Spinel Harzburgites Research Articles

Deformation and melt–rock interaction in the upper mantle: Insights from the layered structure of the Horoman peridotite, Japan

To obtain a better understanding of melt–rock interactions in the upper mantle, microstructural and petrological analyses were conducted on deformed mantle peridotites from the Horoman peridotite complex, Hokkaido, Japan. The Horoman peridotite complex is lithologically heterogeneous and contains various kinds of ultramafic and mafic rocks. We studied an outcrop of 3 × 70 m in size that contains layered spinel harzburgite, plagioclase lherzolite, and mafic rocks. The results indicate that reactive melts migrated preferentially along the foliation in the already deformed peridotite, and that these melt-rich zones became especially prone to further deformation. This inference is supported by (1) the parallelism of the boundaries of rock layers and foliation in the deformed peridotite, and the shape and crystallographic preferred orientations (SPOs and CPOs) of olivine in the peridotites; (2) the diffusive trends of magnesium and modal compositions of pargasite grains near the boundaries between peridotite and mafic layers; (3) variations in the NiO content of olivine crystals; (4) variations in olivine CPOs with orthorhombic (010)[100] slip system patterns and weak fiber-[010] patterns; and (5) the strong pargasite SPOs, the cuspate shapes of the pargasites, and the absence of intercrystallite deformation. The results, combined with previously reported P–T conditions for the Horoman peridotite complex, indicate that the deformed peridotites and mafic rocks with a layered structure represent temperatures of 1050–1150 °C and pressures of 0.7–1.5 GPa. Our results suggest that a decrease in pressure led to the transition from a melt-free to a melt-bearing system with a consequent change in the deformation mechanism, from dislocation creep in the melt-free system to diffusion creep in the melt-bearing system, with strain localization in the fine-grained melt-rich layers. The change in deformation mechanism is likely to have occurred in the uppermost mantle beneath a mid-ocean ridge, where strong rheological contrasts are controlled by spatial variations in the melt fraction.

Extensive oxidizing events recorded by peridotite mantle xenoliths from the Hyblean Plateau: Evidence from combined measurements of ferric iron in spinel with noble gases and fluid inclusions chemistry in olivine

The study of the oxidation state of lithospheric mantle-derived rocks allows modelling the deep cycle of volatiles (e.g., C, H, O, N and S) in the Earth's interior, which in turn plays a role in magma genesis, metasomatism and volcanic degassing. At the oxygen fugacity (i.e., fO2) recorded by residual abyssal peridotites, volatile elements like carbon are predicted to be in the immobile form of graphite. However, the compilation of the redox state of worldwide-distributed continental xenoliths shows evidence of their oxidation and refertilization through time by deeply formed subduction-related metasomatic fluids. The analyses of fluid inclusions in mantle-derived minerals like olivine (or pyroxenes) represent a snapshot of the volatile circulation in depth, whose noble gases signature (He, Ar, Ne) is used to identify their possible source. This study aims to reconstruct the origin of mantle metasomatism underneath the Hyblean Plateau (Sicily, Italy) and its redox history through the investigation of spinel-peridotite nodules, combining fO2 estimates with noble gases and fluid inclusions chemistry from hand-picked olivine grains. We analyzed eight mantle xenoliths classified as spinel lherzolites and spinel harzburgites from the Valle Guffari (Hyblean Plateau, Sicily). The calculated logfO2 is higher than that of most cratonic xenoliths worldwide ranging between 0.28 and 1.27 log units above to the fayalite-magnetite-quartz (FMQ) reference buffer. Micro-Raman measurements on olivine grains with dendritic trails of (metasomatic) fluid inclusions reveal an assemblage made of Mg-Ca carbonates ± sulfide ± elemental sulfur ± CO2 in the most reduced sample, and Mg-Ca carbonates ± sulfates ± CO2 in the most oxidized sample, the latter associated with a silicate glass and (secondary) hydrous phases. Both assemblages are taken as evidence of the product of crystallization of deeply originated volatile-bearing silicate melts. Analyses of He, Ar, and Ne in olivine grains confirm the evidence of a mantle source reworked by metasomatic processes. Our data suggest that an initially residual Hyblean lithospheric mantle was affected by extensive oxidizing events at several depths caused by the interaction with slab-derived CO2-rich silicate metasomatic liquids.

First measurements of the Fe oxidation state of spinel inclusions in olivine single crystals from Vulture (Italy) with the in situ synchrotron micro-Mössbauer technique

