Multistage melt/fluid-peridotite interactions in the refertilized lithospheric mantle beneath the North China Craton: constraints from the Li–Sr–Nd isotopic disequilibrium between minerals of peridotite xenoliths

Elemental and Li–Sr–Nd isotopic data of minerals in spinel peridotites hosted by Cenozoic basalts allow us to refine the existing models for Li isotopic fractionation in mantle peridotites and constrain the melt/fluid-peridotite interaction in the lithospheric mantle beneath the North China Craton. Highly elevated Li concentrations in cpx (up to 24 ppm) relative to coexisting opx and olivine (<4 ppm) indicate that the peridotites experienced metasomatism by mafic silicate melts and/or fluids. The mineral δ⁷Li vary greatly, with olivine (+0.7 to +5.4‰) being isotopically heavier than coexisting opx (−4.4 to −25.9‰) and cpx (−3.3 to −21.4‰) in most samples. The δ⁷Li in pyroxenes are considerably lower than the normal mantle values and show negative correlation with their Li abundances, likely due to recent Li ingress attended by diffusive fractionation of Li isotopes. Two exceptional samples have olivine δ⁷Li of −3.0 and −7.9‰, indicating the existence of low δ⁷Li domains in the mantle, which could be transient and generated by meter-scale diffusion of Li during melt/fluid-peridotite interaction. The ¹⁴³Nd/¹⁴⁴Nd (0.5123–0.5139) and ⁸⁷Sr/⁸⁶Sr (0.7018–0.7062) in the pyroxenes also show a large variation, in which the cpx are apparently lower in ⁸⁷Sr/⁸⁶Sr and slightly higher in ¹⁴³Nd/¹⁴⁴Nd than coexisting opx, implying an intermineral Sr–Nd isotopic disequilibrium. This is observed more apparently in peridotites having low ⁸⁷Sr/⁸⁶Sr and high ¹⁴³Nd/¹⁴⁴Nd ratios than in those with high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd, suggesting that a relatively recent interaction existed between an ancient metasomatized lithospheric mantle and asthenospheric melt, which transformed the refractory peridotites with highly radiogenic Sr and unradiogenic Nd isotopic compositions to the fertile lherzolites with unradiogenic Sr and radiogenic Nd isotopic compositions. Therefore, we argue that the lithospheric mantle represented by the peridotites has been heterogeneously refertilized by multistage melt/fluid-peridotite interactions.     

Oxygen isotope evidence for subduction and rift-related mantle metasomatism beneath the Colorado Plateau–Rio Grande rift transition

Spinel lherzolite and pyroxenite xenoliths from the Rio Puerco Volcanic Field, New Mexico, were analyzed for oxygen isotope ratios by laser fluorination. In lherzolites, olivine δ¹⁸O values are high (+5.5‰), whereas δ¹⁸O values for pyroxenes are low (cpx=+5.1‰; opx=+5.4‰) compared to average mantle values. Pyroxenite δ¹⁸O values (cpx=+5.0‰; opx=+5.3‰) are similar to those of the lherzolites and are also lower than typical mantle oxygen isotope compositions. Texturally and chemically primary calcite in pyroxenite xenoliths is far from isotopic equilibrium with other phases, with δ¹⁸O values of +21‰. The isotopic characteristics of the pyroxenite xenoliths are consistent with a petrogenetic origin from mixing of lherzolitic mantle with slab-derived silicate and carbonatite melts. The anomalously low δ¹⁸O in the pyroxenes reflects metasomatism by a silicate melt from subducted altered oceanic crust, and high δ¹⁸O calcite is interpreted to have crystallized from a high δ¹⁸O carbonatitic melt derived from subducted ophicarbonate. Similar isotopic signatures of metasomatism are seen throughout the Rio Puerco xenolith suite and at Kilbourne Hole in the southern Rio Grande rift. The discrete metasomatic components likely originated from the subducted Farallon slab but were not mobilized until heating associated with Rio Grande rifting occurred. Oxygen diffusion modeling requires that metasomatism leading to the isotopic disequilibrium between calcite and pyroxene in the pyroxenites occurred immediately prior to entrainment. Melt infiltration into spinel-facies mantle (xenoliths) prior to eruption was thus likely connected to garnet-facies melting that resulted in eruption of the host alkali basalt.     

