microcline. The HSE show (i) consistently very low contents in all investigated orogenic lamproites compared to the estimated concentrations in majority of mid-ocean ridge basalts, hotspot-related volcanic rocks (e.g., ocean island basalts, continental flood basalts, komatiites, some intraplate alkaline volcanic rocks such as kimberlites and anorogenic lamproites) and arc lavas, and (ii) marked differences in relative and absolute HSE abundances between the samples from the Moldanubian and Saxo-Thuringian Zone. Such a regional dependence in HSE from mantle-derived melts is exceptional. Orogenic lamproites have highly variable and high initial suprachondritic 187Os/188Os values (up to 0.631) compared with rather chondritic to subchondritic Os isotope values of the young lithospheric mantle below the Bohemian Massif. The highly radiogenic Os isotope component in orogenic lamproites may be derived from preferential melting of metasomatised vein assemblages sitting in depleted peridotite mantle. This process appears to be valid generally in the petrogenesis of orogenic lamproites both from the Bohemian Massif and from the Mediterranean area. As a specific feature of the orogenic lamproites from the Bohemian Massif, originally ultra-depleted mantle component correlative with remnants of the Rheic Ocean lithosphere in the Moldanubian Zone was metasomatised by a mixture of evolved and juvenile material, whereas the lithospheric mantle in the Saxo-Thuringian Zone was enriched through the subduction of evolved crustal material with highly radiogenic Sr isotope signature. As a result, this led to observed unique regionally dependent coupled HSE, Rb–Sr and Re–Os isotope systematics.

Fractionation of Ruthenium from Other Highly Siderophile Elements (HSEs) in Forearc Mantle

AbstractThe geochemical characteristics and behaviors of highly siderophile elements (HSEs) in forearc peridotites remain poorly constrained due to the scarcity of data. Here, we report HSE abundances of mantle peridotites from the New Caledonia ophiolites, a classical ophiolite generated in a forearc setting. Those peridotites show non‐chondritic, strongly fractionated HSE patterns and can be classified into two distinct types (namely Group I and Group II). Group I peridotites have higher HSE contents than Group II peridotites, which might be because intergranular sulfides were completely removed but sulfide inclusions were retained during partial melting of peridotites in a forearc environment, and meanwhile the distribution of sulfide inclusions are not uniform in mantle. Moreover, Group I peridotites display flat patterns from Os to Pt but strongly depleted in Pd, which resemble those patterns of some mantle wedge xenoliths. The Pt–Pd decoupling can be attributed to high degrees of partial melting. However, Group II peridotites are characterized by strongly positive Ru anomaly with highly super‐chondritic Ru/Os and Ru/Ir ratios. Such characteristics are the first reported cases for forearc peridotites. The fractionation of Ru from other HSEs might reflect the stability of refractory Ru‐rich phases in mantle wedge peridotites during different processes, e.g., partial melting and melt/fluid‐rock reactions.

Genetics, crystallization sequence, and age of the South Byron Trio iron meteorites: New insights to carbonaceous chondrite (CC) type parent bodies.

The nucleosynthetic Mo, Ru, and W isotopic compositions of the South Byron Trio iron meteorite grouplet (SBT) are consistent with all three meteorites originating on a single parent body that formed in the carbonaceous chondrite (CC) isotopic domain within the Solar nebula. Consistent with a common origin, the highly siderophile element (HSE) concentrations of the SBT can be related to one another by moderate degrees of fractional crystallization of a parental melt with initially chondritic relative abundances of HSE, and with initial S and P contents of ~7 and ~1 wt. %, respectively. Tungsten-182 isotopic data for the SBT indicate the parent body underwent metal-silicate differentiation 2.1 ± 0.8 Myr after calcium aluminum rich inclusion formation, and thermal modeling suggests the parent body formed 1.1 ± 0.5 Myr after CAI formation. This accretion age is not resolved from the accretion ages of other CC and most noncarbonaceous (NC) type iron meteorite parent bodies. Comparison of the projected parental melt composition of the SBT to those projected for the IVA and IVB iron meteorite groups suggests that at least some portions of the CC nebular domain were more oxidized compared to the NC domain. In addition, comparison of the SBT parental melt S content to estimates for parent bodies of the IIAB, IIIAB, IVA, IID, and IVB "magmatic" iron meteorite groups suggests that CC type iron meteorite parental melts were characterized by a general depletion in S, in addition to depletions in some other moderately volatile elements. Based on chemical and O isotope similarities, prior studies have suggested the possibility of a common parent body for the SBT and the Milton pallasite. Molybdenum and Ru isotopic compositions of Milton also provide permissive evidence for this. The HSE concentrations in the Milton metal, however, cannot be related to the SBT by any known crystal-liquid fractionation or mixing path. Thus, Milton more likely formed on a different, chemically distinct, but genetically identical parent body present in the CC nebular domain.