Abstract. The redox state of the Earth's upper mantle (i.e., oxygen fugacity, fO2) is a key variable that influences numerous processes occurring at depth like the mobility of volatile species, partial melting, and metasomatism. It is linked to the oxidation state of peridotite rocks, which is normally determined through the available oxythermobarometers after measuring the chemical composition of equilibrated rock-forming minerals and the Fe3+ in redox-sensitive minerals like spinel or garnet. To date, accurate measurements of Fe3+ / ∑Fe in peridotites have been limited to those peridotites (e.g., harzburgites and lherzolites) for which an oxythermobarometer exists and where spinel (or garnet) crystals can be easily separated and measured by conventional 57Fe Mössbauer spectroscopy. Wehrlitic rocks have been generally formed by the interaction of a lherzolite with carbonatitic melts and, therefore, have recorded the passage of (metasomatic) fluids at mantle conditions. However, no oxythermobarometer exists to determine their equilibrium fO2. The aim of this study was to retrieve the fO2 of the mantle beneath Mt. Vulture volcano (Italy) through the study of a wehrlitic lapillus emitted during the last eruption (∼ 140 kyr ago) that contain olivines with multiple tiny spinel inclusions with sizes < 40 µm. To our knowledge, the Fe oxidation state of these inclusions has been never determined with the Mössbauer technique due to their small sizes. Here, we present measurements of the Fe3+ / ∑Fe using in situ synchrotron Mössbauer spectroscopy coupled with chemical and spectroscopic analysis of both host olivine and spinel inclusions. The results show Fe3+ / ∑Fe ratios of 0.03–0.05 for olivine and 0.40–0.45 for the included spinels, the latter of which appear higher than those reported in literature for mantle spinel harzburgites and lherzolites. Given the evidence of the mantle origin of the trapped spinels, we propose that the high fO2 (between 0.81 and 1.00 log above the fayalite–magnetite–quartz buffer; FMQ) likely results from the interaction between the pristine spinel lherzolite and a CO2-rich metasomatic agent prior to the spinel entrapment in olivines at mantle depths.

Precambrian history of the Pacific Mantle Domain: New constraints from Woodsreef and Port Macquarie serpentinized spinel harzburgites of the New England Orogen, Australia

Abstract The present-day mantle is divided into the African and Pacific domains by the circum-Pacific subduction girdle. Very little is known about the mantle composition of the Pacific Domain before 120 Ma due to the scarcity of the oceanic record, having mostly been destroyed by subduction processes. Accreted oceanic lithosphere (ophiolites) in orogens along the Paleo-Pacific margins provide rare opportunities to partially fill this knowledge gap. The early Cambrian (530–505 Ma) Weraerai ophiolite mélange in the New England Orogen in Eastern Australia represents fragments of the now-consumed Paleo-Pacific oceanic plate, predecessor of the Panthalassa and Pacific oceanic plates, accreted to east Gondwana during ca. 410–277 Ma. Early work revealed the presence of an accreted volcanic island(s) of possible mantle plume origin. However, due to their heavy alteration and weathering, the geochemical signature of the mafic rocks in the Weraerai ophiolite cannot be used to certify their plume origin with confidence. Therefore, mantle rocks found in the ophiolitic belt offer an alternative way to decipher the origin of the oceanic lithospheric fragments in the Weraerai ophiolite mélange. Here we report the petrographic, major, and trace elements composition, including highly siderophile elements (HSE), and Re-Os isotope composition for 16 serpentinized spinel harzburgite samples from Woodsreef and Port Macquarie. The observed spinel-orthopyroxene symplectite intergrowth textures are interpreted as garnet-breakdown textures due to cooling from an initial high temperature of >1200°C. Silicon and Al contents and Mg# of serpentinized spinel harzburgite, as well as heavy rare earth element modelling results, suggest a high-degree of melt extraction of 20–30% in the garnet stability field and in an anhydrous environment, probably in ocean island or oceanic plateau environments. The samples in this study have HSE concentrations interpreted to have resulted from post-melting processes rather than a melt extraction feature, indicating that their Re-Os model ages need to be interpreted with caution. Nevertheless, the melt depletion ages obtained from the Woodsreef and Port Macquaries samples range between 1.4 and 1.1 Ga, consistent with previous studies on other Pacific-rim ophiolitic rocks. We argue that these ages might be related to a major depletion event during the transition between supercontinents Nuna and Rodinia. Such depletion events affected a large proportion of this section of the mantle before the incorporation of the peridotites into the oceanic lithosphere in the Paleo-Pacific associated with rapid ascent of mantle plumes. This interpretation is consistent with the occurrence of accreted volcanic islands in the Werearai ophiolite mélange, as shown by the OIB chemical signatures of some of the mafic rocks, and their association with shallow water limestones that formed in near-equatorial latitudes. The proposed ca. 530–510 Ma Paleo-Pacific Ocean mantle plume event coincides with a global peak of oceanic mantle plume events that may record the legacy of a circum-Rodinia subduction girdle driving antipodal mantle superplume episodes.

