Constraints on mantle evolution from Os/Os isotopic compositions of Archean ultramafic rocks from southern West Greenland (3.8 Ga) and Western Australia (3.46 Ga)

Initial ¹⁸⁷Os/¹⁸⁸Os isotopic compositions for geochronologically and geologically well -constrained 3.8-Ga spinel peridotites from the Itsaq Gneiss Complex of southern West Greenland and chromite separates from 3.46-Ga komatiites from the Pilbara region of Western Australia have been determined to investigate the osmium isotopic evolution of the early terrestrial mantle. The measured compositions of ¹⁸⁷Os/¹⁸⁸Os(0) = 0.10262 ± 2, from an olivine separate, and 0.10329 ± 3, for a spinel separate from ∼3.8-Ga peridotite G93/42, are the lowest yet reported from any terrestrial sample. The corrections for in situ decay over 3.8 Ga for these low Re/Os phases are minimal and change the isotopic compositions by only 0.5 and 2.2% for the spinel and the olivine, respectively, resulting in ¹⁸⁷Os/¹⁸⁸Os_{(3.8 Ga)} = 0.1021 ± 0.0002 and 0.1009 ± 0.0002, respectively. These data extend direct measurement of Os isotopic compositions to much earlier periods of Earth history than previously documented and provide the best constraints on the Os isotopic composition of the early Archean terrestrial mantle. Analyses of Pilbara chromites yield 3.46-Ga mantle compositions of 0.1042 ± 0.0002 and 0.1051 ± 0.0002.These new data, combined with published initial Os isotopic compositions from late Archean and early Proterozoic samples, are compatible with the mantle, or at least portions of it, evolving from a solar system initially defined by meteorites to a modern composition of ¹⁸⁷Os/¹⁸⁸Os(0) = 0.1296 ± 0.0008 as previously suggested from peridotite xenolith data ( Meisel et al., 2001); the associated ¹⁸⁷Re/¹⁸⁸Os(0) = 0.435 ± 0.005. Thus, chondritic ¹⁸⁷Os/¹⁸⁸Os compositions were a feature of the upper mantle for at least 3.8 billion years, requiring chondritic Re/Os ratios to have been a characteristic of the very early terrestrial mantle. In contrast, nonchondritic initial compositions of some Archean komatiites demonstrate that Os isotopic heterogeneity is an ancient feature of plume materials, reflecting the development of variable Re/Os mantle sources early in Earth history.The lower average ¹⁸⁷Os/¹⁸⁸Os = 0.1247 for abyssal peridotites (Snow and Reisberg, 1995) indicate that not all regions of the modern mantle have evolved with the same Re/Os ratio. The relative sizes of the various reservoirs are unknown, although mass balance considerations can provide some general constraints. For example, if the unradiogenic ¹⁸⁷Os/¹⁸⁸Os modern abyssal peridotite compositions reflect the prevalent upper mantle composition, then the complementary high Re/Os basaltic reservoir must represent 20 to 40% by mass of the upper mantle (taken here as 50% of the entire mantle), depending on the mean storage age. The difficulties associated with efficient long-term storage of such large volumes of subducted basalt suggest that the majority of the upper mantle is not significantly Re-depleted. Rather, abyssal peridotites sample anomalous mantle regions.The existence of 3.8-Ga mantle peridotites with chondritic ¹⁸⁷Os/¹⁸⁸Os compositions and with Os concentrations similar to the mean abundances measured in modern peridotites places an upper limit on the timing of a late accretionary veneer. These observations require that any highly siderophile element -rich component must have been added to the Earth and transported into and grossly homogenized within the mantle by 3.8 Ga. Either large-scale mixing of impact materials occurred on very short (0-100 myr) timescales or (the interpretation preferred here) the late veneer of highly siderophile elements is unrelated to the lunar terminal cataclysm estimated to have occurred at ∼3.8 to 3.9 Ga.     

Nitrogen and xenon in acid residues of iron meteorites

Total nitrogen, measured by neutron activation analysis, is highly enriched in residues from iron meteorites obtained by dissolution of the metal in dilute H₂SO₄, relative to the bulk value. On the average, the residues, representing 3% mass, contain 22% of total N. Group IA has more dissolved N than IIIA. Lithium and Ir show a distribution pattern parallel to N. Total Xe has been measured in several residues and its isotopic composition is, similar to atmospheric Xe for mass numbers 131 to 136 but not for ¹²⁴Xe and ¹²⁶Xe which are strongly depleted in the non-magnetic residues. It is suggested that iron meteorites have trapped in their micro-inclusions, some pre-solar nebular matter which is isotopically heterogeneous.     

