Primitive Upper Mantle Research Articles

Geochronology and geochemistry of the Panjal Traps from the southern Pir Panjal Range, Kashmir, India

The eruption of the Panjal Traps is associated with rifting along the Tethyan margin of Gondwana. A CA-ID-TIMS zircon U-Pb age of basalt collected from the southern Pir Panjal Range (SPPR) yielded a weighted-mean 206Pb/238U age of 288.2 ± 0.3 Ma. The rocks from the SPPR can be divided into three compositionally distinct groups (basalt: SiO2 < 52 wt%; Mg# = 56–36, basaltic andesite: SiO2 = 52–60 wt%; Mg# = 32–48, and silicic: SiO2 > 64.0 wt%; Mg# = 27–23) and are chemically correlated with rocks from the eastern Kashmir Valley rather than the northern Pir Panjal Range (NPPR). The Sr-Nd isotopes (87Sr/86Sri = 0.70860–0.71104; εNd(t) = −6.1 to −4.4) of the mafic rocks are similar and indicate that their magmas were derived from a subduction modified subcontinental lithospheric mantle (SCLM) source. The silicic rocks were derived by partial melting of the continental crust (87Sr/86Sri = 0.71022–0.71093; εNd(t) = −8.7 to −7.2) and their discovery in the SPPR indicates that silicic volcanism was far more extensive than previously thought. The 187Os/188Osi isotopic ratios of basalts from different regions of the Panjal Traps range from 0.1230 to 0.2832. Two samples from the NPPR have ratios of 0.1230 and 0.1256 that are slightly higher than primitive upper mantle at the time of eruption whereas the remaining samples show enriched values (0.1343–0.2832). The new data suggest that it is likely that the mantle source of the Panjal Traps transitioned from a SCLM source to a sublithospheric source over time as seafloor spreading developed.

Oxidation of the deep big mantle wedge by recycled carbonates: Constraints from highly siderophile elements and osmium isotopes

Widespread Cenozoic intraplate basalts from eastern China offer the opportunity to investigate the consequences of interaction between the stagnant Pacific slab and overlying asthenosphere and chemical heterogeneity within this “big mantle wedge”. We present and compile a comprehensive study of highly siderophile elements and Mg-Zn isotopes of this magmatic suite (60 samples including nephelinites, basanites, alkali basalts and tholeiites). The large-scale Mg-Zn isotopic anomalies documented in these basalts have been ascribed to mantle hybridization by recycled Mg-carbonates from the stagnant western Pacific plate. Our results reveal that the nephelinites and basanites are characterized by unfractionated platinum-group element (PGE) patterns normalized to primitive upper mantle (PUM) (e.g., PdN/IrN normalized to PUM = 1.1 ± 0.8, 1σ), relatively high total PGE contents (e.g., Ir = 0.25 ± 0.14 ppb) and modern mantle-like 187Os/188Os (0.142 ± 0.020). These characteristics are coupled with lighter Mg isotope (δ26Mg = −0.48 ± 0.07‰) and heavier Zn isotope (δ66Zn = +0.46 ± 0.06‰) compositions compared to the mantle values (δ26Mg: −0.25 ± 0.07‰; δ66Zn: +0.18 ± 0.05‰). Together, these data are interpreted to reflect the oxidative breakdown of low proportions of mantle sulfides in the sources of these small-degree melts, likely caused by recycled carbonates, which then release chalcophile-siderophile elements into carbonatitic melts. By contrast, the contemporaneous alkali basalts and tholeiites are characterized by highly fractionated PGE patterns (e.g., PdN/IrN = 4.4 ± 3.3; Ir = 0.037 ± 0.027 ppb) and radiogenic 187Os/188Os (0.279 ± 0.115) coupled with less fractionated Mg-Zn isotope compositions (δ26Mg: −0.39 ± 0.05‰; δ66Zn: +0.35 ± 0.03‰). In combination with other isotopic (e.g., Sr-Nd) and chemical (SiO2, Ce/Pb, Ba/Th, Fe/Mn) constraints, the alkali basalts and tholeiites were derived from higher degree melting of ancient pyroxenite-bearing mantle in addition to mixing with the aforementioned nephelinitic and basanitic melts. Collectively, we suggest that deep recycled carbonates promoted melting within the “big mantle wedge” leading to the generation of Cenozoic intraplate basalts across eastern China and the “redox freezing of carbonates” may cause the oxidation of Fe0 and S2-. This process may provide an important mechanism to oxidize mantle sulfides and transfer precious metals from deep mantle to crust.

Heterogeneous sub-ridge mantle of the Neo-Tethys: Constraints from Re-Os isotope and HSE compositions of the Xigaze ophiolites

Luqu harzburgites from the Xigaze ophiolites represent ultra-refractory mantle domains in the Yarlung-Tsangbo Suture Zone, which is accepted as relics of the Neo-Tethys. These ultra-depleted harzburgites provide an excellent opportunity to constrain the ophiolite generation from the perspectives of Re-Os isotopes and highly siderophile elements. The depleted HSE patterns of several samples suggest that these harzburgites had experienced higher extents of partial melting than the normal abyssal peridotites. These conclusions were also evidenced by the petrological observations, such as the low modal contents of clinopyroxenes and the rare occurrence of residual sulfides. Re-depleted model ages (TRD) of two Luqu harzburgites with ultra-low absolute Re abundances yield an estimate of ca. 2.0 Ga for an ancient melting event, which implies that the Luqu peridotites have ancient domains. Even though the compositions of IPGE (Os, Ir, and Ru) in all Luqu samples are quite homogeneous and comparable to those of the primitive upper mantle (PUM), the variations of PPGE (Pt and Pd) and Re indicate that the Luqu harzburgites had experienced late-stage melt-rock interaction. These infiltrating melts are constrained to be silica-rich and sulfur-saturated and might be different from the melt accounted for the metasomatic clinopyroxene. The sulfide-rich melt agents are speculated to be derived from recycling ancient components, which is supported by several samples with elevated 187Os/188Os compositions and enriched Re abundances. Considering the dynamic environments and evolution history of the Neo-Tethys, these ultra-depleted mantle domains represented by Luqu harzburgites are readily formed by multi-stage processes of partial melting and melt-rock interactions in the mid-ocean ridges. Also, fragments of ancient subducted oceanic slabs within the mantle probably provide the sources of the recycling melts pervasive in the Xigaze mantle.

Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: New constraints from Bi and Ag metal-silicate partitioning

The Earth's timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Because Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data are combined with previously reported data, and utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion relevant for Earth and Mars. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) pre-cursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the primitive upper mantle (PUM) Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.

Sulfide Aggregation in Ophiolitic Dunite Channels Explains Os‐Isotope Mismatch between Oceanic Crust and Mantle

AbstractThe osmium‐isotope mismatch commonly reported between mid‐ocean‐ridge basalts (MORBs) and residual mantle might reflect evolution of the MORB Re‐Os system after extraction from the asthenosphere, or preferential contribution of radiogenic Os components from mantle. However, in a MOR system, the role of dunite melt channels from the upper mantle and Moho transition zone in regulating isotopic systems between mantle and crust has rarely been evaluated. We report new Re‐Os isotopic compositions of base‐metal sulfides (BMS), chromites and dunites from dunite lenses with low spinel Cr# [Cr3+/ (Cr3++Al3+) ≤ 0.66] (products of interaction between MORB‐like melts and upper‐mantle harzburgites) from the Zedang ophiolite (South Tibet). Re‐Os isotopic compositions of low‐Cr# dunites from the Oman ophiolite are also shown for comparison. Mineralogical evidence suggests that the Zedang sulfides were originally precipitated as monosulfide solid solutions. The highly variable 187Os/188Os initial ratios (0.1191‐0.1702) and low 187Re/188Os (&lt;0.22) of the sulfides suggest that the chromite acted as a sink for Os‐bearing sulfides, aggregating discrete Os components with heterogeneous isotopic signatures from asthenospheric or lithospheric mantle into dunite channels. The Zedang chromites and dunites show 187Os/188Os ratios similar to the primitive upper mantle (PUM), except for two dunites with sub‐PUM ratios, reflecting the contribution of Os balanced by smaller volumes of Os‐rich, unradiogenic sulfides (likely nucleating on Os nanoparticles) and larger volumes of Os‐poor radiogenic BMS. Such isotopic heterogeneity, despite with less variation, has been observed in dunite channels from the Oman ophiolite and present‐day mid‐ocean ridges. Formation of dunite channels in the upper mantle thus can aggregate Os‐bearing sulfides with chromite, leaving high Re/Os components into the residual melts. Once such channel systems were built up at the crust‐mantle transition zone, the newly incoming MOR magmas would preferentially melt and dissolve the volumetrically abundant radiogenic BMS and retain Os‐rich nanoparticles in the channels, further amplifying the Os‐isotope mismatch between oceanic crust and mantle. This study sheds new light on the multistage evolution and small‐scale behaviors of chalcophile and siderophile elements (e.g., Re‐Os) and their isotopes (e.g., 187Re‐187Os) with sulfides and chromites in a silicate‐dominated melt plumbing system beneath mid‐ocean ridges.

Reconsideration of Neo‐Tethys Evolution Constrained from the Nature of the Dazhuqu Ophiolitic Mantle, Southern Tibet

AbstractThe nature (i.e., sub‐oceanic, sub‐arc or sub‐continental) of ophiolitic mantle peridotites from the eastern Neo‐Tethyan domain in southern Tibet has been hotly debated. This uncertainty limits our understanding of the history and evolution of the eastern Neo‐Tethys Ocean. Here we present petrological, geochemical and Re‐Os isotopic data for the mantle peridotites from the Dazhuqu ophiolite in the central segment of the Yarlung Zangbo suture zone, southern Tibet. Samples collected include both spinel lherzolites and spinel harzburgites. The lherzolites have spinel Cr# [Cr/ (Cr + Al), ∼ 0.3–0.4] comparable to those of typical abyssal peridotites. In contrast, the harzburgites have spinel Cr# (∼0.3–0.7) overlapping with the ranges of both abyssal and fore‐arc peridotites (Day et al., 2017; Parkinson and Pearce, 1998); two samples have spinel Cr# higher than 0.6, which is probably ascribed to intense melt‐rock interactions. Clinopyroxene trace element modeling indicates that the Dazhuqu mantle peridotites have experienced 0–6% garnet‐facies melting followed by 10%–18% melting in the spinel stability field. This is similar to the degree of garnet‐facies melting inferred for many abyssal peridotites (Hellebrand et al., 2002) and implies deep initial melting (&gt; 85 km), which distinguishes the Dazhuqu mantle peridotites from fore‐arc peridotites (commonly &lt;80 km in origin). The Dazhuqu peridotites have unradiogenic 187Os/188Os of 0.11836–0.12922, which are commonly lower than the recommended value of primitive upper mantle (PUM) (Meisel et al., 2001). All but one samples yield relatively younger Re depletion ages (TRD = 0.06–0.81 Ga) with respect to the only one sample having an older TRD age of 1.66 Ga. Re‐Os isotopes and highly siderophile element (HSE) compositions of the Dazhuqu peridotites are similar to those of abyssal peridotites (Day et al., 2017) and the Oman southern massifs (Hangh⊘j et al., 2010) but are distinct from non‐cratonic sub‐continental lithospheric mantle (SCLM) xenoliths and sub‐arc mantle. We emphasize the similarity between the Dazhuqu and Oman ophiolites, both representing Neo‐Tethyan oceanic lithosphere and implying ridge–trench collision.

