Osmium mass balance in peridotite and the effects of mantle-derived sulphides on basalt petrogenesis

Analyses of enriched mantle (EM)-basalts, using lithophile element-based isotope systems, have long provided evidence for discrete mantle reservoirs with variable composition. Upon partial melting, the mantle reservoir imparts its isotopic fingerprint upon the partial melt produced. However, it has increasingly been recognised that it may not be simple to delimit these previously well-defined mantle reservoirs; the “mantle zoo” may contain more reservoirs than previously envisaged.Here we demonstrate that a simple model with varying contributions from two populations of compositionally distinct mantle sulphides can readily account for the observed heterogeneities in Os isotope systematics of such basalts without additional mantle reservoirs. Osmium elemental and isotopic analyses of individual sulphide grains separated from spinel lherzolites from Kilbourne Hole, New Mexico, USA demonstrate that two discrete populations of mantle sulphide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os] and low [Re] with unradiogenic, typically sub-chondritic ¹⁸⁷Os/¹⁸⁸Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulphides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic ¹⁸⁷Os/¹⁸⁸Os ([Os] typically ? 1-2 ppm, ¹⁸⁷Os/¹⁸⁸Os ? 0.3729; this study). This population is thought to represent metasomatic sulphide.Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulphide ([Os] ? 37 ppm; this study). During the early stages of partial melting, supra-chondritic interstitial sulphides are mobilised and incorporated into the melt, adding their radiogenic ¹⁸⁷Os/¹⁸⁸Os signature. Only when sulphides armoured within silicates are exposed to the melt through continued partial melting will enclosed sulphides add their high [Os] and unradiogenic ¹⁸⁷Os/¹⁸⁸Os to the aggregate melt. Platinum-group element data for whole rocks are also consistent with this scenario. The sequence of (i) addition of all of the metasomatic sulphide, followed by (ii) the incorporation of small amounts of armoured sulphide can thus account for the range of both [Os] and ¹⁸⁷Os/¹⁸⁸Os of EM-basalts worldwide without the need for contributions from additional silicate mantle reservoirs.     

Palaeoproterozoic Chibaisong mafic intrusion and mineralization (Northeast China), the oldest Cu–Ni sulphide deposit in China: evidence from Re–Os dating of pyrrhotite

The Chibaisong magmatic Cu–Ni sulphide deposit is located in Tonghua City, Jilin Province, in the eastern part of the northern margin of the North China Craton. The geological characteristics of the deposit have been investigated, and pyrrhotite Re–Os isotope dating has been utilized to constrain the age. Five pyrrhotite samples separated from the Chibaisong Cu–Ni sulphide deposit yielded a Re–Os isotopic isochron age of 2237 ± 62 Ma (mean squared weighted deviation = 1.13, n = 5), indicating that the only Palaeoproterozoic magmatic Cu–Ni sulphide deposit in China is the Chibaisong Cu–Ni sulphide deposit. The geodynamic setting during ore formation was related to the Liaoning–Jilin Palaeoproterozoic rift split. The Re–Os isotope analyses showed an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.778 ± 0.033, and (¹⁸⁷Os/¹⁸⁸Os)_i and γOs(t) values ranged from 0.7531 to 0.8013 (average 0.7734) and from 574 to 617 (average 592), respectively, indicating that abundant crustal material (5–10%) was mixed with the Cu–Ni sulphide ore system during magma ascent and ore formation.     

Granulite sulphides as tracers of lower crustal origin and evolution: An example from the Slave craton, Canada