Age and composition of the subcontinental lithospheric mantle beneath the Xing'an–Mongolia Orogenic Belt: Implications for the construction of microcontinents during accretionary orogenesis

We present major- and trace-element concentrations, Sr–Nd–Hf isotopic compositions, ReOs isotopes, and highly siderophile element (HSE) abundances of 17 xenolithic mantle peridotites from the Nuomin volcanic field to constrain the assembly and evolution of the Xing'an–Mongolia Orogenic Belt (XMOB), Northeast China. The Nuomin peridotites are divided into five groups (harzburgite groups Haz-1, Haz-2, and Haz-3, and lherzolite groups Lhz-1 and Lhz-2). The Haz-1 peridotites are characterized by refractory chemical compositions (Al2O3 contents of 1.03–2.30 wt% and olivine forsterite (Fo) numbers of 90.7–92.5) that are best interpreted as residues after high degrees of mantle partial melting. The Haz-2 and Haz-3 peridotites exhibit slightly more fertile compositions (Al2O3 of 1.72–1.80 wt% and Fo of 89.0–89.9 for the Haz-2, and Al2O3 of 2.86 wt% and Fo of 91.2 for the Haz-3), resulting from refertilization by silicate melts. The Lhz-1 samples are more fertile (Al2O3 of 2.90–3.64 wt% and Fo of 89.1–90.3) than the Lhz-2 samples (Al2O3 of 1.64–2.16 wt% and Fo of 90.9–91.3). The combination of trace-element data (Ti/Eu ratio) and Sr–Nd–Hf isotopic compositions indicates the presence of at least three peridotite end-members (Haz-1, Haz-2, and Lhz-1–Lhz-2) beneath the Nuomin area, which can be explained by the infiltration of two distinct metasomatic agents (MA1: composition similar to potassic basaltic rocks in the Wudalianchi–Erkeshan–Keluo area, and MA2: Fe–Ti-enriched melt). HSE abundances and Os isotopic data show that the Os isotopic compositions of the Haz-1, Lhz-1, and Lhz-2 peridotites were not significantly affected by lithophile-element-dominated metasomatism and can be used to constrain the melt extraction ages of these peridotites. The lower 187Os/188Os ratios of Haz-1 peridotites define a prominent rhenium depletion age (TRD) of ~1.6 Ga and represent fragments of the Paleo–Mesoproterozoic lithospheric mantle rather than reflecting the heterogeneous characteristics of the asthenosphere or extraneous emplacement. In contrast, the Lhz-1 and Lhz-2 lherzolite groups together have a narrow range of 187Os/188Os ratios that give younger TRD ages (~0.5 to 1.0 Ga). Our data demonstrate that both the Paleo–Mesoproterozoic and Neoproterozoic subcontinental lithospheric mantle coexist beneath the XMOB and that they correspond respectively to the bimodal age peaks of crustal growth of ~1.6 Ga and ~0.8 Ga defined by the XMOB granitoids. The XMOB was assembled primarily during the Phanerozoic by multiple blocks that had formed from the Paleoproterozoic to Neoproterozoic. The similar chemical and Sr–Nd–Hf isotopic signatures of both young and old lithospheric mantle indicate that the large-scale metasomatism event involving potassic melts most likely occurred during the evolution of the Paleo–Asian Ocean. The crustal materials carried to the mantle by multiple subduction events could be an effective source of potassium for the origin of potassic basaltic rocks.

182W and HSE constraints from 2.7 Ga komatiites on the heterogeneous nature of the Archean mantle

While the isotopically heterogeneous nature of the terrestrial mantle has long been established, the origin, scale, and longevity of the heterogeneities for different elements and isotopic systems are still debated. Here, we report Nd, Hf, W, and Os isotopic and highly siderophile element (HSE) abundance data for the Boston Creek komatiitic basalt lava flow (BCF) in the 2.7 Ga Abitibi greenstone belt, Canada. This lava flow is characterized by strong depletions in Al and heavy rare earth elements (REE), enrichments in light REE, and initial ε143Nd = +2.5 ± 0.2 and intial ε176Hf = +4.2 ± 0.9 indicative of derivation from a deep mantle source with time-integrated suprachondritic Sm/Nd and Lu/Hf ratios. The data plot on the terrestrial Nd-Hf array suggesting minimal involvement of early magma ocean processes in the fractionation of lithophile trace elements in the mantle source. This conclusion is supported by a mean μ142Nd = −3.8 ± 2.8 that is unresolvable from terrestrial standards. By contrast, the BCF exhibits a positive 182W anomaly (μ182W = +11.7 ± 4.5), yet is characterized by chondritic initial γ187Os = +0.1 ± 0.3 and low inferred source HSE abundances (35 ± 5% of those estimated for the present-day Bulk Silicate Earth, BSE). Collectively, these characteristics are unique among Archean komatiite systems studied so far. The deficit in the HSE, coupled with the chondritic Os isotopic composition, but a positive 182W anomaly, are best explained by derivation of the parental BCF magma from a mantle domain characterized by a predominance of HSE-deficient, differentiated late accreted material. According to the model presented here, the mantle domain that gave rise to the BCF received only ∼35% of the present-day HSE complement in the BSE before becoming isolated from the rest of the convecting mantle until the time of komatiite emplacement at 2.72 Ga. These new data provide strong evidence for a highly heterogeneous Archean mantle in terms of absolute HSE abundances and W isotopic composition, and also indicate slow mixing, on a timescale of at least 1.8 billion years. Additionally, the data are consistent with a stagnant-lid plate tectonic regime in the Hadean and Archean, prior to the onset of modern-style plate tectonics.

