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.     

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.     

山东蓬莱新生代岩石圈地幔的异常锂同位素组成：橄榄岩包体的离子探针分析

应用离子探针技术对山东蓬莱新生代玄武岩中橄榄岩包体的主要组成矿物进行了原位测定,结果显示了强烈偏离正 常地幔矿物组成和平衡的Li 含量和同位素比值。橄榄石、斜方辉石和单斜辉石的Li 含量和δ7Li 分别为（2.0~10.4）×10-6, （2.8~23.8）×10-6 和（3.3~59.7）×10-6;-28.6‰ ~+0.5‰,-12.7‰ ~+12.8‰和-41.5‰ ~+22.6‰。这种强烈的非平衡体系反 映了最近强烈和复杂的地幔交代作用。辉石的高Li（~ 60×10-6）和δ7Li（~ +20‰）反映了最近富Li地幔熔体/ 流体的特征, 而橄榄石的中等Li 富集（<5×10-6）和强烈的δ7Li 亏损（~ -20‰）则可能记录了更早一期低δ7Li 的地幔交代。同位素剖面 的扩散反演以及Li 强烈富集与LREE 相对亏损之间的解耦显示了两期地幔交代作用的短暂性和近期性。因此,我们认为华 北东部克拉通上地幔中存在与再循环有关的锂同位素异常组分,它们的形成应该与中生代以来太平洋板块向东亚大陆下的 俯冲有关. 这些组分能够在地幔中较长的保存直至最近被热扰动所释放,并被橄榄岩包体所记录。     

Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from Shangzhi,NE China: products of recent melt/fluid-peridotite interaction

Lithium elemental and isotopic disequilibrium has frequently been observed in the continental and oceanic mantle xenoliths, but its origin remains controversial. Here, we present a combined elemental and Li isotopic study on variably metasomatised peridotite xenoliths entrained in the Cenozoic basalts from Shangzhi in Northeast (NE) China that provides insight into this issue. Li concentration (0.3–2.7 ppm) and δ⁷Li (mostly 2‰–6‰) in olivine from the Shangzhi peridotites are similar to the normal mantle values and show roughly negative correlations with the indices of melt extraction (such as modal olivine and whole rock MgO). These features are consistent with variable degrees of partial melting. In contrast, clinopyroxene from the Shangzhi xenoliths shows significant Li enrichment (0.9–6.1 ppm) and anomalously light δ⁷Li (??13.8‰ to 7.7‰) relative to normal mantle values. Such features can be explained by Li diffusion from silicate melts or Li-rich fluids occurring over a very short time (several minutes to several hours). Moreover, the light Li isotopic compositions preserved in some bulk samples also indicate that these percolated melts/fluids have not had enough time to isotopically equilibrate with the bulk peridotite. We thus emphasize that Li isotopic fractionation in the Shangzhi mantle xenoliths is mainly related to Li diffusion from silicate melts or Li-rich fluids that took place shortly before or coincident with their entrainment into the host magmas.     

Melt/rock interaction in remains of refertilized Archean lithospheric mantle in Jiaodong Peninsula, North China Craton: Li isotopic evidence