Os isotopic constraints on Archean mantle dynamics

The Re-Os isotopic systematics of two ca. 2.7-Ga komatiite flows from Belingwe, Zimbabwe are examined. Rhenium and Os concentrations in these rocks are similar to concentrations in other Archean, Proterozoic, and Phanerozoic komatiites. Despite the excellent preservation of primary magmatic minerals, the Re-Os systematics of whole-rock samples of the komatiites show open-system behavior. Consistent model ages for several whole-rock samples suggest a disturbance to the system during the Proterozoic. Despite the open-system behavior in the whole rocks, Re-Os systematics for concentrates of primary magmatic olivine and spinel indicate generally closed-system behavior since the magmatic event that produced the rocks. Regression of the data for the mineral concentrates yields an age of 2721 ± 21 Ga, which is consistent with Pb-Pb and Sm-Nd ages that have been previously reported for the komatiites (Chauvel et al., 1993), and an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.11140 ± 84 (γ_Os = +2.8 ± 0.8).The 2 to 3% enrichment in ¹⁸⁷Os/¹⁸⁸Os ratio of the mantle source of the komatiites, relative to the chondritic composition of the contemporaneous convecting upper mantle, most likely reflects either the incorporation of substantially older (≥ 4.2 Ga), Re-rich recycled mafic crust into the mantle source of the komatiites or the contribution of suprachondritic Os to the source from the putative ¹⁸⁷Os-enriched outer core. The former interpretation would indicate the Hadean formation and recycling of mafic crust. The latter interpretation would require early formation of a substantial inner core followed by upwelling of a mantle plume from the core-mantle boundary, at least as far back as the Late Archean. Either interpretation requires large-scale mantle convection during the first half of Earth history.     

Re–Os systematics of the Raobazhai peridotite massifs from the Dabie orogenic zone, eastern China

The Raobazhai ultramafic massif of the ultrahigh pressure Sulu–Dabie orogenic belt, central China, is thought to be a segment of subcontinental lithospheric mantle that was subducted and exhumed during the Triassic collision of the North China and Yangtze cratons. We performed a Re–Os isotopic study of peridotites from the massif, associated with major and trace element analysis and textural examination. Os (1.02 to 6.28 ppb) and Re (0.004 to 0.376 ppb) concentrations are typical of orogenic lherzolite values, and ¹⁸⁷Os/¹⁸⁸Os ratios (0.1157 to 0.1283) are all similar to or lower than the proposed primitive upper mantle value. ¹⁸⁷Os/¹⁸⁸Os is roughly correlated with ¹⁸⁷Re/¹⁸⁸Os, and strongly correlated with Al₂O₃. These correlations can be explained by radiogenic ingrowth of ¹⁸⁷Os since an ancient partial melting event. T_MA model ages (1.7 to 2.0 Ga) of refractory peridotites from the lower massif are consistent with the model age (1.8 Ga) obtained from the ¹⁸⁷Os/¹⁸⁸Os vs. Al₂O₃ correlation at ~1% Al₂O₃. This age cannot distinguish the cratonic provenance of the Raobazhai massif, since similar Re–Os model ages have been obtained from both the North China and the Yangtze cratons. The poor quality of the ¹⁸⁷Os/¹⁸⁸Os vs. ¹⁸⁷Re/¹⁸⁸Os correlation indicates that the Re/Os ratios were disturbed, perhaps during Triassic subduction. The mainly lherzolitic samples of the upper massif, which were most strongly affected by this process, have porphyroclastic textures with fine-grained olivine, pyroxene and amphibole neoblasts, suggesting Re mobility during recrystallization in the presence of fluids.Previous studies of ultramafic xenoliths from arc volcanics demonstrate that slab-derived melts or fluids can both scavenge mantle Os and add substantial amounts of radiogenic Os to the suprasubduction mantle. In Raobazhai, both trace element patterns and the abundance of hydrous phases provide evidence for extensive interaction with fluids during subduction and/or exhumation. Nevertheless, the strong correlation between ¹⁸⁷Os/¹⁸⁸Os and Al₂O₃, and the high Os concentrations of these rocks indicate that Os isotopic ratios, and probably even Os concentrations, were essentially unaffected by this process. Assuming that the arguments favoring a suprasubduction setting for the Raobazhai massif are valid, these data provide evidence that Os systematics are sometimes surprisingly robust, even above subduction zones.     

Effects of melt percolation on highly siderophile elements and Os isotopes in subcontinental lithospheric mantle: A study of the upper mantle profile beneath Central Europe