Highly Siderophile Elements distribution, Os-S isotope systematics and U-Pb dating of mafic-ultramafic-hosted massive sulphide deposits (Southern Urals) – Implications on the sources of metals

The behaviour of Highly Siderophile Elements (HSEs), including the Platinum Group Elements (PGEs), Re and Au, is still poorly known in hydrothermal systems due to their low concentrations in hydrothermal fluids and related ore deposits. In this work, HSE abundances were determined by fire assay and ICP-MS analyses in the Devonian Dergamysh and Ivanovka massive sulphide deposits from the Southern Urals, Russia. These deposits occur within mafic-ultramafic rocks of the Main Urals Fault suture zone, where the East-European continental unit comes into contact with the Magnitogorsk island arc system. Despite mafic-ultramafic host-rock compositions, the measured Pt and Pd contents are lower than those in island arc-hosted massive sulphide deposits from the same metallogenic province. In Dergamysh massive sulphides, the PGEs and Au positively correlate with Cu, whereas Pt also correlates with Co. For Ivanovka mainly disseminated ores and host rocks, two trends can be observed: (a) low to high PGE at low Au in rocks, with negative Ni-Pd correlation; and (b) both PGE and Au are variable in ores with significant correlation between Au and Pd. The Os-Pb-S isotope systematics in the seafloor Dergamysh hydrothermal system was mainly controlled by mixing of hydrothermal fluid with isotopic signature inherited from mafic host-rocks, and Devonian seawater. A possible additional contribution from more radiogenic Os component was attributed to older Precambrian rocks, which acquired radiogenic Os composition since their formation. Possible presence of such old rocks in serpentinitic melange was evidenced by U-Pb ages of zircons from Dergamysh deposit host rocks, ranging from 3.3Ga to 507Ma. These Archaean to Proterozoic zircons are consistent with source from the Volga-Uralia block of the East-European craton, adjacent to the Urals orogenic belt. Light sulphur isotopic composition in Dergamysh ores was attributed to bacterial reduction processes, which was also observed for modern serpentinite-hosted seafloor systems. Disproportionation of magmatic fluid however cannot be completely ruled out.

Highly siderophile element and 182W evidence for a partial late veneer in the source of 3.8 Ga rocks from Isua, Greenland

The higher-than-expected concentrations of highly siderophile elements (HSE) in Earth's mantle most likely indicate that Earth received a small amount of late accreted mass after core formation had ceased, known as the ‘late veneer’. Small 182W excesses in the Moon and in some Archaean rocks – such as the source of 3.8 billion-year-old Isua magmatics – also appear consistent with the late veneer hypothesis, with a lower proportion received. However, 182W anomalies can also relate to other processes, including early mantle differentiation. To better assess the origin of these W isotope anomalies – and specifically whether they relate to the late veneer – we have determined the HSE abundances and 182W compositions of a suite of mafic to ultramafic rocks from Isua, from which we estimate HSE abundances in the source mantle and ultimately constrain the 182W composition of the pre-late veneer mantle.Our data suggest that the Isua source mantle had HSE abundances at around 50–65% of the present-day mantle, consistent with partial, but not complete, isolation from the late veneer. These data also indicate that at least part of the late veneer had been added and mixed into the mantle at the time the Isua source formed, prior to 3.8 Ga. For the same Isua samples we obtained a 13±4 ppm182W excess, compared to the modern terrestrial mantle, in excellent agreement with previous data. Using combined 182W and HSE data we show that the Moon, Isua, and the present-day bulk silicate Earth (BSE) produce a well-defined co-variation between 182W composition and the mass fraction of late-accreted mass, as inferred from HSE abundances. This co-variation is consistent with the calculated effects of various late accretion compositions on the HSE and 182W signatures of Earth's mantle. The empirical relationship, therefore, implies that the Moon, Isua source and BSE received increasing proportions of late-accreted mass, supporting the idea of disproportional late accretion to the Earth and Moon, and consistent with the interpretation that the lunar 182W value of 27±4 ppm represents the composition of Earth's mantle before the late veneer was added. In this case, the Isua source can represent ambient mantle after the giant moon-forming impact, into which only a part of Earth's full late veneer was mixed, rather than an isotopically distinct mantle domain produced by early differentiation, which would probably require survival through the giant Moon-forming impact.