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‰.     

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.     

Mafic and silica-rich glasses in mantle xenoliths from Wau-en-Namus,Libya: Textural and geochemical evidence for peridotite–melt reactions

Anhydrous spinel peridotite xenoliths in Quaternary nepheline-basanite and melilite- or sodalite-bearing lavas of the Wau-en-Namus volcano in S Libya range from lherzolites to harzburgites recording melt extraction in a shallow setting (≤ 2 GPa). Primary clinopyroxenes have distinct trace element characteristics documenting LILE (large ion lithophile element) depletion or enrichment events predating the formation of glass pockets and veins in the xenoliths. These glasses are aluminous and alkali-rich, range in composition from ultrabasic to silicic (43–67 wt.% SiO₂) and may contain empty vugs and micro-phenocrysts of olivine, clinopyroxene, spinel, plagioclase, sodalite, apatite that are similar in composition to phenocrysts in the host lavas. Reactions of infiltrating melt and xenolith minerals are documented by diffuse Fe–Ca-rich rims of olivine in contact with glass, and by spongy-textured reaction domains caused by incongruent dissolution of primary pyroxenes and spinel. Some glasses have trace element characteristics similar to that of the host Ne-basanite, suggesting they were derived from the same source during entrainment and transport to the surface. Incompatible element enrichment and Sr–Nd isotopic compositions of the analyzed host lava are similar to HIMU (high μ; μ = ²³⁸Pb/²⁰⁴Pb)-type magmas, but the Pb isotopic composition is less radiogenic compared to other intra-plate Neogene magmatic rocks from N Africa.     

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.     

Base metal mineral segregation and Fe-Mg exchange inducing extreme compositions of olivine and chromite from the Xiadong Alaskan-type complex in the southern part of the Central Asian Orogenic Belt

The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe³⁺/(Fe³⁺ + Cr + Al) (>70), high 100 × Fe²⁺/(Fe²⁺ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO₂ contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe²⁺/(Mg + Fe²⁺) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.     

Petrology of mafic and ultramafic layered rocks from the Jaboncillo Valley,Sierra de Valle Fértil,Argentina: Implications for the evolution of magmas in the lower crust of the Famatinian arc

This work presents the field setting, petrography, mineralogy and geochemistry of a gabbroic and peridotitic layered body that is lens-shaped and surrounded by gabbronorites, diorites, and metasedimentary migmatites. This body exposed at Jaboncillo Valley is one among several examples of mafic and ultramafic layered sequences in the Sierras Valle Fértil and La Huerta, which formed as part of the lower crust of the Ordovician Famatinian magmatic arc in central-western Argentina. The layered sequence grew at deep crustal levels (20–25 km) within a mafic lower crust. The base of the layered body was detached during the tectonic uplift of the Famatinian lower crust, whereas the roof of the layered body is exposed in the eastern zone. In the inferred roof, olivine-bearing rocks vanish, cumulate textures are less frequent, and the igneous sequence becomes dominated by massive or thinly banded gabbronorites. Mainly based on the petrographic relationships, the inferred order of crystallization in the gabbroic and peridotitic layered sequence is: (1) Cr–Al-spinel + olivine, (2) Cr–Al-spinel + olivine + clinopyroxene + magnetite, (3) Cr–Al-spinel + olivine + plagioclase + magnetite ± orthopyroxene, and (4) Al-spinel + orthopyroxene + amphibole. A strong linear negative correlation between olivine and plagioclase modal proportions combined with field, petrographic and geochemical observations are used to demonstrate that the physical separation of olivine and plagioclase results in rock diversity at scales of a few centimeters to tens of meters. However, the composition of olivine (Fo ～ 0.81) and plagioclase (An > 94%) remains similar throughout the layered sequence. Spinels are restricted to olivine-bearing assemblages, and display chemical trends characteristic of spinels found in arc-related cumulates. Gabbroic and peridotitic layered rocks have trace element concentrations reflecting cumulates of early crystallizing minerals. The trace element patterns still retain the typical features of subduction-related arc magmatism, showing that the process of cumulate formation did not obscure the trace element signature of the parental magma. Using the composition of cumulus minerals and whole-rock chemical trends, we show that the parental magma was mafic (SiO₂ ～ 48 wt.%) with Mg-number around 0.6, and hydrous. The oxygen fugacity (fO₂) of the parental magma estimated between +0.8 and ?0.6 log fO₂ units around the fayalite–magnetite–quartz (FMQ) buffer is also characteristic of primitive hydrous arc magmas. The initially high water content of the parental magma allowed amphibole to crystallize as an interstitial phase all over the crystallization evolution of the layered sequence. Amphibole crystallization in the inter-cumulus assemblage gives rise to the retention of many trace elements which would otherwise be incompatible with the mineral assemblage of mafic–ultramafic cumulates. This study shows that there exist strongly mafic and primitive magmas that are both generated and emplaced within the lower crustal levels of subduction-related magmatic arc. Our findings together with previous studies suggest that the Early Ordovician magmatic paleo-arc from central-northwestern Argentina cannot be regarded as a typical Andean-type tectono-magmatic setting.     