New experimental determination of Li and B partition coefficients during upper mantle partial melting

Despite the growing interest for Li and B as geochemical tracers, especially for material transfer from subducting slabs to overlying peridotites, little is known about the behaviour of these two elements during partial melting of mantle sources. In particular, mineral/melt partition coefficients for B and to a lesser extent Li are still a matter of debate. In this work, we re-equilibrated a synthetic basalt doped with ~10 ppm B and ~6 ppm Li with an olivine powder from a spinel lherzolite xenolith at 1 GPa–1,330°C, and we analyzed Li and B in the run products by secondary ion mass spectrometry (SIMS). In our experiment, B behaved as a highly incompatible element with mineral/melt partition coefficients of the order of 10⁻² (D ^ol/melt = 0.008 (0.004–0.013); D ^opx/melt = 0.024 (0.015–0.033); D ^cpx/melt = 0.041 (0.021–0.061)), and Li as a moderately incompatible element (D ^ol/melt = 0.427 (0.418–0.436); D ^opx/melt = 0.211 (0.167–0.256); D ^cpx/melt = 0.246 (0.229–0.264)). Our partition coefficients for Li are in good agreement with previous determinations. In the case of B, our partition coefficients are equal within error to those reported by Brenan et al. (1998) for all the mineral phases analyzed, but are lower than other coefficients from literature for some of the phases (up to 5 times for cpx). Our measurements complement the data set of Ds for modelling partial melting of the upper mantle and basalt generation, and confirm that, in this context, B is more incompatible than previously anticipated.     

Water contents of the Cenozoic lithospheric mantle beneath the western part of the North China Craton: Peridotite xenolith constraints

Nominally anhydrous phases (clinopyroxene (cpx), orthopyroxene (opx), and olivine (ol)) of peridotite xenoliths hosted by the Cenozoic basalts from Beishan (Hebei province), and Fansi (Shanxi province), Western part of the North China Craton (WNCC) have been investigated by Fourier transform infrared spectrometry (FTIR). The H₂O contents (wt.) of cpx, opx and ol are 30–255 ppm, 14–95 ppm and ~ 0 ppm, respectively. Although potential H-loss during xenolith ascent cannot be excluded for olivine, pyroxenes (cpx and opx) largely preserve the H₂O content of their mantle source inferred from (1) the homogenous H₂O content within single pyroxene grains, and (2) equilibrium H₂O partitioning between cpx and opx. Based on mineral modes and assuming a partition coefficient of 10 for H₂O between cpx and ol, the recalculated whole-rock H₂O contents range from 6 to 42 ppm. In combination with previously reported data for other two localities (Hannuoba and Yangyuan from Hebei province), the H₂O contents of cpx, opx and whole-rock of peridotite xenoliths (43 samples) hosted by the WNCC Cenozoic basalts range from 30 to 654 ppm, 14 to 225 ppm, and 6 to 262 ppm respectively. The H₂O contents of the Cenozoic lithospheric mantle represented by peridotite xenoliths fall in a similar range for both WNCC and the eastern part of the NCC (Xia et al., 2010, Journal of Geophysical Research). Clearly, the Cenozoic lithospheric mantle of the NCC is dominated by much lower water content compared to the MORB source (50–250 ppm). The low H₂O content is not caused by oxidation of the mantle domain, and likely results from mantle reheating, possibly due to an upwelling asthenospheric flow during the late Mesozoic–early Cenozoic lithospheric thinning of the NCC. If so, the present NCC lithospheric mantle mostly represents relict ancient lithospheric mantle. Some newly accreted and cooled asthenospheric mantle may exist in localities close to deep fault.     