Ultra-depleted melt product preserved in the Ladong ophiolitic peridotites of the North Qilian Orogenic Belt, Northern Tibet

In Earths upper mantle, the compositions of both migrating magmas and solid residues are basically controlled by source materials and melting behavior which are related to tectonic dynamics. Thus, infrequent geochemical signatures recorded by ophiolitic lithologies may reflect a unique source or specific melting history. Here, we report whole-rock and mineral compositions of the harzburgite, wehrlite, and olivine websterite in the Ladong ophiolite complex of the North Qilian Orogen Belt (northern Tibet). The dominant spinel harzburgite has high spinel Cr# values of 65–70 and light rare earth element (LREE) depleted patterns (LaN/YbN = 0.04–0.12), resembling the residua after 20% or more of melt extraction. Wehrlite lenses within the harzburgite display extremely depleted LREE patterns (whole-rock LaN/YbN = 0.04–0.05) and low Na and Ti contents in clinopyroxene. They are interpreted as products of reaction between the host harzburgite and an ultra-depleted melt produced by asthenospheric decompression melting. Outcrops of olivine websterite have well-equilibrated triple junction textures between pyroxene grains and high-Mg olivine (Fo = 85–86; bulk rock Mg# = 93), consistent with a cumulate origin. In the olivine websterite, the depleted LREE concentrations (LaN/YbN = 0.05–0.18) in clinopyroxene suggest a less depleted nature than the wehrlite-forming melt. Thus, the Ladong ophiolite records two episodes of melt activity that produced depleted to ultra-depleted magmas, which may have been generated during subduction initiation in eastern Proto-Tethyan belt.

Spinel harzburgite–derived silicate melts forming sulfide-bearing orthopyroxenite in the lithosphere. Part 2: Sulfide compositions and their chalcophile and highly siderophile trace element signatures

In the first article, we have reported petrological data for a new, glass-bearing orthopyroxenite vein cutting a sub-arc mantle xenolith from Kamchatka. As similar veins from the West Bismarck arc, this orthopyroxenite is sulfide-rich and formed by cooling of parental melts derived by partial melting of spinel harzburgite sources. Here, I report new data for the abundances of major base metals and chalcophile and highly siderophile trace elements in vein sulfides from the two localities. Kamchatka vein sulfides are all Cu-poor monosulfide solid solution (MSS). West Bismarck veins contain MSS and a ternary (Fe, Cu, Ni)S solid solution (“xSS”), which ranges between MSS and intermediate solid solution (ISS) in composition. Sulfides follow Ni and Cu enrichment trends and have chondrite-normalized platinum-group element (PGE) patterns with elevated Pt relative to Os, Ir, Ru, and Rh. Pt alloys are frequently associated with sulfides and vugs formed from hydrothermal fluids, which also contain metallic Fe and wüstite. Vein sulfides, ranging from Fe-rich MSS (ca. 1,050–1,100°C) to xSS (≤850°C) through Ni-rich MSS, were formed in a sulfide liquid line of descent under oxygen and sulfur fugacity conditions (fO2 and fS2) down to one log unit below the fayalite–magnetite–quartz and close to the Pt-PtS buffers, respectively. The Ni and Cu enrichment trends in MSS are consistent with cooling and fractionation of Ni-rich and Cu-poor sulfide liquids (original atomic ∑metal/S∼0.9), which will finally solidify as xSS or ISS. Chondrite-normalized Pt/Pd>1 in some of the sulfides is a signature of spinel harzburgite sources. Because it occurs at relatively low fS2, the crystallization sequence of these sulfide liquids is accompanied by the formation of abundant PGE alloys and other metallic phases. Melts derived from spinel harzburgite sources can be originally oxidized to carry up to ∼2,600 ppm S (predominantly as S6+) and follow a sulfide-undersaturated evolution trend, until they are rapidly cooled to crystallize as orthopyroxenite dykes or sills. There, S6+-Fe2+ redox reactions with host rocks, together with the production of high-Mg# andesite derivatives with low S solubility and high-temperature, hydrothermal fluids at decreasing fO2 and fS2, will lead to the local precipitation of abundant sulfides and alloys.

Serpentinization of mantle xenoliths in Kerguelen archipelago: A first petrographic and geochemical study

The spinel harzburgites xenoliths from the Lac Michèle outcrop, Kerguelen archipelago (South Indian Ocean), have the particularity to show unique and unusual evidences of fluids circulation and especially of serpentinization. In this paper, in situ and whole-rock petrographic and geochemical data on a selection of variously serpentinized samples are presented and attest that several episodes of fluid-rock interaction occurred. Serpentinization processes affected notably and with variable degrees the spinel harzburgites leading to changes in their mineralogy and chemical compositions. Degree of serpentinization ranges from very slight (LOI < 3 wt% and Fe 3+ /Fe tot < 0.1) to moderate (4 wt% < LOI < 6 wt% and 0.21 < Fe 3+ /Fe tot < 0.33). Most serpentinized samples show a preferential petrographic direction of serpentinization, forming a subparallel serpentine network, which is sometimes intersected by serpentine veins. As a result, at least two serpentinization episodes were identified within the Lac Michèle samples, without any chemical differences between the two generations except for Cl content. This suggests very few chemical evolution of the system during serpentinization. Due to the significant amount of Cl measured in serpentine minerals (601 ppm on average), the nature of the fluids that interacted with the spinel harzburgites xenoliths during the serpentinization events can be hypothesized to be seawater-like or seawater-derived fluids. • Mantle xenoliths in Loranchet (Kerguelen) are slightly to moderately serpentinized. • Several episodes of fluid-rock interactions affected the peridotite xenoliths. • Fluids are mainly seawater-like or seawater-derived fluids.