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.     

Mineral chemistry of high-Mg diorites and skarn in the Han-Xing Iron deposits of South Taihang Mountains,China: Constraints on mineralization process

The Han-Xing region is located in the south Taihang Mountains (TM) in the central part of the North China Craton, and is an important iron producing area. The iron deposits in this region are of skarn type, related to an Early Cretaceous high-Mg diorite complex, including gabbro diorite, hornblende diorite, diorite, diorite porphyrite, and monzonite. In this study we report the detailed mineral chemistry of the high-Mg diorites and skarn rocks. The olivine in the gabbro diorite shows chemical composition similar to that in mantle peridotite xenoliths. Clinopyroxene in the gabbro diorite is dominantly augite, with only minor diopside, whereas the clinopyroxenes in the diorite and monzonite are diopside. Amphiboles in the high-Mg diorites show compositional range from magnesiohornblende to magnesiohastingsite, with minor pargasite and tschermakite. Most plagioclase in the high-Mg diorite is andesine and oligoclase. The magnesio-biotite in gabbro diorites shows chemical characteristics of re-equilibrated primary biotites and those in calc-alkaline rocks. In the diorite and diorite porphyrite, plagioclase shows complex chemical zoning. Clinopyroxene and garnet in skarn rocks show varying FeO contents, the former containing low FeO (< 9 wt.%) and occurring as the major skarn mineral in large-scale iron deposits, and the latter within small-scale iron deposits with high FeO (mostly > 25 wt.%) content. We computed the pressure, temperature, oxygen fugacity and water contents based on the mineral chemistry of amphibole and biotite. Based on the results, the magma crystallization can be divided into two stages, one within the deep magma chamber, forming clinopyroxene, amphibole and plagioclase phenocrysts; the other after emplacement, forming the rim of phenocrysts and matrix minerals. The magma during the early stage shows high temperature (~ 900 °C–950 °C), pressure (~ 300 MPa–500 MPa), relatively high logfO₂ (NNO–NNO + 2), and H₂O content in melt (4%–8%). During the late stage, the magma temperature dropped to about 750 °C, and pressure came down to less than 100 MPa, with the logfO₂ rising to NNO + 1–NNO + 2.The zoning of amphibole and plagioclase records the process of magma mixing and crystallization, with injection of mafic magma into the felsic magma chamber. The relatively high logfO₂ and H₂O content inhibited partitioning of iron into mafic minerals and favored concentration of Fe in the melt. Iron ore precipitation occurred when the magma was emplaced at shallow level, and was principally controlled by the chemical composition of carbonate wall rocks. The high logfO₂, Fe^3 + rich ore-forming fluid generated andradite and clinopyroxene when it reacted with limestone and dolomitic limestone respectively.     

Dependence of clinopyroxene composition on cooling rate in basaltic magmas: Implications for thermobarometry

The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5 °C/min from 1250 down to 1000 °C) and at isothermal conditions of 1000 °C from a basaltic composition at a pressure of 500 MPa under anhydrous and hydrous (H₂O = 1.3 wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe²⁺ and Si and enriched in Na, Fe³⁺, Al (mainly Al^IV), and Ti. Di and Hd versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH = Di + Hd and TE = CaTs + CaFeTs + En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of ^cpx–meltKd_Fe–Mg remain almost constant. Therefore, the Fe²–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.     

Segregation of magmatic fluids and their potential in the mobilization of platinum-group elements in the South Kawishiwi Intrusion,Duluth Complex,Minnesota — Evidence from petrography,apatite geochemistry and coexisting fluid and melt inclusions