Behaviour of Li and its isotopes during metasomatism of French Massif Central lherzolites

Li behaviour and distribution in the mantle were investigated by ion microprobe in situ measurements on co-existing olivine (ol), orthopyroxene (opx), clinopyroxene (cpx) and amphibole (amp) in xenoliths from the French Massif Central. The fertile spinel lherzolites of this study record increasing degrees of mantle metasomatism, from unmetasomatised anhydrous samples through cryptically metasomatised samples to highly metasomatised amphibole-rich samples. In anhydrous lherzolites, Li is preferentially incorporated into olivine (1.1-1.4 ppm, average values) compared to pyroxenes (0.2-0.9 ppm). The hydrous samples clearly show enrichment of Li in ol (1.5-5.0 ppm), opx (1.1-2.4 ppm) and cpx (2.4-5.4 ppm), while amphibole incorporates less Li than the co-existing phases (0.8-1.3 ppm). Average δ⁷Li values range from +7.6 to +14.5‰ in ol, from 5.1 to +13.7‰ in opx and from 8.8 to +10.3‰ in cpx from the anhydrous lherzolites. A layered peridotite sample (Sdi) shows higher Li content in all phases, with lighter isotopic composition in opx and cpx (−0.6 and −2‰ average δ⁷Li values, respectively). In the hydrous lherzolites average δ⁷Li values both overlap and extend beyond these ranges in ol (up to 17.5 ‰) and in opx (up to 22.9‰), and vary widely in cpx (−2.7 to +9.7‰). Low δ⁷Li values are observed in some opx (−10.4‰) and cpx (−13‰) from sample Sdi, and in cpx from three hydrous samples (from −9.7 to −5.3‰). The different anhydrous phases from the hydrous samples show large intra-grain variations in Li isotopic ratios (e.g., up to 18‰) compared to the same phases from the anhydrous samples (mostly less than 6‰), excepting sample Sdi which has up to 20.4‰ variation in cpx. Similar to the anhydrous silicates, amphiboles show a wide variation of δ⁷Li values on the intra-grain scale (2-27‰). These variations are interpreted to result from fractionation processes during metasomatism by a silicate melt undergoing compositional changes as it percolates through and reacts with the peridotite phases. Thus Li abundances and isotopic in situ measurements are useful for tracing metasomatic processes but the heterogeneities observed in the samples preclude any identification of a specific mantle source by its Li signature.     

Lithium isotopic systematics of peridotite xenoliths from Hannuoba, North China Craton: Implications for melt-rock interaction in the considerably thinned lithospheric mantle

Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ⁷Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ⁷Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ⁷Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ⁷Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ⁷Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.     

Secular evolution of the lithospheric mantle beneath the eastern North China craton: evidence from peridotitic xenoliths from Late Cretaceous mafic rocks in the Jiaodong region,east-central China

The Mesozoic lithospheric mantle beneath the North China craton remains poorly constrained relative to its Palaeozoic and Cenozoic counterparts due to a lack of mantle xenoliths in volcanic rocks. Available data show that the Mesozoic lithospheric mantle was distinctive in terms of its major, trace element, and isotopic compositions. The recent discovery of mantle peridotitic xenoliths in Late Cretaceous mafic rocks in the Jiaodong region provides an opportunity to further quantify the nature and secular evolution of the Mesozoic lithospheric mantle beneath the region. These peridotitic xenoliths are all spinel-facies nodules and two groups, high-Mg# and low-Mg# types, can be distinguished based on textural and mineralogical features. High-Mg# peridotites have inequigranular textures, high Mg# (up to 92.2) in olivines, and high Cr# (up to 55) in spinels. Clinopyroxenes in the high-Mg# peridotites are generally LREE-enriched ((La/Yb)_N>1) with variable REE concentrations, and have enriched Sr–Nd isotopic compositions (⁸⁷Sr/⁸⁶Sr = 0.7046–0.7087; ¹⁴³Nd/¹⁴⁴Nd = 0.5121–0.5126). We suggest that the high-Mg# peridotites are fragments of the Archaean and/or Proterozoic lithospheric mantle that underwent extensive interaction with both carbonatitic and silicate melts prior to or during Mesozoic time. The low-Mg# peridotites are equigranular, are typified by low Mg# ( < 90) in olivines, and by low Cr# ( < 12) in spinels. Clinopyroxenes from low-Mg# peridotites have low REE abundances (ΣREE = 12 ppm), LREE-depleted REE patterns ((La/Yb)_N < 1), and depleted Sr–Nd isotopic features, in contrast to the high-Mg# peridotites. These geochemical characteristics suggest that the low-Mg# peridotites represent samples from the newly accreted lithospheric mantle. Combined with the data of mantle xenoliths from the Junan and Daxizhuang areas, a highly heterogeneous, secular evolution of the lithosphere is inferred for the region in Late Cretaceous time.     