We carried out a detailed study of sulphide minerals, a ubiquitous mineral group in lower crustal mafic to peraluminous granulite xenoliths from the Diavik kimberlites, to assess their use in constraining the origin and tectonothermal evolution of the deep crust, and to obtain additional data on the composition of lower crust beneath ancient continents. Sulphides are overwhelmingly pyrrhotite with minor Ni (0.7-3.9 at.%), Co (0.1-0.7 at.%), and Cu contents (0.4-3.9 at.%). Sulphide modes in mafic granulites range from 0.14 to 0.55 vol%, translating into bulk rock S contents from ∼600 to 2000 ppm, similar to S contents in other mafic igneous rocks and indicating preservation of primary igneous S contents. In mafic granulites, Re and Os abundances in sulphides range from 42.5 to 726 ppb and 3.2 to 180 ppb, respectively, whereas those in peraluminous granulites are distinctly lower (36.1-282 ppb and 1.8-7.2 ppb, respectively), suggestive of Re and Os loss to fractionating sulphides in the more evolved precursors of these rocks.The significant within-sample variability of ¹⁸⁷Os/¹⁸⁸Os and correlation with ¹⁸⁷Re/¹⁸⁸Os indicates the preservation of primary Re-Os isotope systematics and time-integrated decay of the measured ¹⁸⁷Re. Within the large uncertainties inherent in the nature of the samples and technique, sulphides in some granulites may record major tectonothermal events in the central Slave craton spanning several billion years of evolution. Multiple generations of sulphide can occur in a single sample. These data attest to the heterogeneous composition and complex history of the Slave craton lower crust.     

Re-Os isotopic composition of peridotitic sulphide inclusions in diamonds from Ellendale, Australia: Age constraints on Kimberley cratonic lithosphere

Sulphide-bearing diamonds recovered from the ∼20 Ma Ellendale 4 and 9 lamproite pipes in north-western Australia were investigated to determine the nitrogen aggregation state of the diamonds and Re-Os isotope geochemistry of the sulphide inclusions. The majority of diamond studies have been based on diamonds formed in the sub-continental lithospheric mantle (SCLM) below stable cratons, whereas the Ellendale lamproites intrude the King Leopold Orogen, south of the Kimberley craton. The sulphide inclusions consist of pyrrhotite-pentlandite-chalcopyrite assemblages, and can be divided into peridotitic and eclogitic parageneses on the basis of their Ni and Os contents. A lherzolitic paragenesis for the high-Ni sulphide inclusions is suggested from their Re and Os concentrations. Regression analysis of the Re-Os isotope data for the lherzolitic sulphides yields an age of 1426 ± 130 Ma, with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.1042 ± 0.0034. The upper limit of the uncertainty on the ¹⁸⁷Os/¹⁸⁸Os initial ratio gives a Re depletion age of 2.96 Ga, indicating the presence of SCLM beneath Ellendale since at least the Mesoarchaean, with the lherzolitic diamond-forming event much younger and unrelated to the craton keel stabilisation. The nitrogen aggregation state of the diamonds and calculated mantle residence temperatures suggest an origin and storage of the Ellendale diamonds in a stable cratonic SCLM, consistent with the King Leopold Orogen being cratonised by about 1.8 Ga. The diamonds do not show evidence for pervasive deformation or platelet degradation, which suggests that the diamonds had a relatively undisturbed 1.4 billion year mantle storage history.     

Rhenium–Osmium Isotope Measurements in Marine Shale Reference Material SBC‐1: Implications for Method Validation and Quality Control

In this study, the USGS black shale reference material SBC‐1 was investigated as a matrix‐matched reference material for both intra‐laboratory calibration and inter‐laboratory comparison of high‐precision Re‐Os dating for organic‐rich sedimentary rocks. This reference material was analysed for Re‐Os isotopic composition by three digestion protocols – inverse aqua regia, CrO₃‐H₂SO₄ and H₂O₂‐HNO₃. The results for SBC‐1 obtained by inverse aqua regia digestion yielded similar Re mass fractions but slightly (~ 5%) higher Os mass fractions and lower ¹⁸⁷Os/¹⁸⁸Os values than the CrO₃‐H₂SO₄ and H₂O₂‐HNO₃ digestions. The data set of inverse aqua regia digestion exhibited strong correlations in plots of ¹⁸⁷Os/¹⁸⁸Os vs. 1/¹⁹²Os and ¹⁸⁷Os/¹⁸⁸Os vs. ¹⁸⁷Re/¹⁸⁸Os, which may signify the incorporation of detrital Re and Os into organic matter in the Re‐Os system. Similar correlations were also observed for the CrO₃‐H₂SO₄ digestion data set, but not for that of H₂O₂‐HNO₃. The data indicate that there is an amount of non‐hydrogenous Os in SBC‐1 and that CrO₃‐H₂SO₄ and H₂O₂‐HNO₃ digestions would minimise liberation of the non‐hydrogenous Os component. We propose that SBC‐1 may be a more suitable reference material to monitor the influence of detrital Re and Os on Re‐Os isochron age data, especially for samples with less organic matter and more siliceous detritus.     