Li contents and its isotopes of minerals in mantle peridotite xenoliths from late Cretaceous mafic dikes, analyzed in situ by Cameca IMS-1280, reveal the existence of melt/rock interaction in remains of refertilized Archean lithospheric mantle in Qingdao, Jiaodong Peninsula, North China Craton. Two groups of peridotites exist, i.e., low-Mg# lherzolite and high-Mg# harzburgites. The low-Mg# lherzolite has a relatively homogeneous Li concentration (ol: 2.01–2.11 ppm; opx: 1.77–1.88 ppm; cpx: 1.75–1.93 ppm) and Li isotopic composition (δ⁷Li in ol: 4.2–7.6‰; in opx: 6.0–8.3‰; in cpx: 5.3–8.4‰). The similarity in δ⁷Li value to the fresh MORB provides further evidence for the argument that the low-Mg# lherzolite could be the fragment of the newly accreted lithospheric mantle. The high-Mg# harzburgites have heterogeneous Li abundances (ol: 0.83–2.09 ppm; opx: 0.92–1.94 ppm; cpx: 1.12–4.89 ppm) and Li isotopic compositions (δ⁷Li in ol: −0.5 to +11.5‰; in opx: −6.2 to +11.1‰; in cpx: −34.3 to +10.1‰), showing strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The cores of most minerals in these high-Mg# harzburgites have relatively homogeneous δ⁷Li values, which are higher than those of fresh MORB, but similar to those previously reported for arc lavas. These harzburgites have enriched trace elemental and Sr–Nd isotopic compositions. These observations indicate that in the early Mesozoic the lithospheric mantle beneath the southeastern North China Craton was similar to that in arc settings, which is metasomatized by subducted crustal materials. Extremely low δ⁷Li preserved in cpxs requires diffusive fractionation of Li isotopes from later-stage melt into the minerals. Thus, the Li data provide further evidence that the Archean refractory lithospheric mantle represented by the high-Mg# harzburgites was refertilized through melt/rock interaction and transformed to the Mesozoic less refractory and incompatible element and Sr–Nd isotopes enriched lithospheric mantle.     

Geochemistry and oxygen isotopic composition of olivine in kimberlites from the Arkhangelsk province: Contribution of mantle metasomatism

The paper presents data on the composition of olivine macrocrysts from two Devonian kimberlite pipes in the Arkhangelsk diamond province: the Grib pipe (whose kimberlite belongs to type I) and Pionerskaya pipe (whose kimberlite is of type II, i.e., orangeite). The dominant olivine macrocrysts in kimberlites from the two pipes significantly differ in geochemical and isotopic parameters. Olivine macrocrysts in kimberlite from the Grib pipe are dominated by magnesian (Mg# = 0.92–0.93), Ti-poor (Ti < 70 ppm) olivine possessing low Ti/Na (0.05–0.23), Zr/Nb (0.28–0.80), and Zn/Cu (3–20) ratios and low Li concentrations (1.2–2.0 ppm), and the oxygen isotopic composition of this olivine δ¹⁸O = 5.64‰ is higher than that of olivine in mantle peridotites (δ¹⁸O = 5.18 ± 0.28‰). Olivine macrocrysts in kimberlite from the Pionerskaya pipe are dominated by varieties with broadly varying Mg# = 0.90–0.93, high Ti concentrations (100–300 ppm), high ratios Ti/Na (0.90–2.39), Zr/Nb (0.31–1.96), and Zn/Cu (12–56), elevated Li concentrations (1.9–3.4 ppm), and oxygen isotopic composition δ¹⁸O = 5.34‰ corresponding to that of olivine in mantle peridotites. The geochemical and isotopic traits of low-Ti olivine macrocrysts from the Grib pipe are interpreted as evidence that the olivine interacted with carbonate-rich melts/fluids. This conclusion is consistent with the geochemical parameters of model melt in equilibrium with the low-Ti olivine that are similar to those of deep carbonatite melts. Our calculations indicate that the variations in the δ¹⁸O of the olivine relative the “mantle range” (toward both higher and lower values) can be fairly significant: from 4 to 7‰ depending on the composition of the carbonate fluid. These variations were formed at interaction with carbonate fluid, whose δ¹⁸O values do not extend outside the range typical of mantle carbonates. The geochemical parameters of high-Ti olivine macrocrysts from the Grib pipe suggest that their origin was controlled by the silicate (water–silicate) component. This olivine is characterized by a zoned Ti distribution, with the configuration of this distribution between the cores of the crystals and their outer zones showing that the zoning of the cores and outer zones is independent and was produced during two episodes of reaction interaction between the olivine and melt/fluid. The younger episode (when the outer zone was formed) likely involved interaction with kimberlite melt. The transformation of the composition of the cores during the older episode may have been of metasomatic nature, as follows from the fact that the composition varies from grain to grain. The metasomatic episode most likely occurred shortly before the kimberlite melt was emplaced and was related to the partial melting of pyroxenite source material.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

Lithium elemental and isotopic variations in rock-melt interaction

Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ⁷Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ⁷Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ⁷Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ⁷Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ⁷Li, the carbonatite and silicate melts produced remarkably contrasting δ⁷Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ⁷Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.     