Erratum to: Iron isotope variations in spinel peridotite xenoliths from North China Craton: implications for mantle metasomatism

Iron isotopes, together with mineral elemental compositions of spinel peridotite xenoliths and clinopyroxenites from Hannuoba and Hebi Cenozoic alkaline basalts, were analyzed to investigate iron isotopic features of the lithospheric mantle beneath the North China Craton. The results show that the Hannuoba spinel peridotite xenoliths have small but distinguishable Fe isotopic variations. Overall variations in δ⁵⁷Fe are in a range of −0.25 to 0.14‰ for olivine, −0.17 to 0.17‰ for orthopyroxene, −0.21 to 0.27‰ for clinopyroxene, and −0.16 to 0.26‰ for spinel, respectively. Clinopyroxene has the heaviest iron isotopic ratio and olivine the lightest within individual sample. No clear linear relationships between the mineral pairs on “δ-δ” plot suggest that iron isotopes of mineral separates analyzed have been affected largely by some open system processes. The broadly negative correlations between mineral iron isotopes and metasomatic indexes such as spinel Cr#, (La/Yb)_N ratios of clinopyroxenes suggest that iron isotopic variations in different minerals and peridotites were probably produced by mantle metasomatism. The Hebi phlogopite-bearing lherzolite, which is significantly modified by metasomatic events, appears to be much heavier isotopically than clinopyroxene-poor lherzolite. This study further confirms previous conclusions that the lithospheric mantle has distinguishable and heterogeneous iron isotopic variations at the xenoliths scale. Mantle metasomatism is the most likely cause for the iron isotope variations in mantle peridotites.     

Insights into Li and Li isotope cycling and sub-arc metasomatism from veined mantle xenoliths,Kamchatka

Harzburgitic xenoliths cut by pyroxenite veins from Avachinsky volcano, Kamchatka, are derived from the sub-arc mantle and record element transfer from the slab to the arc. Olivine and orthopyroxene in the harzburgites have Li isotopic compositions (δ⁷Li = +2.8 to +5.6) comparable to estimates of the upper mantle (δ⁷Li ~ +4 ± 2). The pyroxenite veins, which represent modal metasomatism and may therefore provide information about the metasomatic agent, have mantle-normalized trace element characteristics that suggest overprinting of their mantle source by an aqueous, slab-derived fluid. These include relative enrichments of Pb over Ce, U over Th and Sr over Nd. Li is enriched relative to the HREE, and ortho- and clinopyroxene from the veins are in Li elemental and isotopic equilibrium with each other and the surrounding harzburgite. Vein samples (δ⁷Li = +3.0 to +5.0) do not record a significant slab-derived δ⁷Li signature. These observations can be reconciled if slab Li diffusively re-equilibrates in the mantle wedge. Modeling demonstrates that Li equilibration of small (1–2 cm width) veins or melt conduits is achieved at mantle wedge temperatures within 10¹–10⁵ years. We conclude that strongly fractionated Li isotopic signatures cannot be sustained for long periods in the sub-arc mantle, at least at shallow (<70 km) depths. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Li isotopes and trace elements as a petrogenetic tracer in zircon: insights from Archean TTGs and sanukitoids

We report δ⁷Li, Li abundance ([Li]), and other trace elements measured by ion probe in igneous zircons from TTG (tonalite, trondhjemite, and granodiorite) and sanukitoid plutons from the Superior Province (Canada) in order to characterize Li in zircons from typical Archean continental crust. These data are compared with detrital zircons from the Jack Hills (Western Australia) with U–Pb ages greater than 3.9 Ga for which parent rock type is not known. Most of the TTG and sanukitoid zircon domains preserve typical igneous REE patterns and CL zoning. [Li] ranges from 0.5 to 79 ppm, typical of [Li] in continental zircons. Atomic ratios of (Y + REE)/(Li + P) average 1.0 ± 0.7 (2SD) for zircons with magmatic composition preserved, supporting the hypothesis that Li is interstitial and charge compensates substitution of trivalent cations. This substitution results in a relatively slow rate of Li diffusion. The δ⁷Li and trace element data constrain the genesis of TTGs and sanukitoids. [Li] in zircons from granitoids is significantly higher than from zircons in primitive magmas in oceanic crust. TTG zircons have δ⁷Li (3 ± 8‰) and δ¹⁸O in the range of primitive mantle-derived magmas. Sanukitoid zircons have average δ⁷Li (7 ± 8‰) and δ¹⁸O higher than those of TTGs supporting genesis by melting of fluid-metasomatized mantle wedge. The Li systematics in sanukitoid and TTG zircons indicate that high [Li] in pre-3.9-Ga Jack Hills detrital zircons is a primary igneous composition and suggests the growth in proto-continental crust in magmas similar to Archean granitoids.     