Pegmatitic and other felsic rock pockets and dike-like intrusions are abundant in the South Kawishiwi Intrusion of the Duluth Complex, including the basal, Cu–Ni–PGE mineralized units. These occurrences are found as pockets, pods or as veins and contain abundant accessory apatite and quartz. Quartz hosts primary fluid inclusions as well as silicate melt inclusions. Combined microthermometry and Raman spectroscopy helped to determine the bulk composition of primary fluid inclusions that are CO₂-rich (95 mol%) and contain small amounts of H₂O (4.5 mol%), CH₄ (0.4 mol%) and trace N₂, respectively. This combined technique also made it possible to measure total homogenization temperatures of the inclusions (Th_tot = ~ 225 ± 10 °C), otherwise not detectable during microthermometry. Silicate melt inclusions have been quenched to produce homogeneous glasses corresponding to the original melt. Composition of the entrapped melt is granitoid, peraluminous and is very poor in mafic components. We interpret the melt as a product of partial melting of the footwall rocks due to the contact effect of the South Kawishiwi Intrusion. The presence of CO₂ in the vapor bubbles of the quenched melt inclusions and petrographic evidence suggest that the fluid and melt inclusion assemblages are coeval. The composition of the fluid and melt phase implies that the fluid originates from the mafic magma of the South Kawishiwi Intrusion and the fluid and melt phases coexisted as a heterogeneous melt–fluid system until entrapment of the inclusions.Coexistence of primary fluid and melt inclusions makes it possible to calculate a minimum entrapment pressure (~ 1.7 kbar) and thus estimate formation depth (~ 5.8 km) for the inclusions. Chlorine is suggested to behave compatibly in the silicate melt phase in the fluid–melt system represented by the inclusions, indicated by the high (up to 0.3%) Cl-concentrations of the silicate melt and CO₂-rich nature of the fluid.Apatite halogen-contents provide further details on the behavior of Cl. Apatite in pegmatitic pockets often has elevated Cl-concentrations compared to troctolitic rocks, suggesting enrichment of Cl with progressive crystallization. Systematic trends of Cl-loss at some differentiated melt pockets suggest that in some places Cl exsolved into a fluid phase and migrated away from its source. The segregation of Cl from the melt is probably inhibited by the presence of CO₂-rich fluids until the last stages of crystallization, increasing the potential for the development of late-stage saline brines.Platinum-group minerals are often present in microcracks in silicate minerals, in late-stage differentiated sulfide veinlets and in association with chlorapatite, indicating the potential role of Cl-bearing fluids in the final distribution of PGEs.     

Melt impregnation phases in the mantle section of the Ślęża ophiolite (SW Poland)

The ultramafic member of the Variscan Ślęża Ophiolite (SW Poland) consists of heavily serpentinised, refractory harzburgites. Those located down to 1.5 km below paleo-Moho contain scarce grains or aggregates of olivine, clinopyroxene and spinel. Non-serpentine phases occur in various assemblages: M1—olivine (Fo 90.2–91.0%, NiO 0.38–0.47 wt.%) and rounded or amaeboidal aluminous chromite, rimmed by Al poor chromite and magnetite; M2—olivine (Fo 90.5–91.5, NiO 0.32–0.44 wt.%), olivine with magnetite inclusions (Fo 87.1–92.5, NiO 0.01–0.68 wt.%), rounded, cleavaged clinopyroxene I (Mg# 91.1–93.2, Al₂O₃ 3.00–4.00 wt.%, Cr₂O₃ 1.00–1.40 wt.%) and elongated clinopyroxene II and clinopyroxene from symplectites with magnetite (Mg# = 92.2–94.1, Al₂O₃ 2.20–3.20 wt.% and Cr₂O₃ 0.80–1.20 wt.%). Clinopyroxene is depleted in REEs relative to chondrite. The M3 assemblage consists of intergrown olivine (Fo 90.8–92.7, NiO 0.20–0.38 wt.%) and clinopyroxene (Mg# = 96.0–98.1, Al₂O₃ 0.00–1.00 wt.% and Cr₂O₃ 0.20–0.60 wt.%).The M1 assemblage contains chromite which records greenschist-facies metamorphism. Textural relationships and chemical composition of clinopyroxene occurring in the M2 assemblage are similar to those formed in oceanic spreading centres by LREE depleted basaltic melt percolation. Olivine occurring in M1 assemblage and part of that from M2 have composition typical of residual olivine from the abyssal harzburgites and of olivine formed in those rocks by melt percolation. The olivine with magnetite inclusions (M2 assemblage) and that from M3 record later deserpentinization event, which supposedly produced also M3 clinopyroxene. The non-serpentine phases from the Ślęża ophiolite mantle member, albeit very poorly preserved, document depleted basaltic melt percolation in the Variscan oceanic spreading centre.     