IMPLICATIONS OF MANTLE XENOLITHS IN THE PLIOCENE-QUATERNARY BASALTS FROM THE SHAWRAN CRATER, BIR ALI AREA, YEMEN

Mantle xenoliths in basalt and tuffaceous volcanoes at the Shawran Crater, Bir Ali area, along the southeastern coast of Yemen are very useful to elucidate the nature of the lithospheric mantle beneath the area, which is characterised by rift tectonic activity and volcanism during the Pliocene–Quaternary period. The studied mantle xenoliths are mostly fresh showing igneous textures and composed mainly of spinel harzburgite and lherzolite, in addition to, less prominently, dunite. Spinel harzburgite and lherzolite are holocrystalline with abundant granular spinel that occurs interstitially to olivine, orthopyroxene, and clinopyroxene. The forsterite content of olivine is high (Fo89–91) attesting its mantle residue origin. Orthopyroxene is mostly enstatite (En89–92), and clinopyroxene is diopsidic in composition (Wo24–47En49–52 Fs2–4). Spinel Cr# (Cr/(Cr + Al) is distinguishable between lherzolites (Cr# = 0.12–0.15) and harzburgites (Cr# = 0.20–0.31). The calculated oxygen fugacity (logfO2) of the studied lherzolites (−1.76 to −0.20) and harzburgite (−2.7 to −0.98) xenoliths, and their equilibration temperature (~ 820–1,145°C) at about 1.5 GPa pressure, along with their mineralogical and petrological characteristics, are all support their evolution by mixed enrichment from a fertile and depleted asthenospheric mantle beneath the Bir Ali area.

The heterogeneous mantle massif in south Tibetan ophiolites and its implication for the tectonic evolution of Neo-Tethys

Ophiolitic mantle peridotites show large variations in their geochemical compositions, which provide important information for the histories of mantle melting, melt metasomatism and prior melt depletion in the context of tectonic evolution of ancient oceans. Here we report new petrological and geochemical data for mantle peridotites from the Zhagabu ophiolite in south Tibet, which could represent fossil upper mantle of the Mesozoic Neo-Tethys oceanic lithosphere. The Zhagabu mantle peridotites, including spinel lherzolites and spinel harzburgites, have highly heterogeneous geochemical compositions, with whole-rock Al2O3 of 0.3–2.0 wt% and CaO of 0.3–2.2 wt%, and spinel Cr# [Cr/(Cr + Al)] of 0.21–0.74 and Mg# [Mg/(Mg + Fe2+)] of 0.44–0.74. The clinopyroxenes from the studied samples show extremely depletion in light rare earth element compositions, some of which however are elevated by post-melting melt-rock interactions. Spinel and clinopyroxene compositions collectively suggest that the Zhagabu mantle peridotites have experienced ~9–20% of fractional melting from a depleted mid-ocean ridge basalt mantle source. Trace element modeling of clinopyroxenes further indicates that some of the studied samples follow the refertilization-hydrous melting trends with variable fluid fluxes. Therefore, the heterogeneous compositions of the Zhagabu mantle peridotites are not comparable to those of either abyssal peridotites or forearc peridotites, but most probably record a dynamic transition from the anhydrous condition beneath the Neo-Tethyan mid-ocean ridge to the hydrous condition above the subducted slab. Considering that a forearc spreading is in contradiction with the low magma budget of Yarlung Zangbo ophiolites, the Neo-Tethyan subduction re-initiation was suggested to be achieved along oceanic detachment faults at ultraslow-spreading ridges. The Zhagabu mantle peridotites represent the very heterogeneous mantle massif in south Tibetan ophiolites, and provide an excellent window to investigate the complex mantle dynamics and tectonic evolution of the Neo-Tethys Ocean.

Diversity of origin and geodynamic evolution of the mantle beneath the Variscan Orogen indicating rapid exhumation within subduction-related mélange (Moldanubian Zone, Bohemian Massif)

A variable assemblage of ultrabasic rocks along with minor eclogites investigated on a small area of a few km2 (Gföhl unit, Moldanubian Zone of the Bohemian Massif) reflects incorporation of contrasting mantle domains within a subduction-related tectonic mélange during the Variscan orogeny. Based on mineral composition, whole-rock chemistry, isotopic signatures, and pressure-temperature (P–T) estimates, four principal lithological types have been distinguished (1) spinel harzburgite (2) garnet lherzolite (3) spinel websterite and (4) eclogite. Spinel harzburgite, exclusively associated with HT migmatized gneisses, corresponds to the refractory oceanic lithosphere, as demonstrated by whole-rock composition (low Al2O3, CaO), chemistry of spinel (Cr# <0.4) and Al-rich pyroxene (Al2O3 up to 9 wt%). By contrast, garnet lherzolite, predominantly enclosed in HP felsic granulite, represents a fragment of the subcontinental mantle wedge, considering the strong fertile character (high Al2O3, TiO2, Yb) and spinel chemistry (Cr# >0.5). Websterites likely represent products of decompression partial melting of the asthenospheric mantle with a variable input of crustal component, whereas eclogites correspond to HP crystal cumulates from partial melts migrating through the Variscan mantle wedge. Both peridotite protoliths experienced various degrees of secondary refertilization, recorded as a cryptic metasomatic overprint, due to interaction with subduction-related silicate melts, from which numerous websterite and rare eclogite layers crystallized. The secondary mantle refertilization via melt-peridotite reaction is well-documented by decreasing bulk Mg# along with MgO/SiO2, elevated Al2O3/SiO2, TiO2 and FeOtot contents, and isotopic composition (87Sr/86Sr338 ~ 0.7051). Moreover, the positive correlation between highly fluid-immobile incompatible trace elements (e.g. Ti, Sc, V, Zr, Yb) and distribution of REE and Li is consistent with the melt refertilization trend.