The origin of hydrous,high-δ<Superscript>18</Superscript>O voluminous volcanism: diverse oxygen isotope values and high magmatic water contents within the volcanic record of Klyuchevskoy volcano,Kamchatka, Russia

Klyuchevskoy volcano, in Kamchatka’s subduction zone, is one of the most active arc volcanoes in the world and contains some of the highest δ¹⁸O values for olivines and basalts. We present an oxygen isotope and melt inclusion study of olivine phenocrysts in conjunction with major and trace element analyses of ¹⁴C- and tephrochronologically-dated tephra layers and lavas spanning the eruptive history of Klyuchevskoy. Whole-rock and groundmass analyses of tephra layers and lava samples demonstrate that both high-Mg (7–12.5 wt% MgO) and high-Al (17–19 wt% Al₂O₃, 3–6.5 wt% MgO) basalt and basaltic andesite erupted coevally from the central vent and flank cones. Individual and bulk olivine δ¹⁸O range from normal MORB values of 5.1‰ to values as high as 7.6‰. Likewise, tephra and lava matrix glass have high-δ¹⁸O values of 5.8–8.1‰. High-Al basalts dominate volumetrically in Klyuchevskoy’s volcanic record and are mostly high in δ¹⁸O. High-δ¹⁸O olivines and more normal-δ¹⁸O olivines occur in both high-Mg and high-Al samples. Most olivines in either high-Al or high-Mg basalts are not in oxygen isotopic equilibrium with their host glasses, and Δ¹⁸O_{olivine–glass} values are out of equilibrium by up to 1.5‰. Olivines are also out of Fe–Mg equilibrium with the host glasses, but to a lesser extent. Water concentrations in olivine-hosted melt inclusions from five tephra samples range from 0.4 to 7.1 wt%. Melt inclusion CO₂ concentrations vary from below detection (<50 ppm) to 1,900 ppm. These values indicate depths of crystallization up to ~17 km (5 kbar). The variable H₂O and CO₂ concentrations likely reflect crystallization of olivine and entrapment of inclusions in ascending and degassing magma. Oxygen isotope and Fe–Mg disequilibria together with melt inclusion data indicate that olivine was mixed and recycled between high-Al and high-Mg basaltic melts and cumulates, and Fe–Mg and δ¹⁸O re-equilibration processes were incomplete. Major and trace elements in the variably high-δ¹⁸O olivines suggest a peridotite source for the parental magmas. Voluminous, highest in the world with respect to δ¹⁸O, and hydrous basic volcanism in Klyuchevskoy and other Central Kamchatka depression volcanoes is explained by a model in which the ascending primitive melts that resulted from the hydrous melt fluxing of mantle wedge peridotite, interacted with the shallow high-δ¹⁸O lithospheric mantle that had been extensively hydrated during earlier times when it was part of the Kamchatka forearc. Following accretion of the Eastern Peninsula terrains several million years ago, a trench jump eastward caused the old forearc mantle to be beneath the presently active arc. Variable interaction of ascending flux-melting-derived melts with this older, high-δ¹⁸O lithospheric mantle has produced mafic parental magmas with a spectrum of δ¹⁸O values. Differentiation of the higher δ¹⁸O parental magmas has created the volumetrically dominant high-Al basalt series. Both basalt types incessantly rise and mix between themselves and with variable in δ¹⁸O cumulates within dynamic Klyuchevskoy magma plumbing system, causing biannual eruptions and heterogeneous magma products. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Lithium enrichment and isotopic variation in minerals from peridotite xenoliths from northwestern Ethiopian plateau