Lithium isotopic disequilibrium of minerals in the spinel lherzolite xenoliths from Boeun,Korea

Spinel lherzolite xenoliths found in Boeun, Korea, have protogranular to porphyroclastic textures and are enclosed in a Miocene alkali basalt. The lithium concentration and isotopic compositions of olivine, clinopyroxene, and orthopyroxene separates from the spinel lherzolite, and whole rocks of the spinel lherzolites and alkali basalt were determined by inductively coupled plasma mass spectrometry (ICP-MS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The lithium concentrations of the olivines and orthopyroxenes range from 2.2 to 5.0 ppm and from 2.1 to 6.4 ppm, respectively. In contrast, the clinopyroxenes have larger lithium concentrations, from 2.0 to 8.4 ppm, which reflect their preferential lithium enrichment. The lithium isotopic compositions (δ⁷Li) of olivines (-5.4 to + 3.5‰), orthopyroxenes (-11.4 to -0.1‰), and clinopyroxenes (-14.4 to -4.7‰) range far beyond the average mantle composition of + 4 ± 2‰. The lithium isotopic composition of the host rock, alkali basalt (3.4‰), is within the range of the intraplate and oceanic island basalts. The spinel lherzolites from Boeun exhibits strong elemental and isotopic disequilibria due to the different lithium and lithium isotope diffusion velocities in the olivine, orthopyroxene, and clinopyroxene minerals after eruption and magma cooling.     

Rare Earth and 3d Transition Element Geochemistry of Peridotitic Rocks: I. Peridotites from the Western Alps

Trace element analyses have been obtained employing RNAA andINAA techniques for 23 bulk-rock specimens and for five pairsof mechanically separated opx and cpx from Western Alpine peridotites.Investigated rocks include 5 garnet lherzolites from Alpe Arami,and spinel (+plagioclase) lherzolites from Finero (2), Balmuccia(7), Baldissero (6) and Lanzo (3). Three pyroxene pairs wereanalysed from Balmuccia and two from Baldissero. All rocks exhibit marked LREE depletions relative to chondriticabundances except for the two Finero samples which appear tobe HREE depleted. Separated minerals also show LREE depletionsand HREE enrichments relative to chondrites. However, intermediaterare earths are markedly depleted in opx whereas they are enrichedin coexisting cpx. Higher overall concentrations and patternssimilar to those of the bulk rocks indicate that REE distributionsin lherzolites are dominated by clinopyroxene chemistry. Incontrast, both opx and cpx appear to contribute equally to the3d transition element geochemistry of the investigated peridotites. Most of the investigated rocks show the effects of early partialmelting of a pre-existing mantle source material characterizedby ‘chondritic’ REE fractionation and by a 3d transitionelement composition near the estimated values of Jagoutz etal. (1979). The melting process probably developed in a closed system (equilibriummelting) and at temperatures which, for the spinel peridotiteprotolith, seemingly were compatible with estimates of Presnallel al. (1979) for the ‘melting at the cusp’ process(T = 1200–1250 °C). In some cases the residual rocksunderwent a further contamination event. This is particularlyevident for the Lanzo peridotites, but possibly also for singleBaldissero and Balmuccia specimens. During ascent to the surface, the rocks underwent subsolidusannealing which occurred at temperatures around 900–1000°C under more or less closed system conditions.     