HFSE and REE Geochemistry and Nd-Sr-Os Systematics of Peridotites in the Subcontinental Lithospheric Mantle of the Siberian Craton and Central Asian Fold Belt Junction Area: Data on Mantle Xenoliths

Mantle xenoliths were found in alkaline basalts of Tokinsky Stanovik (TSt) in the Dzhugdzhur-Stanovoy superterrane (DS) and Vitim plateau (VP) in the Barguzin–Vitim superterrane (BV) (Stanovoy suture area) at junction of the Central Asian Orogenic Belt (CAOB) and the Siberian craton (SC). Xenoliths from TSt basalts are represented by spinel lherzolites, harzburgites, wehrlites; while VP basalts frequently contain spinel–garnet and garnet peridotites lherzolites, and pyroxenites. Xenoliths in kimberlites of the Siberian craton are mainly represented by garnet-bearing lherzolites with abundant eclogite xenoliths (age of 2.7–3.1 Ga), which were not found in mantle of superterranes. The Re-Os determinations point to the Early Archean age of peridotites and eclogites from mantle beneath the Siberian craton. The major and trace (rare-earth and high-filed strength) elements and Nd-Sr-Os composition were analyzed in the peridotites (predominant rocks) of lithospheric mantle at junction of the Central Asian Orogenic Belt and Siberian Craton. The degree of rock depletion in CaO and Al2O3 and enrichment in MgO relative to the primitive mantle in the peridotites of the Dzhugdzhur–Stanovoy superterrane is close to that of the Siberian craton. The peridotites of the Barguzin–Vitim superterrane are characterized by much lower degree of depletion and have mainly a primitive composition. Mantle melting degree reaches up to 45–50% in the Siberian Craton and Dzhugdzhur-Stanovoy superterrane, and is less than 25% in the Barguzin–Vitim terrane. The mantle peridotites of the craton as compared to those of adjacent superterranes are enriched in Ba, Rb, Th, Nb, and Ta and depleted in Y and REE from Sm to Lu. However, all studied peridotites are characterized by mainly superchondritic values of Nb/Ta (>17.4), Zr/Hf (>36.1), Nb/Y (>0.158), and Zr/Y (>2.474). The Nb/Y ratio is predominantly >1.0 in SC peridotites and 0.115 but usually lower than 0.1296 (primitive upper mantle value) in the peridotites of the Dzhugdzhur–Stanovoy and Barguzin–Vitim superterranes. Thus, the geochemical and isotopic composition of peridotites indicates different compositions and types of mantle beneath the Siberian craton and adjacent superterranes of the Central Asian Orogenic Belt in the Early Archean, prior to the formation of 2.7–3.1 Ga eclogites in the cratonic mantle.

Tracing Highly Siderophile Elements through Subduction: Insights from High-pressure Serpentinites and ‘Hybrid’ Rocks from Alpine Corsica

Abstract The highly siderophile elements (HSE) include the economically critical platinum group elements (PGE; Os, Ir, Ru, Rh, Pt, Pd, Au and Re), gold and rhenium. The HSE are redox sensitive in mantle and seafloor environments and have a strong affinity to iron and sulphur, therefore their distribution within the subducted mantle lithosphere record changes to oxidation state and sulphidation. The mobility of the HSE during subduction has important implications for Re–Os isotopic signatures in the mantle, and the formation of Cu–Au arc-related ore deposits. In this study, subducted rock samples from Alpine Corsica are used to track the HSE in serpentinites and hybrid ultramafic–mafic rocks through the subduction cycle. A comparison of bulk-rock HSE concentrations with those in pre-subduction analogues provides insights into the transfer of the HSE throughout the subduction cycle. Serpentinites subducted to blueschist–eclogite-facies conditions have similar HSE concentrations to primitive upper mantle (PUM) concentrations, therefore it is concluded that the HSE are not mobilized from serpentinites on the scale of the whole-rock or greater. Therefore, as suggested in previous studies, crustal lithologies may be more important contributors of the HSE to the sub-arc mantle, particularly Pt, Pd and Re. In contrast, HSE concentrations in hybrid rocks (talc schist and chlorite schist) deviate from protolith concentrations. Rhenium is higher in the talc schist, and Ir and Ru are lower in the chlorite schist than in the PUM, or possible mafic protoliths. Mineral parageneses place temporal constraints on the growth of hosts to the HSE (sulphides, oxides and metal alloys), and record changes to the activities of oxygen and sulphur (aO2–aS2), and hence redox conditions, from pre-subduction to exhumation. Laser ablation inductively coupled plasma mass spectrometry was used to determine the HSE concentrations in sulphides and oxides, and the detection of small (∼2–25 µm2) platinum group minerals utilized high-resolution SEM mapping techniques. The prograde and retrograde sulphides have lower HSE concentrations compared with sulphides from pre-subduction settings. Therefore, the redistribution of the HSE on a mineral scale from sulphides to alloys and/or other sulphides has occurred within the serpentinites, which may reflect more reducing conditions during serpentinization or subduction, consistent with the results of thermodynamic modelling. In contrast, the mineral assemblages in the hybrid rocks imply an increase in the extent of sulphidation and oxidation, and higher fluid:rock ratios during exhumation, coincident with Re enrichment in the talc schist, and a decrease in the concentrations of Ir and Ru in the chlorite schist, at length scales greater than those of the rock samples. Therefore, hybridization of lithologies at the slab–mantle interface may enhance the transfer of the HSE to the sub-arc mantle. If Re transfer from the slab to the sub-arc mantle is possible, this questions the robustness of Re–Os isotope signatures as tracers of crustal recycling.