A major element,PGE and Re–Os isotope study of Middle Atlas (Morocco) peridotite xenoliths: Evidence for coupled introduction of metasomatic sulphides and clinopyroxene

We present major element and PGE (platinum-group-element) abundances in addition to Re–Os isotope data for 11 spinel-facies whole rock peridotites from a single maar from the Middle Atlas Mountains, Morocco.Major element systematics of these xenoliths are generally correlated with indices of depletion. FeO–MgO systematics appear to suggest spinel-facies melting in the range of 5 to 25%. However, Al₂O₃ abundances in these xenoliths appear elevated relative to primitive mantle (Prima). The Al₂O₃ abundances in conjunction with other major elements require distinct re-enrichment of the Middle Atlas continental mantle root due to melt/rock reaction and precipitation of amphibole and/or clinopyroxene from passing silicate melts akin to MORB or OIB that evolved in reverse direction along the melting curves in e.g. FeO–MgO space. Sc and V confirm the range of apparent depletion and also indicate that the currently preserved fO₂ in these peridotites is distinctly different from fO₂ conditions observed in subduction zones.The majority of these xenoliths have low Os and Ir (I-PGEs) concentrations relative to Prima and modelled sulphide- and clinopyroxene-depleted residues of mantle melting under low fO₂, mid-ocean ridge-like conditions. Moreover, Pt and Pd (P-PGE) abundances are elevated when compared to their expected abundances after substantial melt extraction. Importantly, the systematically low Ir abundances in the majority of samples show well-correlated trends with Al₂O₃, MgO and Cu that are inconsistent with established melting trends. Os isotopes in the Middle Atlas xenoliths range from ¹⁸⁷Os/¹⁸⁸Os = 0.11604 to 0.12664 although most samples are close to chondritic. The Os isotope ratios are decoupled from ¹⁸⁷Re/¹⁸⁸Os but, together with Re abundances, also exhibit a good correlation with Al₂O₃, MgO and Cu.The major element, I-PGE and Os isotope correlations suggest that the initial melt depletion led to the exhaustion of sulphide and clinopyroxene (20 to 30%) without significant stabilization of I-PGE-rich alloys. During later modal metasomatism of the refractory Middle Atlas continental mantle root with silicate melts akin to MORB or OIB the introduction of clinopyroxene/amphibole reduced the volume of the melt inducing sulphur saturation in these melts causing precipitation of secondary sulphides. This coupled crystallization of pyroxenes and sulphides (chalcopyrite) resulted in the two-component mixing systematics exhibited by I-PGEs, Os isotopes with major elements and Cu preserved in the Middle Atlas continental mantle root.     

Re–Os dating of sulphides from the Yushui Cu-polymetallic deposit in eastern Guangdong Province,South China

The Yushui Cu-polymetallic deposit, which is associated with Ag, Pb, and Zn, is located in the middle part of the Yongan–Meixian Late Paleozoic Hercynian depression. It was discovered in eastern Guangdong Province in the late 1980s and is one of the richest copper deposits in China with high-grade copper averaging 3.25% and locally reaching 50–60%. The main ore body is located along the unconformity between the Upper Carboniferous Hutian Group limestone and the Lower Carboniferous Zhongxin Formation quartz sandstone with a bedded and lenticular morphology. The ores exhibit massive textures dominated by chalcopyrite, bornite, chalcocite, pyrite, sphalerite, galena, and a trace amount of argentite. Although researchers began studying the Yushui deposit in the early 1990s, the ore genesis remains controversial because of the lack of precise mineralisation age constraints. In this study, direct Re–Os dating of Cu sulphides aided in facilitating a better understanding of the timing of formation of the Yushui deposit. This study is the first attempt to use the Re–Os isotopic system for directly dating chalcopyrite and bornite ores for the Yushui deposit. The contents of Re, common Os, ¹⁸⁷Re and ¹⁸⁷Os in nine sulphides are 1.68–219.35 ppb, 0.003–0.427 ppb, 1.05–137.31 ppb, and 0.045–0.734 ppb, respectively. The isotope data yielded an isochron age of 308 ± 15 Ma (mean square weighted deviates = 2.4) using the ⁸⁷Re/¹⁸⁸Os–¹⁸⁷Os/¹⁸⁸Os plot, which is interpreted to represent the age of formation for these sulphides, suggesting that the mineralisation age of the Yushui deposit is close to the age of the host rocks. The ¹⁸⁷Os/¹⁸⁸Os initial value obtained from the Re–Os isochron is 1.81 ± 0.34, which corresponds to the γOs value of + 1349. This value indicates that the ore-forming materials were derived from the crust without mixing with materials from the mantle, and that the Yushui massive sulphide deposit may be of sedimentary exhalative origin.     