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ⁵⁶Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ²⁶Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_ol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ⁵⁶Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

地幔橄榄岩中橄榄石的指示意义

橄榄石是地幔橄榄岩和辉石岩的主要组成矿物,但也经常以斑晶和捕虏晶的形式出现在玄武质岩石中。结合近年来在地幔橄榄岩的主要元素（如Mg和Fe）组成特征以及Li、Mg和Fe稳定同位素地球化学方面的研究成果,重点对橄榄石的地球化学特征与华北克拉通岩石圈地幔演化过程之间的联系进行了讨论,旨在加深对华北克拉通岩石圈地幔演化过程的理解。现有研究表明：地幔橄榄岩中橄榄石的矿物学特征、元素和同位素地球化学组成能够很好地指示岩石圈地幔的特征及其演化过程,因而具有重要的意义。对于克拉通地区的地幔橄榄岩来说,橄榄石的Mg#通常可以指示岩石圈地幔的属性,古老、难熔的地幔橄榄岩中的橄榄石一般具有较高的Mg#（〉92）,而新生的岩石圈地幔橄榄岩中的橄榄石则具有较低的Mg#（〈91）。因此,地幔橄榄岩中橄榄石的Mg#在一定程度上具有年龄意义。橄榄岩中橄榄石的Li、Mg和Fe同位素组成也可以明确指示岩石圈地幔的属性及其所经历的演化过程,正常地幔的δ7Li、δ26Mg和δ57Fe组成相对均一,如果上述同位素组成偏离正常地幔值,则说明岩石圈地幔经历了熔体/流体的交代作用。华北克拉通地区地幔橄榄岩捕虏体中橄榄石的Li、Mg和Fe同位素组成研究表明：该区的岩石圈地幔经历了多个阶段、不同来源的熔体/流体的改造过程。     

Characteristics of the lithospheric mantle beneath East Serbia inferred from ultramafic xenoliths in Palaeogene basanites

Mantle xenoliths from Paleogene basanites of East Serbia were studied using EMP and LA-ICP-MS techniques in order to better understand mantle characteristics in this region. Five different mantle lithologies have been distinguished: a dunite/harzburgite/lherzolite (D/HZ/L) group, clinopyroxene-rich lherzolites (Cpx-L), clinopyroxene megacrysts (Cpx-M), spinel-rich olivine websterites (OWB₁) and spinel-poor olivine websterites (OWB₂). D/HZ/L xenoliths are the most common and represent normal mantle composed of typical anhydrous spinel peridotites with well equilibrated, unzoned silicates characterized by high Mg# s. Negative correlations between Mg# and TiO₂, Al₂O₃ and CaO wt% in clinopyroxenes (cpx) and orthopyroxenes (opx) and the Cr–Al trend in spinel (sp) suggest depletion via extraction of basaltic melts. The modal composition of D/HZ/L xenoliths and unusual low-Al opx suggest that the lithospheric mantle underneath East Serbia is more depleted than normal European lithosphere. D/HZ/L xenoliths contain numerous pockets and veins filled by Cr-rich cpx, Ti-rich spinel, altered glass, apatite and rare ilmenite and phlogopite. Petrographic observations, supported by major element contents in sp and cpx, and modelling using trace element contents in cpx, indicate that the pockets and veins formed from infiltration of alkaline melts and reaction with peridotite wall-rock causing opx and spinel replacement. The same alkaline melt-related metasomatism gave rise to the Cpx-L and OWB₁ mantle xenoliths and Cpx-M xenocrysts. Trace element contents of cpx in these xenoliths show a distinctively concave downwards REE pattern with a HFSE depletion, very similar to cpx megacrysts from the Pannonian Basin and to vein cpx from Eifel. In contrast, the OWB₂ xenoliths show evidence of precipitation from subduction-related mafic to ultramafic melts, as inferred from their opx-rich lithology and unusual Cr-rich spinels. They are probably related to subduction magmatism during the Late Cretaceous.Milivoje Jovanovi: deceased in April 2004     

Melt- versus fluid-induced metasomatism in spinel to garnet wedge peridotites (Ulten Zone, Eastern Italian Alps): clues from trace element and Li abundances