The effects of melt percolation on highly siderophile element (HSE) concentrations and Re-Os isotopic systematics of subcontinental lithospheric mantle are examined for a suite of spinel peridotite xenoliths from the 4 Ma Kozákov volcano, Bohemian Massif, Czech Republic. The xenoliths have previously been estimated to originate from depths ranging from ∼32 to 70 km and represent a layered upper mantle profile. Prior petrographic and lithophile trace element data for the xenoliths indicate that they were variably modified via metasomatism resulting from the percolation of basaltic melt derived from the asthenosphere. Chemical and isotopic data suggest that lower sections of the upper mantle profile interacted with melt characterized by a primitive, S-undersaturated composition at high melt/rock ratios. The middle and upper layers of the profile were modified by more evolved melt at moderate to low melt/rock ratios. This profile permits an unusual opportunity to examine the effects of variable melt percolation on HSE abundances and Os isotopes.Most HSE concentrations in the studied rocks are significantly depleted compared to estimates for the primitive upper mantle. The depletions, which are most pronounced for Os, Ir and Ru in the lower sections of the mantle profile, are coupled with strong HSE fractionations (e.g., Os_N/Ir_N ratios ranging from 0.3 to 2.4). Platinum appears to have been removed from some rocks, and enriched in others. This enrichment is coupled with lithophile element evidence for the degree of percolating melt fractionation (i.e., Ce/Tb ratio).Osmium isotopic compositions vary considerably from subchondritic to approximately chondritic (γ_Os at 5 Ma from -6.9 to +2.1). The absence of correlations between ¹⁸⁷Os/¹⁸⁸Os and indicators of fertility, as is common in many lithospheric mantle suites, may suggest significant perturbation of the Os isotopic compositions of some of these rocks, but more likely reflect the normal range of isotopic compositions found in the modern convecting mantle. Osmium isotopic compositions correspondingly yield model Re-depletion (T_RD) ages that range from essentially modern to ∼1.3 Ga.Our data provide evidence for large-scale incompatible behavior of HSE during melt percolation as a result of sulfide dissolution, consistent with observations of prior studies. The degree of incompatibility evidently depended on melt/rock ratios and the degree of S-saturation of the percolating melt. The high Pt contents of some of these rocks suggest that the Pt present in this pervasively metasomatized mantle was controlled by a phase unique to the other HSE. Further, high Os concentrations in several samples suggest deposition of Os in a minority of the samples by melt percolation. In these rocks, the mobilized Os was characterized by similar to the ¹⁸⁷Os/¹⁸⁸Os ratios in the ambient rocks. There is no evidence for either the addition of Os with a strongly depleted isotopic composition, or Os with suprachondritic isotopic composition, as is commonly observed under such circumstances.     

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

Nd, Sr and Os isotope systematics in young, fertile spinel peridotite xenoliths from northern Queensland, Australia: A unique view of depleted MORB mantle?

Northeastern Queensland, a part of the Phanerozoic composite Tasman Fold Belt of eastern Australia, has a Paleozoic to Mesozoic history dominated by subduction zone processes. A suite of 13 peridotite xenoliths from the <3 Ma Atherton Tablelands Volcanic Province, predominantly from Mount Quincan, comprise fertile (1.8-3.4 wt.% Al₂O₃ and 38.7-41.9 wt.% MgO) spinel lherzolites free from secondary volatile-bearing phases and with only weak metasomatic enrichment of incompatible trace elements (Sm_N/Yb_N = 0.23-1.1; La_N/Yb_N = 0.11-4.9). The suite is isotopically heterogeneous, with measured Sr (⁸⁷Sr/⁸⁶Sr = 0.7027-07047), Nd (¹⁴³Nd/¹⁴⁴Nd = 0.51249-0.51362), and to a lesser extent, Os (¹⁸⁷Os/¹⁸⁸Os = 0.1228-0.1292) compositions broadly overlapping MORB source mantle (DMM) and extending to more depleted compositions, reflecting evolution in a time-integrated depleted reservoir. Major and rare earth element systematics are consistent with mantle that is residual after low to moderate degrees of melt extraction predominantly in the spinel facies, but with a few samples requiring partial melting at greater pressures in the garnet field or near the garnet-spinel transition. In contrast to most previously studied suites of continental lithospheric mantle samples, the incompatible trace element contents and Sr and Nd isotopic systematics of these samples suggest only minimal modification of the sampled lithosphere by metasomatic processes.Five of six Mount Quincan xenoliths preserving depleted middle to heavy REE patterns form a whole rock Sm-Nd isochron with an age of ∼275 Ma (ε_Ndi = +9), coincident with widespread granitoid emplacement in the overlying region. This isochron is interpreted to indicate the timing of partial melting of a DMM-like source. Xenoliths from other Atherton localities scatter about the isochron, suggesting that the sampled mantle represents addition of DMM mantle to the lithosphere in the Permian, when the region may have broadly been within a subduction zone setting. A sixth middle to heavy REE-depleted Mount Quincan xenolith has a distinct Nd and Os isotopic composition consistent either with an earlier, possibly Precambrian melt extraction event, or with Permian derivation from a mantle source with a less depleted (time-averaged lower Sm/Nd) Nd isotopic composition, but a more depleted (low Re/Os) Os isotopic composition.The range in measured whole rock Os isotopic compositions cannot solely be the result of time-integrated effects of variable melt extraction, especially considering the coherent Sm-Nd systematics of the suite. The Os heterogeneity more likely reflects either a heterogeneous ∼275 Ma DMM source that would have a present-day Os composition (¹⁸⁷Os/¹⁸⁸Os ∼ 0.1265-0.1287) overlapping both abyssal peridotites and chondrites, or significant and variable enrichment within the lithospheric mantle by secondary sulfides carrying radiogenic Os in a cryptic chalcophile enrichment event. Regardless of the origin of the Os isotopic variability, these data highlight the mantle Re-Os isotopic heterogeneity that may be present over small length scales where the lithophile Sm-Nd system may be relatively homogeneous.     