Sulfide in dunite channels reflects long-distance reactive migration of mid-ocean-ridge melts from mantle source to crust: A Re-Os isotopic perspective

The Earth's major heat and mass fluxes are output from the mantle to surface via mid-ocean-ridge-basalt (MORB) magmatism. The variations of MORBs are determined both by the heterogeneity of mantle source and the melt migration processes from mantle source to seafloor. However, before the MORB magmas enter crust, the role of the major melt migration passageways within the mantle (dunite channel systems) in regulating the compositions of MORBs has been rarely evaluated, especially from the perspective of Re-Os isotopes. Here, we report new Re-Os isotopic compositions of base-metal sulfides (BMS), chromites and dunites from dunite lenses with low spinel Cr# [Cr3+/(Cr3++Al3+) ≤0.66] (products of interaction between MORB-like melts and upper-mantle harzburgites) from the Zedang ophiolite (South Tibet). Rhenium-Os isotopic compositions of low-Cr# dunites from the Samail and Wadi Tayin massifs (typical MOR segments) of the Oman ophiolite are also shown for comparison to reveal the melt plumbing processes at mantle depths beneath mid-ocean ridges. Mineralogical evidence suggests that the Zedang sulfides and desulfurized alloy portions were originally precipitated as monosulfide solid solutions. The highly variable 187Os/188Os initial ratios (0.1191-0.1702) and low 187Re/188Os (<0.22) of the sulfides suggest that the chromite acted as a sink for Os-bearing sulfides, aggregating discrete Os components with heterogeneous isotopic signatures from asthenospheric or lithospheric mantle into dunite channels. The Zedang chromites and dunites show 187Os/188Os ratios similar to the primitive upper mantle (PUM), except for two dunites with sub-PUM ratios, reflecting the contribution of Os balanced by smaller volumes of Os-rich, unradiogenic sulfides (likely nucleating on Os nanoparticles) and larger volumes of Os-poor radiogenic BMS. Such isotopic heterogeneity, despite with less variation, has been observed in dunite channels from the Samail and Wadi Tayin massifs of the Oman ophiolite and present-day mid-ocean ridges. Formation of dunite channels in the upper mantle thus can aggregate Os-bearing sulfides with chromite, leaving high Re/Os components into the residual MOR melts. Once such channel systems were built up at the Moho transition zone, the newly incoming MOR magmas would preferentially dissolve the volumetrically abundant radiogenic BMS and retain Os-rich alloys/sulfides in the channels, further amplifying the Os-isotope mismatch observed between global oceanic crust (more radiogenic) and lithospheric mantle (less radiogenic).This study reveals that the long-distance reactive migration of melts from mantle source to at least Moho depths can result in strong Re-Os fractionation and isotopic mismatch between primary MORBs and mantle residues. It also shows that, unlike other lithophile tracers (e.g., Nd-Hf isotopes) whose signatures are almost completely transferred from mantle source to crust, the sub-crustal melt plumbing processes beneath mid-ocean ridges can be finely constrained by the multistage evolution of chalcophile and siderophile elements (e.g., Re-Os) and their isotopes (e.g., 187Re-187Os) with sulfides and chromites. Our study supports that the MORB compositions are actually regulated by their reactive migration processes occurred between melt generation at depth and eruption on seafloor.

Effect of silicon on activity coefficients of Bi, Cd, Sn, and Ag in liquid Fe‐Si, and implications for differentiation and core formation

AbstractThe depletion of volatile siderophile elements (VSE) Sn, Ag, Bi, Cd, and P in mantles of differentiated planetary bodies can be attributed to volatile‐depleted precursor materials (building blocks), fractionation during core formation, fractionation into and retention in sulfide minerals, and/or volatile loss associated with magmatism. Quantitative models to constrain the fractionation due to core formation have not been possible due to the lack of activity and partitioning data. Interaction parameters in Fe‐Si liquids have been measured at 1 GPa, 1600 °C and increase in the order Cd (~6), Ag (~10), Sn (~28), Bi (~46), and P (~58). These large and positive values contrast with smaller and negative values in Fe‐S liquids indicating that any chalcophile behavior exhibited by these elements will be erased by dissolution of a small amount of Si in the metallic liquid. A newly updated activity model is applied to Earth, Mars, and Vesta. Five elements (P, Zn, Sn, Cd, and In) in Earth's primitive upper mantle can largely be explained by metal‐silicate equilibrium at high PT conditions where the core‐forming metal is a Fe‐Ni‐S‐Si‐C metallic liquid, but two other—Ag and Bi—become overabundant during core formation and require a removal mechanism such as late sulfide segregation. All of the VSE in the mantle of Mars are consistent with core formation in a volatile element depleted body, and do not require any additional processes. Only P and Ag in Vesta's mantle are consistent with combined core formation and volatile‐depleted precursors, whereas the rest require accretion of chondritic or volatile‐bearing material after core formation. The concentrations of Zn, Ag, and Cd modeled for Vesta's core are similar to the concentration range measured in magmatic iron meteorites indicating that these volatile elements were already depleted in Vesta's precursor materials.