Re–Os isotopic dating of molybdenite and pyrite in the Baishan Mo–Re deposit, eastern Tianshan, NW China, and its geological significance

The Baishan Mo–Re deposit is located in the eastern section of the eastern Tianshan orogenic belt, NW China. The deposit has a grade of 0.06% Mo and a high content of rhenium of 1.4 g/t. Rhenium and osmium isotopes in sulfide minerals from the Baishan deposit are used to determine the age of mineralization. Rhenium concentrations in molybdenite samples are between 74 and 250 g/g. Analysis of eight molybdenite samples yields an isochron age of 224.8±4.5 Ma (2). Pyrite samples have rhenium and osmium concentrations varying in the range 33.4–330.6 ng/g and 0.08–0.81 ng/g, respectively. Isotope data on seven pyrite samples yield an isochron age of 225±12 Ma (2) on the ¹⁸⁷Re/¹⁸⁸Os versus ¹⁸⁷Os/¹⁸⁸Os plot and an age of 233±14 Ma (2) on the ¹⁸⁷Os versus ¹⁸⁷Re correlation diagram. The ages of molybdenite and pyrite are consistent within the analytical errors. Combined with field observations, the data indicate that Mo–Re mineralization in the Baishan deposit is produced by a magmatic-hydrothermal event in an intracontinental extensional setting after late Paleozoic orogeny. The initial ¹⁸⁷Os/¹⁸⁸Os ratio of pyrite is 0.3±0.07. The ³⁴S values of molybdenite vary from +0.5 to +3.6. Both data indicate that mineralization is derived mainly from a mantle source.Editorial handling: J. Richards     

Magma Mixing as a Trigger for Sulphide Saturation in the UG2 Chromitite (Bushveld): Evidence from the Silicate and Sulphide Melt Inclusions in Chromite

It is of great importance to understand the origin of UG2 chromitite reefs and reasons why some chromitite reefs contain relatively high contents of platinum group elements(PGEs: Os, Ir, Ru, Rh,Pt, Pd) or highly siderophile elements(HSEs: Au, Re, PGE). This paper documents sulphide-silicate assemblages enclosed in chromite grains from the UG2 chromitite. These are formed as a result of crystallisation of sulphide and silicate melts that are trapped during chromite crystallisation. The inclusions display negative crystal shapes ranging from several micrometres to 100 μm in size.Interstitial sulphide assemblages lack pyrrhotite and consist of chalcopyrite, pentlandite and some pyrite. The electron microprobe data of these sulphides show that the pentlandite grains present in some of the sulphide inclusions have a significantly higher iron(Fe) and lower nickel(Ni) content than the pentlandite in the rock matrix. Pyrite and chalcopyrite show no difference. The contrast in composition between inter-cumulus plagioclase(An_(68)) and plagioclase enclosed in chromite(An_(13)), as well as the presence of quartz, is consistent with the existence of a felsic melt at the time of chromite saturation.Detailed studies of HSE distribution in the sulphides and chromite were conducted by LA-ICP-MS(laser ablation-inductively coupled plasma-mass spectrometry), which showed the following.(Ⅰ) Chromite contained no detectable HSE in solid solution.(Ⅱ) HSE distribution in sulphide assemblages interstitial to chromite was variable. In general, Pd, Rh, Ru and Ir occurred dominantly in pentlandite, whereas Os,Pt and Au were detected only in matrix sulphide grains and were clearly associated with Bi and Te.(Ⅲ)In the sulphide inclusions,(a) pyrrhotite did not contain any significant amount of HSE,(b) chalcopyrite contained only some Rh compared to the other sulphides,(c) pentlandite was the main host for Pd,(d)pyrite contained most of the Ru, Os, Ir and Re,(e) Pt and Rh were closely associated with Bi forming a continuous rim between pyrite and pentlandite and(f) no Au was detected. These results show that the use of ArF excimer laser to produce high-resolution trace element maps provides information that cannot be obtained by conventional(spot) LA-ICP-MS analysis or trace element maps that use relatively large beam diameters.     