Isotopic analysis of early solar system objects by an ion microprobe: Parametric studies and initial results

Magnesium, potassium and calcium isotope compositions in terrestrial samples and refractory phases from primitive meteorites are determined using an ion microprobe. A thorough investigation of the different instrument parameters is carried out to ensure that conditions necessary for high mass resolution and high precision isotopic studies are adequately satisfied. The instrument can be tuned to achieve mass resolution (M/ΔM) of up to 10,000 (M≤60); it has a very good dynamic stability (ΔB/B≤10 ppm over durations of ≤40 minutes) and the counting system has an effective dead-time of ≤25 nsec and a dynamic background of ≤0·01 c/s. Reproducibility and precision of isotopic measurements are checked by analyzing magnesium and titanium isotopic compositions in terrestrial standards and isotopically doped silicate glasses. A precision of 2‰ (2σ _m ) was achieved during magnesium isotopic analysis in samples with low Mg content (200 ppm). Results from studies of magnesium and potassium isotopic compositions in several Ca−Al-rich refractory inclusions (CAIs) from the primitive meteorites Efremovka and Grosnaja, representing some of the early solar system objects, are presented. The well-behaved Mg−Al isotopic systematics confirm the pristine nature of the Efremovka CAIs inferred earlier from petrographic and trace element studies. The Grosnaja CAIs that have experienced secondary alterations show disturbed magnesium isotopic systematics. Observation of excess²⁶Mg in several of the analyzed CAIs confirms the presence of the now extinct²⁶Al (t _1/2=7×10⁵ years) in the solar nebula at the time of CAI formation. Our data also suggest a relatively uniform distribution of²⁶Al in the solar nebula. Several Efremovka CAIs with excess²⁶Mg also have excess⁴¹K resulting from the decay of⁴¹Ca (t _1/2≃10⁵ years). This observation constrains the time interval between cessation of nucleosynthetic input to the solar nebula and the formation of some of the first solar system solids (CAIs) to less than a million years.     

A comparison of selected Precambrian Brazilian chromitites: Chromite, PGE-PGM, and Re/Os as parental source indicators

Mineralogical and geochemical studies were carried out in chromitites belonging to the mafic–ultramafic bodies of Niquelândia, Luanga, and Campo Formoso, which are, respectively, included in the Goiás Massif and the Amazon and São Francisco cratons. The main platinum-group minerals (PGM) included or associated with chromite grains are laurite in Niquelândia and Campo Formoso and sperrylite and braggite in Luanga. The most common primary base metal sulfides (BMS) are pentlandite, chalcopyrite, and minor pyrrhotite. Also present are base metal alloys (BMA), such as awaruite, and the BMS millerite, pyrite, and copper as secondary mineral phases linked to later alteration process. The Luanga chromites display the lowest Cr₂O₃/Al₂O₃ and Cr₂O₃/FeO_t ratios. The chondrite-normalized profiles are strongly enriched in the platinum PGE subgroup (PPGE, Pt, Pd, Rh). The average Pd/Ir ratio (24.2) and ¹⁸⁷Os/¹⁸⁸Os values (0.17869–0.18584) are very high. Niquelândia chromites have higher Cr₂O₃/Al₂O₃ and Cr₂O₃/FeO_t ratios than Luanga. Its PGE contents are low and chondrite-normalized profiles depleted, mainly in the PPGE subgroup. The average Pd/Ir ratio (0.45) and ¹⁸⁷Os/¹⁸⁸Os values (0.12598–0.12777) are low. Campo Formoso chromites have the highest Cr₂O₃/Al₂O₃ and Cr₂O₃/FeO_t ratios; its average Pd/Ir ratio (0.72) and chondrite-normalized profiles (except the pronounced Ru spike) are closer to those of Niquelândia. The remarkable differences in terms of chromite bulk-composition, PGE contents and patterns, Pd/Ir ratios, and ¹⁸⁷Os/¹⁸⁸Os values associated with probable distinctions in the inferred geochemical compositions of the respective parental magmas indicate that the Luanga and Niquelândia complexes originated from distinct parental sources. Geochemical and isotopic features indicate that Luanga chromitites and associated rocks are consistent with a parental magma, either originated from an enriched mantle reservoir or strongly contaminated, whereas Niquelândia derives from a depleted mantle source, which displays a slightly positive Os anomaly.     