Reconsideration of Neo-Tethys evolution constrained from the nature of the Dazhuqu ophiolitic mantle, southern Tibet

The nature (i.e., sub-oceanic, sub-arc or sub-continental) of ophiolitic mantle peridotites from the eastern Neo-Tethyan domain in southern Tibet has been hotly debated. This uncertainty limits our understanding of the history and evolution of the eastern Neo-Tethys Ocean. Here we present petrological, geochemical and Re–Os isotopic data for the mantle peridotites from the Dazhuqu ophiolite in the central segment of the Yarlung Zangbo suture zone, southern Tibet. Samples collected include both spinel lherzolites and spinel harzburgites. The lherzolites have spinel Cr# [Cr/(Cr + Al), ~ 0.3–0.4] comparable to those of typical abyssal peridotites. In contrast, the harzburgites have spinel Cr# (~ 0.3–0.7) overlapping with the ranges of both abyssal and fore-arc peridotites; two samples have spinel Cr# higher than 0.6, which is probably ascribed to intense melt–rock interactions. Clinopyroxene trace element modeling indicates that the Dazhuqu mantle peridotites have experienced 0–6% garnet-facies melting followed by 10–18% melting in the spinel stability field. This is similar to the degree of garnet-facies melting inferred for many abyssal peridotites and implies deep initial melting (> 85 km), which distinguishes the Dazhuqu mantle peridotites from fore-arc peridotites (commonly < 80 km in origin). The Dazhuqu peridotites have unradiogenic 187Os/188Os of 0.11836–0.12922, which are commonly lower than the recommended value of primitive upper mantle (PUM). All but one samples yield relatively younger Re depletion ages (TRD = 0.06–0.81 Ga) with respect to the only one sample having an older TRD age of 1.66 Ga. Re–Os isotopes and highly siderophile element (HSE) compositions of the Dazhuqu peridotites are similar to those of abyssal peridotites and the Oman southern massifs but are distinct from non-cratonic sub-continental lithospheric mantle (SCLM) xenoliths and sub-arc mantle. We emphasize the similarity between the Dazhuqu and Oman ophiolites, both representing Neo-Tethyan oceanic lithosphere and implying ridge–trench collision.

Effects of multi-stage rifting and metasomatism on HSE-187Os/188Os systematics of the cratonic mantle beneath SW Greenland

We report highly siderophile element (HSE) abundances and Re–Os isotope compositions, obtained by isotope dilution inductively coupled plasma mass spectrometry, of olivine separates from a suite of multiply metasomatised peridotite xenoliths entrained in kimberlites from SW Greenland. Combined with petrographic and compositional observations on accessory base metal sulphides (BMS), the results reveal new insights into the chemical, physical and mineralogical effects of multi-stage rifting and associated melt percolation on the Archaean lithospheric mantle. Refertilised lherzolites are dominated by rare to frequent small (tens of µm) BMS inclusions in olivine, whereas modally metasomatised phlogopite-bearing lherzolite and wehrlites have higher proportions of more Ni-rich BMS, including abundant large interstitial grains (hundreds of µm). The olivine separates display depleted HSE systematics with Primitive Upper Mantle (PUM)-normalised Pd/Ir of 0.014–0.62, and have both depleted and enriched 187Os/188Os (0.1139–0.2724) relative to chondrite that are not correlated with 187Re/188Os. Four out of ten olivine separates retain similarly depleted Os corresponding to Re-depletion model ages of 2.1–1.8 Ga. They may reflect Palaeoproterozoic refertilisation (lherzolitisation) during Laurentia plate assembly, with re-introduction of clinopyroxene and Os-rich BMS into the originally refractory mantle lithosphere by asthenosphere-derived basaltic melts, followed by recrystallisation and occlusion in olivine. Unradiogenic Os is observed regardless of lithology, including from peridotites that contain abundant interstitial BMS. This reflects addition of Os-poor BMS (<< 1 ppm) during more recent wehrlitisation and phlogopite-introduction, and control of the Os isotopic signature by older Os-rich BMS that precipitated from the basaltic melt. Depletions in compatible HSE (< 0.5 × PUM for Ru, Ir, Os) in all but one olivine separate reflect nugget effects (amount of depleted vs. metasomatic BMS inclusions) and/or loss due to sulphide dissolution into oxidising small-volume melts that invaded the lithosphere during recurrent rifting, the latter supported by similar depletions in published bulk peridotite data. Combined, these multiple metasomatic events destroyed all vestiges of Mesoarchaean or older inheritance in the olivine separates investigated here, and highlight that caution is needed when interpreting Proterozoic Os model ages in terms of Proterozoic lithosphere stabilisation.

Gold in the mantle: A global assessment of abundance and redistribution processes

We have compiled whole-rock analyses in mantle rocks to investigate the abundance of gold in the lithospheric mantle, and how this distribution can be modified. We show that while gold is heterogeneously distributed in peridotites from the upper mantle, the concentrations in most geographical regions cluster around the global median value of 1.2 ppb. This means Au concentration in the modern lithospheric mantle is similar to estimates for the crust and primitive upper mantle, indicating that Au has not been substantially lost from the mantle into the crust, or that it has been effectively recycled between the crust and the mantle, over Earth's history. The only region that shows substantial deviation from the typical lithospheric mantle values is the Eastern Block of the North China Craton, which shows elevated Au contents (median 3.5 ppb) across multiple studies from seven different sampling sites.Au shows no systematic relationship with the LILE, and does not appear to be enriched by hydrous fluids in the mantle, which strongly contrasts with its behaviour in the crust. There is likewise no evidence that Au is enriched by carbonatitic metasomatism in the mantle. A weak correlation with Ta and Hf, along with significantly elevated Ta concentrations in samples with Au concentrations >5 ppb is observed, which possibly indicates the transport of Au by silicate melts in the mantle.We also show that the Au content of pyroxenites is commonly elevated relative to that of peridotites in the lithospheric mantle (median Aupyroxenite = 2.0 ppb; median Auperidotite = 1.2 ppb). The data indicate that the melts from which these pyroxenites have crystallised may be effective metasomatic agents within the lithospheric mantle. Furthermore, these gold-rich pyroxenites may play an important role in mineralisation processes.