Spinel Harzburgite-Derived Silicate Melts Forming Sulfide-Bearing Orthopyroxenite in the Lithosphere. Part 1: Partition Coefficients and Volatile Evolution Accompanying Fluid- and Redox-Induced Sulfide Formation

We report abundances of major trace and volatile elements in an orthopyroxenite vein cutting a sub-arc, mantle-derived, spinel harzburgite xenolith from Kamchatka. The orthopyroxenite contains abundant sulfides and is characterized by the presence of glass (formerly melt) both interstitially and as inclusions in minerals, comparable with similar veins from the West Bismarck arc. The glass formed by quenching of residual melts following crystallization of abundant orthopyroxene, amphibole, and minor olivine and spinel. The interstitial glass has a low-Ti, high-Mg# andesite composition, with a wide range of H2O and S contents but more limited F and Cl variations. We calculate trace element partition coefficients using mineral and glass data, including those for halogens in amphibole, which agree with experimental results from the literature. Despite having a similar, high-Mg# andesite composition, the orthopyroxene-hosted glass inclusions usually contain much more H2O and S than the interstitial glass (4–7 wt% and ∼2,600 ppm, respectively). The initial vein-forming melts were oxidized, recording oxygen fugacity conditions up to ∼1.5 log units above the fayalite–magnetite–quartz oxygen buffer. They intruded the sub-arc mantle lithosphere at ≥1,300°C, where they partially crystallized to form high-Mg# andesitic derivative melts at ca. 1,050–1,100°C. Comparison with literature data on glass-free orthopyroxenite veins from Kamchatka and the glass-bearing ones from West Bismarck reveals fundamental similarities indicating common parental melts, which were originally produced by low-degree melting (≤5%) of spinel harzburgite at ≥1,360°C and ≤1.5 GPa. This harzburgite source likely contained ≤0.05 wt% H2O and a few ppm of halogens. Volatile evolution inferred from glass compositions shows that (i) redox exchange between S6+ in the original melt and Fe2+ in the host mantle minerals, together with (ii) the formation of an S-bearing, (H2O, Cl)-rich hydrothermal fluid from the original melt, provides the conditions for the formation of abundant sulfides in the orthopyroxenites during cooling. During this process, up to 85% of the original melt S content (∼2,600 ppm) is locally precipitated as magmatic and hydrothermal sulfides. As such, melts derived from spinel harzburgite sources can concentrate chalcophile and highly siderophile metals in orthopyroxenite dykes and sills in the lithosphere.

Mineralogy, Geochemistry and Tectonic Setting of the Raobazhai Ultramafic Complex, North Dabie

The Raobazhai ultramafic complex is located in the north of the Dabie Mountains and is composed of spinel peridotites accompanied by a few lenticular mafic metamorphic rocks. The spinel peridotites are mostly harzburgite, along with minor dunite and lherzolite. This study reports the petrological, geochemical, and Re-Os isotopic data of spinel and chromite harzburgites from Raobazhai. The major and trace whole-rock geochemistry characteristics indicate that the rocks are remnants of partial melting to different degrees (6–17%). Both mineral and whole-rock geochemistry showed typical abyssal peridotite affinity. Due to the presence of water-bearing minerals, the Sr, Ba, and U were enriched, and the Nb, Zr, and Hf were depleted, which can be attributed to the strong metasomatism of the boninitic melting/fluid in the fore-arc domain. The flat distribution of platinum group elements (PGE) and the decoupling of Pt-Pd were also the result of the fore-arc melting/fluid interaction. The 187Os/188Os ratios (0.1149–0.1266) were generally lower than the recommended value of the primitive mantle and fell within the abyssal peridotite isotope range. This indicated that the Raobazhai harzburgites were likely mantle peridotites with oceanic characteristics that underwent a fore-arc boninitic melting/fluid transformation event.