Sources of unique rhenium enrichment in fumaroles and sulphides at Kudryavy volcano

Rhenium (Re) is one of the least abundant elements in Earth, averaging 0.28 ppb in the primitive mantle. The unique occurrence of rheniite ReS₂ (74.5 wt% of Re) in Kudryavy volcano precipitates raises questions about recycling of Re-rich reservoirs within the Kurile-Kamchatka volcanic Island arc setting. The sources of this unique Re enrichment have been inferred from studies of Re-Os isotope systematic and trace elements in volcanic gases, sulphide precipitates and host volcanic rocks. The fumarolic gas condensates are enriched in hydrophile trace elements relative to fluid-immobile elements and exhibit high Ba/Nb (133-204), Rb/Y (16-406) and Th/Zr (0.01-0.25) ratios. They are characterised by high Re (7-210 ppb) and Os abundances (0.4-0.9 ppb), with ¹⁸⁷Os/¹⁸⁸Os ratios in a range 0.122-0.152. This Os isotopic compositional range is similar to that of the peridotite xenoliths from the metasomatised mantle wedge above the subducted Pacific plate, the radiogenic isotopic signature of which is probably due to radiogenic addition from a slab-derived fluid.Re- and Os-rich sulphide and oxide minerals precipitate from volcanic gases within fumarolic fields. Molybdenite (MoS₂), powellite (CaMoO₄) and cannizzarite (Pb₄Bi₆S₁₃) contain 1.5-1.7 wt%, 10 ppm, and 65-252 ppb of Re, respectively. Both molybdenite and rheniite contain normal Os concentrations, with total Os abundances in a range from 0.6 to 3.1 ppm for molybdenite, and 2.3-24.3 ppb for the rheniite samples. Repeated analyses of osmium isotope ratios for two rheniite samples form a best-fit line with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.32 ± 0.15 and an age of 79 ± 11 yr, which is the youngest age ever measured in natural samples. The high Re contents in molybdenite and rheniite led to high radiogenic ¹⁸⁷Os values, even in the limited period of time, with ¹⁸⁷Os/¹⁸⁸Os ratios up to 3.3 for molybdenite and up to 4.4 for rheniite.The Os isotopic compositions of andesite-basaltic rocks from the Kudryavy volcano (¹⁸⁷Os/¹⁸⁸Os up to 0.326) are more radiogenic than those of residual peridotites and fumarolic gas condensates that are mainly constituted from magmatic vapor. Such radiogenic values can be attributed either to the addition of a radiogenic Os-rich subduction component to the depleted mantle, or to the assimilation of older dacitic caldera walls (¹⁸⁷Os/¹⁸⁸Os = 0.6) during arc magma ascent and emplacement. The latter hypothesis is supported by the correlation between ¹⁸⁷Os/¹⁸⁸Os ratio and indicators of fractionation such as MgO or Ni, and by low contents of potentially hydrophile trace elements such as Ba, Rb and Th relative to fluid-immobile elements such as Nb, Zr and Y. The high Re flux in the Kudryavy volcano (estimated at ∼46 kg/yr) can be explained by remobilisation of Re by Cl-rich water from an underplated mantle wedge and subducted organic-rich sediments of the Pacific plate.     

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.     

Highly siderophile element behaviour accompanying subduction of oceanic crust: Whole rock and mineral-scale insights from a high-pressure terrain