Os mobilization during melt percolation: The evolution of Os isotope heterogeneities in the mantle sequence of the troodos ophiolite, Cyprus

This study focuses on the origin of the Os isotope heterogeneities and the behaviour of Os and Re during melt percolation and partial melting processes in the mantle sequence of the Troodos Ophiolite Complex. The sequence has been divided into an eastern (Unit 1) and a western part (Unit 2) (Batanova and Sobolev, 2000). Unit 1 consists mainly of spinel-lherzolites and a minor amount of dunites, which are surrounded by cpx-bearing harzburgites. Unit 2 consists of harzburgites, dunites, and contains chromitite deposits.Unit 1 (¹⁸⁷Os/¹⁸⁸Os: 0.1169 to 0.1366) and Unit 2 (¹⁸⁷Os/¹⁸⁸Os 0.1235 to 0.1546) peridotites both show large ranges in their Os isotopic composition. Most of the ¹⁸⁷Os/¹⁸⁸Os ratios of Unit 1 lherzolites and harzburgites are chondritic to subchondritic, and this can be explained by Re depletion during ancient partial melting and melt percolation events. The old Os isotope model ages (>800 Ma) of some peridotites in a young ophiolitic mantle show that ancient Os isotopic heterogeneities can survive in the Earth upper mantle. Most harzburgites and dunites of Unit 2 have suprachondritic ¹⁸⁷Os/¹⁸⁸Os ratios. This is the result of the addition of radiogenic Os during a younger major melt percolation event, which probably occurred during the formation of the Troodos crust 90 Ma ago.Osmium concentrations tend to decrease from spinel-lherzolites (4.35 ± 0.2 ng/g) to harzburgites (Unit 1: 4.06 ± 1.12 ng/g; Unit 2: 3.46 ± 1.38 ng/g) and dunites (Unit 1: 2.71 ± 0.84 ng/g; Unit 2: 1.85 ± 1.20 ng/g). Therefore, this element does not behave compatibly during melt percolation as it is observed during partial melting, but becomes dissolved and mobilized by the percolating melt. The Os contents and Re/Os ratios in the mantle peridotites can be explained if they represent mixing products of old depleted mantle with cpx- and opx-veins, which are crystallization products of the percolating melt. This mixing occurred during the melting of a continuously fluxed mantle in a supra-subduction zone environment.This study shows that Unit 1 and Unit 2 of the Troodos mantle section have a complex and different evolution. However, the Os isotopic characteristics are consistent with a model where the harzburgites and dunites of both units belong to the same melting regime producing the Troodos oceanic crust.     

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

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

Os and Os enrichments and high-He/He sources in the Earth’s mantle: Evidence from Icelandic picrites

Picrites from the neovolcanic zones in Iceland display a range in ¹⁸⁷Os/¹⁸⁸Os from 0.1297 to 0.1381 (γ_Os = + 2.1 to +8.7) and uniform ¹⁸⁶Os/¹⁸⁸Os of 0.1198375 ± 32 (2σ). The value for ¹⁸⁶Os/¹⁸⁸Os is within uncertainty of the present-day value for the primitive upper mantle of 0.1198398 ± 16. These Os isotope systematics are best explained by ancient recycled crust or melt enrichment in the mantle source region. If so, then the coupled enrichments displayed in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os from lavas of other plume systems must result from an independent process, the most viable candidate at present remains core-mantle interaction. While some plumes with high ³He/⁴He, such as Hawaii, appear to have been subjected to detectable addition of Os (and possibly He) from the outer core, others such as Iceland do not.A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He from 9.6 to 19 Ra in Iceland picrites is best modeled as mixtures of 1 Ga or older ancient recycled crust mixed with primitive mantle or incompletely degassed depleted mantle isolated since 1-1.5 Ga, which preserves the high ³He/⁴He of the depleted mantle at the time. These mixtures create a hybrid source region that subsequently mixes with the present-day convecting MORB mantle during ascent and melting. This multistage mixing scenario requires convective isolation in the deep mantle for hundreds of million years or more to maintain these compositionally distinct hybrid sources. The ³He/⁴He of lavas derived from the Iceland plume changed over time, from a maximum of 50 Ra at 60 Ma, to approximately 25-27 Ra at present. The changes are coupled with distinct compositional gaps between the different aged lavas when ³He/⁴He is plotted versus various geochemical parameters such as ¹⁴³Nd/¹⁴⁴Nd and La/Sm. These relationships can be interpreted as an increase in the proportion of ancient recycled crust in the upwelling plume over this time period.The positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He demonstrates that the Iceland lava He isotopic compositions do not result from simple melt depletion histories and consequent removal of U and Th in their mantle sources. Instead their He isotopic compositions reflect mixtures of heterogeneous materials formed at different times with different U and Th concentrations. This hybridization is likely prevalent in all ocean island lavas derived from deep mantle sources.     