Depletion and refertilisation of the lithospheric mantle below the Kapsiki plateau (Northern Cameroon Volcanic Line) deduced from trace element and H2O systematics in mantle xenoliths

Clinopyroxene bearing spinel harzburgites recovered from Cenozoic alkaline basalts from the Kapsiki plateau were investigated with the aim of understanding depletion and enrichment processes in the subcontinental mantle below a major tectonic line. Concentrations of major and trace elements (including H) were determined in-situ in olivine, orthopyroxene, clinopyroxene and spinel by EPMA, LA-ICP-MS and FTIR. The xenoliths are refractory with high olivine (0.91–0.92) and orthopyroxene (0.92–0.93) Mg# coupled with relatively high modal proportions of clinopyroxene (5–8%) and a remarkably wide range in clinopyroxene Mg# (0.91–0.94), interpreted to reflect high degrees of partial melting followed by modal and chemical metasomatic refertilization. A fractional partial melting model of orthopyroxene trace elements in a depleted mantle indicates 20–30% of melting. Clinopyroxenes show two groups based on their CaO contents (18.7–18.9 and 20.6–22.6 wt %) suggesting a secondary origin and modal metasomatism. The low Ca clinopyroxenes were the latest to be formed, and the wide range of clinopyroxene Mg# shows a lack of equilibrium with the coexisting minerals. The high Ca clinopyroxenes record ancient metasomatic events that are also documented in orthopyroxene. Cryptic metasomatism is shown by strong progressive enrichments in LREEs and MREEs of orthopyroxene and clinopyroxene. Th vs La and Sr vs Nd of clinopyroxene are used to identify different generations of metasomatism. Ti/Eu vs (La/Yb)N and Zr/Hf systematics indicate that the metasomatising agent has both a carbonatite and a silicate component. The structural hydroxyl contents of the different mineral phases are very low (<1 ppm for olivine, 40–48 ppm for orthopyroxene and 164–277 ppm for clinopyroxene). The very low water contents compared to typical sub-continental peridotites could be attributed to the depleted nature of the xenoliths or reflect lower water activities of carbonatitic melts relative to alkaline melts. Estimated fO2 values expressed as ΔlogFMQ, (where FMQ corresponds to the fayalite magnetite-quartz oxygen buffer) range from -0.42 to -0.26 and are consistent with minor OH stretching regions of 3520 cm-1 in orthopyroxene, related to a ferric iron defect.The combination of textural investigations, major, and trace element and H2O data suggests that a refractory subcontinental mantle was affected by several episodes of intraplate metasomatism dominated by silicate-carbonatite melts above the North-Eastern end of the Cameroon Volcanic Line.

Recycled crustal carbon in the depleted mantle source of El Hierro volcano, Canary Islands

The Canary Islands, in the eastern Atlantic, are among the most enigmatic Oceanic Island provinces on Earth, as the mantle source feeding its volcanism exhibits wide spatial heterogeneity and a multiplicity of sources. Multi-isotope whole-rock studies have long revealed the presence of a recycled oceanic crust/lithosphere component in the mantle source. However, noble gas systematics have been more challenging to interpret, and the available carbon isotope data is limited and cannot support/dismiss this interpretation. Here, we present the very first isotopic characterisation of CO2 and noble gases (He-Ne-Ar) in fluid inclusions (FI) in minerals hosted in mantle xenoliths from El Hierro, the youngest and westernmost island of the Canary volcanic archipelago. Six fresh xenoliths from El Julan cliff valley were analysed (3 spinel lherzolites and 3 spinel harzburgites). We find carbon isotopic compositions of CO2 in FI (δ13C) ranging from −2.38 to −1.23‰ in pyroxenes and from −0.19 to +0.96‰ in olivines. These unusually positive δ13C values, well above the typical mantle range (−8‰ < δ13C < −4‰), prove, for the first time, the presence of a recycled crustal carbon component in the local source mantle. We interpret this 13C-rich component as inherited from a mantle metasomatism event driven by fluids carrying carbon from C. In contrast, our El Hierro xenoliths identify a depleted mantle-like He signature, with an average Rc/Ra ratio (3He/4He normalised to air ratio and corrected for atmospheric contamination) of 7.45 ± 0.26 Ra. The involvement of depleted mantle-like fluids, variably admixed with air-derived components (possibly recycled via paleo-subduction event(s)), is corroborated by Ne-Ar isotopic compositions. The depleted mantle-like He signature suggests instead the involvement of a primordial He source in the local lithospheric mantle and indicates a marginal role played by past subduction events in modifying the local mantle He budget. When put in the context of previous 3He/4He measurements in FI and surface gases along the Canary archipelago, our results confirm an overall west-to-east decrease of Rc/Ra ratios, which may be interpreted as due to increasing contributions from the African sub-continental mantle, the addition of radiogenic 4He during magma migration in the oceanic crust (whose thickness increases eastward) and/or magma ageing.

Chalcophile-siderophile element systematics and regional-scale magmatic percolation in the Ronda peridotite massif (Spain)