We report Lithium (Li) concentrations and isotopic compositions for co-existing olivine, orthopyroxene (opx), and clinopyroxene (cpx) mineral separates from depleted and metasomatised peridotite xenoliths hosted by basaltic lavas from northwestern Ethiopian plateau (Gundeweyn area). The peridotites contain five lherzolites and one harzburgite and are variably depleted and enriched in LREE relative to HREE. In both depleted and enriched lherzolites, Li is preferentially incorporated into olivine (2.4-3.3 ppm) compared to opx (1.4-2.1 ppm) and cpx (1.4-2.0 ppm) whereas the Li contents of olivines (5.4 ppm) from an enriched harzburgiteare higher than those of lherzolites. Olivines from the samples show higher Li abundances than normal mantle olivines (1.6-1.9 ppm) indicating the occurrence of Li enrichments through melt-preroditite interaction. The average δ⁷ Li values range from +2.2 to +6.0‰ in olivine, from -0.1 to +2.0‰ in opx and from -4.4 to -0.9‰ in cpx from the lherzolites. The Li isotopic composition (3.5‰) of olivines from harzburgite fall within the range of olivine from lherzolites but the opxs show low in δ⁷Li (-2.0‰). Overall Li isotopic compositions of olivines from the peridotites fall within the range of normal mantle olivine, δ⁷Li values of ~+4±2‰ within uncertainty, reflecting metasomatism (enrichment) of the peridotites by isotopically heavy Li-rich asthenospheric melt. Li isotope zonation is also observed in most peridotite minerals. Majority of olivine grains display isotopically heavy cores and light rims and the reverse case is observed for some olivine grains. Orthopyroxene and clinopyroxene grains show irregular distribution in δ⁷Li. These features of Li isotopic compositions within and between grains in the samples reflect the effect of diffusion-driven isotopic fractionation during meltperidotite interaction and cooling processes.     

Li-Sr-Nd isotope signatures of the plume and cratonic lithospheric mantle beneath the margin of the rifted Tanzanian craton (Labait)

Lithium concentrations and isotopic compositions of olivine and ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd of coexisting clinopyroxene from peridotite xenoliths from the Quaternary Labait volcano, Tanzania, document the influence of rift-related metasomatism on the ancient cratonic mantle. Olivines show negative correlations between Fo content and both δ⁷Li and Li concentrations. Olivines in iron-rich peridotites (Fo_85–87) have high Li concentrations (3.2–4.8 ppm) and heavy δ⁷Li (+5.2 to +6.6). In contrast, olivines in ancient, refractory peridotites have lower Li concentrations (∼2 ppm) and relatively light δ⁷Li (+2.6 to +3.5). This reflects mixing between ancient, refractory cratonic lithosphere and asthenosphere-derived rift magmas. A uniquely fertile, deformed, high-temperature garnet lherzolite, interpreted to be from the base of the lithosphere, has a ⁸⁷Sr/⁸⁶Sr of 0.7029 and ¹⁴³Nd/¹⁴⁴Nd of 0.51286, similar to HIMU oceanic basalts. It provides the best estimate of the Sr–Nd isotope composition of the upwelling mantle (i.e., plume, sensu lato) underlying this portion of the East African Rift, and is slightly less radiogenic compared to previous estimates of the plume that were based on rift basalts. Although elevated δ⁷Li are not exclusive to HIMU source regions, the data collectively indicate that the plume beneath Labait has HIMU characteristics in Sr, Nd and Li isotope composition. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A comparative study on isotopic composition of precipitation in wet tropic and semi-arid stations across southern India

Isotopic composition of monthly composite precipitation samples from Kozhikode (n = 31), a wet tropic station and Hyderabad (n = 25), a semi-arid station across southern India were studied for a period of four years from 2005 to 2008. During the study period, the Kozhikode station recorded an average rainfall of 3500 mm while the Hyderabad station showed an average rainfall of 790 mm. The average stable isotope values in precipitation at the Kozhikode station were δ ¹⁸O = −3.52‰, d-excess = 13.72‰; δ ¹⁸O = −2.94‰, d-excess = 10.57‰; and δ ¹⁸O = −7.53‰, d-excess = 13.79‰, respectively during the pre-monsoon (March–May), monsoon (June–September) and post-monsoon (October–February) seasons. For the Hyderabad station, the average stable isotope values were δ ¹⁸O = −5.88‰, d-excess = 2.34‰; δ ¹⁸O = −4.39‰, d-excess = 9.21‰; and δ ¹⁸O = −8.69‰, d-excess = 14.29‰, respectively for the three seasons. The precipitation at the two stations showed distinctive isotopic signatures. The stable isotopic composition of precipitation at the Hyderabad station showed significant variations from the global trend while the Kozhikode station almost followed the global value. These differences are mainly attributed to the latitudinal differences of the two stations coupled with the differences in climatic conditions.     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