Ferropericlase inclusions in ultradeep diamonds from Sao Luiz (Brazil): high Li abundances and diverse Li-isotope and trace element compositions suggest an origin from a subduction mélange

The most remarkable feature of the inclusion suite in ultradeep alluvial and kimberlitic diamonds from Sao Luiz (Juina area in Brazil) is the enormous range in Mg# [100xMg/(Mg + Fe)] of the ferropericlases (fper). The Mg-richer ferropericlases are from the boundary to the lower mantle or from the lower mantle itself when they coexist with ringwoodite or Mg- perovskite (bridgmanite). This, however, is not an explanation for the more Fe-rich members and a lowermost mantle or a “D” layer origin has been proposed for them. Such a suggested ultra-deep origin separates the Fe-rich fper-bearing diamonds from the rest of the Sao Luiz ultradeep diamond inclusion suite, which also contains Ca-rich phases. These are now thought to have an origin in the uppermost lower mantle and in the transition zone and to belong either to a peridotitic or mafic (subducted oceanic crust) protolith lithology. We analysed a new set of more Fe-rich ferropericlase inclusions from 10 Sao Luiz ultradeep alluvial diamonds for their Li isotope composition by solution MC-ICP-MS (multi collector inductively coupled plasma mass spectrometry), their major and minor elements by EPMA (electron probe micro-analyser) and their Li-contents by SIMS (secondary ion mass spectrometry), with the aim to understand the origin of the ferropericlase protoliths. Our new data confirm the wide range of ferropericlase Mg# that were reported before and augment the known lack of correlation between major and minor elements. Four pooled ferropericlase inclusions from four diamonds provided sufficient material to determine for the first time their Li isotope composition, which ranges from δ7Li + 9.6 ‰ to −3.9 ‰. This wide Li isotopic range encompasses that of serpentinized ocean floor peridotites including rodingites and ophicarbonates, fresh and altered MORB (mid ocean ridge basalt), seafloor sediments and of eclogites. This large range in Li isotopic composition, up to 5 times higher than ‘primitive upper mantle’ Li-abundances, and an extremely large and incoherent range in Mg# and Cr, Ni, Mn, Na contents in the ferropericlase inclusions suggests that their protoliths were members of the above lithologies. This melange of altered rocks originally contained a variety of carbonates (calcite, magnesite, dolomite, siderite) and brucite as the secondary products in veins and as patches and Ca-rich members like rodingites and ophicarbonates. Dehydration and redox reactions during or after deep subduction into the transition zone and the upper parts of the lower mantle led to the formation of diamond and ferropericlase inclusions with variable compositions and a predominance of the Ca-rich, high-pressure silicate inclusions. We suggest that the latter originated from peridotites, mafic rocks and sedimentary rocks as redox products between calcite and SiO2.

Metasomatic PGE mobilization by carbonatitic melt in the mantle: Evidence from sub-μm-scale sulfide–carbonaceous glass inclusion in Tahitian harzburgite xenolith

Platinum-group elements (PGEs) are one of the key tracers to reveal early differentiation processes of the Earth due to their preferential distribution into the metallic core. Meanwhile, informative evidence for early differentiation has been greatly disturbed through metasomatic PGE disturbance, which has been demonstrated through a number of PGE data for natural mantle peridotites as well as base-metal sulfide and platinum group mineral grains therein. The mechanism and process of metasomatic PGE mobilization should be investigated in detail for an appropriate estimation of PGE abundance in the primitive upper mantle. However, this has not yet been achieved, because sub-micrometer-scale (i.e. scale of less than a micrometer) descriptions for metasomatic effects imprinted in the mantle peridotites have not been sufficiently recorded.Here, we report a sub-micrometer-sized sulfide–glass inclusion array in a Tahitian harzburgite xenolith. The textural and chemical characteristics were disclosed with employing synchrotron X-ray and transmission electron microscope analyses. The results demonstrate that the sulfide and glass contain appreciable amounts of PGE (9.7 at.% Ir, 4.3 at.% Rh and 5.8 at.% Pt) and carbon (21.2 at.% C), respectively. The sulfide–glass inclusion array is hosted in sodium-enriched clinopyroxene (up to 1.8wt% Na2O) that shows vein-like distribution and partly replaces orthopyroxene. Primitive mantle-normalized trace-element patterns of the clinopyroxene show a general increase from heavy rare-earth elements (REEs) to light REEs with negative anomalies in Pb and high-field-strength elements such as Zr, Hf and Ti, which indicate equilibration with Mg-rich carbonatitic melt. These results suggest that Na-bearing Mg-rich carbonatitic melts were involved in the harzburgite formation and that Ir, Rh and Pt were mobilized through carbonatitic metasomatism and eventually distributed in the sulfides.

Nd-Sr-Os systems of eclogites in the lithospheric mantle of the Kasai Craton (Angola)

We studied the Sm-Nd, Rb-Sr, and Re-Os isotope compositions of mantle xenoliths (eclogites and peridotites) from diamondiferous kimberlites of the Catoca cluster of the Kasai Craton. In the eclogites, the primary strontium isotope composition 87Sr/86Sr varies from 0.7056 to 0.7071, and the neodymium isotope composition eNd, from 1.8 to 2.6. The 187Re/188Os and 187Os/188Os ratios range from 135 to 80 and from 1.3110 to 1.9709, respectively, which indicates a significant portion of radiogenic Os: yOs = 129-147. These isotope values exceed the values assumed for model reservoirs (primitive upper mantle (PUM) and bulk silicate Earth (BSE)) and those of chondrites. The isotope composition of the studied systems indicates the formation of eclogites from a rhenium-enriched source, namely, the subducted oceanic crust transformed as a result of metasomatism and/or melting under upper-mantle conditions.