pg-ng级Os同位素热表面电离质谱高精度分析测试技术

随着Os同位素在地质学领域定年与示踪的广泛应用,对分析测试精度和检出限提出了更高的要求。本文利用热表面电离质谱负离子模式(NTIMS)对Os O-3进行测定,通过试剂纯化、器皿清洗等前处理步骤的优化保证了超低的化学流程空白和获得灵敏而稳定的仪器测量信号,建立了高精度pg-ng级Os同位素分析测试方法。采用逐级剥谱法扣除氧同位素干扰,采用内标迭代法按照指数规律对仪器的质量歧视效应进行校正,全流程Os空白为0.41 pg,1 pg的190Os计数约85000 cps,质量分馏系数在0.1%以内。pg级Os采用离子计数器动态跳峰扫描模式进行测量,187Os/188Os值测量精度小于在0.2%以内;ng级Os采用法拉第杯静态接收模式采集信号,187Os/188Os值测量精度在0.005%以内。经国际上Os同位素标准溶液N2、JMC以及国家一级Re-Os同位素标准物质JCBY的验证,分析精度达到了国际同类实验室先进水平。本方法具有低空白、高灵敏度、高精度的特点,可为地质学研究提供高精度Os同位素数据。     

Tracing crustal contamination of the Cenozoic basalts with OIB-affinity in northern marginal region of North China Craton: An Os perspective

The Cenozoic basalts with OIB-affinity in northern marginal region of the North China Craton are thought to experience minor even no crustal contamination during the magma evolution. The whole-rock Sr-Nd-Pb-Hf isotopes are attributed to a two-component mixing between depleted and enriched mantle sources, while the major element variations are controlled by the fractional crystallization of olivine and clinopyroxene. However, in this study, the new Os isotopic data proposes an opposite model for the Cenozoic basalts in northern marginal region of the North China Craton. In this model, the Jining basalts were contaminated by the Archean mafic rocks during the magma storage and ascent. The crustal contamination process is supported by (1) the highly radiogenic Os isotopic compositions, and (2) the positive correlation between ¹⁸⁷Os/¹⁸⁸Os and 1/Os of the Jining basalts. By modeling the Os isotopic composition of the basalts, an incorporation of < 10% mafic granulites/amphibolites to the parental magma can successfully explain the initial values of highly radiogenic Os. In contrast, the unradiogenic and uniform Os isotopic compositions of the Chifeng basalts suggest negligible crustal contamination. Os isotopic data acts as an indicator of crustal contamination during magma evolution, providing us a novel insight into the evolution of the intra-continental OIB-like basalts worldwide.©2021 China Geology Editorial Office.     

Dissolved osmium in Bengal plain groundwater: Implications for the marine Os budget

We report osmium concentrations and isotopic compositions of 40 groundwater samples from the Bengal plain. Groundwaters have Os concentrations (16.9-191.5 pg/kg), about 5-10 times higher than those published for most rivers or seawater. ¹⁸⁷Os/¹⁸⁸Os varies widely (from 0.96 to 2.79) and is related to the isotopic signatures of the sediments constituting local aquifers. Os contents are correlated with those of soluble elements such as Sr, Mg, and Ca, suggesting that differing extents of solid-solution interaction explain most of the variation in measured Os concentrations. The covariation between Os and Sr allows us to estimate the mean Os content of Bengal groundwater (∼70 pg/kg). This concentration is too low to allow Bengal groundwater to significantly influence the marine Os isotopic composition, if likely fresh groundwater discharge rates to the Bay of Bengal are assumed. However, if Bengal groundwater Os concentrations are typical, the global Os groundwater flux would be expected to be around 180 kg/year, making it the second largest input of Os to the ocean after the river flux. Including this flux in the current Os marine budget, and assuming that this and other fluxes have remained constant with time, would decrease the calculated residence time of Os in the ocean by about 30%.     

The concentration and isotopic composition of hydrogen,carbon and nitrogen in carbonaceous meteorites

Concentrations and isotopic compositions were determined for H₂, N₂ and C extracted by stepwise pyrolysis from powdered meteorites, from residues of meteorites partially dissolved with aqueous HF, and from residues of meteorites reacted with HF-HCl solutions. The meteorites treated were the carbonaceous chondrites, Orgueil, Murray, Murchison, Renazzo and Cold Bokkeveld. Data determined for whole rock samples are in approximate agreement with previously published data. Acidification of the meteorites removed the inorganic sources of H₂, so that H₂ in the HF-HCl acid residues came primarily from insoluble organic matter, which makes up 70–80% fraction of the total carbon in carbonaceous meteorites. The δD in the organic matter differs markedly from previously determined values in organic matter in meteorites. The δD values of organic matter from acid residues of C1 and C2 carbonaceous chondrites range from +650 to + 1150%. The acid residues of the Renazzo meteorite, whose total H₂ has a δD of +930‰, gave a δD value of +2500‰. Oxidation of the HF-HCl residue with H₂O₂ solution removes the high δD and the low δ¹⁵N components. The δ¹³C values range between ?10 and ?21 and δ¹⁵N values range between +40 and ?11. The δ¹⁵N of Renazzo is unusual; its values range between +150 and ?190.There is good correlation between δD and the concentration of H₂ in the acid residues, but no correlation exists between δD, δ¹³C and δ¹⁵N in them. A simple model is proposed to explain the high δD values, and the relationships between δD values and the concentration of H₂. This model depends on the irradiation of gaseous molecules facilitating reaction between ionic molecules, and indicates that an increase in the rate of polymerization and accumulation of organic matter on grains would produce an increase in the deuterium concentration in organic matter.     