Ultra-depleted peridotite xenoliths in the Northern Taihang Mountains: Implications for the nature of the lithospheric mantle beneath the North China Craton

We report the finding of peridotite xenoliths in the Early Cretaceous Longmengou olivine-bearing diabase (138 Ma) in the Northern Taihang Mountains in the central North China Craton. Based on the modal proportions of olivine, clinopyroxene, amphibole and anorthite, these peridotite xenoliths can be divided into three zones: clinopyroxene-bearing olivine zone (COZ), olivine-clinopyroxene zone (OCZ), and amphibole-bearing anorthite-clinopyroxene zone (AACZ). The core of olivine grains in clinopyroxene-bearing olivine zone have higher Mg^# (> 95), SiO₂ (41.80–42.53 wt%) and lower CaO (< 0.07 wt%), FeO (3.91–4.54 wt%) than the rim (Mg^# = 92.5–93.4, SiO₂ = 41.27–41.98 wt%, CaO = 0.20–0.34 wt%, and FeO = 7.02–8.87 wt%), suggesting that rim is reaction product. The core of olivine grains with higher Mg^# (> 95) and lower NiO content (< 0.04 wt%) in the clinopyroxene-bearing olivine zone was derived from ultra-depleted mantle subsequently altered by high Mg^# melts/magma with low Ni. Two generations of olivine grains occur in the OCZ where the first generation shows exsolution of ilmenite and magnetite rods containing up to 0.35 wt% TiO₂, and was likely derived from garnet peridotite hydrated by water. The second generation shows high Mg^# (96.2–97.1) and cataclastic texture, and was possibly formed by decomposition of the COZ. The occurrence of aluminous spinel suggests the role of melts with extremely high Al and Mg. Clinopyroxene in the AACZ shows systematic core-rim compositional variation with CaO and SiO₂ contents increasing towards the rim, and MgO and Fe₂O₃ concentrations decreasing from the core to the rim, indicating that the amphibole-bearing anorthite-clinopyroxene zone is a product of the reaction between mantle xenoliths and mafic magma. Plagioclase with high An value (92.0–99.95, average 97.79) indicates that the metasomatic melts have high Ca/Na and Al/Si ratios, possibly produced by the partial melting of ultra-depleted mantle under “wet” conditions. Combined with the data on other mantle xenoliths discovered in the NCC, our results suggest that the Mesozoic lithospheric mantle beneath the North Taihang Mountains within the central NCC is composed of ultra-depleted Archean and Paleoproterozoic peridotites and dunites modified by complex melts. We also propose that the destruction of eastern part of the NCC mainly occurred during Early Cretaceous, and that the boundary of the lithospheric destruction coincides with the Taihang Mountains.     

Mafic and ultramafic enclaves in Ustica Island lavas: Inferences on composition of lower crust and deep magmatic processes

Ustica Island, southern Tyrrhenian Sea, is constituted of Quaternary alkaline volcanics. A variety of enclaves representative of deep to supra-crustal settings were recently found in a hawaiitic lava flow. Enclaves consist of: (i) Ultramafic meta-cumulates, i.e. clinopyroxenites and wherlites characterized by variably deformed porphyroclastic to granoblastic textures. (ii) Mafic cumulates, i.e. gabbros (± amphibole) and troctolites, the first often characterized by frequent amphibole breakdown coronas (olivine + Ti-augite + plagioclase + magnetite + ilmenite + rhönite) in response to an H₂O decrease during the ascent, while the troctolites interpreted as meta-cumulates. (iii) Microsyenites, consist of anorthoclase and Fe-clinopyroxene organized in a granular sub-ipidiomorphic texture. Amphibole is absent in Ustica lavas and is found only in some old, now exposed, sub-intrusive volcanic bodies. This evidence suggests a late appearance of amphibole on the liquidus, at a high crystal content that inhibits further ascent of the magma. The importance of the amphibole as a medium pressure liquidus phase in Ustica mafic magmas is in the bearings on the geochemistry of lavas e.g. in buffering Na and Ti abundances, in trace elements partitioning, etc.Density measurements pointed out higher values for clinopyroxenites (3160 to 3300 kg/m³) than for gabbros (ca. 2900 kg/m³). Given the density contrast between enclaves and host lavas (2790 kg/m³) and assuming appropriate rheological models, we calculated a minimum ascent rate of 0.01 m/s, corresponding to an ascent time in the range of 5–29 days for a depth of entrapment of 25 km.     