Age and evolution of the lithospheric mantle beneath the Khanka Massif: Geochemical and Re–Os isotopic evidence from Sviyagino mantle xenoliths

New geochemical and Re–Os isotopic data of mantle xenoliths entrained in Cenozoic Sviyagino alkali basalts from the Russian Far East provide insights into the age and evolution of the sub-continental lithospheric mantle (SCLM) beneath the Khanka Massif, within the Central Asian Orogenic Belt (CAOB). These mantle xenoliths are predominantly spinel lherzolites with minor spinel harzburgite. The lherzolites contain high whole-rock concentrations of Al2O3 and CaO, with low forsterite content in olivine (Fo=89.5–90.3%) and low Cr# in spinel (0.09–0.11). By contrast, the harzburgite is more refractory, containing lower whole rock Al2O3 and CaO contents, with higher Fo (91.3%) and spinel Cr# (0.28). Their whole rock and mineral compositions suggest that the lherzolites experienced low-degree (1–4%) batch melting and negligible metasomatism, whereas the harzburgite underwent a higher degree (10%) of fractional melting, and experienced minor post-melting silicate metasomatism. Two-pyroxene rare earth element (REE)-based thermometry (TREE) yields predominant equilibrium temperatures of 884–1043°C, similar to values obtained from two-pyroxene major element-based thermometry (TBKN=942–1054°C). Two lherzolite samples yield high TREE relative to TBKN (TREE−TBKN ≥71°C), suggesting that they cooled rapidly as a result of the upwelling of hot asthenospheric mantle material that underplated a cold ancient lithosphere. The harzburgite with a low Re/Os value has an 187Os/188Os ratio of 0.11458, yielding an Os model age (TMA) relative to the primitive upper mantle (PUM) of 2.09Ga, and a Re depletion ages (TRD) of 1.91Ga; both of which record ancient melt depletion during the Paleoproterozoic (~2.0Ga). The 187Os/188Os values of lherzolites (0.12411–0.12924) correlate well with bulk Al2O3 concentrations and record the physical mixing of ancient mantle domains and PUM-like ambient mantle material within the asthenosphere. This indicates that the SCLM beneath the Khanka Massif had been formed since at least the Paleoproterozoic (~2.0Ga), and was replaced by juvenile (Phanerozoic) mantle material accreted from the asthenosphere. The synthesis of available TRD ages for mantle-derived rocks and sulfides in xenoliths is consistent with the prior existence of a common Paleoproterozoic (~2.0Ga) SCLM beneath the eastern CAOB. Finally, comparing of mantle TRD ages and the ages of crustal rocks suggests temporal and genetic links between crust and mantle formation during the evolution of the CAOB.

Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth’s upper mantle

The zinc (Zn) stable isotope system has great potential for tracing planetary formation and differentiation processes due to its chalcophile, lithophile and moderately volatile character. As an initial approach, the terrestrial mantle, and by inference, the bulk silicate Earth (BSE), have previously been suggested to have an average δ66Zn value of ∼+0.28‰ (relative to JMC 3-0749L) primarily based on oceanic basalts. Nevertheless, data for mantle peridotites are relatively scarce and it remains unclear whether Zn isotopes are fractionated during mantle melting. To address this issue, we report high-precision (±0.04‰; 2SD) Zn isotope data for well-characterized peridotites (n=47) from cratonic and orogenic settings, as well as their mineral separates. Basalts including mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) were also measured to avoid inter-laboratory bias. The MORB analyzed have homogeneous δ66Zn values of +0.28±0.03‰ (here and throughout the text, errors are given as 2SD), similar to those of OIB obtained in this study and in the literature (+0.31±0.09‰). Excluding the metasomatized peridotites that exhibit a wide δ66Zn range of −0.44‰ to +0.42‰, the non-metasomatized peridotites have relatively uniform δ66Zn value of +0.18±0.06‰, which is lighter than both MORB and OIB. This difference suggests a small but detectable Zn isotope fractionation (∼0.1‰) during mantle partial melting. The magnitude of inter-mineral fractionation between olivine and pyroxene is, on average, close to zero, but spinels are always isotopically heavier than coexisting olivines (Δ66ZnSpl-Ol=+0.12±0.07‰) due to the stiffer Zn-O bonds in spinel than silicate minerals (Ol, Opx and Cpx). Zinc concentrations in spinels are 11–88 times higher than those in silicate minerals, and our modelling suggests that spinel consumption during mantle melting plays a key role in generating high Zn concentrations and heavy Zn isotopic compositions of MORB. Therefore, preferential melting of spinel in the peridotites may account for the Zn isotopic difference between spinel peridotites and basalts. By contrast, the absence of Zn isotope fractionation between silicate minerals suggests that Zn isotopes are not significantly fractionated during partial melting of spinel-free garnet-facies mantle. If the studied non-metasomatized peridotites represent the refractory upper mantle, mass balance calculation shows that the depleted MORB mantle (DMM) has a δ66Zn value of +0.20±0.05‰ (2SD), which is lighter than the primitive upper mantle (PUM) estimated in previous studies (+0.28±0.05‰, 2SD, Chen et al., 2013b; +0.30±0.07‰, 2SD, Doucet et al., 2016). This indicates that the Earth’s upper mantle has a heterogeneous Zn isotopic composition vertically, which is probably due to shallow mantle melting processes.