Re-Os and Pd-Ag systematics in Group IIIAB irons and in pallasites

Using improved analytical techniques, which reduce the Re blanks by factors of 8 to 10, we report new Re-Os data on low Re and low PGE pallasites (PAL-anom) and IIIAB irons. The new pallasite samples nearly double the observed range in Re/Os for pallasites and allow the determination of an isochron of slope 0.0775 ± 0.0008 (T = 4.50 ± 0.04 Ga, using the adjusted λ¹⁸⁷Re = 1.66 × 10⁻¹¹ a⁻¹) and initial (¹⁸⁷Os/¹⁸⁸Os)₀ = 0.09599 ± 0.00046. If the data on different groups of pallasites (including the “anomalous” pallasites) are considered to define a whole-rock isochron, their formation would appear to be distinctly younger than for the iron meteorites by ∼60 Ma. Five IIIAB irons (Acuna, Bella Roca, Chupaderos, Grant, and Bear Creek), with Re contents ranging from 0.9 to 2.8 ppb, show limited Re/Os fractionation and plot within errors on the IIAB iron meteorite isochron of slope 0.07848 ± 0.00018 (T = 4.56 ± 0.01 Ga) and initial (¹⁸⁷Os/¹⁸⁸Os)₀ = 0.09563 ± 0.00011. Many of the meteorites were analyzed also for Pd-Ag and show ¹⁰⁷Ag enrichments correlated with Pd/Ag, requiring early formation and fractionation of the FeNi metal, in a narrow time interval, after injection of live ¹⁰⁷Pd (t_1/2 = 6.5 Ma) into the solar nebula. Based on Pd-Ag, the typical range in relative ages of these meteorites is ≤10 Ma. The Pd-Ag results suggest early formation and preservation of the ¹⁰⁷Pd-¹⁰⁷Ag systematics, both for IIIAB irons and for pallasites, while the younger Re-Os apparent age for pallasites suggests that the Re-Os system in pallasites was subject to re-equilibration. The low Re and low PGE pallasites show significant Re/Os fractionation (higher Re/Os) as the Re and PGE contents decrease. By contrast, the IIIAB irons show a restricted range in Re/Os, even for samples with extremely low Re and PGE contents. There is a good correlation of Re and Ir contents. The correlation of Re and Os contents for IIIAB irons shows a similar complex pattern as observed for IIAB irons (Morgan et al., 1995), and neither can be ascribed to a continuous fractional crystallization process with uniform solid-metal/liquid-metal distribution coefficients.     

Separation of Platinum from Palladium and Iridium in Iron Meteorites and Accurate High‐Precision Determination of Platinum Isotopes by Multi‐Collector ICP‐MS

This study presents a new measurement procedure for the isolation of Pt from iron meteorite samples. The method also allows for the separation of Pd from the same sample aliquot. The separation entails a two‐stage anion‐exchange procedure. In the first stage, Pt and Pd are separated from each other and from major matrix constituents including Fe and Ni. In the second stage, Ir is reduced with ascorbic acid and eluted from the column before Pt collection. Platinum yields for the total procedure were typically 50–70%. After purification, high‐precision Pt isotope determinations were performed by multi‐collector ICP‐MS. The precision of the new method was assessed using the IIAB iron meteorite North Chile. Replicate analyses of multiple digestions of this material yielded an intermediate precision for the measurement results of 0.73 for ε¹⁹²Pt, 0.15 for ε¹⁹⁴Pt and 0.09 for ε¹⁹⁶Pt (2 standard deviations). The NIST SRM 3140 Pt solution reference material was passed through the measurement procedure and yielded an isotopic composition that is identical to the unprocessed Pt reference material. This indicates that the new technique is unbiased within the limit of the estimated uncertainties. Data for three iron meteorites support that Pt isotope variations in these samples are due to exposure to galactic cosmic rays in space.     

Petrological and Os Isotopic Characteristics of Zedong Peridotites in the Eastern Yarlung–Zangbo Suture in Tibet