The peridotite bodies of the Ulten Zone (Upper Austroalpine, Italian Eastern Alps) are enclosed in Variscan migmatites and derive from a mantle wedge environment. They display the progressive transformation of porphyroclastic spinel peridotites (T=1,200°C; P=1.5 GPa) into fine-grained garnet–amphibole peridotites (T=850°C; P=3 GPa). Detailed bulk-rock and mineral trace element analyses of a sample suite documenting the entire metamorphic evolution of the peridotites revealed several stages of metasomatism. The spinel peridotites derive from a depleted mantle that became enriched in some large ion lithophile element (LILE) and light rare earth elements (LREE). The same signature pertains to clinopyroxene and orthopyroxene, indicating that this metasomatic signature was acquired at the recorded temperature of 1,200°C. Such a temperature is considerably above the wet peridotite solidus and hence the metasomatic agent must have been a hydrous melt. Moreover, the Li-enrichment of the spinel-facies pyroxenes (up to 24 ppm Li) reflects disequilibrium distribution after exchange with a presumably mafic melt. ^cpx/opx D _Li=3–7 and ^cpx/ol D _Li=2.7–8 indicate that the spinel-facies clinopyroxene hosts higher Li amounts than the coexisting minerals. LREE fractionation, variable LREE enrichment, LILE enrichment with respect to HFSE (average clinopyroxene Pb _N /Nb _N =16–90) in spinel lherzolites can be related to chromatographic effects of porous melt flow. The significant enrichment of pyroxenes from the spinel lherzolites in Pb, U and Li indicates that the metasomatic melt was subduction-related. All these features suggest that the spinel lherzolites formed a mantle wedge layer percolated by melts carrying recycled crustal components and rising from a deeper source of subduction magmas. The garnet + amphibole peridotites equilibrated at temperatures well below the wet solidus in the presence of an aqueous fluid. Bulk-rock trace element patterns display pronounced positive anomalies in Cs, Ba, Pb and U and moderate enrichment in Li, indicating addition of a crustal component to the mantle rocks. Amphibole hosts most of these trace elements. Clinopyroxene displays high LILE/HFSE (Pb _N /Nb _N =300–600), low Ce/Pb (1.4–2.7 in garnet-facies clinopyroxene compared with 2.6–24.5 in the spinel-facies one) and variable LILE and LREE enrichments. The coupled increase of modal amphibole, Sr and Pb, together with positive Pb–Sr and Pb–U correlations, further indicate that incompatible element influx in these samples was fluid-mediated. In the garnet-facies samples, amphibole and, interestingly, olivine have similarly high Li concentrations as clinopyroxene, leading to ^cpx/amph D _Li=0.7 and ^cpx/ol D _Li=0.7–0.8, the latter being up to ten times lower than in the spinel-facies rocks. Due to its high modal abundance, olivine is the main host of Li in the garnet–amphibole peridotites. The observed metasomatic features provide evidence for the infiltration of an aqueous fluid in the mantle wedge above a subducting slab. This fluid most likely derived from subducted crustal rocks that underwent partial melting. Successive retrograde re-equilibration during exhumation of the garnet peridotite is accompanied by garnet and clinopyroxene breakdown and amphibole formation. This process produced minor changes, such as an increase of HREE and Li in amphibole, and an increase of Li in olivine. The general trace element signature remains essentially unchanged during retrogression and further hydration, indicating that fluids with a similar composition to the one present at the garnet–amphibole peridotite formation, were responsible for increased amphibole formation. The combined evidence from the metamorphic and metasomatic evolution indicates that the peridotites experienced first corner flow in a mantle wedge, followed by subduction and finally entrapment and exhumation within a crustal slab. During their entire history the Ulten peridotites were percolated first by melts and then by aqueous fluids, which added recycled crustal components to the mantle wedge.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

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.     

Lithium isotopic composition of Central American volcanic arc lavas: implications for modification of subarc mantle by slab-derived fluids: correction

Our previously reported lithium isotope data for the least enriched members of the Central American Volcanic Arc were in error due to problems in ion extraction from high MgO rocks. This paper presents reanalyses of the entire suite of the CAVA lavas after a systematic investigation of the elution behavior of Li as a function of the rock composition. The most significant correction pertains to the mantle end members of the Nicaragua and Costa Rica series, which now display MORB-like δ⁶Li values (−4.5‰) and not much lighter (+1‰ to +3‰) as previously reported. Also revised is the composition of a peridotite from Zabargad Island (Red Sea), considered to represent undepleted upper mantle, whose corrected δ⁶Li also resembles MORB. These new data therefore remove the speculation that Earth's primitive mantle has extremely light Li isotopic composition and that the mantle beneath CAVA contains such isotopically light domains. The δ⁶Li range for the arc segment from Costa Rica to Guatemala has now been reset to −4.5‰ to −6.4‰. Despite the narrower range, Li isotopic values remain well correlated with other subduction-related properties, including LILE and fluid-mobile elements. Model calculations show that the isotopic compositions of the lavas are consistent with small additions of slab-derived fluids to the enriched and depleted domains of the subarc mantle.     