186Os/188Os variations in upper mantle peridotites: Constraints on the Pt/Os ratio of primitive upper mantle, and implications for late veneer accretion and mantle mixing timescales

186Os/188Os variations in mantle peridotites provide constraints on the long-term Pt/Os evolution of the depleted mantle and the Pt/Os ratio of the primitive upper mantle (PUM). We report new 186Os/188Os data for mantle peridotites from continental (Rio Grande Rift and Colorado Plateau) and oceanic (Lena Trough and Hawaiian Islands) settings that span a wide range in fertility (Al2O3 ≈0.67-4.42 wt.%) and 187Os/188Os ratios (0.1138-0.1305). Although peridotite 186Os/188Os values span only a narrow range (from 0.1198345 to 0.1198384), 186Os/188Os broadly correlates with indices of melt depletion including bulk rock Al2O3, spinel Cr#, and clinopyroxene Cr#, consistent with Pt depletion in residual peridotites.PUM 186Os/188Os is estimated to be 0.1198378±23 (2 SD) based on extrapolation of 186Os/188Os-fertility trends, which is very slightly lower than H-chondrites [≈0.1198398±16 (2 SD); Brandon et al., 2006]. This value is consistent with a PUM Pt/Os of 1.7±0.2, similar to average Pt/Os ratios of fertile continental peridotites. The inferred PUM Pt/Os is slightly lower than but within error of Pt/Os values measured in several classes of chondrites [Carbonaceous ≈1.8±0.2, Ordinary ≈1.9±0.1, and Enstatite ≈1.9±0.1 (Brandon et al., 2006)] indicating that PUM Pt/Os is broadly chondritic. In contrast, estimates for PUM Ru/Ir and Pd/Ir (cf. Becker et al., 2006) are suprachondritic. The addition of a chondritic late veneer alone cannot create a combination of chondritic and suprachondritic HSE ratios for the PUM. Instead, minor core segregation occurring concurrently with the addition of a late veneer may explain the observed mantle HSE abundances and ratios.Combined 186Os/188Os-187Os/188Os isotopic and Pt/Os and Re/Os variability in peridotites suggest an average mantle homogenization timescale of ~1.2 Ga. In contrast, combined Hf-Nd isotopic and Lu/Hf and Sm/Nd variability in peridotites indicate much shorter homogenization timescales (<0.4 Ga), potentially reflecting enhanced homogenization by melt-rock interaction to which the Pt-Os and Re-Os systems are relatively immune. The mechanical mixing timescale inferred from Os isotopes is consistent with timescales predicted for whole mantle convection.

Age and Sr-Nd-Hf isotopes of the sub-continental lithospheric mantle beneath the Cameroon Volcanic Line: Constraints from the Nyos mantle xenoliths

To better constrain the age and composition of the sub-continental lithospheric mantle (SCLM) beneath the Cameroon Volcanic Line (CVL), we present Sr-Nd-Hf-Os isotopes of the Nyos mantle xenoliths (nine lherzolites and four harzburgites). The Nyos lherzolites have fertile compositions with 37.69–41.12wt.% MgO and 2.49–4.38wt.% Al2O3, whereas the harzburgites are more refractory containing 43.2–45.42wt.% MgO and 1.43–2.1wt.% Al2O3. The MgO contents of the Nyos xenoliths overall show negative correlations with CaO, Al2O3, Na2O and TiO2 contents, indicating that they represent mantle residues after melt depletion. Modal minerals like pargasitic amphibole have only been discovered in one Nyos lherzolite, suggesting modal metasomatism locally occurred. Clinopyroxenes in most Nyos xenoliths show enriched trace element compositions, indicating pervasive cryptic metasomatism within the SCLM. Clinopyroxenes in the Nyos lherzolites have less radiogenic Sr and more radiogenic Nd isotopes than the Nyos harzburgites. Clinopyroxene Hf isotopes of the harzburgites are comparable to those of the lherzolites. Although the CVL basalts have similar Sr-Nd isotopes with the Nyos harzburgites, they have different Hf isotopes. Therefore, the CVL basalts could not be sourced solely from the lithospheric mantle. The Nyos lherzolites show consistent HSE patterns, with slight depletion in both Re and Pt over Pd. The harzburgites are remarkably depleted in Pt, Pd and Re relative to Os, Ir and Ru. The Nyos lherzolites have variable 187Os/188Os ratios ranging from 0.11700 to 0.13129, yielding Os model ages (TMA) relative to the primitive upper mantle (PUM) of 0.27–2.18Ga and Re depletion ages (TRD) of 0.12–1.76Ga. In comparison, four harzburgites have more unradiogenic 187Os/188Os ratios of 0.11485–0.11705. Three of the four harzburgites with low Re/Os ratios yield similar TMA and TRD ages, i.e., 1.91–2.43Ga vs. 1.87–2.05Ga, respectively. The 187Os/188Os ratios of the Nyos xenoliths show a good correlation with bulk Al2O3 contents. An initial 187Os/188Os ratio of 0.11064 can be inferred from the 187Os/188Os-Al2O3 correlation, giving an Archean TRD age of ~2.6Ga. This suggests that the Nyos mantle xenoliths have been subjected to melt depletion events during the Paleoproterozoic convergence of the Congo and West Africa cratons, which formed the lithospheric mantle intruded by the CVL. The SCLM beneath the CVL is coeval with or slightly younger than the charnockite and tonalite-trondhjemite-granodiorite in the Ntem Complex of NW Congo Craton. We proposed that the old SCLM was a part of the Congo cratonic mantle. Therefore, our results suggest that old cratonic mantle beneath the CVL has not been completely removed during the Pan-African Orogeny, although the overlying crust might have been strongly deformed and reworked.