The Zedong ophiolites in the eastern Yarlung–Zangbo suture zone of Tibet represent a mantle slice of more than 45 km~2. This massif consists mainly of mantle peridotites, with lesser gabbros, diabases and volcanic rocks. The mantle peridotites are mostly harzburgite, lherzolite; a few dike-like bodies of dunite are also present. Mineral structures show that the peridotites experienced plastic deformation and partial melting. Olivine(Fo89.7–91.2), orthopyroxene(En_(88–92)), clinopyroxene(En_(45–49) Wo_(47–51) Fs_(2–4)) and spinel [Mg~#=100×Mg/(Mg+Fe)]=49.1–70.7; Cr~#=(100×Cr/(Cr+Al)=18.8–76.5] are the major minerals. The degree of partial melting of mantle peridotites is 10%–40%, indicating that the Zedong mantle peridotites may experience a multi–stage process. The peridotites are characterized by depleted major element compositions and low REE content(0.08–0.62 ppm). Their "spoon–shaped" primitive–mantle normalized REE patterns with(La/Sm)_N being 0.50–6.00 indicate that the Zedong ultramafic rocks belong to depleted residual mantle rocks. The PGE content of Zedong peridotites(18.19–50.74 ppb) is similar with primary mantle with Pd/Ir being 0.54–0.60 and Pt/Pd being 1.09–1.66. The Zedong peridotites have variable, unradiogenic Os isotopic compositions with ~(187)Os/~(188)Os=0.1228 to 0.1282. A corollary to this interpretation is that the convecting upper mantle is heterogeneous in Os isotopes. All data of the Zedong peridotites suggest that they formed originally at a mid-ocean ridge(MOR) and were later modified in supra–subduction zone(SSZ) environment.     

Variations in Os isotope ratios of pyrrhotite as a result of water-rock and magma-rock interaction: Constraints from Virginia Formation-Duluth Complex contact zones

Os isotope ratios in pyrrhotite-bearing pelitic rocks of the ∼1.85 Ga Virginia Formation are variable, with perturbations linked to the emplacement of the ∼1.1 Ga Duluth Complex. Pyrrhotite in footwall rocks of the contact aureole show evidence for a mixing event at 1.1 Ga involving a low ¹⁸⁷Os/¹⁸⁸Os fluid. However, because rocks with perturbed pyrrhotite Os isotope ratios occur 1½ km or more from the Duluth Complex, the fluid is unlikely to have been of magmatic origin. Fluid inclusions in layer-parallel quartz veins provide evidence of the involvement of a boiling fluid at temperatures between ∼300 and 400 °C. Analyses of fluid inclusions via LA-ICP-MS show that the fluids contain up to 1.7 wt% Na, 1.1 wt% K, 4330 ppm Fe, 2275 ppm Zn, and 415 ppm Mg. The veins also contain pyrite or pyrrhotite, plus minor amounts of chalcopyrite, bornite, pentlandite, and sphalerite. The Re-Os isotopic ratios of pyrite from the veins indicate that they crystallized from low ¹⁸⁷Os/¹⁸⁸Os fluids (<0.2). δ¹⁸O values of vein quartz range from 7.7‰ to 9.5‰, consistent with an origin involving fluid with a relatively low δ¹⁸O value between 2‰ and 5‰. Meteoric water with such a low δ¹⁸O value could have interacted with the igneous rocks of the Complex and would have acquired Os with a low ¹⁸⁷Os/¹⁸⁸Os ratio. Strongly serpentinized olivine-rich rocks of the Complex are commonly characterized by such low δ¹⁸O values and we propose that the fluid involved in serpentinization was also responsible for the perturbation of the Os isotopic system recorded by pyrrhotite in the Virginia Formation. Two important observations are that only pyrrhotite-bearing assemblages in the contact aureole show isotopic perturbation and that intervals showing Os exchange are spatially restricted, and not uniformly distributed. Os exchange and mixing has occurred only where temperatures were sufficient to convert pyrite to pyrrhotite, and where time-integrated water-rock ratios in the aureole were high enough to provide a supply of Os.Troctolitic and gabbroic rocks of the Partridge River Intrusion, Duluth Complex, are characterized by Os isotope ratios that are indicative of variable degrees of crustal contamination (γ_Os values of ∼0-543). Xenoliths of carbonaceous and sulfidic pelitic rocks of the Virginia Formation found in the igneous rocks provide evidence that Os was released by organic matter and pyrite in the sedimentary rocks and assimilated by mantle-derived magma. However, residual pyrrhotite produced as a result of pyrite breakdown in the xenoliths is characterized by ¹⁸⁷Os/¹⁸⁸Os ratios that are much lower than anticipated and similar to those of pyrrhotite in the contact aureole. The Os exchange and addition shown by pyrrhotite in the xenoliths highlight an unusual cycle of Re-Os liberation during devolatilization, kerogen maturation, and pyrite to pyrrhotite conversion (processes that contribute to magma contamination), followed by Os uptake by pyrrhotite during back reaction involving magma and/or fluid characterized by a relatively low ¹⁸⁷Os/¹⁸⁸Os ratio. The extreme Os uptake recorded by pyrrhotite in the xenoliths, as well as the lesser degree of uptake recorded by pyrrhotite in the contact aureole, is in line with the high Os diffusivity in pyrrhotite experimentally determined by Brenan et al. (2000). Our data confirm that Os isotope ratios in pyrrhotite-bearing rocks may be readily perturbed. For this reason caution should be exercised in the interpretation of Os isotope ratios in rocks where pyrrhotite may be the primary host of Os.