A mafic intrusion of “arc affinity” in a post-orogenic extensional setting: A case study from Ganluogou gabbro in the northern Yidun Arc Belt,eastern Tibetan Plateau

Generally, arc-related or subduction-related mafic magmas are formed during or slightly postdate subduction, and characterized by depletion in high field strength elements (HFSEs) relative to the large ion lithophile elements (LILEs) and light rare-earth elements (LREEs). Combining with mineral chemistry and Sr–Nd isotopes, these geochemical characteristics were usually used to define an arc setting, especially for some ancient arcs that had been strongly modified by later tectonic activities. However, we report an exceptional case from the northern part of the Triassic Yidun Arc Belt, eastern Tibetan Plateau. The Ganluogou gabbro (∼152 Ma) occurs as several intrusive bodies. Its mineral assemblage is olivine (chrysolite), plagioclase (anorthite), clinopyroxene (diopside), amphibole (edenite and pargasite) and phlogopite. Whole rock geochemistry shows low SiO₂ (42.87–46.99 wt.%), total rear earth elements (ΣREE = 22.8–28.4 ppm), Na₂O + K₂O (0.92–1.34 wt.%), and high Al₂O₃, MgO and FeO contents. It has small variations of initial ⁸⁷Sr/⁸⁶Sr ((⁸⁷Sr/⁸⁶Sr)_i = 0.7053–0.7055) and ε_Nd(t) values (−4.8 to −1.8). All the samples exhibit enrichment in LILEs including Th and U, but strongly depleted in HFSEs, including Nb, Ta, Zr and Hf. For the mineral chemistry, there are two type amphiboles. Amp(I) show higher V, Sc, Cr, Sr, Nb and Zr contents, but lower Th and U contents than those of Amp(II). Their REE patterns range from convex shape without Eu anomaly to LREE-enriched pattern with weak positive Eu anomaly. We suggest that Amp(I) was crystallized from a liquid that was mainly buffered by olivine, clinopyroxene and plagioclase, while Amp(II) crystallized from later melt that was mainly buffered by olivine. Based on clinopyroxene chemistry, compositions of coexisting olivine and plagioclase, and whole rock Sr–Nd isotopes, the parental magma of the Ganluogou gabbro is interpreted as a tholeiitic arc-affinity magma, which might be derived from an N-MORB mantle that had been metasomatised by slab-derived melts in the late Triassic (237–206 Ma). Thus, the Ganluogou gabbro provides an example that magmas exhibiting arc-affinity could in fact be formed in a post-orogenic extensional setting.     

Martian regolith in Elephant Moraine 79001 shock melts? Evidence from major element composition and sulfur speciation

Shock veins and melt pockets in Lithology A of Martian meteorite Elephant Moraine (EETA) 79001 have been investigated using electron microprobe (EM) analysis, petrography and X-ray Absorption Near Edge Structure (XANES) spectroscopy to determine elemental abundances and sulfur speciation (S²⁻ versus S⁶⁺). The results constrain the materials that melted to form the shock glasses and identify the source of their high sulfur abundances. The XANES spectra for EETA79001 glasses show a sharp peak at 2.471 keV characteristic of crystalline sulfides and a broad peak centered at 2.477 keV similar to that obtained for sulfide-saturated glass standards analyzed in this study. Sulfate peaks at 2.482 keV were not observed. Bulk compositions of EETA79001 shock melts were estimated by averaging defocused EM analyses. Vein and melt pocket glasses are enriched in Al, Ca, Na and S, and depleted in Fe, Mg and Cr compared to the whole rock. Petrographic observations show preferential melting and mobilization of plagioclase and pyrrhotite associated with melt pocket and vein margins, contributing to the enrichments. Estimates of shock melt bulk compositions obtained from glass analyses are biased towards Fe- and Mg- depletions because, in general, basaltic melts produced from groundmass minerals (plagioclase and clinopyroxene) will quench to a glass, whereas ultramafic melts produced from olivine and low-Ca pyroxene megacrysts crystallize during the quench. We also note that the bulk composition of the shock melt pocket cannot be determined from the average composition of the glass but must also include the crystals that grew from the melt - pyroxene (En_72-75Fs_20-21Wo_5-7) and olivine (Fo_75-80). Reconstruction of glass + crystal analyses gives a bulk composition for the melt pocket that approaches that of lithology A of the meteorite, reflecting bulk melting of everything except xenolith chromite.Our results show that EETA79001 shock veins and melt pockets represent local mineral melts formed by shock impedance contrasts, which can account for the observed compositional anomalies compared to the whole rock sample. The observation that melts produced during shock commonly deviate from the bulk composition of the host rock has been well documented from chondrites, rocks from terrestrial impact structures and other Martian meteorites. The bulk composition of shock melts reflects the proportions of minerals melted; large melt pockets encompass more minerals and approach the whole rock whereas small melt pockets and thin veins reflect local mineralogy. In the latter, the modal abundance of sulfide globules may reach up to 15 vol%. We conclude the shock melt pockets in EETA79001 lithology A contain no significant proportion of Martian regolith.     