Highly siderophile element concentrations (HSE: Re and platinum-group elements (PGE)) are presented for gabbros, gabbroic eclogites and basaltic eclogites from the high-pressure Zermatt-Saas ophiolite terrain, Switzerland. Rhenium and PGE (Os, Ir, Ru, Rh, Pt, Pd) abundances in gabbro- and eclogite-hosted sulphides, and Re-Os isotopes and elemental concentrations in silicate phases are also reported. This work, therefore, provides whole rock and mineral-scale insights into the PGE budget of gabbroic oceanic crust and the effects of subduction metamorphism on gabbroic and basaltic crust.Chondrite-normalised PGE patterns for the gabbros are similar to published mid-ocean ridge basalts (MORB), but show less inter-element fractionation. Mean Pt and Pd contents of 360 and 530 pg/g, respectively, are broadly comparable to MORB, but gabbros have somewhat higher abundances of Os, Ir and Ru (mean: 64, 57 and 108 pg/g). Transformation to eclogite has not significantly changed the concentrations of the PGE, except Pd which is severely depleted in gabbroic eclogites relative to gabbros (∼75% loss). In contrast, basaltic eclogites display significant depletion of Pt (?60%), Pd (>85%) and Re (50-60%) compared with published MORB, while Os, Ir and Ru abundances are broadly comparable. Thus, these data suggest that only Pt, Pd and Re, and not Os, Ir and Ru, may be significantly fluxed into the mantle wedge from mafic oceanic crust. Re-Os model ages for gabbroic and gabbroic eclogite minerals are close to age estimates for igneous crystallisation and high-pressure metamorphism, respectively, hence the HSE budgets can be related to both igneous and metamorphic behaviour. The gabbroic budget of Os, Ir, Ru and Pd (but not Pt) is dominated by sulphide, which typically hosts >90% of the Os, whereas silicates account for most of the Re (with up to 75% in plagioclase alone). Sulphides in gabbroic eclogites tend to host a smaller proportion of the total Os (10-90%) while silicates are important hosts, probably reflecting Os inheritance from precursor phases. Garnet contains very high Re concentrations and may account for >50% of Re in some samples. The depletion of Pd in gabbroic eclogites appears linked, at least in part, to the loss of Ni-rich sulphide.Both basaltic and gabbroic oceanic crust have elevated Pt/Os ratios, but Pt/Re ratios are not sufficiently high to generate the coupled ¹⁸⁶Os-¹⁸⁷Os enrichments observed in some mantle melts, even without Pt loss from basaltic crust. However, the apparent mobility of Pt and Re in slab fluids provides an alternative mechanism for the generation of Pt- and Re-rich mantle material, recently proposed as a potential source of ¹⁸⁷Os-¹⁸⁶Os enrichment.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.     

Comparison of reductive accumulation of Re and Os in seawater-sediment systems

In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO₂, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high ¹⁸⁷Re/¹⁸⁸Os ratio can occur only in reducing sediments, such as black shales. The high¹⁸⁷Re/¹⁸⁸Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower ¹⁸⁷Re/¹⁸⁸Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the ¹⁸⁷Os/¹⁸⁸Os ratio cannot grow significantly due to its extremely low ¹⁸⁷Re/¹⁸⁸Os ratio.     

The first finds of rhenium minerals in Karelia

Rhenium is one of the rarest elements of the earth crust (abundance ratio 0.7 mg/t). In the Karelian region, Re and accompanying Os were discovered in a copper-molybdenum-porphyry ore formation, represented by the Lobash deposit, the Jalonvaara occurrences etc., and in a noble-metal-Cu-U-vanadium ore formation (Padma Group occurrences). Molybdenites from the above deposits are enriched in Re and Os (Lobash: 13–187 g/t Re, 0.4–6 g/t Os). So far, however, no rhenium minerals proper have been revealed in the Karelian deposits and occurrences of the above formations or elsewhere. As a result of the microprobe study of mineral assemblages of cupreous sandstones from the Voronov Bor deposit (bornite ore) and sulphide-copper-nickel ore from the Rybozero deposit, osmium-cupreous rheniite (Re, Cu, Os, Fe)₁S₂ that contains 56.53–60.25% Re, 4.61–10.99% Cu, 1.52–3.77% Os and up to 4.75% Fe was revealed and studied for the first time.     