Eighteen samples from the south-western part of the Ronda lherzolitic massif have been analysed with bulk-rock and in-situ techniques to unravel the fate of Cu, platinum-group element and chalcogens (S, Se) in a middle Proterozoic subcontinental lithospheric mantle segment variably overprinted by kilometre-scale porous flow percolation of asthenosphere-derived silicate melts during the Alpine orogeny. Chalcogen elements (S, Se Cu) and PGE systematics fit well the published data base for orogenic mantle peridotites as a whole. Positive correlations between S, Se, Cu and fertility result from progressive removal of sulfides from the mantle at increasing degrees of melting. A few harzburgites preserved the S-, Se- and Pd-depleted (Pd/Ir < 1)-chondrite normalized PGE patterns of residues after partial melting. The Oligocene thermo-mechanical erosion event triggered secondary partial melting of the sulfide phase liberating a Cu-Ni-rich sulfide melt now identified through Cu-Ni-rich sulfide inclusions (pentlandite + chalcopyrite ± bornite) and a wide range of intergranular Cu-rich sulfides and alloys. Residual monosulfide solid solution (coexisting with refractory platinum group minerals (laurite-erlichmanite) in spinel tectonites) survived throughout all of the tectonometamorphic domains, thus preserving relative and absolute abundances of compatible platinum group elements (Os, Ir, Ru, Rh). Local scale redistribution of the Cu-Ni-rich sulfide melt accounts for the enrichment/depletion trends of Te, Pd, Pt, Au, Ag, Cu identified in granular peridotites. On cooling, the sulfide melt produced pentlandite by reacting with monosulfide solid solution at T < 870 °C while transfering incompatible elements that generated micrometric Pt-Cu-Te-As-bearing platinum-group mineral inclusions (e.g. malanite CuPt2IrS4, moncheite PtTe2, Pt arsenide, secondary Pt–Cu alloys), in addition to superchondritic Pd/Ir and nearly chondritic Se/Te identified in mantle sulfides of metasomatic origin. By contrast, micrometer-sized Au particles identified in Au-enriched spinel harzburgites are clearly primary precipitates from volatile-rich small melt fractions.

Silica-rich spinel harzburgite residues formed by fractional hybridization-melting of the intra-oceanic supra-subduction zone mantle: New evidence from TUBAF seamount peridotites

Recent studies of serpentine-free, spinel peridotite xenoliths from the mantle lithosphere beneath the active Kamchatka and West Bismarck arcs have shown that these rocks are enriched in silica and highly depleted in incompatible elements in comparison with melting residues of either primitive or mid-ocean ridge mantle. It has been suggested that the silica-rich nature of peridotites from the intra-oceanic, fore- and sub-arc mantle lithosphere, collectively referred to as ‘Supra-Subduction Zone (SSZ) peridotites’, is primarily of residual origin and inherited from source processes during partial melting in the SSZ mantle asthenosphere (mantle wedge). However, quantifying the contribution of post-melting processes to the silica-rich nature of SSZ peridotites has remained challenging.Here we report petrological and major and trace element data for a new suite of spinel harzburgite xenoliths from the mantle lithosphere beneath TUBAF seamount, located in the fore-arc region of New Ireland (Papua New Guinea area). All samples are fresh peridotites displaying coarse-grained protogranular textures, and sometimes high orthopyroxene (up to ∼29 wt%) at low clinopyroxene (≤4 wt%) contents, which are typical for SSZ peridotites worldwide. TUBAF peridotites in this study have suffered very little post-melting metasomatism through the formation of ≤1 wt% amphibole, which subsequently experienced decompression-induced breakdown during the xenolith ascent. Otherwise, the rocks display a high degree of inter-mineral equilibration and melting signatures preserved through sub-solidus re-equilibration. The bulk-rock chemistry of TUBAF peridotites record a Fe-Al correlation along the 25–30% melting isopleths from ∼2 to <1 GPa, in combination with the distinctive enrichment in silica and (TiO2, Al2O3, Na2O)-depletion of SSZ peridotites. This strongly supports the melting origin of these ‘residual SSZ signatures’. Bulk-rock and mineral lithophile trace element compositions of TUBAF xenoliths are similar to those of other residual SSZ peridotites, consistent with 25–30% of nearly-pure fractional melt extraction (critical mass porosity <0.001%) in the presence of a fluxing agent enriched in highly incompatible elements.We re-assess earlier interpretations of the origins of TUBAF peridotites by melting at mid-ocean ridges. Instead, we show that these rocks have experienced their last melting event in the mantle wedge, similar to samples from the Izu-Bonin-Mariana fore-arc and the Kamchatka and West Bismarck arcs. We also demonstrate that post-melting metasomatism (including fibrous orthopyroxene that are absent from the samples in this study) is unrelated to the residual SSZ mantle signatures, for which we present the results of polybaric and isothermal flux-melting models including minor element partitioning parameterizations. These models imply that residual SSZ signatures form when previously depleted mantle protoliths are hybridized by hydrous, silica-rich liquids. From the unique Fe-Al correlation in TUBAF peridotites and their low temperatures of equilibration, it appears that fractional hybridization-melting processes forming these rocks occurred in a fore-arc environment with shallow mantle decompression, likely during Oligocene to Miocene subduction along the Manus-Kilinailau trench.