Mineralogical evidence for crystallization conditions and petrogenesis of ilmenite-series I-type granitoids at the Baogutu reduced porphyry Cu deposit (Western Junggar,NW China): Mössbauer spectroscopy,EPM and LA-(MC)-ICPMS analyses

Primary ore-forming minerals retain geochemical signatures of magmatic crystallization information and can reveal the petrochemical conditions prevalent at the time of their formation. The Baogutu deposit is a typical reduced porphyry Cu deposit. Amphibole and biotite Fe³⁺/ΣFe ratios, minerals (feldspar, biotite, amphibole, zircon and apatite), in situ elemental and apatite Nd isotopic compositions were determined by Mössbauer spectroscopy, electron probe microanalysis, and laser ablation multiple-collection inductively coupled plasma mass spectrometry, respectively, to investigate the magma oxidation state, petrogenesis, source features, and to constrain the carbon species at magmatic stages for the intrusive phases. The results show that the primary plagioclase and amphibole in the mineralized diorite to granodiorite porphyry and post ore hornblende diorite porphyry are distinct (An_26-55 versus An_60-69; Mg-hornblende versus tschermakite). In particular, the amphibole shows distinct major and trace element compositions with light rare earth element enrichments and negative Eu anomalies in Mg-hornblende and light rare earth element depletions and no Eu anomalies in tschermakite. All the analyzed biotites are primary igneous phases with a biotite phenocryst profile showing significant variations of Zn, Cr, Sc and Sr from core to rim. These results may indicate the occurrence of mixing between two distinct magmas during mineral formation. Titanium in zircon and Si¹ in amphibole thermometries indicate that magma crystallized at >900 °C and continued to ∼650 °C. In situ apatite Nd isotope (εNd(t) = 5.6–7.6, T_DM2 = 620–460 Ma), indicate absence of significant reduced sedimentary contamination and the source of juvenile lower crust. Slightly decreasing Fe³⁺/ΣFe ratios from biotite and amphibole to whole rock indicate decreasing oxygen fugacity during magma crystallization. Recalculated biotite compositions according to Fe³⁺/ΣFe ratios indicate fO₂ values of less than Ni-NiO buffer (NNO) which show slightly lower values than that estimated according to zircon/melt distribution coefficients Ce anomalies (∼ΔNNO + 0.6). These values are consistent with the features of reduced porphyry Cu deposits. Crystallization of other mineral phases significantly affects the reliability of oxybarometer of zircon/melt distribution coefficients Eu anomalies and Mn contents in apatite. This oxidation state suggests that only CO₂ was present at the magmatic stage, and implies that CH₄ formed during CO₂ reduction occurring later hydrothermal alteration. The alteration of primary amphibole to actinolite released Ti, Al, Fe, Mn, Na and K to the fluid with later precipitation of titanite, albite and minor ilmenite and magnetite during actinolite alteration.     

Metasomatism in mantle xenoliths from Gees,West Eifel,Germany: evidence for the genesis of calc-alkaline glasses and metasomatic Ca-enrichment

 We have investigated new samples from the Gees mantle xenolith suite (West Eifel), for which metasomatism by carbonatite melt has been suggested. The major metasomatic change is transformation of harzburgites into phlogopite-rich wehrlites. Silicate glasses are associated with all stages of transformation, and can be resolved into two major groups: a strongly undersaturated alkaline basanite similar to the host magma which infiltrated the xenoliths during ascent, and Si-Al-enriched, variably alkaline glass present exclusively within the xenoliths. Si-Al-rich glasses (up to 72 wt% SiO₂ when associated with orthopyroxene (Opx) are usually interpreted in mantle xenoliths as products of decompressional breakdown of hydrous phases like amphibole. In the Gees suite, however, amphibole is not present, nor can the glass be related to phlogopite breakdown. The Si-Al-rich glass is compositionally similar to glasses occurring in many other xenolith suites including those related to carbonatite metasomatism. Petrographically the silicate glass is intimately associated with the metasomatic reactions in Gees, mainly conversion of harzburgite orthopyroxene to olivine + clinopyroxene. Both phases crystallize as microlites from the glass. The chemical composition of the Si-Al-enriched glass shows that it cannot be derived from decompressional melting of the Gees xenoliths, but must have been present prior to their entrainment in the host magma. Simple mass-balance calculations, based on modal analyses, yield a possible composition of the melt prior to ascent of the xenoliths, during which glass + microlite patches were modified by dissolution of olivine, orthopyroxene and spinel. This parental melt is a calc-alkaline andesite (55–60 wt% SiO₂), characterized by high Al₂O₃ (ca. 18 wt%). The obtained composition is very similar to high-alumina, calc-alkaline melts that should form by AFC-type reactions between basalt and harzburgite wall rock according to the model of Kelemen (1990). Thus, we suggest that the Si-Al-enriched glasses of Gees, and possibly of other suites as well, are remnants of upper mantle hybrid melts, and that the Gees suite was metasomatized by silicate and not carbonatite melts. High-Mg, high-Ca composition of metasomatic olivine and clinopyroxene in mantle xenoliths have been explained by carbonatite metasomatism. As these features are also present in the Gees suite, we have calculated the equilibrium Ca contents of olivine and clinopyroxene using the QUI1F thermodynamical model, to show that they are a simple function of silica activity. High-Ca compositions are attained at low a SiO₂ and can thus be produced during metasomatism by any melt that is Opx-undersaturated, irrespective of whether it is a carbonatite or a silicate melt. Such low a SiO₂ is recorded by the microlites in the Gees Si-Al-rich glasses. Our results imply that xenolith suites cannot confidently be related to carbonatite metasomatism if the significance of silicate glasses, when present, is not investigated. Received: 2 March 1995 / Accepted: 12 June 1995     