The remarkable Re–Os chronometer in molybdenite: how and why it works

The Re–Os (rhenium–osmium) chronometer applied to molybdenite (MoS₂) is now demonstrated to be remarkably robust, surviving intense deformation and high‐grade thermal metamorphism. Successful dating of molybdenite is dependent on proper preparation of the mineral separate and analysis of a critical quantity of molybdenite, unique to each sample, such that recognized spatial decoupling of ¹⁸⁷Re parent and ¹⁸⁷Os daughter within individual molybdenite crystals is overcome. Highly precise, accurate and reproducible age results are derived through isotope dilution and negative thermal ion mass spectrometry (ID‐NTIMS). Spatial decoupling of parent–daughter precludes use of the laser ablation ICP‐MS microanalytical technique for Re–Os dating of molybdenite. The use of a reference or control sample is necessary to establish laboratory credibility and for interlaboratory comparisons. The Rb–Sr, K–Ar and ⁴⁰Ar/³⁹Ar chronometers are susceptible to chemical and thermal disturbance, particularly in terranes that have experienced subsequent episodes of hydrothermal/magmatic activity, and therefore should not be used as a basis for establishing accuracy in Re–Os dating of molybdenite, as has been done in the past. Re–Os ages for molybdenite are almost always in agreement with observed geological relationships and, when available, with zircon and titanite U–Pb ages. For terranes experiencing multiple episodes of metamorphism and deformation, molybdenite is not complicated by overgrowths as is common for some minerals used in U–Pb dating (e.g. zircon, monazite, xenotime), nor are Re and Os mobilized beyond the margins of individual crystals during solid‐state recrystallization. Moreover, inheritance of older molybdenite cores, incorporation of common Os, and radiogenic Os loss are exceedingly rare, whereas inheritance, common Pb and Pb loss are common complications in U–Pb dating techniques. Therefore, molybdenite ages may serve as point‐in‐time markers for age comparisons.     

Highly siderophile element composition of the Earth’s primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths

Osmium, Ru, Ir, Pt, Pd and Re abundances and ¹⁸⁷Os/¹⁸⁸Os data on peridotites were determined using improved analytical techniques in order to precisely constrain the highly siderophile element (HSE) composition of fertile lherzolites and to provide an updated estimate of HSE composition of the primitive upper mantle (PUM). The new data are used to better constrain the origin of the HSE excess in Earth’s mantle. Samples include lherzolite and harzburgite xenoliths from Archean and post-Archean continental lithosphere, peridotites from ultramafic massifs, ophiolites and other samples of oceanic mantle such as abyssal peridotites. Osmium, Ru and Ir abundances in the peridotite data set do not correlate with moderately incompatible melt extraction indicators such as Al₂O₃. Os/Ir is chondritic in most samples, while Ru/Ir, with few exceptions, is ca. 30% higher than in chondrites. Both ratios are constant over a wide range of Al₂O₃ contents, but show stronger scatter in depleted harzburgites. Platinum, Pd and Re abundances, their ratios with Ir, Os and Ru, and the ¹⁸⁷Os/¹⁸⁸Os ratio (a proxy for Re/Os) show positive correlations with Al₂O₃, indicating incompatible behavior of Pt, Pd and Re during mantle melting. The empirical sequence of peridotite-melt partition coefficients of Re, Pd and Pt as derived from peridotites () is consistent with previous data on natural samples. Some harzburgites and depleted lherzolites have been affected by secondary igneous processes such as silicate melt percolation, as indicated by U-shaped patterns of incompatible HSE, high ¹⁸⁷Os/¹⁸⁸Os, and scatter off the correlations defined by incompatible HSE and Al₂O₃. The bulk rock HSE content, chondritic Os/Ir, and chondritic to subchondritic Pt/Ir, Re/Os, Pt/Re and Re/Pd of many lherzolites of the present study are consistent with depletion by melting, and possibly solid state mixing processes in the convecting mantle, involving recycled oceanic lithosphere. Based on fertile lherzolite compositions, we infer that PUM is characterized by a mean Ir abundance of 3.5 ± 0.4 ng/g (or 0.0080 ± 0.0009*CI chondrites), chondritic ratios involving Os, Ir, Pt and Re (Os/Ir_PUM of 1.12 ± 0.09, Pt/Ir_PUM = 2.21 ± 0.21, Re/Os_PUM = 0.090 ± 0.002) and suprachondritic ratios involving Ru and Pd (Ru/Ir_PUM = 2.03 ± 0.12, Pd/Ir_PUM = 2.06 ± 0.31, uncertainties 1σ). The combination of chondritic and modestly suprachondritic HSE ratios of PUM cannot be explained by any single planetary fractionation process. Comparison with HSE patterns of chondrites shows that no known chondrite group perfectly matches the PUM composition. Similar HSE patterns, however, were found in Apollo 17 impact melt rocks from the Serenitatis impact basin [Norman M.D., Bennett V.C., Ryder G., 2002. Targeting the impactors: siderophile element signatures of lunar impact melts from Serenitatis. Earth Planet. Sci. Lett, 217-228.], which represent mixtures of chondritic material, and a component that may be either of meteoritic or indigenous origin. The similarities between the HSE composition of PUM and the bulk composition of lunar breccias establish a connection between the late accretion history of the lunar surface and the HSE composition of the Earth’s mantle. Although late accretion following core formation is still the most viable explanation for the HSE abundances in the Earth’s mantle, the “late veneer” hypothesis may require some modification in light of the unique PUM composition.     