Water partitioning between mantle minerals from peridotite xenoliths

The speciation and amount of water dissolved in nominally anhydrous silicates comprising eight different mantle xenoliths has been quantified using synchrotron micro-FTIR spectroscopy. Samples studied are from six geographic localities and represent a cross-section of the major upper mantle lithologies from a variety of tectonic settings. Clinopyroxene contains between 342 and 413 ppm H₂O. Orthopyroxene, olivine and garnet contain 169–201, 3–54 and 0 to <3 ppm H₂O, respectively. Pyroxenes water contents and the distribution of water between ortho- and clinopyroxene is identical regardless of sample mineralogy (D _water^cpx/opx = 2.1 ± 0.1). The total water contents of each xenolith are remarkably similar (113 ± 14 ppm H₂O). High-resolution spectroscopic traverses show that the concentration and speciation of hydrous defects dissolved in each phase are spatially homogeneous within individual crystals and identical in different crystals interspersed throughout the xenolith. These results suggest that the amount of water dissolved in the silicate phases is in partial equilibrium with the transporting melt. Other features indicate that xenoliths have also preserved OH signatures of equilibrium with the mantle source region: Hydroxyl stretching modes in clinopyroxene show that garnet lherzolites re-equilibrated under more reducing conditions than spinel lherzolites. The distribution of water between pyroxenes and olivine differs according to xenolith mineralogy. The distribution of water between clinopyroxene and olivine from garnet peridotites (D _water^cpx/oliv(gnt) = 22.2 ± 24.1) is a factor of four greater than mineral pairs from spinel-bearing xenoliths (D _water^cpx/oliv(sp) = 88.1 ± 47.8). Such an increase in olivine water contents at the spinel to garnet transition is likely a global phenomenon and this discontinuity could lead to a reduction of the upper mantle viscosity by 0.2–0.7 log units and a reduction of its electrical resistivity by a factor of 0.5–0.8 log units.     

安徽女山地幔橄榄岩捕虏体的同位素组成:中国东部新生代岩石圈地幔时代制约

位于安徽省境内的女山新生代碱性玄武岩中含有大量而且类型丰富的地幔橄榄岩包体,主要类型有尖晶石相、石榴石相、尖晶石-石榴子石过渡相二辉橄榄岩以及少量的方辉橄榄岩,其中部分尖晶石二辉橄榄岩样品中出现富含挥发分的角闪石、金云母和磷灰石。本文选择该区的尖晶石二辉橄榄岩和方辉橄榄岩包体进行了较为详细的岩石学、矿物学、地球化学研究工作。结果显示,除2个方辉橄榄岩表现难熔特征外,其它25件尖晶石相二辉橄榄岩均具有饱满的主量元素组成。二辉橄榄岩样品的Sr-Nd-Hf同位素均表现为亏损地幔的性质,不同于古老克拉通型难熔、富集的岩石圈地幔。富含挥发份交代矿物的出现以及轻稀土元素不同程度的富集,表明女山岩石圈地幔经历了较为强烈的交代作用,然而Re-Os同位素及PGE分析结果表明交代作用并没有显著改变Os同位素组成。二辉橄榄岩样品均具有较高的Os同位素组成,结合其饱满的主量元素组成,亏损的同位素特征,表明女山地区岩石圈地幔整体为新生岩石圈地幔。但1个方辉橄榄岩样品给出了较低的Os同位素比值0.1184,其Re亏损年龄为1.5Ga,它可能来自于软流圈中残留的古老难熔地幔。