The pressure and temperature conditions and timing of glass formation in mantle-derived xenoliths from Baarley, West Eifel, Germany: the case for amphibole breakdown, lava infiltration and mineral – melt reaction

Summary Mantle-derived xenoliths from Baarley in the Quaternary West Eifel volcanic field contain six distinct varieties of glass in veins, selvages and pools. 1) Silica-undersaturated glass rich in zoned clinopyroxene microlites that forms jackets around and veins within the xenoliths. This glass is compositionally similar to groundmass glass in the host basanite. 2) Silica-undersaturated alkaline glass that contains microlites of Cr-diopside, olivine and spinel associated with amphibole in peridotites. This glass locally contains corroded primary spinel and phlogopite. 3) Silica-undersaturated glass associated with diopside, spinel ± olivine and rh?nite microlites in partly to completely broken down amphibole grains in clinopyroxenites. 4) Silica-undersaturated to silica-saturated, potassic glass in microlite-rich fringes around phlogopite grains in peridotite. 5) Silica-undersaturated potassic glass in glimmerite xenoliths. 6) Silica-rich glass around partly dissolved orthopyroxene crystals in peridotites. Geothermometry of orthopyroxene–clinopyroxene pairs (P = 1.5 GPa) gives temperatures of ∼ 850 °C for unveined xenoliths to 950–1020 °C for veined xenoliths. Clinopyroxene – melt thermobarometry shows that Cr-diopside – type 2 glass pairs in harzburgite formed at 1.4 to 1.1 GPa and ∼ 1250 °C whereas Cr-diopside – type 2 glass pairs in wehrlite formed at 0.9 to 0.7 GPa and 1120–1200 °C. This bimodal distribution in pressure and temperature suggests that harzburgite xenoliths may have been entrained at greater depth than wehrlite xenoliths. Glass in the Baarley xenoliths has three different origins: infiltration of an early host melt different in composition from the erupted host basanite; partial melting of amphibole; reaction of either of these melts with xenolith minerals. The composition of type 1 glass suggests that jackets are accumulations of relatively evolved host magma. Mass balance modelling of the type 2 glass and its microlites indicates that it results from breakdown of disseminated amphibole and reaction of the melt with the surrounding xenolith minerals. Type 3 glass in clinopyroxenite xenoliths is the result of breakdown of amphibole at low pressure. Type 4 and 5 glass formed by reaction between phlogopite and type 2 melt or jacket melt. Type 6 glass associated with orthopyroxene is due to the incongruent dissolution of orthopyroxene by any of the above mentioned melts. Compositional gradients in xenolith olivine adjacent to type 2 glass pools and jacket glass can be modelled as Fe–Mg interdiffusion profiles that indicate melt – olivine contact times between 0.5 and 58 days. Together with the clinopyroxene – melt thermobarometry calculations these data suggest that the glass (melt) formed over a short time due to decompression melting of amphibole and infiltration of evolved host melt. None of the glass in these xenoliths can be directly related to metasomatism or any other process that occurred insitu in the mantle. Received November 23, 1999; revised version accepted September 5, 2001     

Melting phase relations of the Udachnaya-East Group-I kimberlite at 3.0–6.5 GPa: Experimental evidence for alkali-carbonatite composition of primary kimberlite melts and implications for mantle plumes