Osmium isotope and highly siderophile element geochemistry of mantle xenoliths from NW Turkey: implications for melt depletion and metasomatic history of the sub-continental lithospheric mantle

Ultramafic xenoliths entrained in the late Miocene alkali basalts and basanites from NW Turkey include refractory spinel-harzburgites and dunites accompanied by subordinate spinel-lherzolites. Whole-rock major and trace element characteristics indicate that the xenoliths are mostly the solid residues of varying degrees of partial melting (～4–～15%), but some have geochemical signatures reflecting the processes of melt/rock interaction. Mantle-normalized trace element patterns for the peridotites vary from LREE-depleted to strongly LREE-enriched, reflecting multistage mantle processes from simple melt extraction to metasomatic enrichment. Rhenium and platinum group element (PGE) abundances and ¹⁸⁷Os/¹⁸⁸Os systematics of peridotites were examined in order to identify the nature of the mantle source and the processes effective during variable stages of melt extraction within the sub-continental lithospheric mantle (SCLM). The peridotites are characterized by chondritic Os/Ir and Pt/Ir ratios and slightly supra-chondritic Pd/Ir and Rh/Ir ratios, representing a mantle region similar in composition to the primitive mantle (PM). Moderate enrichment in PPGE (Pd–Pt–Rh)/IPGE (Ir–Os–Ru) ratios with respect to the PM composition in the metasomatized samples, however, reflects compositional modification by sulphide addition during possible post-melting processes. The ¹⁸⁷Os/¹⁸⁸Os ratios of the peridotites range from 0.11801 to 0.12657. Highly unradiogenic Os isotope compositions (γOs at 10 Ma from –7.0 to –3.2) in the chemically undisturbed mantle residues are accompanied by depletion in Re/Os ratios, suggesting long-term differentiation of SCLM by continuous melt extraction. For the metasomatized peridotites, however, systematic enrichments in PPGE and Re abundances, and the observed positive covariance between ¹⁸⁷Re/¹⁸⁸Os and γOs can most likely be explained by interaction of solid residues with basaltic melts produced by melting of relatively more radiogenic components in the mantle. Significantly, the wide range of ¹⁸⁷Os/¹⁸⁸Os ratios characterizing the entire xenolith suite seems to be consistent with multistage evolution of SCLM and suggests that parts of the lithospheric mantle contain materials that have experienced ancient melt removal (～1.3 Ga) which created time-integrated depletion in Re/Os ratios; in contrast, some other parts display evidence indicative of recent perturbation in the Re–Os system by sulphide addition during interaction with metasomatizing melts.     

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.     

Re-Os elemental and isotopic systematics in crude oils

Analysis of 12 worldwide oil samples show that Re and Os abundances are positively correlated with the asphaltene content of oil. Light oils with <1% asphaltene content have basically no measurable Re or Os. Within oil, Re and Os are present dominantly in the asphaltene fraction (>83%), with <14% Re and Os found in the maltene fraction, this distribution is similar to other trace metals such as V and Mo. Rhenium and Os could be present in oil as metalloporphyrin complexes, but given their abundance in the asphaltene component they are also likely bound by heteroatomic ligands. The ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os values in asphaltene calculated at the estimated time of oil generation (Os_i) are similar to those of the whole oil, as expected from the elemental results. This suggests that the asphaltene fraction can be used to approximate the Re-Os isotopic compositions of the whole oil. Os isotopic compositions in oils show a considerable range, from ¹⁸⁷Os/¹⁸⁸Os of 1.9-6.0, and they correlate positively with the age of the proposed source rock. Re/Os ratios also show a large range and overlap the Re/Os ratios found in typical oil source rocks such as organic rich shale.