Na,K, P and Ti in garnet,pyroxene and olivine from peridotite and eclogite xenoliths from African kimberlites

Electron microprobe analyses sensitive to 20ppmw (2σ) were made for Na, P, K and Ti in garnet, pyroxenes and olivine from peridotite and eclogite xenoliths from African kimberlites and volcanic rocks in Tanzania. Average concentrations (ppmw) in peridotite (mostly garnet lherzolite) are: Na₂O gt 340 ol 90 opx 1070 cpx 2.1 (wt.%); P₂O₅ gt 460 ol 130 opx 50 cpx 350; K₂O gt <20 ol <20 opx 30 cpx 170; TiO₂ gt 1470 ol 130 opx 480 cpx 1630. For eclogites and a cpx megacryst with gt inclusions: Na₂O gt 610 cpx 4.3 (wt.%); P₂O₅ gt 530 cpx 300; K₂O gt <20 cpx 370; TiO₂ gt 1990 cpx 1980.In garnet, Na can be explained by coupled substitution with P and Ti, and there is no need to invoke six-coordinated silicon. The Na distribution between garnet and clinopyroxene correlates with the Fe/Mg distribution for both eclogites and peridotites, and for the peridotites correlates with estimates of pressure and temperature from pyroxene composition. When calibrated experimentally, the Na distribution may be a useful indicator of physical conditions at depths for which the Fe/Mg distribution is insensitive; furthermore the Na distribution may be less sensitive to oxidation state.     

Xenolith evidence for lithospheric melting above anomalously hot mantle under the northern Canadian Cordillera

A comparison of mantle xenolith suites along the northern Canadian Cordillera reveals that the xenoliths from three suites exhibit bimodal populations whereas the xenoliths from the other four suites display unimodal populations. The bimodal suites contain both fertile lherzolite and refractory harzburgite, while the unimodal suites are dominated by fertile lherzolite xenoliths. The location of the three bimodal xenolith suites correlates with a newly discovered P-wave slowness anomaly in the upper mantle that is 200 km in width and extends to depths of 400–500 km (Frederiksen AW, Bostock MG, Van Decar JC, Cassidy J, submitted to Tectonophysics). This correlation suggests that the bimodal xenolith suites may either contain fragments of the anomalously hot asthenospheric mantle or that the lithospheric upper mantle has been affected by the anomalously hot mantle. The lherzolite xenoliths in the bimodal suites display similar major element compositions and trace element patterns to the lherzolite xenoliths in the unimodal suites, suggesting that the lherzolites represent the regional lithospheric upper mantle. In contrast, the harzburgite xenoliths are highly depleted in terms of major element composition, but their clinopyroxenes [Cpx] have much higher incompatible trace element contents than those in the lherzolite xenoliths. The major element and mildly incompatible trace element systematics of the harzburgite and lherzolite xenoliths indicate that they could be related by a partial melting process. The lack of textural and geochemical evidence for the former existence of garnet argues against the harzburgite xenoliths representing actual fragments of the deeper anomalous asthenospheric mantle. Furthermore, the calculated P-wave velocity difference between harzburgite and lherzolite end-members is only 0.8%, with the harzburgites having higher P-wave velocities. Therefore the 3% P-wave velocity difference detected teleseismically cannot be produced by the compositional difference between the lherzolite and harzburgite xenoliths. If temperature is responsible for the observed 3% P-wave velocity perturbation, the anomalous mantle is likely to be at least 200 °C higher than the surrounding mantle. Taken together these data indicate that the refractory harzburgite xenoliths represent the residue of 20–25% partial melting of a lherzolite lithospheric mantle. The incompatible trace element enrichment of the harzburgites suggests that this melting was accompanied by the ingress of fluids. The association of the bimodal xenolith suites with the mantle anomaly detected teleseismically suggests that anomalously hot asthenospheric mantle provided both the heat and volatiles responsible for the localized melting and enrichment of the lithospheric mantle. Received: 16 May 1997 / Accepted: 25 October 1997     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.

Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) ¹⁸O/¹⁶O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ¹⁸O_ol (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ¹⁸O_ol values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ¹⁸O_ol values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ¹⁸O_ol is weakly correlated (R ² = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ¹⁸O values for HIMU-peridotite (δ¹⁸O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ¹⁸O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ¹⁸O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ¹⁸O (<5 ‰), rather than higher-δ¹⁸O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ¹⁸O_ol and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.     

Oxygen isotopes composition of sapphires from the French Massif Central: implications for the origin of gem corundum in basaltic fields

Alluvial and colluvial gem sapphires are common in the basaltic fields of the French Massif Central (FMC) but sapphire-bearing xenoliths are very rare, found only in the Menet trachytic cone in Cantal. The O-isotope composition of the sapphires ranges between 4.4 and 13.9‰. Two distinct groups have been defined: the first with a restricted isotopic range between 4.4 and 6.8‰ (n = 22; mean δ¹⁸O = 5.6 ± 0.7‰), falls within the worldwide range defined for blue-green-yellow sapphires related to basaltic gem fields (3.0 < δ¹⁸O < 8.2‰, n = 150), and overlaps the ranges defined for magmatic sapphires in syenite (4.4 < δ¹⁸O < 8.3‰, n = 29). A second group, with an isotopic range between 7.6 and 13.9‰ (n = 9), suggests a metamorphic sapphire source such as biotite schist in gneisses or skarns. The δ¹⁸O values of 4.4–4.5‰ for the blue sapphire-bearing anorthoclasite xenolith from Menet is lower than the δ¹⁸O values obtained for anorthoclase (7.7–7.9‰), but suggest that these sapphires were derived from an igneous reservoir in the subcontinental spinel lherzolitic mantle of the FMC. The presence of inclusions of columbite-group minerals, pyrochlore, Nb-bearing rutile, and thorite in these sapphires provides an additional argument for a magmatic origin. In the FMC lithospheric mantle, felsic melts crystallized to form anorthoclasites, the most evolved peraluminous variant of the alkaline basaltic melt. The O-isotopic compositions of the first group suggests that these sapphires crystallized from felsic magmas under upper mantle conditions. The second group of isotopic values, typified for example by the Le Bras sapphire with a δ¹⁸O of 13.9‰, indicates that metamorphic sapphires from granulites were transported to the surface by basaltic magma.     

Multiple origins of zircons in jadeitite

Jadeitites form from hydrothermal fluids during high pressure metamorphism in subduction environments; however, the origin of zircons in jadeitite is uncertain. We report ion microprobe analyses of δ¹⁸O and Ti in zircons, and bulk δ¹⁸O data for the jadeitite whole-rock from four terranes: Osayama serpentinite mélange, Japan; Syros mélange, Greece; the Motagua Fault zone, Guatemala; and the Franciscan Complex, California. In the Osayama jadeitite, two texturally contrasting groups of zircons are identified by cathodoluminescence and are distinct in δ¹⁸O: featureless or weakly zoned zircons with δ¹⁸O = 3.8 ± 0.6‰ (2 SD, VSMOW), and zircons with oscillatory or patchy zoning with higher δ¹⁸O = 5.0 ± 0.4‰. Zircons in phengite jadeitite from Guatemala and a jadeitite block from Syros have similar δ¹⁸O values to the latter from Osayama: Guatemala zircons are 4.8 ± 0.7‰, and the Syros zircons are 5.2 ± 0.5‰ in jadeitite and 5.2 ± 0.4‰ in associated omphacitite, glaucophanite and chlorite-actinolite rinds. The δ¹⁸O values for most zircons above fall within the range measured by ion microprobe in igneous zircons from oxide gabbros and plagiogranites in modern ocean crust (5.3 ± 0.8‰) and measured in bulk by laser fluorination of zircons in equilibrium with primitive magma compositions or the mantle (5.3 ± 0.6‰). Titanium concentrations in these zircons vary between 1 and 19 ppm, within the range for igneous zircons worldwide. Values of δ¹⁸O (whole-rock) ≅ δ¹⁸O (jadeite) and vary from 6.3 to 10.1‰ in jadeitites in all four areas.