Experiments on the origin of the Udachnaya-East kimberlite (UEK) have been performed using a Kawai-type multianvil apparatus at 3–6.5 GPa and 900–1500 °C. The studied composition represents exceptionally fresh Group-I kimberlite containing (wt.%): SiO₂ = 25.9, TiO₂ = 1.8, Al₂O₃ = 2.8, FeO = 9.0, MgO = 30.1, CaO = 12.7, Na₂O = 3.4, K₂O = 1.3, P₂O₅ = 1.0, Cl = 0.9, CO₂ = 9.9, and H₂O = 0.5. The super-solidus assemblage consists of melt, olivine (Ol), Ca-rich (26.0–30.2 wt.% CaO) garnet (Gt), Al-spinel (Sp), perovskite (Pv), a CaCO₃ phase (calcite or aragonite), and apatite. The low pressure assemblage (3–4 GPa) also includes clinopyroxene. The apparent solidus was established between 900 and 1000 °C at 6.5 GPa. At 6.5 GPa and 900 °C Na–Ca carbonate with molar ratio of (Na + K)/Ca ≈ 0.44 was observed. The UEK did not achieve complete melting even at 1500 °C and 6.5 GPa, due to excess xenogenic Ol in the starting material. In the studied P–T range, the melt has a Ca-carbonatite composition (Ca# = molar Ca/(Ca + Mg) ratio = 0.62–0.84) with high alkali and Cl contents (7.3–11.4 wt.% Na₂O, 2.8–6.7 wt.% K₂O, 1.6–3.4 wt.% Cl). The K, Na and Cl contents and Ca# decrease with temperature. It is argued that the primary kimberlite melt at depths > 200 km was an essentially carbonatitic (< 5 wt.% SiO₂), but evolved toward a carbonate–silicate composition (up to 15–20 wt.% SiO₂) during ascent. The absence of orthopyroxene among the run products indicates that xenogenic orthopyroxene was preferentially dissolved into the kimberlite melt. The obtained subliquidus phase assemblage (Ol + Sp + Pv + Ca-rich Gt) at P–T conditions of the UEK source region, i.e. where melt was in the last equilibrium with source rock before magma ascent, differs from the Opx-bearing peridotitic mineral assemblage of the UEK source region. This difference can be ascribed to the loss of substantial amounts of CO₂ from the kimberlite magma at shallow depths, as indicated by both petrological and experimental data. Our study implies that alkali-carbonatite melt would be a liquid phase within mantle plumes generated at the core–mantle boundary or shallower levels of the mantle, enhancing the ascent velocity of the plumes. We conclude that the long-term activity of a rising hot mantle plume and associated carbonatite melt (i.e. kimberlite melt) causes thermo-mechanical erosion of the subcontinental lithosphere mantle (SCLM) roots and creates hot and deformed metasomatic regions in the lower parts of the SCLM, which corresponds to depths constrained by P–T estimates of sheared Gt-peridotite xenoliths. The sheared Gt-peridotites undoubtedly represent samples of these regions.     

High-P amphibolite-facies metamorphism in the Adrar–Souttouf Metamafic Complex,Oulad Dlim Massif (West African Craton margin,Morocco)

The Oulad Dlim Massif represents the northern segment of the Mauritanide belt that thrusts over the western margin of the Reguibat Shield, north of the West African Craton (WAC). This belt includes various metamorphic units of Archean, Neoproterozoic and Palaeozoic ages that were stacked and thrust eastward during the Variscan orogeny. The core of the Oulad Dlim Massif comprises the Adrar–Souttouf Metamafic Complex that represents a large tectonic unit made of high-grade mafic rocks and vast exposures of amphibolites. A characterisation of the metamorphism in these amphibolites is essential to understand the relationships of the Oulad Dlim Massif with the southern segments of the Mauritanide belt and to provide constraints on the geodynamic evolution of the western margin of the WAC. Here we determine the P–T conditions of metamorphism of two samples of garnet amphibolites collected at the northernmost end of the Adrar–Souttouf Metamafic Complex. The samples show a main mineral assemblage of garnet + low-Ti pargasite + oligoclase + phengite + epidote + quartz + rutile ± paragonite ± K-feldspar. We calculated their P–T conditions using the amphibole–plagioclase NaSi–CaAl exchange thermometer, and the garnet–amphibole–plagioclase–quartz and the amphibole–plagioclase Si–Al partitioning barometers. The thermobarometric results indicate that this mineral assemblage was formed at high-P amphibolite-facies conditions at 650–700 °C and 10–13 kbar. The observed stability of paragonite and phengite reveals fluid-absent conditions or the presence of a fluid phase with reduced H₂O activity during the peak of metamorphism. We found no relicts of eclogite-facies mineral assemblage in the garnet amphibolites. This contrasts with the eclogite-facies metamorphism found due south in the Tarf Magneïna unit. This suggests that the northernmost end of the Adrar–Souttouf Metamafic Complex may have been buried to shallower depths than the units further south, probably during the Variscan orogeny. However, precise absolute radiometric dating of the high-P amphibolite-facies metamorphism is required to confirm these findings.