Olivine melilitites, mantle xenoliths, and xenocrysts of the Takarindiona district: Petrogenesis, magmatic evolution, and the sub-continental lithospheric mantle of east-central Madagascar

The olivine melilitites from the southern part of the 6.8 Ma-old Takarindiona volcanic field (Eastern Madagascar) are olivine ± chromite -phyric lavas, with zoned titanaugite, perovskite, melilite, nepheline, monticellite, Ba–Ti-mica and Fe–Ti oxides as microphenocrysts and groundmass phases. The rocks are very primitive, rich in incompatible trace elements (e.g., Ba = 1049 ± 153 ppm, Sr = 1050 ± 167 ppm, Nb = 98 ± 13 ppm; La/Ybn = 41 ± 5; La/Nb = 0.88 ± 0.05), and have restricted ranges of initial 87Sr/86Sr (0.70391–0.70410) and 143Nd/144Nd (0.51272–0.51282). The rocks follow a differentiation trend controlled by ab. 20% removal/addition of phenocryst olivine ± chromite. The olivine melilititic magmas are the product of small degrees of partial melting (1–3%) of a peridotitic source, enriched in highly incompatible trace elements by CO2-, F-, and H2O-rich melts, located within the garnet stability field (3–3.5 GPa and ~100 km depth) of sub-continental lithospheric mantle, where carbonates (dolomite) and possibly phlogopite were stable phases. Mantle xenoliths within the volcanics are mostly spinel harzburgites having mineral modes and chemical compositions suggesting variable degrees of “basalt” melt extraction. Based on textural and chemical evidence, and quantitative thermobarometric estimates, the xenoliths were incorporated at a pressure of ~1.1 GPa (~35–40 km depth), far shallower than the source of the melilititic magmas, and along a predictably cool geotherm beneath Archean continental lithosphere. Highly resorbed orthopyroxene xenocrysts mantled by augite indicate that the melilitites may have also entrained lower crustal materials or underplated subalkaline rocks. The mantle sources of the lavas and mantle xenoliths of the Takarindiona district indicate stratification of the lithospheric mantle, and help constraining the lithospheric features and the magmatic history of the Eastern Madagascar craton.

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

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

Melt-rock interaction in the subarc mantle: records from the plagioclase peridotites of the southern Palawan Ophiolite, Philippines

ABSTRACT The interaction between migrating melts and the upper mantle largely affects the composition of the ascending melt and residual peridotites. In island arcs, melt-rock interactions and products which involved highly depleted mantle peridotites are still largely undocumented despite their petrological importance. In this contribution, the petrographic and geochemical signatures of refractory and refertilized peridotites comprising the mantle section of the southern Palawan Ophiolite, Philippines are investigated. The peridotites are dominantly comprised of residual spinel harzburgites with minor dunite and plagioclase peridotites. Spinel harzburgites are similar to other highly depleted residual mantle materials of other suprasubduction zone ophiolites. Plagioclase peridotites, which are cut by gabbroic intrusions, preserve distinct petrological characteristics indicating melt-rock interaction. The melts preserved as gabbroic dikes have signatures transitional between mid-ocean ridge and island arc, and are comparable to back-arc basin lavas. We therefore propose that the plagioclase peridotites were formed due to the reaction between highly depleted mantle peridotites beneath an intraoceanic arc and migrating BABB-like magmas possibly during the incipient stages of back-arc rifting.

Refertilization of lithospheric mantle beneath the North China Craton in Mesozoic: Evidence from in situ Sr isotopes of Fuxin peridotite

The Mesozoic was a critical period for the evolution of the North China Craton (NCC). We present the petrological observations and in situ mineral major and trace elements and Sr isotopic data for spinel harzburgite and lherzolite xenoliths in Late Cretaceous Fuxin basalts from the northern margin of the NCC. These data are used to investigate the nature and evolution of the subcontinental lithospheric mantle (SCLM) beneath the NCC during the Mesozoic. The peridotite xenoliths commonly have porphyroclastic and granoblastic textures, and can be divided into high-Mg# and low-Mg# peridotites. Compared with the low-Mg# peridotites, the high-Mg# peridotites have higher olivine Fo (>91) and spinel Cr# values (>35), and their clinopyroxenes are light REE-enriched with uniform 87Sr/86Sr ratios (ca. 0.7042). These observations suggest that the high-Mg# peridotites could be relics of old SCLM and were metasomatized by melts derived from subducted Paleo-Asian oceanic slab. The low-Mg# peridotites are characterized by minerals with sieve textures and melt pockets. The olivine Fo of the low-Mg# peridotites are low and variable (81.2–90.4), and decrease from core to rim in some crystals. Thus, the low-Mg# peridotites underwent extensive peridotite–melt interactions. Their clinopyroxenes are enriched in LREE and show large variations in the 87Sr/86Sr ratios (0.7039–0.7052). Moreover, 87Sr/86Sr ratios positively correlate with MgO and negatively correlate with Al2O3, Eu and Dy contents. These observations suggest that the low-Mg# peridotites experienced multiple stages of mantle metasomatism, involving high-87Sr/86Sr melts derived from the subducted Paleo-Asian oceanic crust in early stage and low-87Sr/86Sr melts derived from more recent asthenospheric upwelling. Therefore, the low-Mg# peridotites are representative of SCLM fragments that were strongly modified beneath the Fuxin region during the Late Cretaceous. Combined with previous studies, our findings suggest that refertilization of the SCLM by asthenospheric melts beneath the northern margin of the NCC commenced before eruption of the Fuxin basalts (ca. 100 Ma), which is much earlier than previously thought. This process resulted in a highly heterogeneous SCLM. In addition, the Tan–Lu Fault contributed substantially to the evolution of the SCLM beneath the NCC during the Mesozoic.